JPH06173048A - Method for recovering waste metal surface treating acid - Google Patents
Method for recovering waste metal surface treating acidInfo
- Publication number
- JPH06173048A JPH06173048A JP32529092A JP32529092A JPH06173048A JP H06173048 A JPH06173048 A JP H06173048A JP 32529092 A JP32529092 A JP 32529092A JP 32529092 A JP32529092 A JP 32529092A JP H06173048 A JPH06173048 A JP H06173048A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- recovered
- waste
- volatile
- metal
- 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.)
- Granted
Links
- 239000002253 acid Substances 0.000 title claims abstract description 113
- 239000002699 waste material Substances 0.000 title claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 42
- 239000002184 metal Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 64
- 150000003839 salts Chemical class 0.000 claims abstract description 26
- 238000004821 distillation Methods 0.000 claims abstract description 21
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 27
- 238000000502 dialysis Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 238000005649 metathesis reaction Methods 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 7
- 238000004381 surface treatment Methods 0.000 claims description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000011034 membrane dialysis Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- -1 nitric acid aluminum Chemical compound 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- ing And Chemical Polishing (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は金属表面処理廃酸の処理
回収法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating and recovering waste acid treated with metal surface.
【０００２】[0002]
【従来技術とその問題点】従来、普通鋼、ステンレス鋼
及びアルミニウム材の酸洗いやエッチングなどの表面処
理には、塩酸、硝酸などのような揮発性酸の単酸又は混
合酸が、必要に応じ少量の硫酸を添加して使用されてい
る。2. Description of the Related Art Conventionally, for surface treatment such as pickling and etching of ordinary steel, stainless steel and aluminum materials, simple acids or mixed acids of volatile acids such as hydrochloric acid and nitric acid are required. It is used by adding a small amount of sulfuric acid.
【０００３】而して上記の金属表面処理工程から排出さ
れる廃酸中には、揮散性酸の遊離酸並びにその金属塩例
えば塩化鉄（塩化アルミニウム）、硝酸鉄（硝酸アルミ
ニウム）などが含まれている。Thus, the waste acid discharged from the above metal surface treatment step contains a free acid of a volatile acid and its metal salts such as iron chloride (aluminum chloride) and iron nitrate (aluminum nitrate). ing.
【０００４】このような廃酸の処理回収法として、蒸留
法の適用が考えられる。例えば塩酸系廃酸の場合には、
ＨＣｌは比揮発度が大きいのでベーパーとして留出し易
く、特に廃酸中に含まれる金属塩の溶解度が高いこと
と、高濃度の金属塩溶液中ではＨＣｌの比揮発度はさら
に大きくなることから蒸留缶内に残留する母液内のＨＣ
ｌ濃度が非常に低くなり、大部分のＨＣｌを留出回収で
きる。また硝酸系廃酸の場合も、ＨＮＯ3 はＨＣｌ程で
はないが、比揮発度はかなり大であり、また塩酸系と同
様、金属塩の溶解度も極めて大きいので、大部分のＨＮ
Ｏ3 を留出回収できる。As a method for treating and recovering such waste acid, it is possible to apply a distillation method. For example, in the case of hydrochloric acid waste acid,
Since HCl has a large relative volatility, it is easy to distill out as a vapor. Especially, the solubility of metal salts contained in waste acid is high and the relative volatility of HCl becomes even higher in a high-concentration metal salt solution. HC in the mother liquor remaining in the can
The 1 concentration becomes very low, and most of HCl can be recovered by distilling. Also, in the case of nitric acid-based waste acid, HNO 3 is not as high as HCl, but its relative volatility is considerably large, and the solubility of metal salts is also extremely large, as in the case of hydrochloric acid, so most HN 3
O 3 can be distilled and recovered.
【０００５】しかしながら、塩酸系及び硝酸系廃酸にお
いて、蒸留法で処理回収し得るのは、当然のことながら
遊離酸のみであり、金属塩として存在する揮散性酸分の
回収は困難である。However, of the hydrochloric acid-based and nitric acid-based waste acids, of course, only the free acid can be treated and recovered by the distillation method, and it is difficult to recover the volatile acid component existing as the metal salt.
【０００６】またこのような廃酸は、イオン交換膜によ
る透析処理、例えば陰イオン交換膜（以下ＡＭと記す）
を用いた拡散透析装置（以下ＤＤ装置と記す）やＡＭと
陽イオン交換膜（以下ＣＭと記す）とを用いた電気透析
装置（以下ＥＤ装置と記す）などを用いて回収処理する
ことができる。Such waste acid is treated by dialysis with an ion exchange membrane, for example, an anion exchange membrane (hereinafter referred to as AM).
The recovery treatment can be performed using a diffusion dialysis device (hereinafter, referred to as DD device) using AM, an electrodialysis device (hereinafter, referred to as ED device) using AM and a cation exchange membrane (hereinafter, referred to as CM), and the like. .
【０００７】例えば硝酸によるアルミニウム箔のエッチ
ング廃酸は、遊離のＨＮＯ3 及びＡｌ（ＮＯ3 ）3 を含
む水溶液であり、これをＤＤ装置により処理すれば、廃
酸中の遊離のＨＮＯ3 はＡＭを透過するので回収できる
が、Ａｌ（ＮＯ3 ）3 中のＮＯ3 1-分はＨＮＯ3 として
回収されないで、逆にＡｌ（ＮＯ3 ）3 として回収酸中
に一部混入する。これはＡｌ（ＮＯ3 ）3 の透析係数は
ＨＮＯ3 の透析係数に比し小さいとはいえ数十分の一の
オーダーであり、混入を完全に阻止することはできない
からである。Etching of aluminum foil with nitric acid For example, waste acid is an aqueous solution containing free HNO 3 and Al (NO 3 ) 3. If this is treated with a DD device, free HNO 3 in the waste acid is AM. can be recovered because it transmits, but Al (nO 3) nO 3 1- min 3 without being recovered as HNO 3, mixed partially in the recovered acid to reverse as Al (nO 3) 3. This is because although the dialysis coefficient of Al (NO 3 ) 3 is smaller than the dialysis coefficient of HNO 3 , it is on the order of several tenths, and it is impossible to completely prevent contamination.
【０００８】又ＥＤ装置に於いてもＨＮＯ3 は、Also in the ED device, HNO 3 is
【０００９】[0009]
【数１】 [Equation 1]
【００１０】と電離しているので、Ｈ1+は陰極側へ、Ｎ
Ｏ3 1-は陽極側へ移動し、交互に接合されたＣＭとＡＭ
の間を通過する清水側に透過してＨＮＯ3 として回収さ
れる。然るにＡｌ（ＮＯ3 ）3 塩の方は理論的にはSince H 1+ is ionized to the cathode side,
O 3 1- moves to the anode side, and CM and AM alternately joined
It is permeated to the fresh water side passing through the space and is recovered as HNO 3 . However, the Al (NO 3 ) 3 salt is theoretically more
【００１１】[0011]
【数２】 [Equation 2]
【００１２】の如く電離するが、弱電解質であり、電離
度が小さいので殆ど大部分がＡｌ（ＮＯ3 ）3 のまま存
在しており、従ってＨＮＯ3 として回収されるのは当初
から存在する遊離のＨＮＯ3 が大部分でありＡｌ（ＮＯ
3 ）3 からのＮＯ3 1-はＨＮＯ3 として殆ど回収されな
い。Although it is ionized as described above, since it is a weak electrolyte and its ionization degree is small, almost all of it remains as Al (NO 3 ) 3 and, therefore, it is recovered as HNO 3 from the beginning. Most of the HNO 3 is Al (NO
3) NO from 3 3 1 it is hardly recovered as HNO 3.
【００１３】これを要するに、上記廃酸をＤＤ装置やＥ
Ｄ装置を適用して処理回収した場合も蒸留法同様回収し
得るのは遊離の揮発性酸のみであり、金属塩として存在
するものは回収できないのみならず回収酸中には金属イ
オンがかなり同伴されるので、回収酸の純度が再使用に
支障を及ぼすなどの問題点があり、透析処理の利用に限
界がある。In short, this waste acid is treated by a DD device or an E
Similar to the distillation method, only the free volatile acid can be recovered when the treatment and recovery are performed by applying the D device, and the existing metal salt cannot be recovered, and the recovered acid is considerably accompanied by metal ions. Therefore, there is a problem in that the purity of the recovered acid hinders reuse, and there is a limit to the use of dialysis treatment.
【００１４】本発明はこのような従来の問題点を一掃す
ることを目的としてなされたものである。The present invention has been made for the purpose of eliminating such conventional problems.
【００１５】[0015]
【問題点を解決するための手段】本発明は、塩酸、硝酸
などのような揮発性酸並びにその金属塩を含む金属表面
処理廃酸の処理回収法であって、上記廃酸中に溶存する
金属に対し、反応当量を超える量の硫酸を添加して廃酸
中に溶存する金属塩を複分解しつつイオン交換膜により
透析処理することにより、該廃酸中より揮発性酸を回収
する一方、透析廃液は硫酸塩主体の溶液として回収する
工程、上記工程よりの回収酸中に硫酸を添加し、硫酸濃
度を２５〜６０％に維持しつつ蒸留処理することによ
り、該回収酸中より揮発性酸を留出回収する工程、及び
硫酸濃度が２５〜６０％の蒸留缶缶出液を金属塩複分解
のために、イオン交換膜により透析処理される廃酸中に
供給する工程、とを含むことを特徴とする金属表面処理
廃酸の処理回収法に係る。The present invention is a method for treating and recovering a metal surface-treated waste acid containing a volatile acid such as hydrochloric acid and nitric acid, and a metal salt thereof, which is dissolved in the waste acid. With respect to the metal, by adding an amount of sulfuric acid in excess of the reaction equivalent and dialysis treatment with an ion exchange membrane while metathesis of the metal salt dissolved in the waste acid, while recovering the volatile acid from the waste acid, A step of recovering the dialysis waste liquid as a solution mainly containing a sulfate, by adding sulfuric acid to the acid recovered from the above step and performing a distillation treatment while maintaining the sulfuric acid concentration at 25 to 60%, the volatile matter is more volatile than the recovered acid. A step of distilling and recovering an acid, and a step of supplying a bottom liquid of a distillation can having a sulfuric acid concentration of 25 to 60% into a waste acid dialyzed by an ion exchange membrane for metal salt metathesis. A method for treating and recovering metal surface treatment waste acid characterized by That.
【００１６】本発明により処理回収される金属表面処理
廃酸は、先に述べたように遊離の揮発性酸と、その金属
塩とを含んでいる。廃酸の種類としては塩酸系廃酸、硝
酸系廃酸及び之等の混酸系廃酸を例示でき、また之等の
揮発性酸と塩を形成する金属としては、鉄又はアルミニ
ウムを例示できる。尚アルミニウムのエッチング処理に
は、之等の揮発性酸に少量の硫酸を添加して用いる場合
があるが、本発明では下記に述べるように廃酸中に硫酸
を加えて処理するので、廃酸中に少量の遊離硫酸やその
金属塩が含まれていても特に問題はない。また廃酸によ
っては、まれではあるが遊離の揮発性酸を高濃度例えば
１０％以上含む場合があるが、このような場合は、本発
明法により処理回収する前に、イオン交換膜による透析
手段例えばＤＤ装置を適用して、遊離の揮発性酸の一部
を前もって回収してもよい。The metal surface-treated waste acid treated and recovered according to the present invention contains a free volatile acid and a metal salt thereof as described above. Examples of the type of waste acid include hydrochloric acid waste acid, nitric acid waste acid and mixed acid waste acid such as iron, and the metal forming a salt with volatile acid such as iron may be iron or aluminum. Although a small amount of sulfuric acid may be added to a volatile acid to be used for the etching treatment of aluminum, in the present invention, since sulfuric acid is added to the waste acid to be treated as described below, the waste acid There is no particular problem even if a small amount of free sulfuric acid or its metal salt is contained therein. In addition, depending on the waste acid, there may be rare cases where a free volatile acid is contained at a high concentration, for example, 10% or more. In such a case, before the treatment and recovery by the method of the present invention, a dialysis means using an ion exchange membrane is used. For example, a DD device may be applied to recover some of the free volatile acids in advance.
【００１７】本発明法を適用して上記廃酸を処理回収す
るに際しては、先ず上記廃酸中に、該廃酸中に溶存する
金属に対して反応当量より少し過剰となるように硫酸が
添加される。When the above-mentioned waste acid is treated and recovered by applying the method of the present invention, first, sulfuric acid is added to the above-mentioned waste acid so as to be slightly in excess of the reaction equivalent to the metal dissolved in the waste acid. To be done.
【００１８】過剰の硫酸を添加し乍ら透析処理すること
により、廃酸中に溶存している金属塩は実質的に全てが
複分解し、硫酸塩と揮発性酸とに移行するのでイオン交
換膜による透析処理、例えばＤＤ装置及び／又はＥＤ装
置の適用により処理することにより、廃酸中にもともと
遊離状態に存在していた揮発性酸はもとより、金属塩と
して存在していた揮発性酸分をもうまく回収できる。By adding an excess amount of sulfuric acid and performing dialysis treatment, substantially all the metal salts dissolved in the waste acid undergo metathesis and are converted into a sulfate salt and a volatile acid. By dialysis treatment by means of, for example, application of a DD device and / or an ED device, not only volatile acids originally present in a free state in the waste acid but also volatile acid components existing as a metal salt are removed. Can be collected well.
【００１９】例えば硝酸のアルミニウム箔エッチング廃
酸には、ＨＮＯ3 及びＡｌ（ＮＯ3）3 を含む水溶液が
あり、これにＡｌの反応当量より過剰のＨ2 ＳＯ4 を添
加すると、For example, nitric acid aluminum foil etching waste acid has an aqueous solution containing HNO 3 and Al (NO 3 ) 3 , and when H 2 SO 4 in excess of the reaction equivalent of Al is added thereto,
【００２０】[0020]
【数３】 [Equation 3]
【００２１】の如く複分解し、ＨＮＯ3 が遊離される。
これをＤＤ装置により処理すると、生成ＨＮＯ3 が直ち
にＡＭを通して透過されるため、過剰のＨ2 ＳＯ4 の存
在と相俟って本反応は右向きの反応が支配的な不可逆反
応となりもともとの遊離ＨＮＯ3 はもとよりＡｌ（ＮＯ
3 ）3 塩中のＮＯ3 1-もまたＨＮＯ3 として回収され
る。この際Ａｌ2 （ＳＯ4 ）3 のうちの一部が、従来法
として述べたＡｌ（ＮＯ3）3 の場合と同様に回収酸中
に透析し不純物として混入する。As described above, HNO 3 is liberated by metathesis.
When this is treated with a DD device, the produced HNO 3 is immediately permeated through the AM, and in combination with the presence of excess H 2 SO 4 , this reaction becomes an irreversible reaction in which the rightward reaction is dominant and the original free HNO 3 is reacted. 3 as well as Al (NO
3 ) NO 3 1− in the 3 salt is also recovered as HNO 3 . At this time, a part of Al 2 (SO 4 ) 3 is dialyzed into the recovered acid and mixed as an impurity, as in the case of Al (NO 3 ) 3 described as the conventional method.
【００２２】またＥＤ装置に於てもＨ2 ＳＯ4 の添加に
より生成したＨＮＯ3 は直ちにAlso in the ED apparatus, HNO 3 produced by addition of H 2 SO 4 immediately
【００２３】[0023]
【数４】 [Equation 4]
【００２４】に電離し、もともと存在していた遊離のＨ
ＮＯ3 と同様に、それぞれＡＭとＣＭを透過してＨＮＯ
3 として回収される。これにより上記（１）式の反応
は、右向きの反応が支配的な不可逆反応となり、Ａｌ
（ＮＯ3 ）3 中のＮＯ3 1-もまたＨＮＯ3 として回収さ
れる。これに反して添加Ｈ2 ＳＯ4 の過剰分は一応、Free H that was originally present after being ionized to
Similar to NO 3 , HNO is transmitted through AM and CM respectively.
Recovered as 3 . As a result, the reaction of the above formula (1) becomes an irreversible reaction in which the rightward reaction is dominant, and
NO 3 1− in (NO 3 ) 3 is also recovered as HNO 3 . On the contrary, the excess amount of added H 2 SO 4 is,
【００２５】[0025]
【数５】 [Equation 5]
【００２６】の如く電離するが、ＳＯ4 イオンは同じ陰
イオンであり、ＮＯ3 1-に比して透析係数は小さいが少
量透析混入する。Although ionized as described above, SO 4 ions are the same anion and a small amount of dialysis is mixed in, although the dialysis coefficient is smaller than that of NO 3 1- .
【００２７】上記置換反応に用いる硫酸は余り過剰にな
りすぎると未反応のＨ2 ＳＯ4 の、回収酸への混入量が
増えるので、廃酸中の金属分例えばＡｌ分に対し、１．
０５〜１．４０特に１．１〜１．２当量程度が適当であ
る。If the amount of sulfuric acid used in the above-mentioned substitution reaction is excessively excessive, the amount of unreacted H 2 SO 4 mixed in the recovered acid increases, so that 1.
05 to 1.40, especially 1.1 to 1.2 equivalents are suitable.
【００２８】このように廃酸に対し、廃酸中に溶存する
金属に対し当量以上、好ましくは１．１〜１．２当量の
硫酸を添加し乍らＤＤ装置及び／又はＥＤ装置にて処理
することにより廃酸中にもともと遊離状態で存在してい
た揮発性酸はもとより、金属と結合し金属塩となってい
た揮発性酸分をも殆んど大部分、回収することができ
る。Thus, sulfuric acid is added to the waste acid in an equivalent amount or more, preferably 1.1 to 1.2 equivalents to the metal dissolved in the waste acid, and treated with a DD apparatus and / or an ED apparatus. By doing so, not only the volatile acid that was originally present in the waste acid in a free state but also the volatile acid content that has bound to the metal to form a metal salt can be recovered almost in large part.
【００２９】一方透析廃液は、僅かのＨ2 ＳＯ4 並びに
揮発性酸分を含むが、硫酸塩主体の溶液であるので、例
えばアルミニウム系酸の場合はこれをさらに濃縮し凝集
剤として有用な液体硫酸バンド〔Ａｌ2 （ＳＯ4 ）3 〕
として利用出来る。又鉄系廃酸の場合は、冷却晶析によ
りＦｅＳＯ4 ・７Ｈ2 Ｏを副生させることにより、有効
利用できる。On the other hand, the dialysis waste liquid contains a small amount of H 2 SO 4 and volatile acid content, but since it is a solution mainly containing a sulfate, for example, in the case of an aluminum acid, this is further concentrated and a liquid useful as a coagulant. Sulfuric acid band [Al 2 (SO 4 ) 3 ]
Can be used as In the case of iron-based waste acid, FeSO 4 .7H 2 O can be effectively used as a by-product by cooling crystallization.
【００３０】尚イオン交換膜の透析処理により回収され
た回収酸中には、先に述べたように、揮発性酸に加え少
量のＳＯ4 2-や金属分などが含まれるので、これをその
まま再使用するには純度的に適当でない。よって本発明
では上記回収酸を蒸留により精製する。The recovered acid recovered by the dialysis treatment of the ion exchange membrane contains a small amount of SO 4 2− and a metal component in addition to the volatile acid as described above. Purity is not suitable for reuse. Therefore, in the present invention, the recovered acid is purified by distillation.
【００３１】本発明において、回収酸の蒸留は、蒸留缶
内の硫酸濃度を２５〜６０％に維持しながら行なわれ
る。In the present invention, distillation of the recovered acid is carried out while maintaining the sulfuric acid concentration in the distillation can at 25 to 60%.
【００３２】図１はＨ2 Ｏ、Ｈ2 ＳＯ4 及びＨＮＯ3 を
含む３成分系の気液平衡線図を、また図２はＨ2 Ｏ、Ｈ
2 ＳＯ4 及びＨＣｌを含む３成分系の気液平衡線図をそ
れぞれ示している。FIG. 1 is a vapor-liquid equilibrium diagram of a ternary system containing H 2 O, H 2 SO 4 and HNO 3 , and FIG. 2 is H 2 O, H.
The vapor-liquid equilibrium diagrams of the ternary system containing 2 SO 4 and HCl are shown, respectively.
【００３３】図１及び図２から明らかなように蒸留缶内
の硫酸濃度を２５〜６０％、好ましくは４０〜５０％に
維持しつつ回収酸の蒸留を行なうことにより、蒸留缶内
に残留する揮発性酸濃度を低く抑える一方、留出回収酸
濃度を高めつつ、蒸留処理を行なうことが可能になる。
ちなみに蒸留缶内の硫酸濃度が２５％に達しない場合は
蒸留缶内に残留する揮散性酸の割合が高くなりまた６０
％を上回ると、蒸留缶内で硫酸塩が多量に析出する等の
問題があり、いずれも好ましくない。As is clear from FIGS. 1 and 2, the recovered acid is distilled while the sulfuric acid concentration in the distillation can is maintained at 25 to 60%, preferably 40 to 50%, so that the acid remains in the distillation can. It is possible to carry out the distillation treatment while increasing the concentration of distillate recovered acid while suppressing the concentration of volatile acid to be low.
By the way, if the concentration of sulfuric acid in the distillation can does not reach 25%, the proportion of volatile acid remaining in the distillation can becomes high and
If it exceeds%, there is a problem that a large amount of sulfate is precipitated in the distillation can, which is not preferable.
【００３４】このようにイオン交換膜による透析により
回収した回収酸を、蒸留缶内の硫酸濃度を２５〜６０％
に維持しつつ蒸留することにより、高純度、高濃度の揮
発性酸を留出回収できる。The recovered acid thus recovered by dialysis with an ion-exchange membrane is adjusted to a sulfuric acid concentration of 25 to 60% in the distillation can.
By distilling while maintaining at 1, the volatile acid with high purity and high concentration can be distilled and recovered.
【００３５】蒸留缶内の母液は硫酸塩の外に多量の遊離
硫酸も含むので、その一部が、イオン交換膜による透析
処理を受ける前の廃酸中に供給され、該廃酸中の金属塩
を複分解するための硫酸として利用され、又これにより
蒸留缶内における硫酸塩の蓄積を防止する効果が得られ
る。尚添加硫酸は硫酸塩の生成に消費されるので、これ
に見合う当量以上の硫酸は新硫酸として補給することが
必要である。Since the mother liquor in the distillation still contains a large amount of free sulfuric acid in addition to the sulfate, a part of the mother liquor is supplied to the waste acid before being subjected to the dialysis treatment by the ion exchange membrane, and the metal in the waste acid is supplied. It is used as sulfuric acid for metathesis of the salt, and this has the effect of preventing the accumulation of sulfate in the distillation can. Since the added sulfuric acid is consumed for the production of sulfate, it is necessary to replenish the sulfuric acid in an amount equivalent to or more than this as new sulfuric acid.
【００３６】本発明処理回収法において、硫酸は、蒸留
缶内を所定の硫酸濃度に維持し、高濃度の揮発性酸を留
出させるために利用された後、廃酸と共にイオン交換膜
透析装置中に送られ、該廃酸中の金属塩を複分解し、遊
離揮発性酸と、利用価値の高い硫酸塩を生成させるため
に利用される。In the treatment and recovery method of the present invention, sulfuric acid is used for maintaining a predetermined sulfuric acid concentration in the distillation can and distilling out a high-concentration volatile acid, and then is used together with waste acid in an ion exchange membrane dialysis device. The metal salt in the waste acid is sent to the metathesis and used to generate a free volatile acid and a sulfate having a high utility value.
【００３７】以下に実施例を掲げる。Examples will be given below.
【００３８】[0038]
【実施例】図３に示すフロー図にもとづき、本発明法を
実施した。その結果を示すと、表１及び表２の通りであ
る。尚表１は塩酸系廃酸の場合を、また表２は硝酸系廃
酸の場合をそれぞれ示している。また図３中、各ライン
の要所に（１）〜（９）の符号が入れられ、各要所の液
量及び液組成は、表１及び表２の通りである。EXAMPLE The method of the present invention was carried out based on the flow chart shown in FIG. The results are shown in Tables 1 and 2. Table 1 shows the case of hydrochloric acid waste acid, and Table 2 shows the case of nitric acid waste acid. Further, in FIG. 3, the symbols (1) to (9) are put in the important points of each line, and the liquid amounts and the liquid compositions of the respective important points are as shown in Tables 1 and 2.
【００３９】[0039]
【表１】 [Table 1]
【００４０】[0040]
【表２】 [Table 2]
【００４１】本発明処理回収法によれば、表１から明ら
かなように１８％のＴ・ＨＣｌを含む塩酸系廃酸１，２
００Kg/hから１３．３％の高純度塩酸１５２４Kg/hを回
収できる。According to the treatment and recovery method of the present invention, as is clear from Table 1, hydrochloric acid waste acids 1 and 2 containing 18% T.HCl are
Highly pure hydrochloric acid 1524 kg / h of 13.3% can be recovered from 00 kg / h.
【００４２】また表２から明らかなように、１０．２％
のＴ・ＨＮＯ3 を含む硝酸系廃酸９３１Kg/hから７．５
％の高純度硝酸１０６５．５Kg/hを回収できる。As is clear from Table 2, 10.2%
Of waste nitric acid containing T ・ HNO 3 from 931 Kg / h to 7.5
% High purity nitric acid 1065.5 Kg / h can be recovered.
【００４３】[0043]
【発明の効果】本発明処理回収法によれば、金属表面処
理廃酸中に含まれる揮発性酸を、遊離のものはもとよ
り、金属と結合して金属塩となっている揮発性酸分をも
含めて、その大部分を高純度揮発性酸として有効に回収
できると共に、廃酸中に溶存している金属、例えばＡ
ｌ，Ｆｅなどは利用価値の高い硫酸塩の状態で回収する
ことが可能になる。EFFECTS OF THE INVENTION According to the treatment and recovery method of the present invention, the volatile acid contained in the metal surface-treated waste acid is not only free but also the volatile acid component which is bound to the metal to form a metal salt. Including the above, most of it can be effectively recovered as a high-purity volatile acid, and the metal dissolved in the waste acid such as A
It becomes possible to recover l, Fe, etc. in the form of sulfate having high utility value.
【図１】ＨＮＯ3 を含む３成分系の気液平衡線図であ
る。FIG. 1 is a vapor-liquid equilibrium diagram of a ternary system containing HNO 3 .
【図２】ＨＣｌを含む３成分系の気液平衡線図である。FIG. 2 is a vapor-liquid equilibrium diagram of a three-component system containing HCl.
【図３】本発明の１実施状況を概略的に示すフロー図で
ある。FIG. 3 is a flow chart schematically showing one embodiment of the present invention.
フロントページの続き (72)発明者 壁谷 進自 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 神崎 信義 大阪府門真市大字門真1006番地 松下電器 産業株式会社内Front page continuation (72) Inventor Susumu Kadani 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Nobuyoshi Kanzaki 1006 Kadoma, Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd.
Claims (1)
その金属塩を含む金属表面処理廃酸の処理回収法であっ
て、上記廃酸中に溶存する金属に対し、反応当量を超え
る量の硫酸を添加して廃酸中に溶存する金属塩を複分解
しつつイオン交換膜により透析処理することにより、該
廃酸中より揮発性酸を回収する一方、透析廃液は硫酸塩
主体の溶液として回収する工程、上記工程よりの回収酸
中に硫酸を添加し、硫酸濃度を２５〜６０％に維持しつ
つ蒸留処理することにより、該回収酸中より揮発性酸を
留出回収する工程、及び硫酸濃度が２５〜６０％の蒸留
缶缶出液を金属塩複分解のために、イオン交換膜により
透析処理される廃酸中に供給する工程、とを含むことを
特徴とする金属表面処理廃酸の処理回収法。1. A method for treating and recovering a metal surface treatment waste acid containing a volatile acid such as hydrochloric acid, nitric acid and the like, and a metal salt thereof, which is more than a reaction equivalent amount with respect to the metal dissolved in the waste acid. The volatile acid is recovered from the waste acid by performing a dialysis treatment with an ion exchange membrane while metathesis of the metal salt dissolved in the waste acid by adding sulfuric acid as described above, while the dialysis waste liquid is a solution mainly containing a sulfate salt. A step of recovering, a step of adding sulfuric acid to the acid recovered from the above step and performing a distillation treatment while maintaining the sulfuric acid concentration at 25 to 60% to distill and recover a volatile acid from the recovered acid, and And a step of supplying a bottom product of a distillation can having a sulfuric acid concentration of 25 to 60% into a waste acid dialyzed by an ion exchange membrane for metal salt metathesis. Treatment and recovery method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4325290A JP2949545B2 (en) | 1992-12-04 | 1992-12-04 | Treatment and recovery of metal surface treatment waste acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4325290A JP2949545B2 (en) | 1992-12-04 | 1992-12-04 | Treatment and recovery of metal surface treatment waste acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06173048A true JPH06173048A (en) | 1994-06-21 |
| JP2949545B2 JP2949545B2 (en) | 1999-09-13 |
Family
ID=18175167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4325290A Expired - Lifetime JP2949545B2 (en) | 1992-12-04 | 1992-12-04 | Treatment and recovery of metal surface treatment waste acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2949545B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100613257B1 (en) * | 2001-12-22 | 2006-09-25 | 재단법인 포항산업과학연구원 | Recycling method of waste acid etching solution |
| KR101009026B1 (en) * | 2005-12-26 | 2011-01-17 | 대일개발 주식회사 | Method for recovering acid from mixed waste acid occupied in preparing process of liquid crystal display |
| CN102828192A (en) * | 2012-08-29 | 2012-12-19 | 南京化工职业技术学院 | Resourceful treatment method for pickling waste liquor in steel industry |
| KR101382646B1 (en) * | 2008-01-29 | 2014-04-10 | 재단법인 포항산업과학연구원 | Method for recovering acid from mixed waste acid by using solvent extraction method and vacuum evaporation |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102409343B (en) * | 2010-09-24 | 2013-08-21 | 比亚迪股份有限公司 | Regeneration method of waste acid in polysilicon texturing process and waste acid regeneration system |
-
1992
- 1992-12-04 JP JP4325290A patent/JP2949545B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100613257B1 (en) * | 2001-12-22 | 2006-09-25 | 재단법인 포항산업과학연구원 | Recycling method of waste acid etching solution |
| KR101009026B1 (en) * | 2005-12-26 | 2011-01-17 | 대일개발 주식회사 | Method for recovering acid from mixed waste acid occupied in preparing process of liquid crystal display |
| KR101382646B1 (en) * | 2008-01-29 | 2014-04-10 | 재단법인 포항산업과학연구원 | Method for recovering acid from mixed waste acid by using solvent extraction method and vacuum evaporation |
| CN102828192A (en) * | 2012-08-29 | 2012-12-19 | 南京化工职业技术学院 | Resourceful treatment method for pickling waste liquor in steel industry |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2949545B2 (en) | 1999-09-13 |
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