Deprecated: The each() function is deprecated. This message will be suppressed on further calls in /home/zhenxiangba/zhenxiangba.com/public_html/phproxy-improved-master/index.php on line 456
JP7202250B2 - Wastewater treatment equipment and wastewater treatment method - Google Patents
[go: Go Back, main page]

JP7202250B2 - Wastewater treatment equipment and wastewater treatment method - Google Patents

Wastewater treatment equipment and wastewater treatment method Download PDF

Info

Publication number
JP7202250B2
JP7202250B2 JP2019086327A JP2019086327A JP7202250B2 JP 7202250 B2 JP7202250 B2 JP 7202250B2 JP 2019086327 A JP2019086327 A JP 2019086327A JP 2019086327 A JP2019086327 A JP 2019086327A JP 7202250 B2 JP7202250 B2 JP 7202250B2
Authority
JP
Japan
Prior art keywords
fluorine
solid
aluminum
liquid separation
liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
JP2019086327A
Other languages
Japanese (ja)
Other versions
JP2019122961A (en
Inventor
俊彦 安部
祐一 須田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Heavy Industries Environment Co Ltd
Original Assignee
Sumitomo Heavy Industries Environment Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Heavy Industries Environment Co Ltd filed Critical Sumitomo Heavy Industries Environment Co Ltd
Priority to JP2019086327A priority Critical patent/JP7202250B2/en
Publication of JP2019122961A publication Critical patent/JP2019122961A/en
Application granted granted Critical
Publication of JP7202250B2 publication Critical patent/JP7202250B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Removal Of Specific Substances (AREA)

Description

本発明は、排水処理装置及び排水処理方法に関する。 TECHNICAL FIELD The present invention relates to a wastewater treatment apparatus and a wastewater treatment method.

従来、フッ素を含有する排水からフッ素を除去する排水処理装置として、排水にアルミ系無機凝集剤を混合して水酸化アルミニウム(Al2(OH)3)のフロックを生成させ、当該フロックによってフッ素を吸着し共沈させる方法が知られている(非特許文献1参照)。 Conventionally, as a wastewater treatment device for removing fluorine from wastewater containing fluorine, the wastewater is mixed with an aluminum-based inorganic coagulant to generate flocs of aluminum hydroxide (Al 2 (OH) 3 ), and the flocs remove fluorine. A method of adsorption and coprecipitation is known (see Non-Patent Document 1).

和田祐司、「フッ素含有排水の高度処理法」、科学と工業、2002年、第76巻、p.557-564Yuji Wada, "Advanced Treatment Method for Fluorine Containing Wastewater", Science and Industry, 2002, Vol.76, p. 557-564

しかしながら、上記のアルミ系無機凝集剤を用いる方法では、排水から除去できるフッ素の量が、混合するアルミ系無機凝集剤の量に対応するため、フッ素を充分に除去しようとすると大量のアルミ系無機凝集剤を使用する必要がある。また、これにより大量の余剰スラッジが発生してしまう。 However, in the above method using an aluminum-based inorganic flocculant, the amount of fluorine that can be removed from the waste water corresponds to the amount of the aluminum-based inorganic flocculant that is mixed. A flocculant must be used. In addition, a large amount of excess sludge is generated as a result.

これに対し、排水からフッ素を除去する別の方法として、排水にカルシウム系の薬剤を添加してフッ化カルシウム(CaF2)を生成させる方法がある。しかしながら、この方法では、排水がフッ素の他に硫酸マグネシウム(Mg(SO)4)等の硫酸塩を含有する場合、添加されたカルシウム系の薬剤と硫酸塩とが反応して石膏(Ca(SO)4)を生成するため、フッ化カルシウムの生成に大量のカルシウム(Ca)を必要としてしまう。従って、このような硫酸塩を含有するフッ素含有排水においてはアルミ系無機凝集剤を用いる方法を適用せざるを得ない場合があり、この場合、上述したように、大量のアルミ系無機凝集剤を使用すると共に大量の余剰スラッジが発生するという問題があった。 On the other hand, as another method for removing fluorine from waste water, there is a method of adding a calcium-based agent to the waste water to generate calcium fluoride (CaF 2 ). However, in this method, if the wastewater contains sulfate such as magnesium sulfate (Mg(SO) 4 ) in addition to fluorine, the added calcium-based chemical reacts with the sulfate to produce gypsum (Ca(SO) ) 4 ), a large amount of calcium (Ca) is required for the production of calcium fluoride. Therefore, in fluorine-containing wastewater containing such sulfates , it may be necessary to apply a method using an aluminum-based inorganic flocculant. In this case, as described above, a large amount of aluminum-based inorganic flocculant is used. There was a problem that a large amount of surplus sludge was generated as it was used.

本発明は、上記課題を解決するために為されたものであり、硫酸塩を含有するフッ素含有排水において、アルミ系無機凝集剤の使用量を削減できると共に余剰スラッジの発生量を低減できる排水処理装置及び排水処理方法を提供することを目的とする。 The present invention has been made to solve the above problems, and is a wastewater treatment that can reduce the amount of aluminum-based inorganic flocculants used and the amount of excess sludge generated in fluorine-containing wastewater containing sulfate. An object of the present invention is to provide an apparatus and a wastewater treatment method.

本発明に係る排水処理装置は、硫酸塩を含有するフッ素含有排水からフッ素を除去する排水処理装置において、硫酸塩を含有するフッ素含有排水とアルミ系無機凝集剤とを混合する混合部と、混合部で混合された混合液を固液分離する固液分離部と、固液分離部で固液分離して得た固形分を混合部に供給するための供給手段と、を備える。 A wastewater treatment apparatus according to the present invention is a wastewater treatment apparatus for removing fluorine from fluorine -containing wastewater containing sulfate, and a mixing unit for mixing fluorine-containing wastewater containing sulfate and an aluminum-based inorganic flocculant. A solid-liquid separation section for solid-liquid separation of the mixed liquid mixed in the section, and a supply means for supplying the solid content obtained by the solid-liquid separation in the solid-liquid separation section to the mixing section.

また、本発明に係る排水処理方法は、硫酸塩を含有するフッ素含有排水からフッ素を除去する排水処理方法において、硫酸塩を含有するフッ素含有排水とアルミ系無機凝集剤とを混合部で混合し、混合部で混合された混合液を固液分離部で固液分離し、固液分離部で固液分離して得た固形分を混合部に供給する。 Further, the wastewater treatment method according to the present invention is a wastewater treatment method for removing fluorine from fluorine-containing wastewater containing sulfate, in which fluorine-containing wastewater containing sulfate and an aluminum-based inorganic coagulant are mixed in a mixing unit. , the liquid mixture mixed in the mixing section is solid-liquid separated in the solid-liquid separation section, and the solid content obtained by the solid-liquid separation in the solid-liquid separation section is supplied to the mixing section.

この排水処理装置及び排水処理方法によれば、混合部で硫酸塩を含有するフッ素含有排水とアルミ系無機凝集剤とが混合されると、フロックが混合液中に生成し、このフロックが混合液中のフッ素を吸着して液中から除去する。そして、固液分離部において、既にフッ素を吸着したフロックをフッ素と共に共沈させ、また、未だフッ素を吸着していないフロックも沈降させて固液分離し、これらの固液分離した固形分は混合部に供給される。その結果、未だフッ素を吸着していないフロック及び既にフッ素を吸着したが更にフッ素を吸着することができる状態のフロックが混合液中のフッ素を吸着して液中から除去する。これにより、フッ素の吸着・共沈のために使用されたアルミ系無機凝集剤を再びフッ素の吸着・共沈に活用できる。以上により、硫酸塩を含有するフッ素含有排水において、アルミ系無機凝集剤の使用量を削減できると共に、このアルミ系無機凝集剤の使用量を削減すること及び固液分離して得た固形分を混合部に供給することにより余剰スラッジの発生量を低減できる。 According to this wastewater treatment apparatus and wastewater treatment method, when the fluorine-containing wastewater containing sulfate and the aluminum-based inorganic flocculant are mixed in the mixing unit, flocs are generated in the mixed solution, and the flocs form in the mixed solution. Absorbs fluorine and removes it from the liquid. Then, in the solid-liquid separation unit, the flocs that have already adsorbed fluorine are co-precipitated with fluorine, and the flocs that have not yet adsorbed fluorine are also precipitated to separate solid and liquid, and these solid-liquid separated solids are mixed. supplied to the department. As a result, the flocs that have not yet adsorbed fluorine and the flocs that have already adsorbed fluorine but are capable of further adsorbing fluorine adsorb fluorine in the mixed liquid and remove it from the liquid. As a result, the aluminum-based inorganic coagulant used for fluorine adsorption/coprecipitation can be reused for fluorine adsorption/coprecipitation. As described above, in fluorine-containing wastewater containing sulfate, the amount of aluminum-based inorganic flocculant used can be reduced, and the amount of this aluminum-based inorganic flocculant used can be reduced, and the solid content obtained by solid-liquid separation can be reduced. The amount of excess sludge generated can be reduced by supplying it to the mixing section.

ここで、本発明に係る排水処理装置において、混合部は、pHを調整するpH調整手段を有していてもよい。この場合、pHを調整することで、硫酸塩を含有するフッ素含有排水とアルミ系無機凝集剤とが反応し、フロックを生成する最適な値とできるため、フロックを効率良く生成でき、アルミ系無機凝集剤の使用量に対して効率良くフッ素を吸着・共沈させて液中から除去できる。 Here, in the waste water treatment apparatus according to the present invention, the mixing section may have pH adjusting means for adjusting pH. In this case, by adjusting the pH, the fluorine-containing wastewater containing sulfate and the aluminum-based inorganic flocculant react and can be set to the optimum value for generating flocs, so flocs can be efficiently generated, and the aluminum-based inorganic Fluorine can be efficiently adsorbed and co-precipitated with respect to the amount of coagulant used, and removed from the liquid.

本発明によれば、硫酸塩を含有するフッ素含有排水において、アルミ系無機凝集剤の使用量を削減できると共に余剰スラッジの発生量を低減できる。 According to the present invention, it is possible to reduce the amount of aluminum-based inorganic flocculant used and the amount of excess sludge generated in fluorine-containing waste water containing sulfate .

実施形態に係る排水処理装置を示す概略構成図である。BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic block diagram which shows the waste water treatment apparatus which concerns on embodiment. 変形例に係る排水処理装置を示す概略構成図である。It is a schematic block diagram which shows the waste water treatment apparatus which concerns on a modification.

以下、本発明に係る排水処理装置及び排水処理方法の一実施形態について、図面を参照して詳細に説明する。 BEST MODE FOR CARRYING OUT THE INVENTION An embodiment of a wastewater treatment apparatus and a wastewater treatment method according to the present invention will be described in detail below with reference to the drawings.

図1は、実施形態に係る排水処理装置を示す概略構成図である。本実施形態に係る排水処理装置は、フッ素及び硫酸塩を含有する排水(以下、硫酸塩を含有するフッ素含有排水という)からフッ素を除去して所定のフッ素濃度以下とする装置であり、当該装置による処理水のフッ素濃度を、例えば放流先の水質基準で定められるフッ素濃度(一例として、15mg/l)を下回るようにするものである。なお、硫酸塩には、硫酸イオン及び硫酸化合物が含まれる。また、硫酸化合物としては、硫酸アンモニウム、硫酸ナトリウム及び硫酸マグネシウム等が該当する。 FIG. 1 is a schematic configuration diagram showing a waste water treatment apparatus according to an embodiment. The wastewater treatment device according to the present embodiment is a device that removes fluorine from wastewater containing fluorine and sulfate (hereinafter referred to as fluorine-containing wastewater containing sulfate ) to a predetermined fluorine concentration or less, and the device The fluorine concentration of the treated water is made to fall below the fluorine concentration (eg, 15 mg/l) specified by the water quality standard of the discharge destination, for example. Sulfate includes sulfate ions and sulfate compounds. Moreover, ammonium sulfate, sodium sulfate, magnesium sulfate, etc. correspond to a sulfate compound.

ここで、フッ化カルシウムの溶解度の理論値は16mg/l(25℃)でフッ素濃度としては7.8mg/lだが、硫酸塩を含む処理水のフッ素濃度としてフッ素濃度を15mg/l以下にする場合は、カルシウム系の薬剤とアルミ系無機凝集剤との併用処理が必要であり、アルミ系無機凝集剤単独で行う場合にはアルミ系無機凝集剤を大量に添加する必要があった。本発明は、アルミ系無機凝集剤を大量に添加することなくフッ素濃度を15mg/l以下にする場合に有効なものである。以下、詳説する。 Here, the theoretical value of the solubility of calcium fluoride is 16 mg/l (25°C) and the fluorine concentration is 7.8 mg/l, but the fluorine concentration of treated water containing sulfate is set to 15 mg/l or less. In this case, a combined treatment with a calcium-based chemical and an aluminum-based inorganic flocculant is required, and when the aluminum-based inorganic flocculant is used alone, a large amount of aluminum-based inorganic flocculant must be added. The present invention is effective in reducing the fluorine concentration to 15 mg/l or less without adding a large amount of aluminum-based inorganic flocculant. A detailed description will be given below.

図1に示すように、排水処理装置1は、主ラインL1と、主ラインL1に併設された副ラインL2と、を備えている。主ラインL1は、排水処理装置1の上流側から流入する硫酸塩を含有するフッ素含有排水からフッ素を除去し、所定のフッ素濃度以下となった処理水を下流側へ排出するためのラインであり、副ラインL2は、主ラインL1において得られた固形分の一部を主ラインL1における上流側に還流すると共に、残部を当該装置1の外部へ排出するためのラインである。この主ラインL1には、混合槽(混合部)2と、凝集槽(凝集部)3と、固液分離槽(固液分離部)4と、が上流から下流へ向かってこの順に設けられている。 As shown in FIG. 1, the wastewater treatment apparatus 1 includes a main line L1 and a sub-line L2 provided side by side with the main line L1. The main line L1 is a line for removing fluorine from sulfate-containing fluorine-containing wastewater flowing from the upstream side of the wastewater treatment apparatus 1 and for discharging treated water having a predetermined fluorine concentration or less to the downstream side. , the secondary line L2 is a line for refluxing a part of the solid content obtained in the main line L1 to the upstream side of the main line L1 and for discharging the remainder to the outside of the apparatus 1. The main line L1 is provided with a mixing tank (mixing section) 2, a flocculation tank (aggregation section) 3, and a solid-liquid separation tank (solid-liquid separation section) 4 in this order from upstream to downstream. there is

混合槽2は、排水処理装置1の上流側から第1ラインL11を介して流入する硫酸塩を含有するフッ素含有排水と、無機凝集剤供給ラインL15を介して供給されるアルミ系無機凝集剤と、を混合して混合液とし、このとき生成するフロック(すなわち、凝集剤を用いて水酸化アルミニウムを含む粒子を集合させた集合体)にフッ素を吸着させるための槽である。ここで、アルミ系無機凝集剤としては、例えばポリ塩化アルミニウム(PAC)、硫酸アルミニウム(硫酸バンド)等を用いることができるが、これに限定されない。 The mixing tank 2 contains fluorine-containing waste water containing sulfate that flows from the upstream side of the waste water treatment apparatus 1 through the first line L11, and an aluminum-based inorganic coagulant supplied through the inorganic coagulant supply line L15. are mixed to form a mixed solution, and fluorine is adsorbed on flocs (ie aggregates in which particles containing aluminum hydroxide are aggregated using a flocculant) formed at this time. Here, as the aluminum-based inorganic flocculant, for example, polyaluminum chloride (PAC), aluminum sulfate (aluminum sulfate), or the like can be used, but it is not limited thereto.

混合槽2は、混合槽2内でのSS濃度(すなわち、混合液中における浮遊物質の重量濃度)を測定するSS濃度センサ5を槽内に有している。 The mixing tank 2 has an SS concentration sensor 5 for measuring the SS concentration in the mixing tank 2 (that is, the weight concentration of suspended solids in the mixed liquid).

また、混合槽2は、混合液のpHを測定するpHセンサ6を槽内に有し、このpHセンサ6によって測定したpHに基づきpHを調整するための薬剤を当該混合槽2に供給する薬剤供給ライン(pH調整手段)L16を有している。薬剤としては、酸性薬剤(例えば、塩酸、硫酸等)、又はアルカリ性薬剤(例えば、苛性ソーダ等)が好適に用いられる。pHセンサ6としては特に限定されず、公知のものを用いることができる。 Further, the mixing tank 2 has a pH sensor 6 for measuring the pH of the mixed liquid in the tank, and based on the pH measured by the pH sensor 6, a chemical for adjusting the pH is supplied to the mixing tank 2. It has a supply line (pH adjusting means) L16. As the chemical, an acidic chemical (eg, hydrochloric acid, sulfuric acid, etc.) or an alkaline chemical (eg, caustic soda, etc.) is preferably used. The pH sensor 6 is not particularly limited, and known sensors can be used.

凝集槽3は、第2ラインL12を介して混合槽2から流入する混合液に、高分子凝集剤供給ラインL17を介して供給される高分子凝集剤を混合して、混合液中のフロックが沈殿し易くなるように当該フロックをより大きく形成するための槽である。高分子凝集剤としては、例えばアニオン系高分子凝集剤等を用いることができる。 The flocculating tank 3 mixes the liquid mixture flowing from the mixing tank 2 via the second line L12 with the polymer flocculant supplied via the polymer flocculant supply line L17 so that the flocs in the liquid mixture are A tank for making the floc larger so that it is easier to settle. As the polymer flocculant, for example, an anionic polymer flocculant or the like can be used.

固液分離槽4は、第3ラインL13を介して凝集槽3から流入する混合液を固液分離するための槽である。固液分離槽4は、混合液を固形分と固形分以外の液とに固液分離する。すなわち、固形分とは、固液分離槽4において固液分離された混合液のうちの液以外の部分である。固形分には、フッ素を吸着していないフロック及びフッ素を吸着したフロックの両方が含まれている。固液分離槽4の底面は、例えば下方へ狭まる漏斗状をなしており、その頂点部分には固液分離槽4から固形分を排出するための排出口4aが設けられている。 The solid-liquid separation tank 4 is a tank for solid-liquid separation of the mixed liquid flowing from the aggregation tank 3 via the third line L13. The solid-liquid separation tank 4 solid-liquid separates the mixed liquid into a solid content and a liquid other than the solid content. That is, the solid content is the portion other than the liquid in the mixed liquid separated into solid and liquid in the solid-liquid separation tank 4 . The solid content includes both flocs that have not adsorbed fluorine and flocs that have adsorbed fluorine. The bottom surface of the solid-liquid separation tank 4 has, for example, a funnel shape that narrows downward, and a discharge port 4a for discharging the solid content from the solid-liquid separation tank 4 is provided at the apex thereof.

副ラインL2は、固液分離槽4の排出口4aに接続されると共に、排出口4aとは反対側において、固形分還流ライン(供給手段)L21と余剰スラッジ排出ラインL22とに分岐している。この三つ又の分岐点には、固形分還流ラインL21又は余剰スラッジ排出ラインL22にそれぞれ流入する固形分の量を調整するため、例えば三方弁等の弁(不図示)が設けられている。 The secondary line L2 is connected to the discharge port 4a of the solid-liquid separation tank 4, and is branched into a solid content reflux line (supply means) L21 and an excess sludge discharge line L22 on the side opposite to the discharge port 4a. . This three-way branch point is provided with a valve (not shown) such as a three-way valve in order to adjust the amount of solid content flowing into the solid content recirculation line L21 or the excess sludge discharge line L22.

固形分還流ラインL21は、第1ラインL11に接続され、固液分離槽4で固液分離して得た固形分の一部を、硫酸塩を含有するフッ素含有排水に合流させて混合槽2に供給するためのラインである。固形分還流ラインL21の構成は特に限定されず、あらゆる態様とすることができる。例えば、固形分還流ラインL21は、配管内を固形分が自重又はポンプ等による圧力で圧送される構成を含んでもよい。 The solid content reflux line L21 is connected to the first line L11, and a part of the solid content obtained by solid-liquid separation in the solid-liquid separation tank 4 is combined with the fluorine-containing waste water containing sulfate and mixed tank 2 It is a line for supplying to The configuration of the solid content reflux line L21 is not particularly limited, and can be in any manner. For example, the solid content reflux line L21 may include a configuration in which the solid content is pumped through the pipe by its own weight or pressure from a pump or the like.

余剰スラッジ排出ラインL22は、固液分離槽4で固液分離して得た固形分のうちの余剰スラッジ(すなわち、固形分のうち、固形分還流ラインL21を介して硫酸塩を含有するフッ素含有排水に合流され混合槽2に供給される量を超えた余剰分)を排水処理装置1の外部へ排出するためのラインである。 The surplus sludge discharge line L22 is the surplus sludge of the solid content obtained by solid-liquid separation in the solid-liquid separation tank 4 (that is, the fluorine-containing This is a line for discharging to the outside of the waste water treatment apparatus 1 the surplus amount that is merged with the waste water and exceeds the amount supplied to the mixing tank 2 .

続いて、排水処理装置1の動作について説明する。 Next, operation of the waste water treatment apparatus 1 will be described.

まず、硫酸塩を含有するフッ素含有排水が排水処理装置1の上流側から第1ラインL11を通じて混合槽2に流入すると共に、混合槽2にはアルミ系無機凝集剤が無機凝集剤供給ラインL15を介して供給される。そして、混合槽2において硫酸塩を含有するフッ素含有排水とアルミ系無機凝集剤とが混合されて混合液とされ、これにより、水酸化アルミニウムを含むフロックが混合液中に生成し、このフロックが混合液中のフッ素を吸着する。 First, fluorine-containing waste water containing sulfate flows into the mixing tank 2 from the upstream side of the waste water treatment apparatus 1 through the first line L11, and the aluminum-based inorganic coagulant is supplied to the mixing tank 2 through the inorganic coagulant supply line L15. supplied via Then, in the mixing tank 2, the fluorine-containing waste water containing sulfate and the aluminum-based inorganic coagulant are mixed to form a mixed solution, whereby flocs containing aluminum hydroxide are generated in the mixed solution. Adsorbs fluorine in the mixed liquid.

ここで、SS濃度センサ5によって混合槽2内でのSS濃度が測定されることにより、アルミ系無機凝集剤の添加量をより適正に判断することができる。これにより、一例として、混合槽2内でのSS濃度が5000~8000mg/lとなるようにアルミ系無機凝集剤を混合槽2に供給することによって、アルミ系無機凝集剤の添加量をフロックが生成する最適な値とできる。その結果、混合液中にフロックが効率良く生成し、混合液中のフッ素がより多く吸着される。 Here, by measuring the SS concentration in the mixing tank 2 with the SS concentration sensor 5, the addition amount of the aluminum-based inorganic flocculant can be determined more appropriately. As a result, as an example, by supplying the aluminum-based inorganic flocculant to the mixing tank 2 so that the SS concentration in the mixing tank 2 is 5000 to 8000 mg / l, the amount of the aluminum-based inorganic flocculant added is adjusted to the floc. Optimal value to generate. As a result, flocs are efficiently generated in the mixed liquid, and more fluorine in the mixed liquid is adsorbed.

また、pHセンサ6によって混合液のpHが測定され、測定されたpHに基づいて、混合液のpHが中性又は弱酸性(例えばpHが5以上8以下、特に好ましくは6.5以上7.0以下)となるように、薬剤供給ラインL16を介して混合槽2に酸性薬剤又はアルカリ性薬剤が供給される。具体的には、測定されたpHが所定値より低く酸性寄りの場合、薬剤供給ラインL16から混合槽2にアルカリ性薬剤が供給される。一方、測定されたpHが所定値より高くアルカリ性寄りの場合、薬剤供給ラインL16から混合槽2に酸性薬剤が供給される。混合液のpHを上記範囲内の中性又は弱酸性とすることで、混合液中にフロックが効率良く生成し、その結果、混合液中のフッ素がより多く吸着される。 Further, the pH of the mixed liquid is measured by the pH sensor 6, and based on the measured pH, the pH of the mixed liquid is neutral or weakly acidic (for example, pH is 5 or more and 8 or less, particularly preferably 6.5 or more and 7.5. 0 or less), the acidic chemical or alkaline chemical is supplied to the mixing tank 2 through the chemical supply line L16. Specifically, when the measured pH is lower than a predetermined value and more acidic, an alkaline chemical is supplied to the mixing tank 2 from the chemical supply line L16. On the other hand, when the measured pH is higher than the predetermined value and closer to alkaline, an acidic chemical is supplied to the mixing tank 2 from the chemical supply line L16. By making the pH of the mixed liquid neutral or weakly acidic within the above range, flocs are efficiently generated in the mixed liquid, and as a result, more fluorine in the mixed liquid is adsorbed.

次いで、混合液が第2ラインL12を通じて凝集槽3に流入すると共に、凝集槽3には高分子凝集剤が高分子凝集剤供給ラインL17を介して供給される。そして、高分子凝集剤の混合により、混合液中のフロックがより大きく形成され(粗大フロック)、その結果、当該フロックが沈殿し易くなる。 Next, the mixture flows into the aggregation tank 3 through the second line L12, and the polymer flocculant is supplied to the aggregation tank 3 through the polymer flocculant supply line L17. By mixing the polymer flocculant, larger flocs (coarse flocs) are formed in the mixed solution, and as a result, the flocs are likely to precipitate.

次いで、混合液が第3ラインL13を介して固液分離槽4に流入すると共に、固形分と固形分以外の液とに固液分離される。このとき、固形分には、フッ素を吸着していないフロック及びフッ素を吸着したフロックの両方が含まれている。ここで、フッ素を吸着したフロックが固液分離されて沈殿することでフッ素が共沈される。沈殿した固形分は、排出口4aから副ラインL2へ排出される。 Next, the liquid mixture flows into the solid-liquid separation tank 4 through the third line L13, and is separated into solids and liquids other than the solids. At this time, the solid content includes both flocs that have not adsorbed fluorine and flocs that have adsorbed fluorine. Here, fluorine is coprecipitated by solid-liquid separation of flocs that have adsorbed fluorine and precipitation. The precipitated solid content is discharged from the discharge port 4a to the secondary line L2.

一方、固形分以外の液は、所定のフッ素濃度(一例として、15mg/l)以下までフッ素が除去された処理水として、固液分離槽4から第4ラインL14を通じて排水処理装置1の後段へ排出される。 On the other hand, the liquid other than the solid content is treated as treated water in which fluorine has been removed to a predetermined fluorine concentration (eg, 15 mg/l) or less, and is sent from the solid-liquid separation tank 4 to the latter stage of the wastewater treatment apparatus 1 through the fourth line L14. Ejected.

副ラインL2に流入した固形分のうちの一部は、固形分還流ラインL21を通じて第1ラインL11に供給され、第1ラインL11を通じて混合槽2に供給される。一方、固形分のうちの残部は、余剰スラッジとして余剰スラッジ排出ラインL22を通じて排出される。 A part of the solid content that has flowed into the secondary line L2 is supplied to the first line L11 through the solid content reflux line L21, and is supplied to the mixing tank 2 through the first line L11. On the other hand, the remainder of the solid content is discharged as excess sludge through the excess sludge discharge line L22.

混合槽2に供給された固形分のうち、未だフッ素を吸着していないフロック及び既にフッ素を吸着したが更にフッ素を吸着することができる状態のフロックが、混合液中のフッ素を吸着する。そして、前述したのと同様に、このフロックが固液分離槽4において固液分離されて沈殿することで、混合液中のフッ素を共沈させて液中から除去し、この一連の動作が繰り返される。 Of the solids supplied to the mixing tank 2, flocs that have not yet adsorbed fluorine and flocs that have already adsorbed fluorine but are capable of further adsorbing fluorine adsorb fluorine in the liquid mixture. Then, in the same manner as described above, the flocs are solid-liquid separated and precipitated in the solid-liquid separation tank 4, so that the fluorine in the mixed liquid is coprecipitated and removed from the liquid, and this series of operations is repeated. be

以上、説明したように、本実施形態に係る排水処理装置1及び排水処理方法によれば、混合槽2で硫酸塩を含有するフッ素含有排水とアルミ系無機凝集剤とを混合することにより、フロックが混合液中に生成し、このフロックが混合液中のフッ素を吸着して液中から除去する。そして、固液分離槽4において、既にフッ素を吸着したフロックをフッ素と共に共沈させ、また、未だフッ素を吸着していないフロックも沈降させて固液分離し、これらの固液分離した固形分を混合槽2に供給する。その結果、未だフッ素を吸着していないフロック及び既にフッ素を吸着したが更にフッ素を吸着することができる状態のフロックが混合液中のフッ素を吸着して液中から除去する。これにより、フッ素の吸着・共沈のために使用されたアルミ系無機凝集剤を再びフッ素の吸着・共沈に活用できる。以上により、硫酸塩を含有するフッ素含有排水において、アルミ系無機凝集剤の使用量を削減できると共に、このアルミ系無機凝集剤の使用量を削減すること及び固液分離して得た固形分を混合槽2に供給することにより余剰スラッジの発生量を低減できる。 As described above, according to the wastewater treatment apparatus 1 and the wastewater treatment method according to the present embodiment, by mixing fluorine-containing wastewater containing sulfate and an aluminum-based inorganic flocculant in the mixing tank 2, flocculation is generated in the mixed liquid, and this floc adsorbs fluorine in the mixed liquid and removes it from the liquid. Then, in the solid-liquid separation tank 4, the flocs that have already adsorbed fluorine are coprecipitated together with fluorine, and the flocs that have not yet adsorbed fluorine are also sedimented for solid-liquid separation. It is supplied to the mixing tank 2. As a result, the flocs that have not yet adsorbed fluorine and the flocs that have already adsorbed fluorine but are capable of further adsorbing fluorine adsorb fluorine in the mixed liquid and remove it from the liquid. As a result, the aluminum-based inorganic coagulant used for fluorine adsorption/coprecipitation can be reused for fluorine adsorption/coprecipitation. As described above, in fluorine-containing wastewater containing sulfate, the amount of aluminum-based inorganic flocculant used can be reduced, and the amount of this aluminum-based inorganic flocculant used can be reduced, and the solid content obtained by solid-liquid separation can be reduced. By supplying to the mixing tank 2, the amount of excess sludge generated can be reduced.

特に、排水処理装置1及び排水処理方法は、流入水のフッ素濃度が高い場合に有効で、このような硫酸塩を含有するフッ素含有排水において一層顕著な効果を奏する。一般に高濃度のフッ素を含有する排水からフッ素を除去する別の方法として、フッ素を含有する排水にカルシウム系の薬剤を添加してフッ化カルシウム(CaF2)を生成させることが知られている。しかしながら、硫酸塩を含有するフッ素含有排水においては、カルシウム系の薬剤を添加するとカルシウム系の薬剤が硫酸塩と反応して石膏(Ca(SO)4)を生成してしまい、フッ化カルシウムの生成が阻害されるという問題がある。これに対し、本実施形態によれば、硫酸塩を含有するフッ素含有排水に対して石膏を生成させることなく効果的にフッ素を除去することができる。 In particular, the wastewater treatment apparatus 1 and the wastewater treatment method are effective when the fluorine concentration of the influent is high, and the effect is more pronounced in fluorine-containing wastewater containing such sulfates . As another method for removing fluorine from wastewater containing high concentrations of fluorine, it is generally known to add a calcium-based agent to the fluorine-containing wastewater to generate calcium fluoride (CaF 2 ). However, in fluorine-containing wastewater containing sulfate , when a calcium-based agent is added, the calcium-based agent reacts with the sulfate to form gypsum (Ca(SO) 4 ), which results in the formation of calcium fluoride. is hindered. In contrast, according to the present embodiment, fluorine can be effectively removed from fluorine-containing wastewater containing sulfate without generating gypsum.

また、本実施形態に係る排水処理装置1では、混合槽2が、pHを調整するために酸性薬剤又はアルカリ性薬剤を供給する薬剤供給ラインL16を有している。これにより、pHを調整することで、硫酸塩を含有するフッ素含有排水とアルミ系無機凝集剤とが反応し、フロックを生成する最適な値とできるため、フロックを効率良く生成でき、アルミ系無機凝集剤の使用量に対して効率良くフッ素を吸着・共沈させて液中から除去できる。 In addition, in the waste water treatment apparatus 1 according to this embodiment, the mixing tank 2 has a chemical supply line L16 for supplying an acidic chemical or an alkaline chemical for adjusting the pH. As a result, by adjusting the pH, the fluorine-containing wastewater containing sulfate and the aluminum-based inorganic flocculant react and can be set to the optimum value for generating flocs, so that flocs can be efficiently generated, and the aluminum-based inorganic Fluorine can be efficiently adsorbed and co-precipitated with respect to the amount of coagulant used, and removed from the liquid.

なお、本発明に係る排水処理装置1及び排水処理方法は、上記実施形態に限定されない。例えば、上記実施形態ではアルミ系無機凝集剤によりフッ素を含有する硫酸塩を含有するフッ素含有排水からフッ素を除去するが、例えばヒ素、ホウ素又はセレンを含有する硫酸塩を含有するフッ素含有排水から、アルミ系無機凝集剤によりそれぞれヒ素、ホウ素又はセレンを除去する構成としてもよい。これらの場合であっても、上記実施形態と同様の構成を有する排水処理装置及び同様の工程を有する排水処理方法によって同様の作用効果が得られる。 In addition, the waste water treatment apparatus 1 and the waste water treatment method according to the present invention are not limited to the above embodiments. For example, in the above embodiment, fluorine is removed from fluorine-containing wastewater containing sulfate containing fluorine by an aluminum-based inorganic flocculant. Arsenic, boron, or selenium may be removed by an aluminum-based inorganic flocculant. Even in these cases, the same effect can be obtained by the wastewater treatment apparatus having the same configuration as the above embodiment and the wastewater treatment method having the same steps.

また、上記実施形態では、アルミ系無機凝集剤の添加量をより適正に判断できるように、SS濃度センサ5によって混合槽2内でのSS濃度を測定している。しかしながら、SS濃度センサ5に代えて、水酸化アルミニウム濃度を測定する水酸化アルミニウム濃度センサを混合槽2に設けてもよい。この場合、一例として、混合槽2内での水酸化アルミニウム濃度が3000~5000mg/lとなるようにアルミ系無機凝集剤を混合槽2に供給することにより、アルミ系無機凝集剤の添加量をフロックが生成する最適な値とできる。その結果、混合液中にフロックが効率良く生成し、混合液中のフッ素がより多く吸着される。 Further, in the above-described embodiment, the SS concentration in the mixing tank 2 is measured by the SS concentration sensor 5 so that the addition amount of the aluminum-based inorganic flocculant can be determined more appropriately. However, instead of the SS concentration sensor 5, the mixing tank 2 may be provided with an aluminum hydroxide concentration sensor for measuring the aluminum hydroxide concentration. In this case, as an example, by supplying the aluminum-based inorganic flocculant to the mixing tank 2 so that the concentration of aluminum hydroxide in the mixing tank 2 is 3000 to 5000 mg / l, the amount of the aluminum-based inorganic flocculant added is reduced. It can be the optimal value generated by the flock. As a result, flocs are efficiently generated in the mixed liquid, and more fluorine in the mixed liquid is adsorbed.

また、上記実施形態において、無機凝集剤供給ラインL15は混合槽2へ直接接続されているが、混合槽2より上流である第1ラインL11へ接続されていてもよい。この場合であっても、第1ラインL11に供給されたアルミ系無機凝集剤は、第1ラインL11を通じて混合槽2に供給される。 Further, in the above embodiment, the inorganic coagulant supply line L15 is directly connected to the mixing tank 2, but may be connected to the first line L11 upstream of the mixing tank 2. Even in this case, the aluminum-based inorganic flocculant supplied to the first line L11 is supplied to the mixing tank 2 through the first line L11.

また、固液分離槽4は、遠心分離機を有し、遠心分離によって固液分離を行うこととしてもよい。 Moreover, the solid-liquid separation tank 4 may have a centrifugal separator and perform solid-liquid separation by centrifugation.

また、固形分還流ラインL21としては、配管等の設備を用いず、人力によって固形分を混合槽2に供給する構成としてもよい。 Further, the solid content reflux line L21 may be configured to manually supply the solid content to the mixing tank 2 without using equipment such as piping.

また、上記実施形態において、固形分還流ラインL21は固形分を第1ラインL11に供給するが、混合槽2に直接供給してもよい。 Further, in the above embodiment, the solid content reflux line L21 supplies the solid content to the first line L11, but the solid content may be directly supplied to the mixing tank 2.

また、図2に示されるように、混合槽2を無くし、第1ラインL11と第2ラインL12とを接続して第5ラインL18とすると共に、この第5ラインL18に無機凝集剤供給ラインL15を接続し、第5ラインL18と無機凝集剤供給ラインL15との接続点から凝集槽3までのラインを、硫酸塩を含有するフッ素含有排水(すなわち、フッ素及び硫酸塩を含有する排水)とアルミ系無機凝集剤とを混合する混合部としてもよい。なお、混合部には、当該混合部内での混合液のSS濃度を測定するSS濃度センサ5が設けられていてもよい。また、混合部には、当該混合部内での混合液のpHを測定するpHセンサ6が設けられていてもよく、更に、このpHセンサ6によって測定したpHに基づきpHを調整するための薬剤を当該混合部に供給する薬剤供給ラインL16が接続されていてもよい。 Further, as shown in FIG. 2, the mixing tank 2 is eliminated, the first line L11 and the second line L12 are connected to form a fifth line L18, and the inorganic coagulant supply line L15 is connected to the fifth line L18. , and the line from the connection point between the fifth line L18 and the inorganic flocculant supply line L15 to the flocculation tank 3 is filled with fluorine-containing wastewater containing sulfate (that is, wastewater containing fluorine and sulfate) and aluminum It is good also as a mixing part which mixes with a system inorganic flocculant. The mixing section may be provided with an SS concentration sensor 5 for measuring the SS concentration of the liquid mixture in the mixing section. In addition, the mixing section may be provided with a pH sensor 6 for measuring the pH of the mixed liquid in the mixing section, and a chemical for adjusting the pH based on the pH measured by the pH sensor 6 may be added. A drug supply line L16 for supplying to the mixing section may be connected.

1…排水処理装置、2…混合槽(混合部)、4…固液分離槽(固液分離部)、L21…固形分還流ライン(供給手段)。
DESCRIPTION OF SYMBOLS 1... Waste water treatment apparatus, 2... Mixing tank (mixing part), 4... Solid-liquid separation tank (solid-liquid separation part), L21... Solid content reflux line (supply means).

Claims (3)

フッ素含有排水からフッ素を除去する排水処理装置において、
前記フッ素含有排水は、硫酸塩を含有し、
前記フッ素含有排水とアルミ系無機凝集剤とを混合する混合部と、
前記混合部で混合された混合液を固液分離する固液分離部と、を備え
アルミ系無機凝集剤は、混合部に添加され、
固液分離部で分離された固形分は、フッ素含有排水に合流する排水処理装置。
In wastewater treatment equipment for removing fluorine from fluorine-containing wastewater,
The fluorine-containing waste water contains sulfate,
a mixing unit for mixing the fluorine-containing waste water and an aluminum-based inorganic flocculant;
a solid-liquid separation unit that solid-liquid separates the mixed liquid mixed in the mixing unit ;
The aluminum-based inorganic flocculant is added to the mixing section,
A wastewater treatment equipment in which the solid content separated by the solid-liquid separation unit joins the fluorine-containing wastewater .
前記固液分離部で固液分離して得た固形分を前記混合部に供給するための供給手段と、を備え、
前記固形分は、フッ素を吸着したフロックを含有することを特徴とする請求項1に記載の排水処理装置。
a supply means for supplying the solid content obtained by solid-liquid separation in the solid-liquid separation unit to the mixing unit;
2. A waste water treatment apparatus according to claim 1, wherein said solid content contains flocs on which fluorine is adsorbed.
フッ素含有排水からフッ素を除去する排水処理方法において、
前記フッ素含有排水は、硫酸塩を含有し、
前記フッ素含有排水とアルミ系無機凝集剤とを混合部で混合し、
前記混合部で混合された混合液を固液分離部で固液分離し、
アルミ系無機凝集剤は、混合部に添加され、
固液分離部で分離された固形分は、フッ素含有排水に合流する排水処理方法。
In a wastewater treatment method for removing fluorine from fluorine-containing wastewater,
The fluorine-containing waste water contains sulfate,
The fluorine-containing waste water and the aluminum-based inorganic flocculant are mixed in a mixing unit,
solid-liquid separation in the solid-liquid separation unit the mixed liquid mixed in the mixing unit,
The aluminum-based inorganic flocculant is added to the mixing section,
A wastewater treatment method in which the solid content separated by the solid-liquid separation unit joins the fluorine-containing wastewater .
JP2019086327A 2019-04-26 2019-04-26 Wastewater treatment equipment and wastewater treatment method Active JP7202250B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2019086327A JP7202250B2 (en) 2019-04-26 2019-04-26 Wastewater treatment equipment and wastewater treatment method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2019086327A JP7202250B2 (en) 2019-04-26 2019-04-26 Wastewater treatment equipment and wastewater treatment method

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
JP2015068766A Division JP6826806B2 (en) 2015-03-30 2015-03-30 Wastewater treatment equipment and wastewater treatment method

Publications (2)

Publication Number Publication Date
JP2019122961A JP2019122961A (en) 2019-07-25
JP7202250B2 true JP7202250B2 (en) 2023-01-11

Family

ID=67397198

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2019086327A Active JP7202250B2 (en) 2019-04-26 2019-04-26 Wastewater treatment equipment and wastewater treatment method

Country Status (1)

Country Link
JP (1) JP7202250B2 (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003340210A (en) 2002-05-28 2003-12-02 Japan Organo Co Ltd Cleaning method for filter apparatus
JP2005125153A (en) 2003-10-21 2005-05-19 Kurita Water Ind Ltd Method and apparatus for treating fluorine-containing wastewater

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4159246A (en) * 1975-09-10 1979-06-26 Kohei Deguchi Removal of fluorine from water
JPS5622627A (en) * 1979-07-27 1981-03-03 Sumitomo Metal Mining Co Ltd Purifying method for fluorine impurity-containing sodium sulfate
JPS6097091A (en) * 1983-10-31 1985-05-30 Kurita Water Ind Ltd Treatment method for water containing fluoride ions
JP3192557B2 (en) * 1994-08-26 2001-07-30 シャープ株式会社 Wastewater treatment device and wastewater treatment method
JP2003126866A (en) * 2001-10-29 2003-05-07 Mitsubishi Heavy Ind Ltd Removing method of fluorine in drainage and the system
JP2003145170A (en) * 2001-11-09 2003-05-20 Misuzu Kogyo:Kk Method and apparatus for treating fluorine-containing wastewater
JP4253203B2 (en) * 2003-03-31 2009-04-08 財団法人電力中央研究所 How to remove fluorine from gypsum
JP2009241011A (en) * 2008-03-31 2009-10-22 Daikin Ind Ltd Treatment method of fluorine-containing waste water
JP2010075928A (en) * 2009-11-27 2010-04-08 Kurita Water Ind Ltd Treatment method and treatment device for fluorine-containing waste water
JP5943176B2 (en) * 2010-10-29 2016-06-29 三菱マテリアル株式会社 Method and apparatus for treating harmful substance-containing water.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003340210A (en) 2002-05-28 2003-12-02 Japan Organo Co Ltd Cleaning method for filter apparatus
JP2005125153A (en) 2003-10-21 2005-05-19 Kurita Water Ind Ltd Method and apparatus for treating fluorine-containing wastewater

Also Published As

Publication number Publication date
JP2019122961A (en) 2019-07-25

Similar Documents

Publication Publication Date Title
CN104603068A (en) Method for removing sulphate, calcium and/or other soluble metals from waste water
CN103025403A (en) A process for reducing the sulfate concentration in a wastewater stream
US20160176739A1 (en) Water treatment device and water treatment method
TWI631081B (en) Installation for the preparation of an aqueous solution comprising at least one earth alkali hydrogen carbonate
CN103319026B (en) Device and method for treating waste liquor of gas desulphurization system during ship washing
US10183879B2 (en) Method for removing mercury and selenium from sulfate-containing waste water
CN105228957A (en) Method for optimizing chemical precipitation processes in water or wastewater treatment plants
CN107445328A (en) The processing method and system of salt solution
CN106277169B (en) A kind of industrial water de silicon method and device
WO2005005321A1 (en) Car washing wastewater treatment system
JP7083274B2 (en) Water treatment method and water treatment equipment
JP7202250B2 (en) Wastewater treatment equipment and wastewater treatment method
JP2010075928A (en) Treatment method and treatment device for fluorine-containing waste water
JP6826806B2 (en) Wastewater treatment equipment and wastewater treatment method
JP6687056B2 (en) Water treatment method and water treatment device
JP2927255B2 (en) Treatment method for wastewater containing fluorine
CN204958619U (en) Adopt tubular micro -filtration membrane's fluoride waste processing system
JP7295324B1 (en) Method for producing iodine component-containing aqueous solution using inorganic flocculant capable of selectively removing fluoride ions and phosphate ions
JP5210948B2 (en) Chemical injection control method for water purification plant
CN110818136B (en) High-precision defluorination sewage treatment system and sewage treatment method
CN116477790A (en) Method and system for silicon and fluorine removal of steel wastewater with zero discharge
JP5149323B2 (en) Fluorine-containing water treatment method
JP4524796B2 (en) Method and apparatus for treating fluorine-containing wastewater
CN107673518A (en) A kind of method using the fluorine-containing early-stage rainwater of coagulating sedimentation adsorption treatment
JP7117101B2 (en) Water treatment method and device

Legal Events

Date Code Title Description
A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20190522

A625 Written request for application examination (by other person)

Free format text: JAPANESE INTERMEDIATE CODE: A625

Effective date: 20190523

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20200602

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20200729

A02 Decision of refusal

Free format text: JAPANESE INTERMEDIATE CODE: A02

Effective date: 20201215

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20210315

C60 Trial request (containing other claim documents, opposition documents)

Free format text: JAPANESE INTERMEDIATE CODE: C60

Effective date: 20210315

A911 Transfer to examiner for re-examination before appeal (zenchi)

Free format text: JAPANESE INTERMEDIATE CODE: A911

Effective date: 20210322

C21 Notice of transfer of a case for reconsideration by examiners before appeal proceedings

Free format text: JAPANESE INTERMEDIATE CODE: C21

Effective date: 20210323

A912 Re-examination (zenchi) completed and case transferred to appeal board

Free format text: JAPANESE INTERMEDIATE CODE: A912

Effective date: 20210416

C211 Notice of termination of reconsideration by examiners before appeal proceedings

Free format text: JAPANESE INTERMEDIATE CODE: C211

Effective date: 20210420

C22 Notice of designation (change) of administrative judge

Free format text: JAPANESE INTERMEDIATE CODE: C22

Effective date: 20220329

C22 Notice of designation (change) of administrative judge

Free format text: JAPANESE INTERMEDIATE CODE: C22

Effective date: 20220517

C13 Notice of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: C13

Effective date: 20220726

C19 Decision taken to dismiss amendment

Free format text: JAPANESE INTERMEDIATE CODE: C19

Effective date: 20220802

C30A Notification sent

Free format text: JAPANESE INTERMEDIATE CODE: C3012

Effective date: 20220802

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20220926

C23 Notice of termination of proceedings

Free format text: JAPANESE INTERMEDIATE CODE: C23

Effective date: 20221115

C03 Trial/appeal decision taken

Free format text: JAPANESE INTERMEDIATE CODE: C03

Effective date: 20221213

C30A Notification sent

Free format text: JAPANESE INTERMEDIATE CODE: C3012

Effective date: 20221213

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20221223

R150 Certificate of patent or registration of utility model

Ref document number: 7202250

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

S531 Written request for registration of change of domicile

Free format text: JAPANESE INTERMEDIATE CODE: R313531

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350