JPH0598500A - Method for perfectly recycling free acid from waste aluminum electrolytic solution - Google Patents
Method for perfectly recycling free acid from waste aluminum electrolytic solutionInfo
- Publication number
- JPH0598500A JPH0598500A JP15257491A JP15257491A JPH0598500A JP H0598500 A JPH0598500 A JP H0598500A JP 15257491 A JP15257491 A JP 15257491A JP 15257491 A JP15257491 A JP 15257491A JP H0598500 A JPH0598500 A JP H0598500A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- electrolytic
- aluminum
- free acid
- solution
- 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
- 239000002253 acid Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000002699 waste material Substances 0.000 title claims abstract description 35
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 31
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000008151 electrolyte solution Substances 0.000 title description 8
- 238000004064 recycling Methods 0.000 title description 3
- 239000013078 crystal Substances 0.000 claims abstract description 30
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 23
- 238000000502 dialysis Methods 0.000 claims abstract description 19
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 14
- 238000009792 diffusion process Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims description 23
- 238000000926 separation method Methods 0.000 claims description 11
- 239000011888 foil Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 abstract description 30
- 239000000243 solution Substances 0.000 description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 13
- 238000005868 electrolysis reaction Methods 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 239000011133 lead Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010066901 Treatment failure Diseases 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、アルミニウム電解コン
デンサー、アルミニウムサッシ等のアルミニウム又はア
ルミニウム合金製品を硫酸単独又は塩酸と硫酸との混合
酸で表面処理をする際に発生するアルミニウムを含有す
る電解廃液から酸を回収して循環使用するための、無公
害で、完全クローズドプロセス化した酸の有効使用方法
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolytic waste liquid containing aluminum generated when surface treating aluminum or aluminum alloy products such as aluminum electrolytic capacitors and aluminum sashes with sulfuric acid alone or a mixed acid of hydrochloric acid and sulfuric acid. The present invention relates to an effective use method of a pollution-free, completely closed process acid for recovering and recycling the acid from the acid.
【０００２】[0002]
【従来の技術】アルミニウム電解コンデンサー、アルミ
ニウムサッシ等のアルミ製品の電解処理工程では電解液
として、硫酸単独又は塩酸と硫酸との混合酸が多量に使
用されるが、これら酸液中にはアルミニウムが溶解しそ
の溶解量がある量以上となると良好な電解処理ができな
くなるため、連続式では常に新しい酸の補給が必要であ
り、バッチ式では一定時間後に新しい電解液との交換が
必要である。しかしてこの電解廃液中には硫酸アルミニ
ウムと酸が存在するため、これらの有効利用が従来より
考えられている。その一つとして、従来、電解廃液より
硫酸アルミニウム結晶を製造する方法が提案されてお
り、例えば特公昭48−41157号、同49− 29821号、同51
−6034号、同51−6035号及び特開平 1−153517号公報に
記載された方法が知られているが、これらの方法はいず
れも硫酸アルミニウム結晶を分離する方法が主体であ
り、その分離濾過液を電解工程へ戻して再利用すること
は示されているが、特に不純物の混入をきらうアルミニ
ウム電解コンデンサー及びアルミニウムサッシの表面処
理等の精度の高い電解に対しては、循環酸液中の不純物
が電解処理に悪影響を与えるので、完全に再利用でき
ず、廃棄せざるをえなかった。それ故、最近の廃棄物を
減少させようとする傾向に反していたため、廃棄物のな
い完全クローズドプロセスが望まれていた。2. Description of the Related Art A large amount of sulfuric acid alone or a mixed acid of hydrochloric acid and sulfuric acid is used as an electrolytic solution in the electrolytic treatment process of aluminum products such as aluminum electrolytic capacitors and aluminum sashes. If it dissolves and the amount of dissolution exceeds a certain amount, a good electrolytic treatment cannot be performed. Therefore, in the continuous system, a new acid must always be replenished, and in the batch system, a new electrolytic solution must be exchanged after a certain period of time. However, since aluminum sulfate and acid are present in this electrolytic waste liquid, their effective use has been conventionally considered. As one of them, conventionally, a method of producing aluminum sulfate crystals from an electrolytic waste liquid has been proposed, for example, Japanese Patent Publication Nos. 48-41157, 49-29821, 51-51.
No. 6034, No. 51-6035 and the method described in JP-A-1-153517 are known, but all of these methods are mainly methods for separating aluminum sulfate crystals, and separation and filtration thereof. Although it has been shown that the solution is returned to the electrolysis step and reused, the impurities in the circulating acid solution are particularly effective for highly accurate electrolysis such as surface treatment of aluminum electrolytic capacitors and aluminum sashes that do not accept impurities. Has a bad influence on the electrolytic treatment, so it could not be completely reused and had to be discarded. Therefore, a completely waste-free closed process was desired, as opposed to the recent tendency to reduce waste.
【０００３】[0003]
【発明が解決しようとする課題】近年、アルマイト処理
における電解浴の安定化法として、イオン交換膜による
拡散透析法が提案されている。この方法によれば電解廃
液中の酸（遊離硫酸）と塩（硫酸アルミニウム）が分離
されるが、この拡散透析法では長時間放置すると交換膜
の両側の組成が同一となることから、塩の漏洩（リー
ク）も生じ、完全に酸のみを分離することはできない。
アルミ電解廃液は硫酸アルミニウムのほかに、被電解物
であるアルミニウム素材中に含まれる鉄等の不純物を含
むため、これら不純物がイオン交換膜を通過して循環酸
液中に含まれるが、蓄積されると電解処理性能に悪影響
を及ぼすほか、イオン交換膜の透析能力を低下させるな
どの不都合を生じさせる。また、上記のことからわかる
ように、透析法においては被透析液中に不純物等が多量
に含まれないほうがより効率よく遊離酸を分離できる。
そのため、これら不純物を系外に排出させる必要があ
る。本発明は、工業的規模で電解廃液中の不純物を除去
でき、イオン交換膜による拡散透析処理を効果的に行う
ことのできる遊離酸の完全リサイクル使用方法を提供せ
んとするものである。In recent years, a diffusion dialysis method using an ion exchange membrane has been proposed as a method for stabilizing an electrolytic bath in alumite treatment. According to this method, the acid (free sulfuric acid) and salt (aluminum sulfate) in the electrolysis waste liquid are separated, but in this diffusion dialysis method, the composition on both sides of the exchange membrane becomes the same when left for a long time, so Leakage also occurs and it is not possible to completely separate the acid.
In addition to aluminum sulfate, the aluminum electrolytic waste liquid contains impurities such as iron contained in the aluminum material to be electrolyzed, so these impurities pass through the ion exchange membrane and are contained in the circulating acid solution, but they are accumulated. This adversely affects the electrolytic treatment performance and causes inconveniences such as a decrease in the dialysis ability of the ion exchange membrane. Further, as can be seen from the above, in the dialysis method, the free acid can be separated more efficiently when the liquid to be dialyzed does not contain a large amount of impurities and the like.
Therefore, it is necessary to discharge these impurities out of the system. The present invention is intended to provide a method for completely recycling and using a free acid capable of removing impurities in an electrolytic waste liquid on an industrial scale and effectively performing a diffusion dialysis treatment with an ion exchange membrane.
【０００４】[0004]
【課題を解決するための手段】従来の方法によって、ア
ルミ箔電解廃液より有価物として硫酸アルミニウム結晶
を製造し、残りの酸液を電解液に循環使用した場合、表
面処理工程の電解溶液にアルミ素材中の不純物が蓄積し
てゆき表面処理不良となる不純物濃度の限度まで上昇す
るため、遠心分離濾過液を繰り返し循環使用することは
できないことが判明した。本発明者らは種々研究した結
果、硫酸アルミニウムは結晶の成長にしたがって酸液中
の水分を結晶水としてとり込むため酸濃度は増大し、そ
のため拡散透析したとき透析効率が向上すること、及び
硫酸アルミニウム結晶特にその六角板状結晶を分離する
とき結晶に付着して液中の不純物が除去されることを見
出して本発明を完成した。[Means for Solving the Problems] When aluminum sulfate crystals are produced as valuables from an aluminum foil electrolytic waste liquid by the conventional method, and the remaining acid solution is circulated and used as the electrolytic solution, aluminum is used as the electrolytic solution in the surface treatment step. It has been found that the centrifugal filtrate cannot be repeatedly circulated because the impurities in the material accumulate and increase to the limit of the impurity concentration that causes surface treatment failure. As a result of various studies conducted by the present inventors, aluminum sulfate takes in water in an acid solution as water of crystallization as crystals grow, so that the acid concentration increases, and therefore, dialysis efficiency is improved when diffusion dialysis is performed. The present invention has been completed by discovering that aluminum crystals, particularly hexagonal plate crystals, are attached to the crystals to remove impurities in the liquid when the crystals are separated.
【０００５】従って、本発明の電解廃液からの遊離酸の
回収使用方法は、アルミ箔電解廃液又はアルミサッシ電
解廃液等のアルミ電解廃液より遊離酸を回収し電解調整
液に循環再使用する方法において、アルミ電解廃液より
硫酸アルミニウム結晶を晶析させて濾過分離し、分離後
の電解廃液をイオン交換膜による拡散透析法により遊離
酸を回収することを特徴とする。イオン交換膜による拡
散透析では、酸廃液中の遊離酸を純水側へ回収し、塩は
透析残液側に残す。この拡散透析では操作条件によって
異なるが、通常塩が５〜10％リークするのが普通であ
る。同様に不純物もその存在量に応じてリークする。回
収酸は電解液に調整して循環使用するが、その際不純物
は濃縮〜晶析の循環系で濃度はアップして行くが、本発
明によれば不純物は硫酸アルミニウム結晶に付着して排
出されある値にバランスする。よって、電解浴槽へ不純
物を多量に戻すことなく、遊離酸と硫酸アルミニウム結
晶を回収することができる。硫酸アルミニウム結晶は結
晶水を１６分子含むもので六角板状結晶体が回収酸液の
濃縮化と不純物除去の点で好ましい。このことより、電
解液を電解工程、濃縮工程、晶出分離工程、酸回収工程
を繰り返し循環させながら電解工程で溶解したアルミ分
を硫酸アルミニウム結晶として系外へ抜き出すことによ
り、電解廃液中に蓄積される不純物が系外に排出され、
イオン交換膜による酸回収が純度よく且効率よく行わ
れ、完全クローズド化が可能となった。Therefore, the method of recovering and using the free acid from the electrolytic waste solution of the present invention is a method of recovering the free acid from the aluminum electrolytic waste solution such as the aluminum foil electrolytic waste solution or the aluminum sash electrolytic waste solution, and circulating and reusing the free acid. The method is characterized in that aluminum sulfate crystals are crystallized from an aluminum electrolytic waste solution and separated by filtration, and the separated electrolytic waste solution is subjected to a diffusion dialysis method using an ion exchange membrane to recover free acid. In the diffusion dialysis using an ion exchange membrane, the free acid in the acid waste liquid is recovered on the pure water side, and the salt is left on the dialysis residual liquid side. In this diffusion dialysis, 5 to 10% of salt is usually leaked although it depends on the operating conditions. Similarly, impurities leak according to the amount of impurities. The recovered acid is adjusted to an electrolytic solution and circulated for use. At that time, the concentration of impurities increases in a circulation system of concentration to crystallization, but according to the present invention, the impurities are attached to aluminum sulfate crystals and discharged. Balance to a certain value. Therefore, the free acid and aluminum sulfate crystals can be recovered without returning a large amount of impurities to the electrolytic bath. The aluminum sulfate crystal contains 16 molecules of crystal water, and a hexagonal plate crystal is preferable in terms of concentration of the recovered acid solution and removal of impurities. As a result, the aluminum component dissolved in the electrolysis process is extracted as aluminum sulfate crystals outside the system by repeatedly circulating the electrolysis process through the electrolysis process, the concentration process, the crystallization separation process, and the acid recovery process, thereby accumulating in the electrolysis waste liquid. Impurities are discharged out of the system,
The acid recovery by the ion-exchange membrane was carried out with high purity and efficiency, and it became possible to make it completely closed.
【０００６】[0006]
【実施例】次に本発明を実施例により説明するが、本発
明はこれらに限定されるものではない。 実施例 アルミ電解コンデンサ用高純度アルミ箔（Al 99.99％以
上、Fe0.004％以下、Cu＋Si 0.010％以下）を塩酸と硫
酸との混合酸で電解処理したときに生じる酸廃液（分析
値は表１(A) 参照、以下同様）を10Ｌ／Hrの流量で連続
的に真空濃縮工程へ供給し、該濃縮工程で真空度 310 T
or、沸点90℃の濃縮条件でドレンを６Ｌ／Hr留出させ、
濃縮酸液を４Ｌ／Hr得た。この濃縮酸液を晶出分離工程
へと移送し、従来技術の硫酸アルミニウム結晶の製造法
にて六角板状結晶を晶析させ、生じた結晶を遠心分離機
で分離して濾過液を 3.5Ｌ／Hrの合計液量で連続的に得
た。この濾過液を酸回収工程へ送り、該工程で濾過液中
の濃度アップされた遊離酸分は、拡散透析槽にて透析さ
れ回収される。この回収工程で膜回収酸 3.5Ｌ／Hrと透
析残液 3.5Ｌ／Hrとを得た。酸回収工程での膜回収酸と
濃縮工程のドレンは混合調整し、不足する酸分を必要に
応じて追加して電解工程の電解液として再利用する。電
解廃液、濃縮工程、晶出分離工程、酸回収工程の各工程
での廃液及び回収酸に含まれるアルミ分、酸分及び不純
物量を表−１に示す。表−１からわかるように硫酸アル
ミニウム結晶分離後の遠心分離濾過液中の不純物量は減
少している。硫酸アルミニウム結晶の晶析・分離工程を
行う本発明の方法では、透析残液にアルミ分及び特に
鉄、銅、鉛等の不純物が蓄積されることがないため、直
接電解廃液をイオン交換膜で酸回収する従来の方法に比
べ、イオン交換膜の交換回数を３分の１以下とすること
ができた。EXAMPLES The present invention will now be described with reference to examples, but the present invention is not limited thereto. Example An acid waste liquid produced when electrolytically treating a high-purity aluminum foil for an aluminum electrolytic capacitor (Al 99.99% or more, Fe 0.004% or less, Cu + Si 0.010% or less) with a mixed acid of hydrochloric acid and sulfuric acid (analytical values are shown in Table 1). (See (A), the same applies below) is continuously supplied to a vacuum concentration step at a flow rate of 10 L / Hr, and the vacuum degree is 310 T in the concentration step.
Drain 6 L / Hr of distilled water under a condensing condition of boiling point of 90 ° C,
4 L / Hr of concentrated acid solution was obtained. This concentrated acid solution is transferred to a crystallization separation step, a hexagonal plate crystal is crystallized by a conventional aluminum sulfate crystal production method, the generated crystal is separated by a centrifuge, and a filtrate is 3.5 L. / Hr was continuously obtained at the total liquid volume. The filtrate is sent to the acid recovery step, and the free acid content of which the concentration is increased in the filter in the step is dialyzed and recovered in a diffusion dialysis tank. In this recovery step, 3.5 L / Hr of acid recovered from the membrane and 3.5 L / Hr of dialysis residual liquid were obtained. The film-recovered acid in the acid recovery step and the drain in the concentration step are mixed and adjusted, and a deficient acid component is added as necessary and reused as an electrolytic solution in the electrolysis step. Table 1 shows the amounts of aluminum, acid and impurities contained in the waste liquid and the recovered acid in each step of the electrolytic waste liquid, the concentration step, the crystallization separation step and the acid recovery step. As can be seen from Table-1, the amount of impurities in the centrifugal separation filtrate after the aluminum sulfate crystal separation is reduced. In the method of the present invention for carrying out the crystallization / separation step of aluminum sulfate crystals, since the aluminum content and particularly impurities such as iron, copper and lead are not accumulated in the dialysis residual liquid, the electrolytic waste liquid is directly passed through the ion exchange membrane. Compared with the conventional method of recovering the acid, the number of exchanges of the ion exchange membrane could be reduced to one third or less.
【０００７】 本発明の上記効果は、アルミサッシの電解処理廃液（Al
15 g/Ｌ、H2SO4 250g/Ｌ、Fe 150ppm 、Cu 0.3ppm 、P
b 3 ppm ）の場合も上記アルミ箔電解廃液の場合と同
様に得られ、電解工程をクローズド化でき、遊離酸を長
時間イオン交換膜を交換することなく回収することがで
きた。[0007] The above-mentioned effects of the present invention are achieved by the electrolytic treatment waste liquid (Al
15 g / L, H2SO4 250 g / L, Fe 150 ppm, Cu 0.3 ppm, P
b 3 ppm) was obtained in the same manner as in the case of the aluminum foil electrolytic waste solution, the electrolysis process could be closed, and the free acid could be recovered for a long time without exchanging the ion exchange membrane.
【０００８】従来技術では、電解廃液を濃縮し硫酸アル
ミニウムを晶析し、晶析した結晶スラリーを遠心分離機
にて遠心分離し、この遠心分離濾過液を電解調整液とし
て循環再使用するか、又は硫酸アルミニウムを晶析・分
離することなく直接電解廃液をイオン交換膜にて酸を透
析分離していた。しかし表−１に示した如く、前者の硫
酸アルミニウムを晶析・分離する方法でも不純物（Fe、
Cu、Pb）は増加して行き、繰り返しにより電解廃液中の
不純物濃度は高くなり電解不能となる。また後者の直接
電解廃液をイオン交換膜処理する方法では、電解廃液を
透析できる濃度の酸液に濃縮し、この濃縮酸液を透析処
理するため濃縮酸液中に不純物が次第に蓄積し、不純物
量が多すぎて回収酸液中にリークする不純物量も多くな
り、繰り返すうちには電解液として使用できなくなる。
そのためこの従来法では、ある時期に濃縮酸液を廃棄す
る必要があった。In the prior art, the electrolytic waste liquid is concentrated to crystallize aluminum sulfate, and the crystal slurry thus crystallized is centrifuged in a centrifuge, and this centrifugal separation filtrate is circulated and reused as an electrolytic adjustment solution, or Alternatively, the electrolytic waste liquid was directly dialyzed and separated with an ion exchange membrane without crystallization and separation of aluminum sulfate. However, as shown in Table 1, impurities (Fe, Fe,
Cu and Pb) increase and the concentration of impurities in the electrolytic waste solution increases due to repetition, making electrolysis impossible. In the latter method of directly treating the electrolytic waste solution with an ion-exchange membrane, the electrolytic waste solution is concentrated to an acid solution of a concentration that can be dialyzed, and the concentrated acid solution is dialyzed, so that impurities gradually accumulate in the concentrated acid solution and the amount of impurities is increased. Is too much, the amount of impurities leaking into the recovered acid solution also increases, and it cannot be used as an electrolytic solution during repeated use.
Therefore, in this conventional method, it was necessary to discard the concentrated acid solution at a certain time.
【０００９】上記に対し、本発明は硫酸アルミニウム結
晶に不純物を付着させて系外に除き、残った遠心分離濾
過液より次工程の拡散透析槽で酸を分離回収するため回
収酸液中の不純物量は著しく少なく、電解調整液として
何回も再循環させることができる。なお、拡散透析の際
の不純物を含めて塩のリーク量はほぼ１０％程度である
ことから、本発明方法によらない拡散透析処理の回収酸
液中の不純物量は本発明方法の場合の２倍以上となる。
回収した硫酸アルミニウム結晶は酸液で洗浄することに
より容易に不純物を除去することができる。よって本発
明は従来技術よりクローズド化が進んだプロセスと言
え、排出された硫酸アルミニウム結晶は製紙工場等の排
水処理薬剤として、代替有効利用できるものである。In contrast to the above, according to the present invention, impurities are adhered to the aluminum sulfate crystal to remove it from the system, and the acid is separated and recovered from the remaining centrifugal separation filtrate in the diffusion dialysis tank in the next step. The amount is remarkably small and can be recirculated as the electrolytic adjusting solution many times. Since the amount of salt leakage including impurities during diffusion dialysis is about 10%, the amount of impurities in the recovered acid solution in the diffusion dialysis treatment not according to the method of the present invention is 2% of that in the method of the present invention. More than double.
Impurities can be easily removed by washing the recovered aluminum sulfate crystals with an acid solution. Therefore, it can be said that the present invention is a process that is more closed than the prior art, and the discharged aluminum sulfate crystals can be effectively used as a waste water treatment chemical in a paper mill or the like.
Claims (2)
廃液等のアルミ電解廃液より遊離酸を回収し電解調整液
に循環再使用する方法において、アルミ電解廃液より硫
酸アルミニウム結晶を晶析させて濾過分離し、分離後の
電解廃液をイオン交換膜による拡散透析法により遊離酸
を回収することからなるクローズド化された遊離酸の回
収使用方法。1. A method of recovering a free acid from an aluminum electrolytic waste solution such as an aluminum foil electrolytic waste solution or an aluminum sash electrolytic waste solution, and circulating and reusing the electrolytic acid as an electrolytic adjustment solution, wherein aluminum sulfate crystals are crystallized from the aluminum electrolytic waste solution and separated by filtration. Then, the electrolytic waste liquid after separation is recovered by a diffusion dialysis method using an ion exchange membrane to recover the free acid, and a method for recovering and using the closed free acid.
あることを特徴とする請求項１記載の遊離酸の回収使用
方法。2. The method for recovering and using free acid according to claim 1, wherein the aluminum sulfate crystal is a hexagonal plate crystal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15257491A JPH0598500A (en) | 1991-05-28 | 1991-05-28 | Method for perfectly recycling free acid from waste aluminum electrolytic solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15257491A JPH0598500A (en) | 1991-05-28 | 1991-05-28 | Method for perfectly recycling free acid from waste aluminum electrolytic solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0598500A true JPH0598500A (en) | 1993-04-20 |
Family
ID=15543455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15257491A Pending JPH0598500A (en) | 1991-05-28 | 1991-05-28 | Method for perfectly recycling free acid from waste aluminum electrolytic solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0598500A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7033463B1 (en) | 1998-08-11 | 2006-04-25 | Ebara Corporation | Substrate plating method and apparatus |
| JP2010260009A (en) * | 2009-05-08 | 2010-11-18 | Nosaka Denki:Kk | Acid concentrating method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4990699A (en) * | 1972-12-29 | 1974-08-29 | ||
| JPS5014621A (en) * | 1973-06-14 | 1975-02-15 | ||
| JPS5288232A (en) * | 1976-01-17 | 1977-07-23 | Katsukawa Heitarou | Circulation method of regenerating sulfuric acid electrolyte for treating aluminum or its alloy |
| JPS5460235A (en) * | 1977-10-22 | 1979-05-15 | Showa Denko Kk | Treatment of electrolytic waste acid in electrolytic oxidation treatment of aluminium plate and moldings |
-
1991
- 1991-05-28 JP JP15257491A patent/JPH0598500A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4990699A (en) * | 1972-12-29 | 1974-08-29 | ||
| JPS5014621A (en) * | 1973-06-14 | 1975-02-15 | ||
| JPS5288232A (en) * | 1976-01-17 | 1977-07-23 | Katsukawa Heitarou | Circulation method of regenerating sulfuric acid electrolyte for treating aluminum or its alloy |
| JPS5460235A (en) * | 1977-10-22 | 1979-05-15 | Showa Denko Kk | Treatment of electrolytic waste acid in electrolytic oxidation treatment of aluminium plate and moldings |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7033463B1 (en) | 1998-08-11 | 2006-04-25 | Ebara Corporation | Substrate plating method and apparatus |
| JP2010260009A (en) * | 2009-05-08 | 2010-11-18 | Nosaka Denki:Kk | Acid concentrating method |
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