JPS60225689A - Treatment of waste boric acid solution - Google Patents
Treatment of waste boric acid solutionInfo
- Publication number
- JPS60225689A JPS60225689A JP8029284A JP8029284A JPS60225689A JP S60225689 A JPS60225689 A JP S60225689A JP 8029284 A JP8029284 A JP 8029284A JP 8029284 A JP8029284 A JP 8029284A JP S60225689 A JPS60225689 A JP S60225689A
- Authority
- JP
- Japan
- Prior art keywords
- boric acid
- solution
- liquid
- acid
- concentrated
- 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.)
- Pending
Links
Abstract
Description
【発明の詳細な説明】
本発明はアルミニウム箔電解コンデンサーの製造工程で
使用されるほう酸電解槽の更新時に発生する濃厚はう酸
含有排液と製品の洗浄時に発生する希薄はう酸含有洗浄
排液の処理に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention aims to improve wastewater containing concentrated boric acid generated during renewal of boric acid electrolytic cells used in the manufacturing process of aluminum foil electrolytic capacitors and cleaning wastewater containing dilute boric acid generated during product cleaning. This relates to liquid processing.
アルミニウム箔電解コンデンサー製造工程は、苛性アル
カリ等によるアルミニウム箔の脱脂を行った後、塩酸等
の浴液を用いてアルミニウム箔を陽極とし、浴液側を陰
極としアルミニウム箔表面のエツチングを行ない、アル
ミニウム箔の有効面積を増大ならしめ、その後充分に洗
浄した後当該アルミニウム箔をほう酸電解槽に浸漬し、
陽極電解酸化によってアルミニウム箔表面上に酸化アル
ミニウムを被膜形成ぜしめ、水洗、乾燥等の工程を経て
コンデンサーとするものである。The manufacturing process for aluminum foil electrolytic capacitors involves degreasing the aluminum foil with caustic alkali, etc., and then etching the surface of the aluminum foil using a bath solution such as hydrochloric acid, using the aluminum foil as an anode and the bath solution side as a cathode. The effective area of the foil is increased, and after thorough cleaning, the aluminum foil is immersed in a boric acid electrolytic bath.
A film of aluminum oxide is formed on the surface of an aluminum foil by anodic electrolytic oxidation, and a capacitor is formed through processes such as washing with water and drying.
□上記はう酸電解槽はアルミニウム箔表面の酸化被膜を
均質化せしめるため、高温下に飽和状態のほう酸水溶液
を使用するのが一般的である。□ In order to homogenize the oxide film on the surface of the aluminum foil, the above-mentioned boric acid electrolytic cell generally uses a saturated aqueous solution of boric acid at high temperature.
かかるほう酸電解槽の溶液は長時間連続的にアルミニウ
ム箔と接触電解を行々うと、アルミニウム箔の一部が浴
液に溶解し、液性が微酸性であるため水酸化アルミニウ
ムが析出するが、溶解アルミニウムの濃度の増加および
水酸化アルミニウムの析出量の増加によって電解電流効
率の低下をまねき、かつアルミニウム箔表面の酸化被膜
形成のバラツキを惹起する。したがって従来ではかかる
浴液は。When the solution in such a boric acid electrolytic bath is subjected to contact electrolysis with aluminum foil continuously for a long time, part of the aluminum foil dissolves in the bath liquid, and aluminum hydroxide precipitates because the liquid is slightly acidic. An increase in the concentration of molten aluminum and an increase in the amount of precipitated aluminum hydroxide lead to a decrease in electrolytic current efficiency and cause variations in the formation of an oxide film on the surface of the aluminum foil. Therefore, in the past, such bath liquid.
次の如き工程に従い浴液を更新している。The bath liquid is renewed according to the following steps.
まず、浴液を高温のま捷フィルタープレスのごとき加圧
型濾過器に圧入し、混在する水酸化アルミニウムを濾別
する。次いで濾液を常温下に冷却することによりほう酸
の温度による溶解度差を利用してほう酸を晶析せしめ濾
別回収する。First, the bath liquid is pressurized into a pressurized filter such as a high-temperature filter press, and aluminum hydroxide present in the bath is filtered out. Next, the filtrate is cooled to room temperature to crystallize boric acid by taking advantage of the temperature-dependent solubility difference of boric acid, and is collected by filtration.
当該晶析したほう酸は再び溶解することにより前記はう
酸電解槽に用いることができるが、はう酸の結晶を濾別
した飽和はう酸液には塩酸等の鉱酸イオンと鉄、ニッケ
ル、クロム等の重金属イオンが許容量以上含有される場
合があり、このような飽和はう酸液は回収使用すること
ができない。The crystallized boric acid can be used in the above-mentioned holic acid electrolytic cell by redissolving it, but the saturated boric acid solution from which the boric acid crystals have been filtered contains mineral acid ions such as hydrochloric acid, iron, and nickel. , chromium, and other heavy metal ions may be contained in an amount exceeding the allowable amount, and such a saturated oxalic acid solution cannot be recovered and used.
すなわち塩素イオン等の鉱酸イオンがｌ ｍｇ／１以上
および重金属イオンが０．５ｍｇ／１以上含まれている
飽和はう酸液をほう酸電解槽に用いるとアルミニウム箔
上の酸化被膜に欠陥が生じ、仕上り製品コンデンサーの
劣化が極めて犬となる。In other words, if a saturated holic acid solution containing 1 mg/1 or more of mineral acid ions such as chlorine ions and 0.5 mg/1 or more of heavy metal ions is used in a boric acid electrolytic cell, defects will occur in the oxide film on the aluminum foil. , the deterioration of the finished product capacitor will be extremely severe.
したがってかかる重金属イオン、鉱酸イオンを含む飽和
はう酸液は電解浴液として使用することができないので
、従来では産業廃棄物として処理業者に委託するかもし
くは、希釈することにより河川、近海域へ放流せざるを
えなかったものである。Therefore, the saturated oxide solution containing heavy metal ions and mineral acid ions cannot be used as an electrolytic bath solution, so conventionally it has been either entrusted to a disposal company as industrial waste or diluted and disposed of in rivers and nearby waters. It had no choice but to be released.
しかしながらほう酸イオンは、植物生育のだめの微量元
素として必要とされているが。However, borate ions are required as trace elements for plant growth.
（例えば用水廃水便覧Ｐ８５０記載）をみてもあきらか
である。(For example, see page 850 of the Water and Wastewater Handbook).
したがって当該飽和はう酸液を希釈して排出することは
公害問題を惹起する恐れがある。Therefore, diluting and discharging the saturated hydric acid solution may cause pollution problems.
また、当該飽和はう酸液を近海域に排出することは希少
金属であるほう素を海域に投棄することであり、貴重資
源の浪費といわざるをえないものである。Furthermore, discharging the saturated acrylic acid solution into nearby waters means dumping boron, a rare metal, into the sea, which can only be said to be a waste of valuable resources.
またアルミニウム箔電解コンデンサーの製造工程におい
ては前記飽和はう酸液のような濃厚はう酸含有排液の他
に、アルミニウム箔をほう酸電解槽で処理した後の水洗
においても希薄はう酸含有洗浄排液が発生する。当該洗
浄排液には２００〜４００ｐｐｍのほう酸イオンが存在
するが、当該洗浄排液も前述したごとく−５−
植物栽培に不都合を招集するのでそのまま放流すること
は好ましくない。In addition, in the manufacturing process of aluminum foil electrolytic capacitors, in addition to the concentrated borosemic acid-containing wastewater such as the above-mentioned saturated hydric acid solution, dilute borosemic acid-containing waste water is also used in water washing after aluminum foil is treated in a boric acid electrolytic bath. Drainage occurs. Although 200 to 400 ppm of boric acid ions are present in the washing waste liquid, it is not preferable to discharge the washing waste liquid as it is, as it may cause inconvenience to plant cultivation as described above.
本発明は以上述べたようなアルミニウム箔電解コンデン
サーの製造工程において発生する濃厚はう酸含有排液と
希薄はう酸含有洗浄排液から不純物を除去し、再びほう
酸電解槽に用いることを目的とするもので、その第１発
明はアルミニウム箔電解コンデンサーの製造工程におけ
るほう酸電解槽の更新時に発生する濃厚はう酸含有排液
を処理するにあたり。The purpose of the present invention is to remove impurities from the concentrated hydric acid-containing waste liquid and the dilute borosemic acid-containing cleaning effluent generated in the manufacturing process of aluminum foil electrolytic capacitors as described above, and to reuse the waste liquid in a boric acid electrolytic cell. The first invention is for treating concentrated boric acid-containing wastewater generated during renewal of boric acid electrolytic cells in the manufacturing process of aluminum foil electrolytic capacitors.
当該排液をキレート形成樹脂とアニオン交換樹脂に通液
し、当該排液中の重金属イオンおよび鉱酸イオンを除去
し、当該処理液を回収してほう酸電解槽に再び用いるこ
とを特徴とするほう酸排液の処理方法であり、その第２
発明はアルミニウム箔電解コンデンサーの製造工程にお
けるほう酸電解槽の更新時に発生する濃厚はう酸含有排
液と、製品の洗浄時に発生する希薄はう酸含有洗浄排液
を処理するにあたり、前記希薄はう酸含有洗浄排液を逆
＝ ６ −
浸透膜装置で処理してほう酸を濃縮し、当該濃縮液と前
記濃厚はう酸含有排液を混合して当該混合液をキレート
形成樹脂とアニオン交換樹脂に通液し、当該混合液中の
重金属イオンおよび鉱酸イオンを除去し、当該処理液を
回収してほう酸電解槽に再び用いることを特徴とするほ
う酸排液の処理方法である。Boric acid characterized in that the waste liquid is passed through a chelate forming resin and an anion exchange resin to remove heavy metal ions and mineral acid ions in the waste liquid, and the treated liquid is recovered and used again in a boric acid electrolytic cell. This is the second method for treating wastewater.
The present invention uses the dilute boric acid to treat the concentrated boric acid-containing wastewater generated when renewing a boric acid electrolytic cell in the manufacturing process of aluminum foil electrolytic capacitors, and the dilute boric acid-containing cleaning wastewater generated during product cleaning. The acid-containing cleaning waste liquid is reversed = 6 - treated with a osmotic membrane device to concentrate boric acid, the concentrated liquid and the concentrated boric acid-containing waste liquid are mixed, and the mixed liquid is converted into a chelate-forming resin and an anion exchange resin. This method of treating boric acid waste liquid is characterized by passing the liquid through the mixed liquid to remove heavy metal ions and mineral acid ions in the mixed liquid, and recovering the treated liquid to be used again in the boric acid electrolytic cell.
以下に本発明を図面を参照１〜て詳細に説明する。The present invention will be described in detail below with reference to the drawings.
第１図は本発明の第１発明の実施態様のフローを示す説
明図であるが、はう酸電解浴槽ｌにおいてアルミニウム
箔１８を電解酸化し。FIG. 1 is an explanatory diagram showing the flow of the first embodiment of the present invention, in which an aluminum foil 18 is electrolytically oxidized in a hydrolic acid electrolytic bath l.
アルεニウム箔表面上に酸化被膜を形成させ次いで洗浄
水槽２において該アルミニウム箔を純水１２で洗浄し、
製品となすが、はう酸電解浴槽ｌ中の飽和はう酸液にア
ルミニウムイオン、水酸化アルミニウムが蓄積した際に
。forming an oxide film on the surface of the aluminum foil, and then washing the aluminum foil with pure water 12 in a washing water tank 2;
When aluminum ions and aluminum hydroxide accumulate in the saturated hydric acid solution in the ferrous acid electrolytic bath.
電解浴液ポンプ〒を介してフィルタープレス。Filter press via electrolytic bath liquid pump.
オリバーフィルターのごとき濾過器３で当該はう酸液と
水酸化アルミニウムのごとき不溶性金属塩を濾別する。A filter 3 such as an Oliver filter is used to separate the oxalic acid solution and an insoluble metal salt such as aluminum hydroxide.
かかる工程では水温は高ければ高い程はう酸の水への溶
解度が高いので、効率弁よくほう酸を濾別することがで
きる。In this process, the higher the water temperature, the higher the solubility of boric acid in water, so boric acid can be filtered out with high efficiency.
次いで濾液を冷却器１５で液温を低下せしめることによ
りほう酸を析出せしめ結晶１６を分離し、はう酸電解浴
槽］−へ戻し再使用する。結晶を分離した液にはほう酸
が飽和状態で溶解しており、この濃厚はう酸液には重金
属として、鉄、ニッケル、クロムが１〜２ｍｇ／ｌ、隘
イオンとしては塩素イオン等の鉱酸イオンが２〜３ｍｇ
／Ｉ溶解しているので、まず。Next, the temperature of the filtrate is lowered in a cooler 15 to precipitate boric acid, and crystals 16 are separated and returned to the ferrous acid electrolytic bath for reuse. Boric acid is dissolved in a saturated state in the liquid from which the crystals are separated, and this concentrated boric acid liquid contains 1 to 2 mg/l of iron, nickel, and chromium as heavy metals, and mineral acids such as chloride ions as ions. 2 to 3 mg of ions
/I is dissolved, so first.
キレート形成樹脂化例えばアンバーライト（登録商標、
以下同様） Ｉ Ｒｅ −７１８を充填した吸着塔に通
液し、当該水溶液中の鉄、ニッケル、クロム等の重金属
イオンを吸着除去せしめる。Chelate-forming resins such as Amberlite (registered trademark)
The same applies hereinafter) The solution is passed through an adsorption tower filled with IRe-718, and heavy metal ions such as iron, nickel, and chromium in the aqueous solution are adsorbed and removed.
吸着反応式は（］）式の通りである。The adsorption reaction formula is as shown in equation (]).
Ｒ−Ｉ■＋ Ｍｅｔａｌ→Ｒ−Ｍｅｔａｌ＋Ｈ＋・・・
・・・・・・・・・・・・・・・・・・（１）（キレー
ト形成樹脂）
重金属を吸着したキレート形成樹脂は塩酸。R-I■+ Metal→R-Metal+H+...
・・・・・・・・・・・・・・・・・・(1) (Chelate-forming resin) The chelate-forming resin that has adsorbed heavy metals is hydrochloric acid.
硫酸等の鉱酸を通液して脱着する。Desorb by passing a mineral acid such as sulfuric acid through it.
脱着反応式は（２）式の通りである。The desorption reaction formula is as shown in formula (2).
ＴＴＯ＋
Ｒ，−Ｍｅｔａｌ ＋→Ｒ−Ｈ＋Ｍｅｔａｌ−塩・・・
・・・・・・（２）ｔ１２ｓｏ。TTO+ R, -Metal +→R-H+Metal-salt...
......(2) t12so.
吸着塔で重金属イオンを吸着する際の通液速度はＳＶ
（空間速度ｌ／１ｌ）１〜５０．好ましくは１〜ｌＯが
よい。The liquid flow rate when adsorbing heavy metal ions in an adsorption tower is SV
(Space velocity l/1l) 1-50. Preferably it is 1 to 1O.
重金属イオンの脱着は１〜ＩＯＮ鉱酸水溶液好ましくは
１〜５Ｎ鉱酸水溶液を用いる。当該脱着によりカチオン
再生廃液１３をうるが。For desorption of heavy metal ions, a 1-ION mineral acid aqueous solution, preferably a 1-5N mineral acid aqueous solution, is used. A cation regeneration waste liquid 13 is obtained by the desorption.
このカチオン再生廃液は、はう酸を全く含まず、金属の
鉱酸塩水溶液であるから、これは苛性ソーダ、消石灰等
のアルカリ剤を添加することにより金属水酸化物となし
、固液分離を行ない処分する。Since this cation regeneration waste liquid does not contain any ferrous acid and is an aqueous solution of metal mineral salts, it is converted into metal hydroxide by adding an alkaline agent such as caustic soda or slaked lime, and then subjected to solid-liquid separation. dispose.
キレート形成樹脂４で処理した重金属を含まない濃厚は
う酸液を次いでアニオン交換樹脂５を充填した吸着塔に
通水する。使用するアニオン交換樹脂としては、 ＯＨ
型の強塩基−９−
性アニオン交換樹脂、たとえばアンバーライアンバーラ
イ） ＩＲＡ−９３等を用いることができる。このよう
表アニオン交換樹脂に濃厚はう酸を通液することにより
、当該液中に存在する塩素イオン等の鉱酸イオンを吸着
除去せしめることができる。The heavy metal-free concentrated oxalic acid solution treated with the chelate-forming resin 4 is then passed through an adsorption tower filled with an anion exchange resin 5. The anion exchange resin used is OH
A strongly basic 9-type anion exchange resin such as Amber IRA-93 or the like can be used. By passing a concentrated hydrolic acid solution through the surface anion exchange resin in this manner, mineral acid ions such as chlorine ions present in the solution can be adsorbed and removed.
このようにキレート形成樹脂とアニオン交換樹脂で処理
した濃厚はう酸液は、不純物を含まないほう酸飽和水溶
液として精製されるのであり精製液６としてほう酸電解
浴槽１へ戻すことができる。当該アニオン交換樹脂５に
おける吸着反応式は（３）式の通りであり。The concentrated boric acid solution treated with the chelate-forming resin and anion exchange resin in this manner is purified into a saturated aqueous solution of boric acid that does not contain any impurities, and can be returned to the boric acid electrolytic bath 1 as the purified solution 6. The adsorption reaction formula in the anion exchange resin 5 is as shown in formula (3).
Ｃ１０１
Ｒ，−ＯＨ＋（（ｓｏ、−＋Ｒ−（ｓｏ４）＋０Ｔ（−
＝°−°°゛−°−゛−（３）また脱着は苛性ソーダ等
のアルカリを通液するもので、その時の反応式は（４）
式の通りであ−１０＝
アニオン再生廃液１４はほう酸を含まないので中和して
放流できる。C101 R, -OH+((so, -+R-(so4)+0T(-
=°−°°゛−°−゛−(3) Also, desorption involves passing an alkali such as caustic soda through it, and the reaction formula at that time is (4)
As per the formula -10= The anion regeneration waste liquid 14 does not contain boric acid, so it can be neutralized and discharged.
当該吸着塔への通水速度は８Ｖｌ〜５０．好ましくは１
〜１０がよく、脱着は１−１ＯＮ好ましくは１〜５Ｎの
苛性ソーダ水溶液を用いる。The water flow rate to the adsorption tower is 8 Vl to 50 Vl. Preferably 1
~10 is good, and desorption uses a 1-1ON, preferably 1-5N aqueous solution of caustic soda.
第１図に示した実施態様においては濃厚はう酸液をまず
キレート形成樹脂４に通液し。In the embodiment shown in FIG. 1, a concentrated oxalic acid solution is first passed through the chelate-forming resin 4.
次いで当該処理液をアニオン交換樹脂５に通液している
が１通液の順序はこれに限定されるものでなく、先にア
ニオン交換樹脂５に通液し１次にキレート形成樹脂４に
通液してもさしつかえない。Next, the treatment liquid is passed through the anion exchange resin 5, but the order of passing the liquid is not limited to this. First, the process liquid is passed through the anion exchange resin 5, and then through the chelate forming resin 4. It is okay to use liquid.
第２図は本発明の第２発明の実施態様のフローを示す説
明図であり、第２図で示したごとく被電解アルミニウム
箔は次の工程として洗浄水槽２に於て純水１２によって
清浄になるまで洗浄される。この折この水洗水には。FIG. 2 is an explanatory diagram showing the flow of the embodiment of the second invention of the present invention, and as shown in FIG. It will be washed until it is clean. At this time of the year, this flush water is used.
はう酸電解浴槽ｌより被電解アルミニウム箔に付着同伴
せるほう酸が混入することはまぬがれない。従ってこの
水洗水中のほう酸は微量とはいえ、前述した如く公害問
題の提起または資源投棄という問題があるので、洗浄水
ポンプ８．高圧ポンプ１７を介して逆浸透装置９に導入
し、加圧下において洗浄水中の水を透過水１０として分
離せしめ洗浄水として回収し、純水１２として使用する
。逆浸透装置９における加圧は５〜５０ｋｇ／ａｆｌ、
好ましくはｌＯ〜３０ｋｇ／ｃｒＦｌがよい。一方濃縮
側は洗浄水中のほう酸が５０〜５００倍に濃縮されてい
るので。It is inevitable that boric acid, which is attached to and entrained in the aluminum foil to be electrolyzed, will be mixed in from the bolic acid electrolytic bath l. Therefore, although the amount of boric acid in this washing water is small, it poses a problem of pollution or waste of resources as mentioned above, so the washing water pump 8. The water is introduced into the reverse osmosis device 9 via the high-pressure pump 17, and under pressure, the water in the washing water is separated as permeated water 10, recovered as washing water, and used as pure water 12. The pressure in the reverse osmosis device 9 is 5 to 50 kg/afl,
Preferably it is 10 to 30 kg/crFl. On the other hand, on the concentrated side, the boric acid in the washing water is concentrated 50 to 500 times.
当該濃縮水１１を前述の結晶を分離した濃厚はう酸液と
合流せしめ共存する陽イオン、陰イオンをキレート形成
樹脂４およびアニオン交換樹脂５に通水し精製を行なう
。The concentrated water 11 is combined with the concentrated oxalic acid solution from which the crystals have been separated, and the coexisting cations and anions are passed through the chelate-forming resin 4 and the anion exchange resin 5 for purification.
以上説明したごとく本発明はほう酸水溶液を完全にクロ
ーズド化し、外部への投棄を一切行なわないので、省資
源対策および公害問題を提起する恐れはなく、かつ経済
的な方法である。As explained above, the present invention completely closes the boric acid aqueous solution and does not dump it outside at all, so it is an economical method that does not pose any risk of resource saving or pollution problems.
本発明の効果をより明確とするために以下に実施例を説
明する。Examples will be described below to make the effects of the present invention more clear.
実施例−１
はう酸濃度３５．ｏｏｏｍｇ／ｘ （１０℃に於て飽和
濃度）にニッケル硫酸塩、クロム硫酸塩を金属として１
〜２ ｍｇ／ ｔ 、食塩（Ｎａ１ｌ ）を塩素イオン
濃度として１〜２ｍｇ／ｌになるよう添加したものを原
水となし、キレート型形成樹脂、 ｏｒ−■型強塩基性
アニオン交換樹脂をそれぞれ２００ｍ１を別個のカラム
に充填し、原水１０１をシリーズに通したところ次の結
果をえた。Example-1 Hydrolic acid concentration 35. ooomg/x (saturated concentration at 10°C) with nickel sulfate and chromium sulfate as metals.
~2 mg/t, salt (Na1l) was added to make the chloride ion concentration 1 to 2 mg/l as raw water, and 200ml each of chelate type forming resin and or-■ type strong basic anion exchange resin were added. A separate column was packed and raw water 101 was passed through the series with the following results.
実施例−２ はう酸濃度３５．０００ ｍｇ／ Ｌに不純物として。Example-2 As an impurity at a concentration of 35.000 mg/L of oxalic acid.
Ｎｉ” ｌ−５ｍｇ／ｊ ＋ Ｏｒ” ０．８ｍｇ／ｊ
、 Ｏｌ−１３０ｍｇ／ｊを添加したものを原水とし
、その１０ｊまずキレート型形成樹脂カラム（樹脂量２
００ｍ１）に通水し２次いで１０１を２等分し、各５１
づつｉＯＨ型強塩基性アニオン交換樹脂カラム（樹−１
３−
脂量２００ｍ１ ）とＯＨ型中塩基性アニオン交換樹脂
カラム（樹脂量２００ｍ１ ）にそれぞれ通水したとこ
ろ２強塩基性アニオン交換樹脂カラムよりえられた５１
の分析値はＮｉ”Ｏｍｇ／ｊ 。Ni" l-5mg/j + Or" 0.8mg/j
, 130mg/j of Ol-1 was added to the raw water, and 10j of it was first added to a chelate type forming resin column (with a resin amount of 2
00m1), then divide 101 into two equal parts, each with 51
iOH type strongly basic anion exchange resin column (Ji-1
When water was passed through an OH type medium basic anion exchange resin column (resin amount 200 m1), 51 was obtained from the 2 strongly basic anion exchange resin column.
The analysis value is Ni”Omg/j.
Ｏｒ”” Ｏｍｇ／ｌ、 Ｏｌ−０，８ｍｇ／ｌであり
、中塩基性アニオン交換樹脂カラムよりえられた５１の
分析値はＮｉ” Ｏｍｇ／ｊ 、 Ｃｒ３＋Ｏｍｇ／Ｅ
、 Ｏｌ−０，７ｍｇ／ｌであり、極めてよく精製さ
れていることが判った。Or""Omg/l, Ol-0.8mg/l, and the analytical values of 51 obtained from the medium basic anion exchange resin column are Ni"Omg/j, Cr3+Omg/E.
, Ol-0.7 mg/l, indicating that it was extremely well purified.
これ等精製液をそれぞれ３１を採取し、電解被膜特性を
ブランクと比較したところ、電解被膜形成電圧及び立上
り所要時間ならびに電解被膜劣化テストにおいてもブラ
ンクの測定値と全く異なるところはなく精製液として充
分利用可能であることが判った。When we sampled 31 samples of each of these purified liquids and compared the electrolytic film properties with the blank, we found that there was no difference in the electrolytic film formation voltage, rise time, and electrolytic film deterioration test from the blank measurement values, making it sufficient as a purified liquid. It turned out to be available.
実施例−３
はう酸イオン２００〜３００ｍｇ／ｌ 、塩素イオン０
．１ｍｇ／！の水溶液１ｍ’／ｈ（希薄はう酸含有洗浄
排液の組成に相当する）を２０〜３０ｋｇ／ａＭに印加
し、逆浸透装置（例えばモジュール・東−１４−
し製８０−１．０００４本）に通水したところ透過液側
液量０・１ ｍ’／ ｈ （９０％回収）時の組成は。Example-3 Oxalate ion 200-300mg/l, chloride ion 0
．． 1mg/! An aqueous solution of 1 m'/h (corresponding to the composition of dilute fluoric acid-containing cleaning waste liquid) is applied at 20 to 30 kg/aM, ) When the permeate side liquid volume was 0.1 m'/h (90% recovery), the composition was as follows.
はう酸イオン１０〜２０ｍｇ／ｌ、塩素イオンｔ ｒａ
ｃｅであった。従って本透過液は、洗浄水ラインに導入
し、洗浄水として再使用することは充分可能である。Oxalate ion 10-20mg/l, chloride ion tra
It was ce. Therefore, this permeate can be introduced into the washing water line and reused as washing water.
また、濃縮液組成は、はう酸イオン１．８００〜３．０
００ ｍｇ／ ｔ ＋塩素イオンｏ、ｓ 〜１．ｏｍｇ
、＃ であった。本濃縮液を実施例−２で用いた濃厚は
う酸液と混合し、実施例−２と同じ条件でキレート形成
樹脂カラムと強塩基性アニオン交換樹脂カラムで処理す
ることによりほう酸は完全に精製されることが判った。In addition, the concentrate composition is 1.800 to 3.0 oxalic acid ions.
00 mg/t + chloride ions o, s ~1. omg
,# Met. Boric acid was completely purified by mixing this concentrated solution with the concentrated boric acid solution used in Example-2 and treating it with a chelate-forming resin column and a strong basic anion exchange resin column under the same conditions as in Example-2. It turned out that it would be done.
第１図は本発明の第１発明の実施態様のフローを示す説
明図であり、第２図は本発明の第２発明の実施態様のフ
ローを示す説明図である。
ｌ・・・はう酸電解槽 ２・・・洗浄水槽３・・・濾過
器 ４・・・キレート形成樹脂５・・・アニオン交換樹
脂 ６・・・精製液７・・・電解浴液ポンプ ８・・・
洗浄水ポンプ９・・・逆浸透装置 １０・・・透過水１
１・・・濃縮水 １２・・・純水
１３・・・カチオン再生廃液 １４・・・アニオン再生
廃液１５・・・冷却器 １６・・・結晶
１７・・・高圧ポンプ １８・・・アルミニウム箔手続
補正書（自発）
昭和６０年６月２ｚ日
特許庁長官 志 賀 学 殿
１、事件の表示
昭和５９年特許願第８０２９２号
２、発明の名称
はう酸排液の処理方法
３、補正をする者
事件との関係 特許出願人
住 所 東京都文京区本郷５丁目５番１６号名 称 （
４４０） オルガノ株式会社代表者 永 井 邦 夫
４゜代理人〒１１３
住 所 東京都文京区本５Ｉ！ｌ１５丁目５番１６号オ
ルガノ株式会社内
氏名 （６３７６）弁理士高橋 装
置、 ８１２−５１５１
５、補正の対象
明細書中の下記事項を訂正願います。
１、第２頁１４行目〜１５行目に記載されている「アル
ミニウム箔を陽極とし、浴液側を陰極とし」という文章
を削除する。
２、第１３頁下から４行目に１その１０７！まず」とあ
るのを１そのＩｏｎをまず」と訂正する。
３、第１３頁６行目および同頁下から４行目〜下から３
行目に「キレート型形成樹脂」とあるのを「キレート形
成樹脂」と訂正する。
以上FIG. 1 is an explanatory diagram showing the flow of the embodiment of the first invention of the present invention, and FIG. 2 is an explanatory diagram showing the flow of the embodiment of the second invention of the invention. l...Fallic acid electrolytic tank 2...Washing water tank 3...Filter 4...Chelate forming resin 5...Anion exchange resin 6...Purified liquid 7...Electrolytic bath liquid pump 8 ...
Washing water pump 9... Reverse osmosis device 10... Permeated water 1
1... Concentrated water 12... Pure water 13... Cation regeneration waste liquid 14... Anion regeneration waste liquid 15... Cooler 16... Crystal 17... High pressure pump 18... Aluminum foil procedure Written amendment (spontaneous) June 2, 1985 Manabu Shiga, Commissioner of the Patent Office1, Indication of the case: Patent Application No. 80292 of 19802, Title of the invention: Process for treating oxalic acid wastewater3, Amendments are made. Relationship with the Patent Case Patent Applicant Address 5-5-16 Hongo, Bunkyo-ku, Tokyo Name (
440) Organo Co., Ltd. Representative Kunio Nagai 4゜ Agent 113 Address Hon 5I, Bunkyo-ku, Tokyo! 15-5-16 Organo Co., Ltd. Name (6376) Patent Attorney Takahashi Equipment, 812-5151 5. Please correct the following matters in the specification subject to amendment. 1. Delete the sentence "Use the aluminum foil as an anode and the bath liquid side as a cathode" written in lines 14 and 15 of page 2. 2. 1 No. 107 on page 13, 4th line from the bottom! Correct "first of all" to "first of all". 3. Page 13, line 6 and line 4 from the bottom of the same page - 3 from the bottom
In the first line, "chelate-forming resin" should be corrected to "chelate-forming resin."that's all
Claims (2)
けるほう酸電解槽の更新時に発生する濃厚はう酸含有排
液を処理するにあたり。 当該排液をキレート形成樹脂とアニオン交換樹脂に通液
し、当該排液中の重金属イオンおよび鉱酸イオンを除去
し、当該処理液を回収してほう酸電解槽に再び用いるこ
とを特徴とするほう酸排液の処理方法(1) To treat the concentrated boric acid-containing wastewater generated when updating the boric acid electrolyzer in the manufacturing process of aluminum foil electrolytic capacitors. Boric acid characterized in that the waste liquid is passed through a chelate forming resin and an anion exchange resin to remove heavy metal ions and mineral acid ions in the waste liquid, and the treated liquid is recovered and used again in a boric acid electrolytic cell. How to treat wastewater
けるほう酸電解槽の更新時に発生する濃厚はう酸含有排
液と、製品の洗浄時に発生する希薄はう酸含有洗浄排液
を処理するにあたり、前記希薄はう酸含有洗浄排液を逆
浸透膜装置で処理してほう酸を濃縮し。 当該濃縮液と前記濃厚はう酸含有排液を混合して当該混
合液をキレート形成樹脂とアニオン交換樹脂に通液し、
当該混合液中の重金属イオンおよび鉱酸イオンを除去し
。 当該処理液を回収してほう酸電解槽に再び用いることを
特徴とするほう酸排液の処理方法(2) When treating the concentrated boric acid-containing wastewater generated when renewing the boric acid electrolyzer in the manufacturing process of aluminum foil electrolytic capacitors, and the dilute boric acid-containing cleaning wastewater generated during product cleaning, the dilute Boric acid-containing cleaning waste liquid is treated with a reverse osmosis membrane device to concentrate boric acid. mixing the concentrated liquid and the concentrated fluoric acid-containing waste liquid and passing the mixed liquid through a chelate-forming resin and an anion exchange resin;
Remove heavy metal ions and mineral acid ions from the mixed solution. A method for treating boric acid waste liquid, characterized in that the treated liquid is recovered and used again in a boric acid electrolytic cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8029284A JPS60225689A (en) | 1984-04-23 | 1984-04-23 | Treatment of waste boric acid solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8029284A JPS60225689A (en) | 1984-04-23 | 1984-04-23 | Treatment of waste boric acid solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60225689A true JPS60225689A (en) | 1985-11-09 |
Family
ID=13714192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8029284A Pending JPS60225689A (en) | 1984-04-23 | 1984-04-23 | Treatment of waste boric acid solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60225689A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003010845A (en) * | 2001-07-05 | 2003-01-14 | Nippon Denko Kk | Method for recovering high purity boron solution and apparatus therefor |
| JP2003053342A (en) * | 2001-08-10 | 2003-02-25 | Nippon Denko Kk | Method and device for removing impurity in boron- containing solution |
| CN103910454A (en) * | 2014-04-24 | 2014-07-09 | 山西阳煤丰喜肥业(集团)有限责任公司 | Device and method for decreasing temperature of DSD (4,4'-diamido diphenylethylene-disulfonic acid) wastewater |
| CN109850919A (en) * | 2019-04-01 | 2019-06-07 | 南京简迪环境工程有限公司 | A kind of technique that recycling refines potassium chloride in organic chemical waste water |
| JP2019188300A (en) * | 2018-04-23 | 2019-10-31 | オルガノ株式会社 | Method of removing metal in liquid, and anion exchange resin-mixed h chelate resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51104449A (en) * | 1975-03-13 | 1976-09-16 | Sankyo Alu Ind | Aruminiumuno yokyokusankashoryoyokusosei |
| JPS52123554A (en) * | 1976-04-06 | 1977-10-17 | Bayer Ag | Method of selectively removing heavy metal |
| JPS53127329A (en) * | 1977-04-12 | 1978-11-07 | Unitika Ltd | Recycling method for washing water from metal surface treating process |
-
1984
- 1984-04-23 JP JP8029284A patent/JPS60225689A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51104449A (en) * | 1975-03-13 | 1976-09-16 | Sankyo Alu Ind | Aruminiumuno yokyokusankashoryoyokusosei |
| JPS52123554A (en) * | 1976-04-06 | 1977-10-17 | Bayer Ag | Method of selectively removing heavy metal |
| JPS53127329A (en) * | 1977-04-12 | 1978-11-07 | Unitika Ltd | Recycling method for washing water from metal surface treating process |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003010845A (en) * | 2001-07-05 | 2003-01-14 | Nippon Denko Kk | Method for recovering high purity boron solution and apparatus therefor |
| JP4691276B2 (en) * | 2001-07-05 | 2011-06-01 | 日本電工株式会社 | Method and apparatus for recovering high purity boron-containing water |
| JP2003053342A (en) * | 2001-08-10 | 2003-02-25 | Nippon Denko Kk | Method and device for removing impurity in boron- containing solution |
| CN103910454A (en) * | 2014-04-24 | 2014-07-09 | 山西阳煤丰喜肥业(集团)有限责任公司 | Device and method for decreasing temperature of DSD (4,4'-diamido diphenylethylene-disulfonic acid) wastewater |
| JP2019188300A (en) * | 2018-04-23 | 2019-10-31 | オルガノ株式会社 | Method of removing metal in liquid, and anion exchange resin-mixed h chelate resin |
| CN109850919A (en) * | 2019-04-01 | 2019-06-07 | 南京简迪环境工程有限公司 | A kind of technique that recycling refines potassium chloride in organic chemical waste water |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102459096B (en) | Method for recovering water and metals from plating wastewater resulting from washing | |
| CN108002580B (en) | Method for treating acidic flue gas washing wastewater and application thereof | |
| CN101234827B (en) | Treatment and resource reclaiming method for chromium-containing wastewater containing high concentration sodium sulfate | |
| EP0159349A1 (en) | Processes for treating waste streams | |
| CN110759532A (en) | High-salt concentrated water treatment process for producing iron phosphate by sodium method | |
| CN113754162A (en) | Method and system for recovering chloride by crystallizing acidic washing wastewater | |
| US4124459A (en) | Process for removing mercury from brine sludges | |
| CN110759554A (en) | Recycling and zero-discharge treatment method for ammonium adipate wastewater generated in aluminum foil formation | |
| JPS60225689A (en) | Treatment of waste boric acid solution | |
| CN211972015U (en) | Ammonium adipate wastewater recycling treatment process device | |
| CN104370389A (en) | Process for removing fluorine in pickling waste liquid in steel and iron industry | |
| US4566912A (en) | Method of regenerating alkali-containing wash solutions utilized for cleaning containers | |
| CN207958039U (en) | A kind of pickle liquor Treatment and recovery utilizes device | |
| US6936177B2 (en) | Method for removing metal from wastewater | |
| Germain et al. | Plating and cyanide wastes | |
| US4654131A (en) | Recovery of tungsten valves from alkaline solutions | |
| CN113754125A (en) | Recycling process of electroplating heavy metal ions and water | |
| TW200305543A (en) | Effluent water treatment method | |
| CN108002581B (en) | Method for cleaning high ammonia nitrogen wastewater containing metal ions | |
| RU2343225C2 (en) | Method of regeneration treatment of alkaline solutions of copper coating | |
| JPH03130400A (en) | Method for recovering valuable metallic matter from waste plating solution | |
| Mindler et al. | Metal recovery by cation exchange | |
| JPS5836695A (en) | Treatment of waste liquid of chemical washing | |
| RU2748040C1 (en) | Method for water purification from heavy metals by catalytic deposition | |
| JPS59222292A (en) | Treatment of waste liquid of chemical cleaning containing ethylenediamine tetraacetate |