JP3150990B2 - Treatment method for Ga-As polishing wastewater - Google Patents
Treatment method for Ga-As polishing wastewaterInfo
- Publication number
- JP3150990B2 JP3150990B2 JP05994991A JP5994991A JP3150990B2 JP 3150990 B2 JP3150990 B2 JP 3150990B2 JP 05994991 A JP05994991 A JP 05994991A JP 5994991 A JP5994991 A JP 5994991A JP 3150990 B2 JP3150990 B2 JP 3150990B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- polishing
- filtered water
- polishing wastewater
- water
- 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.)
- Expired - Fee Related
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Description
【０００１】[0001]
【産業上の利用分野】この発明はＧａ−Ａｓ研磨排水の
処理方法に関する。さらに詳しくは、再度Ｇａ−Ａｓ研
磨水として用いることのできる研磨排水の処理方法に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating Ga-As polishing wastewater. More specifically, the present invention relates to a method for treating polishing wastewater that can be used again as Ga-As polishing water.
【０００２】[0002]
【従来の技術】Ｇａ−Ａｓはエレクトロセラミックス、
詳しくは光電素子材料として用いられる。その光電素子
材料の生産において、たとえばＧａ−Ａｓウエハーを加
工する工程としてスライシング、グラインディングおよ
びダイシングといった工程があり、Ｇａ−Ａｓ微粒子を
含む水を排出する。この水をＧａ−Ａｓ研磨排水と呼ぶ
ことにする。2. Description of the Related Art Ga-As is an electroceramic,
Specifically, it is used as a photoelectric element material. In the production of the photoelectric device material, for example, there are processes such as slicing, grinding and dicing as processes for processing a Ga-As wafer, and water containing Ga-As fine particles is discharged. This water is called Ga-As polishing wastewater.
【０００３】Ｇａ−Ａｓは固体の時は毒性がない。しか
しＧａ−Ａｓ研磨排水中では一部のヒ素が酸化されて毒
性を示すヒ酸および亜ヒ酸に変化する。本発明者らは有
害物質の拡散を防止し、水資源の有効利用と研磨水とし
ての再利用を目的にＧａ−Ａｓ研磨排水を系外に出さな
いクローズドシステムを考えた。そのシステムは限外濾
過システムまたは精密濾過システムと、ダイサーまたは
グラインダー、および沈降槽からなるものである。この
システムでは、ダイサーまたはグラインダーから排出さ
れるＧａ−Ａｓ研磨排水は沈降槽に送られ、Ｇａ−Ａｓ
微粒子の一部が沈降する。沈降槽の上澄液は限外濾過シ
ステムまたは精密濾過システムの循環タンクに送られ
る。ここに送られた液は濾過システム内を循環し、限外
濾過膜または精密濾過膜で濾過される。濾過水はダイサ
ーまたはグラインダーにＧａ−Ａｓ研磨水として送られ
る。循環タンク内のＧａ−Ａｓ微粒子は初期濃度の２０
０倍に濃縮されて自動的に定期的に排出される。[0003] Ga-As has no toxicity when solid. However, part of arsenic is oxidized in the Ga-As polishing wastewater to change into toxic arsenic and arsenite. The present inventors have considered a closed system in which Ga-As polishing wastewater is not discharged out of the system for the purpose of preventing the diffusion of harmful substances and effectively using water resources and reusing polishing water. The system consists of an ultrafiltration or microfiltration system, a dicer or grinder, and a settling tank. In this system, Ga-As polishing wastewater discharged from a dicer or grinder is sent to a sedimentation tank and Ga-As
Part of the fine particles settle. The supernatant of the settling tank is sent to a circulation tank of an ultrafiltration system or a microfiltration system. The liquid sent here circulates through a filtration system and is filtered by an ultrafiltration membrane or a microfiltration membrane. The filtered water is sent to a dicer or grinder as Ga-As polishing water. The Ga-As fine particles in the circulation tank have an initial concentration of 20%.
It is concentrated to 0 times and automatically discharged periodically.
【０００４】[0004]
【発明が解決しようとする課題】このシステムで稼動を
続けた結果、濾過水にヒ素が徐々に溶解してヒ酸または
亜ヒ酸となり、濾過水のｐＨが下がってＧａ−Ａｓ研磨
水としての水質が悪くなることが判明した。As a result of the continuous operation of this system, arsenic gradually dissolves in the filtered water to become arsenic acid or arsenite, and the pH of the filtered water decreases, so that the Ga-As polishing water is used. The water quality was found to be poor.
【０００５】[0005]
【課題を解決するための手段】この発明は前記のクロー
ズドシステム化されたGａ−Ａｓ研磨排水処理方法を改
善するものである。この発明のＧａ−Ａｓ研磨排水の処
理方法の特徴は、 Ｇａ−Ａｓ研磨排水を濾過膜で濾過
し、得られた濾過水を陰イオン交換樹脂または亜ヒ酸及
びヒ酸イオンを選択的に吸着するキレート樹脂を充填し
たカラムに通液することにある。SUMMARY OF THE INVENTION The present invention is to improve the above-described closed-system Ga-As polishing wastewater treatment method. The feature of the treatment method of the Ga-As polishing wastewater of the present invention is as follows.
And passing the solution through a column packed with a chelate resin that selectively adsorbs arsenate and arsenate .
【０００６】本発明に用いる濾過膜は、Ｇａ−Ａｓ微粒
子をカットするものであれば何でもよいが、Ｇａ−Ａｓ
微粒子の大きさが一般的に数ミクロンなので、膜の孔径
が１０オングストロームから２ミクロンの限外濾過膜お
よび精密濾過膜が適している。膜の材質としてはポリス
ルホン樹脂、ポリエーテルスルホン樹脂、ポリオレフィ
ン樹脂、フッソ樹脂、ポリ四フッ化エチレン樹脂、アセ
チルセルロース樹脂、ポリビニルクロライド樹脂、ポリ
アミド樹脂等の有機質膜およびアルミナ、ジルコニア等
の無機質膜が使用できる。The filtration membrane used in the present invention may be of any type as long as it can cut Ga-As fine particles.
Ultrafiltration and microfiltration membranes having a pore size of 10 Angstroms to 2 microns are suitable, since the size of the microparticles is typically a few microns. As the material of the membrane, an organic film such as polysulfone resin, polyether sulfone resin, polyolefin resin, fluorine resin, polytetrafluoroethylene resin, acetylcellulose resin, polyvinyl chloride resin, polyamide resin and an inorganic film such as alumina and zirconia are used. it can.
【０００７】濾過水中に含まれる亜ヒ酸およびヒ酸イオ
ンの吸着に用いるイオン交換樹脂は、陰イオン交換樹脂
のＯＨ型であれば特に限定するものではない。ＯＨ型選
択の目的は、樹脂のＯＨイオンと亜ヒ酸およびヒ酸イオ
ンを交換し、濾過水中のＨイオンと反応させ、濾過水の
ｐＨを中性化することにある。樹脂の例としてはスチレ
ンにビニルベンゼンを共重合し、１〜３級アミンまたは
４級アンモニウムを導入したものがある。濾過水中から
亜ヒ酸およびヒ酸イオンを除去するために、キレート樹
脂を用いてもよい。キレート樹脂としては、イミノプロ
ピオン酸型、ジチゾン型、チオ尿素型、チオール型、リ
ン酸型、ポリアミン型などが用いられる。The ion exchange resin used to adsorb arsenite and arsenate ions contained in the filtered water is not particularly limited as long as it is an OH type anion exchange resin. The purpose of the OH type selection is to exchange OH ions of the resin with arsenite and arsenite ions and react with H ions in the filtered water to neutralize the pH of the filtered water. As an example of the resin, there is a resin obtained by copolymerizing styrene with vinylbenzene and introducing a tertiary amine or a quaternary ammonium. A chelating resin may be used to remove arsenite and arsenate ions from the filtered water. As the chelate resin, iminopropionic acid type, dithizone type, thiourea type, thiol type, phosphoric acid type, polyamine type and the like are used.
【０００８】長時間使用して、吸着効率の低下したイオ
ン交換樹脂およびキレート樹脂は、強塩基性濃厚水溶液
と接触させて再生処理できる。例えば１〜４規定の水酸
化ナトリウムで処理すれば、少量で洗浄できるので、吸
着したヒ素化合物を濃縮回収することができる。The ion-exchange resin and the chelate resin having reduced adsorption efficiency after being used for a long time can be subjected to a regeneration treatment by bringing them into contact with a strongly basic concentrated aqueous solution. For example, by treating with 1 to 4 N sodium hydroxide, it can be washed with a small amount, so that the adsorbed arsenic compound can be concentrated and recovered.
【０００９】[0009]
【実施例】以下、この発明を実施例および参考例によっ
て具体的に説明する。 参考例 クローズドシステム化した精密濾過装置で０．１〜１０
ミクロンの粒子径分布を持ったＧａ−Ａｓ濃度１００ｐ
ｐｍの研磨排水の処理を行った。濾過装置は旭化成工業
株式会社製のＭＬ２２００３を用い、膜モジュールとし
て旭化成工業株式会社製のＰＳＶ−３１３（孔径０．１
ミクロンのポリオレフィン系中空糸型精密濾過膜内蔵）
を用いた。稼動１日目の濾過水のｐＨは６．８であった
が１月後は４．０に低下した。The present invention will be specifically described below with reference to examples and reference examples. Reference example 0.1 to 10 with a closed system microfiltration device
Ga-As concentration with micron particle size distribution 100p
pm of polishing wastewater was treated. As a filtration device, ML22003 manufactured by Asahi Kasei Kogyo Co., Ltd. was used, and PSV-313 manufactured by Asahi Kasei Kogyo Co., Ltd. (pore diameter 0.1
Micron polyolefin hollow fiber type microfiltration membrane built-in)
Was used. The pH of the filtrate on the first day of operation was 6.8, but dropped to 4.0 after one month.
【００１０】実施例 １ 参考例で得たｐＨ４．０の濾過水２ｌをＯＨ型の弱塩基
性イオン交換樹脂（三菱化成株式会社製のダイヤイオン
ＷＡ−２０）１５０ｍｌを充填した直径４０ｍｍのカラ
ムに３００ｍｌ／ｍｉｎの速度で流した。その結果、濾
過水のｐＨは４．０から７．２へ変化した。Example 1 2 liters of the filtered water having a pH of 4.0 obtained in the reference example was placed in a 40 mm diameter column packed with 150 ml of an OH type weakly basic ion exchange resin (Diaion WA-20 manufactured by Mitsubishi Kasei Corporation). The flow was at a rate of 300 ml / min. As a result, the pH of the filtered water changed from 4.0 to 7.2.
【００１１】実施例 ２ 参考例で得たｐＨ４．０の濾過水２ｌをＯＨ型に処理し
た強塩基性イオン交換樹脂（三菱化成株式会社製のダイ
ヤイオンＳＡ−１０Ａ）１５０ｍｌを充填した直径４０
ｍｍのカラムに３００ｍｌ／ｍｉｎの速度で流した。そ
の結果、濾過水のｐＨは４．０から７．４へ変化した。Example 2 Diameter 40 filled with 150 ml of a strongly basic ion exchange resin (Diaion SA-10A manufactured by Mitsubishi Kasei Co., Ltd.) obtained by treating 2 liters of filtered water having a pH of 4.0 obtained in the reference example into OH type.
The column was flowed at a rate of 300 ml / min through a column of mm. As a result, the pH of the filtered water changed from 4.0 to 7.4.
【００１２】実施例 ３ 参考例で得たｐＨ４．０の濾過水２ｌをポリアミン型キ
レート樹脂（三菱化成株式会社製のダイヤイオンＣＲ−
２０）１５０ｍｌを充填した直径４０ｍｍのカラムに３
００ｍｌ／ｍｉｎの速度で流した。その結果、濾過水の
ｐＨは４．０から６．８へ変化した。Example 3 2 liters of the filtered water having a pH of 4.0 obtained in Reference Example was mixed with a polyamine-type chelate resin (Diaion CR- manufactured by Mitsubishi Kasei Corporation).
20) 3 columns in a 40 mm diameter column packed with 150 ml
It flowed at a rate of 00 ml / min. As a result, the pH of the filtered water changed from 4.0 to 6.8.
【００１３】実施例 ４ 参考例のクローズドシステム化した精密濾過装置に、Ｏ
Ｈ型の弱塩基性イオン交換樹脂（三菱化成株式会社製の
ダイヤイオンＷＡ−２０）５７ｌを充填したポリッシャ
ーを接続し、濾過水を３０ｌ／ｍｉｎの速度で流した。
その結果、濾過水のｐＨは４．０から７．２へ変化し
た。１月連続運転後のｐＨは６．８であった。Embodiment 4 A microfiltration apparatus having a closed system according to the reference example is provided with O
A polisher filled with 57 l of H-type weakly basic ion exchange resin (Diaion WA-20 manufactured by Mitsubishi Kasei Co., Ltd.) was connected, and filtered water was flowed at a rate of 30 l / min.
As a result, the pH of the filtered water changed from 4.0 to 7.2. After continuous operation for one month, the pH was 6.8.
【００１４】[0014]
【発明の効果】以上より明らかなごとく、この発明によ
ればＧａ−Ａｓ研磨排水を処理して得られる濾過水の水
質が向上するため、再度Ｇａ−Ａｓ研磨水として使用で
きる。また、装置に与える悪影響がなくなるとともに濾
過水の排出が不要となるため、有害物質の拡散防止に役
立ち、産業上極めて有用である。As is clear from the above, according to the present invention, since the quality of the filtered water obtained by treating the Ga-As polishing wastewater is improved, it can be reused as Ga-As polishing water. In addition, since there is no adverse effect on the apparatus and no drainage of filtered water is required, it is useful for preventing the diffusion of harmful substances and extremely useful in industry.
フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C02F 1/44 C02F 1/58 Continuation of front page (58) Field surveyed (Int.Cl. 7 , DB name) C02F 1/44 C02F 1/58
Claims (1)
得られた濾過水を陰イオン交換樹脂または亜ヒ酸及びヒ
酸イオンを選択的に吸着するキレート樹脂を充填したカ
ラムに通液することを特徴とする Ｇａ−Ａｓ研磨排水
の処理方法1. A Ga-As polishing wastewater is filtered through a filtration membrane,
Resulting filtered water anion exchange resin or nitrous arsenate and arsenate
A method for treating waste water from polishing of Ga-As, characterized in that the solution is passed through a column filled with a chelate resin that selectively adsorbs acid ions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05994991A JP3150990B2 (en) | 1991-03-25 | 1991-03-25 | Treatment method for Ga-As polishing wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05994991A JP3150990B2 (en) | 1991-03-25 | 1991-03-25 | Treatment method for Ga-As polishing wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04293587A JPH04293587A (en) | 1992-10-19 |
| JP3150990B2 true JP3150990B2 (en) | 2001-03-26 |
Family
ID=13127906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05994991A Expired - Fee Related JP3150990B2 (en) | 1991-03-25 | 1991-03-25 | Treatment method for Ga-As polishing wastewater |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3150990B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3384530B2 (en) * | 1996-03-25 | 2003-03-10 | 信越半導体株式会社 | Apparatus and method for polishing semiconductor wafer |
| JP2002119964A (en) * | 2000-10-13 | 2002-04-23 | Enzan Seisakusho:Kk | Waste water circulation system in semiconductor manufacturing process |
| JP4072323B2 (en) * | 2001-04-27 | 2008-04-09 | シャープ株式会社 | Method for treating gallium arsenide-containing wastewater and apparatus for treating gallium arsenide-containing wastewater |
| JP4973901B2 (en) * | 2001-06-19 | 2012-07-11 | 栗田工業株式会社 | Method for treating gallium-containing wastewater |
| JP2003001275A (en) * | 2001-06-19 | 2003-01-07 | Kurita Water Ind Ltd | Equipment for treatment of waste water containing gallium-arsenic |
-
1991
- 1991-03-25 JP JP05994991A patent/JP3150990B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04293587A (en) | 1992-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6368510B2 (en) | Method and apparatus for the removal of arsenic from water | |
| JPS6331505A (en) | Selective dialysis using polymeric hydrophilic adsorbent andsize selective membrane | |
| KR20040106478A (en) | Method and apparatus for fluid treatment by reverse osmosis under acidic conditions | |
| GB2056314A (en) | Purification of water involving ultrafiltration | |
| KR100985707B1 (en) | Method and system for the treatment of liquid effluents containing pollutants in a suspension | |
| US5665240A (en) | Point-of-use removal of lead in drinking water using phosphate and carbonate minerals | |
| CN105321589B (en) | A kind of method that radioactive wastewater is handled using full embrane method | |
| JP2006320847A (en) | Organic arsenic-containing water treatment method, and its apparatus | |
| JPS62132501A (en) | Scrubbing method for high feed concentration | |
| WO2017056947A1 (en) | Metal-contamination preventive agent, metal-contamination preventive membrane, metal-contamination preventive method, and product-cleansing method | |
| JP3150990B2 (en) | Treatment method for Ga-As polishing wastewater | |
| AU2023282288A1 (en) | Method and system for removing radioactive nuclides from water | |
| JPH1085743A (en) | Method and apparatus for treating water containing boron | |
| JPH10216721A (en) | Ultrapure water producing device | |
| WO2015063147A1 (en) | Water purification method | |
| JPH0638953B2 (en) | High-purity water manufacturing equipment | |
| WO1999047456A1 (en) | Method of water purification | |
| JP2002119964A (en) | Waste water circulation system in semiconductor manufacturing process | |
| JPH10128075A (en) | Reverse osmosis membrane device and treatment using the same | |
| Rajca | The use of chitosan and pressure-driven membrane processes to remove natural organic matter from regenerative brine recovery | |
| RU2273066C1 (en) | Method for recovering liquid radioactive wastes | |
| JPS60102905A (en) | Treatment of waste liquid | |
| KR101495601B1 (en) | Membrane regenerating apparatus | |
| JPH11244846A (en) | Treatment of diluted liquid to be treated and device therefor | |
| JP3861283B2 (en) | Method for treating gallium-containing wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20010109 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080119 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090119 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090119 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100119 Year of fee payment: 9 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100119 Year of fee payment: 9 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110119 Year of fee payment: 10 |
|
| LAPS | Cancellation because of no payment of annual fees |