JPH0346550B2 - - Google Patents
Info
- Publication number
- JPH0346550B2 JPH0346550B2 JP57074318A JP7431882A JPH0346550B2 JP H0346550 B2 JPH0346550 B2 JP H0346550B2 JP 57074318 A JP57074318 A JP 57074318A JP 7431882 A JP7431882 A JP 7431882A JP H0346550 B2 JPH0346550 B2 JP H0346550B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrochloric acid
- pickling
- solution
- pickling solution
- copper ions
- 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 - Lifetime
Links
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
-
- 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
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
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)
- Separation Using Semi-Permeable Membranes (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Removal Of Specific Substances (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Description
【発明の詳細な説明】
本発明は、特殊鋼、特にはステンレス鋼の塩
酸々洗液の処理方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for treating special steel, particularly stainless steel, with a hydrochloric and pickling solution.
ステンレス鋼は、フエライト系、マルテンサイ
ト系、オーステナイト系に大別されるが、いずれ
も錆にくいという特長からして、需要が多く、帯
鋼、平鋼、棒鋼、線、板、管などの種々の形状
で、製造される。そして、これらステンレス鋼
は、化学工業、航空機械、建築材、車輛機械、家
庭厨戻器材、食器などとして、多くの方面に使用
されている。 Stainless steel is broadly classified into ferritic, martensitic, and austenitic types, all of which are in high demand due to their resistance to rust, and are used in a variety of products such as steel strips, flat steel, steel bars, wires, plates, and tubes. Manufactured in the shape of. These stainless steels are used in many fields such as the chemical industry, aircraft machinery, construction materials, vehicle machinery, household cooking equipment, and tableware.
ステンレス鋼の製造は、その最終過程にてステ
ンレス鋼に付着乃至発生した油類、汚れ等を落す
ために、酸液中にて所定時間浸漬するという酸洗
が必須の工程として行なわれている。かかる酸洗
で使用される酸は、ステンレス鋼の種類によつ
て、硝酸、フツ酸などの一種以上の各種の酸が使
用されるが、効果的に洗浄が可能なことから塩酸
も広く使用されている。塩酸を使用する場合、ス
テンレス鋼の酸洗は、通常濃度５〜25％の塩酸を
用い、温度40〜80℃にてステンレス鋼を５分〜１
時間浸漬することにより実施されている。 In the final process of manufacturing stainless steel, pickling is an essential step in which stainless steel is immersed in an acid solution for a predetermined period of time in order to remove oils, dirt, etc. that adhere to or occur on the stainless steel. Depending on the type of stainless steel, one or more of various acids such as nitric acid and hydrofluoric acid are used for pickling, but hydrochloric acid is also widely used because it can be cleaned effectively. ing. When using hydrochloric acid, stainless steel is usually pickled using hydrochloric acid with a concentration of 5 to 25% at a temperature of 40 to 80°C for 5 minutes to 1 hour.
This is done by soaking for a period of time.
一方、かかるステンレス鋼の塩酸酸洗工程にお
いては、酸洗につれて、酸洗液中の塩酸濃度が下
降するが、塩酸濃度が小さくなつた場合、ステン
レス鋼の酸洗スピードが低下する。更に、ステン
レス鋼の酸洗スピードは、本発明者等の知見によ
ると、洗浄塩酸中に銅イオンが蓄積され、該イオ
ンが所定濃度に達した場合には、酸洗スピードが
急激に低下することが見い出された。 On the other hand, in the process of pickling stainless steel with hydrochloric acid, the concentration of hydrochloric acid in the pickling liquid decreases as the pickling progresses, but when the concentration of hydrochloric acid decreases, the speed of pickling the stainless steel decreases. Furthermore, according to the findings of the present inventors, when copper ions accumulate in the cleaning hydrochloric acid and the ions reach a predetermined concentration, the pickling speed of stainless steel decreases rapidly. was discovered.
ステンレス鋼には、その耐食性、耐酸化性、耐
熱性、切削性或いは加工性を改善するために、モ
リブデン、銅、チタン、ニオブ、マンガン、窒素
などの各種の元素が微量添加される場合がある。
そして、ステンレス鋼の酸洗過程では、酸洗によ
り、鉄、クロム、ニツケルなどの主成分ととも
に、上記の微量成分も酸中に一部溶出するが、そ
のうち銅イオンのみが、酸洗スピードに特に大き
な影響を与えることは興味深いことである。 Trace amounts of various elements such as molybdenum, copper, titanium, niobium, manganese, and nitrogen may be added to stainless steel to improve its corrosion resistance, oxidation resistance, heat resistance, machinability, or workability. .
In the pickling process of stainless steel, along with the main components such as iron, chromium, and nickel, some of the trace components mentioned above are also eluted into the acid, but only copper ions are particularly important for pickling speed. It's interesting that it has such a big impact.
かくして、酸洗スピードが低下した洗浄塩酸液
は、そのなかに、未だ十分な塩酸が残有している
にもかかわらず、酸洗過程からとり出し、これを
廃液として捨てざるを得ない。しかしながら、か
かる塩酸残存廃液を、そのまま捨てることは、単
に有用成分の損失となるばかりでなく、公害上の
対策から、従来は大量のアルカリにて中和処理な
どが必要とされ、その廃液には、多大の費用を要
していた。 Thus, the cleaning hydrochloric acid solution whose pickling speed has been reduced has no choice but to be removed from the pickling process and discarded as waste, even though there is still sufficient hydrochloric acid remaining therein. However, discarding such residual hydrochloric acid waste liquid as it is not only results in the loss of useful components, but also requires neutralization treatment with a large amount of alkali to prevent pollution. , which required a great deal of expense.
本発明は、上記ステンレス鋼の塩酸々洗過程か
ら得られる酸洗液中に含まれる塩酸を分離、回収
し再使用を図るとともに、たとえ酸洗液を最終的
に廃棄するにしても、その中和に使用されるアル
カリの量を大幅に減少できる塩酸々洗液の新規な
処理方法を提供することを目的とする。 The present invention aims to separate, recover, and reuse the hydrochloric acid contained in the pickling solution obtained from the hydrochloric pickling process of stainless steel, and even if the pickling solution is ultimately discarded, the hydrochloric acid contained in the pickling solution is It is an object of the present invention to provide a new method for treating a hydrochloric and acidic washing solution that can significantly reduce the amount of alkali used in washing.
かかる目的は、上記ステンレス鋼の塩酸々洗過
程で得られる銅成分を含む酸洗液を、予めそのな
かに含まれる銅イオンを800ppm以下に除去した
後、かかる液を陰イオン交換膜を介して水と接触
させて透析を行うことによつて、酸洗液中の鉄、
ニツケル、クロム、モリブデン等の金属イオンは
陰イオン交換膜を透過し実質上水側に移行するこ
となく、ほぼ塩酸のみが選択的に水側に移行し、
酸洗液中の塩酸が効率的に分離回収できることが
見い出された。もつとも、酸洗液に多量に含まれ
る鉄イオンは、透析中、膜を通じて若干量水側に
移行し、回収塩酸中に混入するが、かかる塩酸を
再び酸洗過程に再使用する場合には、全く問題な
く再使用可能である。 This purpose is to first remove the copper ions contained in the pickling solution containing copper components obtained in the hydrochloric pickling process of stainless steel to 800 ppm or less, and then pass the solution through an anion exchange membrane. By contacting with water and performing dialysis, iron in the pickling solution,
Metal ions such as nickel, chromium, and molybdenum pass through the anion exchange membrane and do not substantially migrate to the water side, while almost only hydrochloric acid selectively migrates to the water side.
It has been found that hydrochloric acid in the pickling solution can be efficiently separated and recovered. However, a small amount of iron ions contained in the pickling solution migrate to the water side through the membrane during dialysis and are mixed into the recovered hydrochloric acid, but when such hydrochloric acid is reused in the pickling process, It can be reused without any problems.
本発明にて、陰イオン交換膜を用いた透析工程
の前に、塩酸々洗液中に含まれる銅イオンを除去
することは重要である。本発明者の知見による
と、銅イオンが含まれる塩酸々洗液をそのまま透
析工程に移した場合には、そのメカニズムは必ず
しも明らかではないが、酸洗液中の銅イオンは、
陽イオンであるにもかかわらず、陰イオン交換膜
を透過してしまうことが見い出された。上記した
ように、酸洗液の銅イオンは、酸洗スピードを低
下させる要因となるので、回収塩酸中に銅イオン
が含まれるときには、酸洗工程での再使用はでき
なくなる。かくして、透析工程の前に酸洗液中の
銅イオンは、除去せしめられる。 In the present invention, it is important to remove copper ions contained in the hydrochloric acid-acid washing solution before the dialysis step using an anion exchange membrane. According to the findings of the present inventor, when the hydrochloric acid pickling solution containing copper ions is directly transferred to the dialysis process, the copper ions in the pickling solution are
It was discovered that even though it is a cation, it permeates through an anion exchange membrane. As described above, copper ions in the pickling solution become a factor that reduces the pickling speed, so when recovered hydrochloric acid contains copper ions, it cannot be reused in the pickling process. Thus, the copper ions in the pickling solution are removed before the dialysis step.
酸洗液中に含まれる銅イオンを除去する手段と
しては、銅イオンと反応して不溶性物を生成する
窒素又はイオウ含有有機物を酸洗液に添加する手
段が効率的にも、コスト的にも安いので有利に採
用される。上記窒素又はイオウ含有有機物として
は、チオ尿素、システイン、チオアセトアニド、
チオグリコール酸、ジエスチルジチオカルバミン
酸などが例示される。 As a means of removing copper ions contained in the pickling solution, it is efficient and cost-effective to add nitrogen or sulfur-containing organic substances that react with copper ions to produce insoluble substances. It is used advantageously because it is cheap. The nitrogen- or sulfur-containing organic substances include thiourea, cysteine, thioacetanide,
Examples include thioglycolic acid and diesterdithiocarbamic acid.
酸洗液中の銅イオンは、可及的に少量になるよ
うに除去するのが好ましいが、通常酸洗液中約
1000〜1500ppm含まれる銅イオンが、好ましくは
800ppm以下、更には500ppm以下になるように低
下させるのが好ましい。なお、銅イオンと反応し
て不溶性物を生成する化学物質を添加して銅イオ
ンを除去する場合には、生成した不溶性物を濾過
などにより積極的に分離してもよく、更には酸洗
液を沈降槽に導き、不溶性物を分離してもよい。 It is preferable to remove copper ions in the pickling solution to the lowest possible amount, but usually approximately
Copper ions containing 1000-1500 ppm are preferably
It is preferable to lower it to 800 ppm or less, more preferably 500 ppm or less. In addition, when removing copper ions by adding a chemical substance that reacts with copper ions to produce insoluble substances, the produced insoluble substances may be actively separated by filtration, etc. may be introduced into a sedimentation tank to separate insoluble materials.
銅イオンが除去された酸洗液は、次いで透析工
程に移される。透析行程は、添付図面に示される
態様にて実施される。図において、Ａは陰イオン
交換膜を表わし、該陰イオン交換膜は、図のよう
に配列された複数の隔室を形成する。かかる構成
を有するところの種々の装置が適用可能である
が、例えば適宜の締付枠体間に、液の供給及び排
出機構を有す室枠、網目状のスペーサーを介して
複数の陰イオン交換膜を配列し、締付けてなる所
謂フイルタープレス型（締付型）の透析槽が良好
に使用される。 The pickling solution from which copper ions have been removed is then transferred to a dialysis step. The dialysis process is carried out in the manner shown in the accompanying drawings. In the figure, A represents an anion exchange membrane, which forms a plurality of compartments arranged as shown in the figure. Various devices having such a configuration can be applied, but for example, a chamber frame having a liquid supply and discharge mechanism, a plurality of anion exchange devices via a mesh spacer, and a chamber frame having a liquid supply and discharge mechanism between appropriate clamping frames. A so-called filter press type (tightening type) dialysis tank in which membranes are arranged and tightened is often used.
処理される酸洗液のは、装置中の一つおきの
隔室に好ましくは、0.5〜5.0／hr・m2の流量で
供給され、一方、陰イオン交換膜を隔てて上記隔
室に隣接するそれぞれの隔室には、水が、上記
処理原液とほぼ同等の流量にて供給される。水
は、必ずしも純粋な水でなくともよく、酸洗より
も塩酸濃度の低い水溶液も使用できる。かくし
て、透析工程では、酸液と水とが陰イオン交換膜
を隔てて対置させることになり、酸洗液中の塩酸
は水側との濃度勾配及び陰イオン交換基の作用に
より陰イオン交換膜を通じて水側にに選択的に移
行する。陰イオン交換膜としては、その機能を有
する限りいずれのものも使用できるが、強塩基の
スチレン−ジビニルベンゼン系のものの使用が好
ましい。透析処理せしめられた酸洗液は、装置外
に排出されるが、必要ならばこれを再びに戻
し、塩酸が十分に回収されるまで循環させてもよ
い。かくして、好ましくは10〜80℃にて透析さ
れ、十分な量の塩酸が除去された排液は、本発
明の処理を行なわない場合に比べて少量のアルカ
リにて中和されて廃棄される。一方、回収系であ
る塩酸は、そのまま或いは必要に応じてに戻し
て循環し、塩酸濃度が所定の値に達した後に装置
外に取り出される。塩酸は少量の鉄を含むもの
の、酸洗液中に含まれるニツケル、クロム、モリ
ブデンそして銅などの酸洗に支障となる不純金属
は、ほとんど含まないので、ステンレス鋼、鋼の
酸洗その他において有効裡に再使用できる。 The pickling solution to be treated is preferably supplied to every other compartment in the apparatus at a flow rate of 0.5 to 5.0/hr·m 2 , while the pickling solution adjacent to said compartment is separated by an anion exchange membrane. Water is supplied to each compartment at a flow rate approximately equal to that of the stock solution. The water does not necessarily have to be pure water, and an aqueous solution with a lower concentration of hydrochloric acid than that used for pickling can also be used. Thus, in the dialysis process, the acid solution and water are placed opposite each other across the anion exchange membrane, and the hydrochloric acid in the pickling solution crosses the anion exchange membrane due to the concentration gradient with the water side and the action of the anion exchange group. selectively migrates to the water side through the water. Any anion exchange membrane can be used as long as it has the desired function, but it is preferable to use a strong base styrene-divinylbenzene membrane. The dialyzed pickling solution is discharged outside the apparatus, but if necessary, it may be returned to the outside and circulated until the hydrochloric acid is sufficiently recovered. Thus, the effluent, preferably dialyzed at 10 to 80° C. and from which a sufficient amount of hydrochloric acid has been removed, is neutralized with a smaller amount of alkali and discarded than in the case where the treatment of the present invention is not performed. On the other hand, the hydrochloric acid in the recovery system is circulated as it is or returned as necessary, and is taken out of the apparatus after the hydrochloric acid concentration reaches a predetermined value. Although hydrochloric acid contains a small amount of iron, it contains almost no impurity metals such as nickel, chromium, molybdenum, and copper, which are contained in the pickling solution and can interfere with pickling, so it is effective for pickling stainless steel and steel. Can be reused inside.
本発明で処理される塩酸々洗液は、上記したよ
うな銅を含む特殊鋼、特にステンレスの酸洗過程
で得られる酸洗液が全て含まれる。かかる酸洗液
は、鋼の種類、塩酸の濃度によつても多少異なる
が、ステンレス鋼の場合、通常、塩酸100〜250
ｇ／、鉄10〜100ｇ／のほかに、ニツケル0.5
〜５ｇ／、銅0.8〜1.5ｇ／、その他、微量の
クロム、モリブデンなどを含有する。 The hydrochloric acid pickling solution treated in the present invention includes all pickling solutions obtained in the process of pickling special steel containing copper, especially stainless steel, as described above. The pickling solution varies somewhat depending on the type of steel and the concentration of hydrochloric acid, but in the case of stainless steel, it is usually 100 to 250% hydrochloric acid.
g/, iron 10-100g/, and nickel 0.5
Contains ~5g/, copper 0.8~1.5g/, and trace amounts of chromium, molybdenum, etc.
このようにして、本発明によれば、その処理に
多大の費用を要する酸洗液から塩酸を選択的且つ
効率的に分離回収でき、酸洗廃液の処理コストを
低下させるだけでなく、回収された塩酸を再使用
することにより、酸洗過程の処理コストを低下さ
せ、更には酸洗操作の容易化及び製造された鋼の
品質を向上させることができる。即ち、従来は、
その処理に多大の費用を要するため、酸洗液中の
不純物金属イオンが許容量に達するギリギリまで
使用するため、酸洗された鋼に不純物が付着し、
その品質を低下させたり、或いはかかる不純物の
影響を避けるため運転、管理により多くの注意を
要していた。しかし、本発明によれば、酸洗液を
低コストで処理可能であるので、これらの難点を
解消できる。 In this way, according to the present invention, it is possible to selectively and efficiently separate and recover hydrochloric acid from the pickling solution, which requires a great deal of cost to process, which not only reduces the processing cost of the pickling waste solution, but also reduces the amount of recovered hydrochloric acid. By reusing the hydrochloric acid, it is possible to reduce the treatment cost of the pickling process, facilitate the pickling operation, and improve the quality of the manufactured steel. That is, conventionally,
Because the process requires a lot of money, the impurity metal ions in the pickling solution are used until they reach the allowable amount, which causes impurities to adhere to the pickled steel.
In order to avoid degrading the quality or being affected by such impurities, greater care has been required in operation and management. However, according to the present invention, the pickling solution can be processed at low cost, so these difficulties can be overcome.
以下に本発明を更に具体的に説明するために実
施例を挙げるが、本発明は、これらに限定される
ものではない。 Examples are given below to further specifically explain the present invention, but the present invention is not limited thereto.
実施例 １
ステンレス鋼の酸洗工場から取り出した塩酸
150ｇ／、鉄47ｇ／、ニツケル2.5ｇ／、銅
1200ppmその他微量のクロム及びモリブデンを含
む塩酸々洗液に、銅イオンの当量に相当するチオ
尿素24ｇを添加した。チオ尿素の添加に伴なつ
て、自色擬乳状の沈澱が生成した。該沈澱物を含
む酸洗液を沈降槽に導き、沈澱物を十分に沈降さ
せた。Example 1 Hydrochloric acid taken from a stainless steel pickling factory
150g/, Iron 47g/, Nickel 2.5g/, Copper
24 g of thiourea, equivalent to the equivalent of copper ions, was added to a hydrochloric acid washing solution containing 1200 ppm and trace amounts of chromium and molybdenum. As thiourea was added, a self-colored pseudo-milky precipitate was formed. The pickling solution containing the precipitate was introduced into a settling tank, and the precipitate was sufficiently settled.
沈降槽の上澄液たる酸洗液は、銅イオンの濃度
のみが、200ppmに低下しており、他の成分は、
原液と同じであつた。かかる酸洗液を、陰イオン
交換膜“セレミオンDMV”（旭硝子社、強塩基
性スチレン−ジビニルベンゼン系膜商品名、大き
さ16cm×24cm）を19枚を組込んだフイルタープレ
ス型セレミオン透析装置Ｔ−Ｏ型（旭硝子社透析
槽の商品名、有効膜面積3.971cm2）の一つおきの
隔室に0.79／hrの流量で供給し、一方その隔室
に隣接するそれぞれの隔室には回収系として水を
上記酸洗液と同じ流量で、それぞれ対向流となる
ように供給した。なお、透析槽の液温は、25℃を
保持し、かくして10時間透析を続行したが、処理
中透析係数はほぼ一定に保持され、膜面における
析出物の発生もなく、安定して行なうことができ
た。透析槽の原液側からは塩酸22.5ｇ／、鉄43
ｇ／、ニツケル2.2ｇ／、銅80ppmその他不
純物を含む液が得られ、一方回収側からは、塩酸
127.5ｇ／、鉄４ｇ／なる液が安定して得ら
れた。 In the pickling solution, which is the supernatant liquid of the sedimentation tank, only the concentration of copper ions has been reduced to 200 ppm, and the other components are
It was the same as the original solution. The pickling solution was transferred to a filter press type Selemion dialysis device T incorporating 19 anion exchange membranes "Selemion DMV" (Asahi Glass Co., Ltd., strong basic styrene-divinylbenzene membrane product name, size 16 cm x 24 cm). - Supplied at a flow rate of 0.79/hr to every other compartment of the O-type (trade name of Asahi Glass dialysis tank, effective membrane area 3.971 cm 2 ), while each compartment adjacent to that compartment was collected. Water was supplied as a system at the same flow rate as the pickling solution, so that they were in countercurrent flow. The liquid temperature in the dialysis tank was maintained at 25°C, and dialysis was continued for 10 hours, but the dialysis coefficient remained almost constant during the process, and there was no precipitate on the membrane surface, making it stable. was completed. Hydrochloric acid 22.5g/, iron 43 from the undiluted side of the dialysis tank
A liquid containing 2.2 g/g/nickel, 80 ppm copper, and other impurities was obtained, while from the recovery side, hydrochloric acid
A liquid containing 127.5 g/4 g of iron was stably obtained.
回収側からの塩酸は、金属として実質上鉄しか
含まれていないので、酸洗工場における酸洗用塩
酸として十分に使用可能であり。一方原液側の排
出液は塩酸がほぼ処理前酸洗液の約1/7に減少し
ているので、これを廃棄するにしても中和に要す
るアルカリがそれだけ節減できる。 Since the hydrochloric acid from the recovery side contains substantially only iron as a metal, it can be fully used as hydrochloric acid for pickling in pickling plants. On the other hand, the amount of hydrochloric acid in the discharged solution on the raw solution side has been reduced to approximately 1/7 of that in the pickling solution before treatment, so even if this is discarded, the amount of alkali required for neutralization can be saved.
比較例
実施例と同じ組成を有する酸洗液であるが、透
析処理する前に予め銅イオンを除去する処理する
ことなく、そのまま実施例と同じ透析槽に供給
し、且つ同様にして10時間透析処理を行なつたと
ころ、回収側からは、塩酸130.5ｇ／、鉄4.7
ｇ／、とともに、銅840ppmという液が得られ
た。該塩酸は、十分な濃度の塩酸を含むものの多
量の銅を含むので、ステンレス鋼の酸洗液として
再使用することはできなかつた。Comparative Example A pickling solution having the same composition as in the example was supplied as it was to the same dialysis tank as in the example without being treated to remove copper ions before dialysis treatment, and dialyzed for 10 hours in the same manner. When the treatment was carried out, 130.5g of hydrochloric acid and 4.7g of iron were recovered from the recovery side.
A liquid with a copper content of 840 ppm was obtained. Although the hydrochloric acid contained a sufficient concentration of hydrochloric acid, it contained a large amount of copper, so it could not be reused as a pickling solution for stainless steel.
添付図面は、本発明を実施する場合の具体的プ
ロセスの態様を示したものである。
Ａ……陰イオン交換膜、……被酸洗液、…
…水、……処理後の排液。
The accompanying drawings illustrate specific process aspects for carrying out the present invention. A... Anion exchange membrane,... pickling liquid,...
...Water, ...Effluent after treatment.
Claims (1)
む酸洗液を処理して塩酸を回収、再使用するにあ
たり、酸洗液に銅イオンと反応して不溶性物を生
成する窒素又はイオウ含有有機物を添加して生成
する沈澱を分離することにより酸洗液中の銅イオ
ンを800ppm以下に除去し、次いでかかる液を陰
イオン交換膜を介して水と接触させて透析せし
め、上記液から塩酸を選択的に水側に分離回収せ
しめることを特徴とする特殊鋼の塩酸酸洗液の処
理方法。 ２ 窒素又はイオウ含有有機物が、チオ尿素であ
る特許請求の範囲１の方法。 ３ 分離回収された塩酸を特殊鋼の塩酸酸洗過程
に循環、再使用する特許請求の範囲１又は２の方
法。 ４ 特殊鋼がステンレスである特許請求の範囲
１、２又は３の方法。[Scope of Claims] 1. When treating a pickling solution containing copper components obtained in the process of pickling special steel with hydrochloric acid to recover and reuse hydrochloric acid, insoluble matter is removed by reacting with copper ions in the pickling solution. Copper ions in the pickling solution are removed to 800 ppm or less by adding nitrogen or sulfur-containing organic matter to separate the produced precipitate, and then the solution is brought into contact with water through an anion exchange membrane and dialyzed. A method for treating special steel with a hydrochloric acid pickling solution, which comprises selectively separating and recovering hydrochloric acid from the solution to the water side. 2. The method according to claim 1, wherein the nitrogen- or sulfur-containing organic substance is thiourea. 3. The method according to claim 1 or 2, wherein the separated and recovered hydrochloric acid is recycled and reused in the hydrochloric acid pickling process of special steel. 4. The method according to claim 1, 2 or 3, wherein the special steel is stainless steel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57074318A JPS58193378A (en) | 1982-04-30 | 1982-04-30 | Treatment of hydrochloric acid pickling liquid for special steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57074318A JPS58193378A (en) | 1982-04-30 | 1982-04-30 | Treatment of hydrochloric acid pickling liquid for special steel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58193378A JPS58193378A (en) | 1983-11-11 |
| JPH0346550B2 true JPH0346550B2 (en) | 1991-07-16 |
Family
ID=13543645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57074318A Granted JPS58193378A (en) | 1982-04-30 | 1982-04-30 | Treatment of hydrochloric acid pickling liquid for special steel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58193378A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6054394B2 (en) * | 1982-05-21 | 1985-11-29 | 株式会社トクヤマ | How to prepare pickling solution |
| DE3521952A1 (en) * | 1985-06-20 | 1987-01-02 | Henkel Kgaa | AQUEOUS COMPOSITIONS FOR THE HILITE AND FLUX PROCESS AND THEIR USE |
| JPH0815536B2 (en) * | 1990-09-29 | 1996-02-21 | 株式会社トクヤマ | Anion exchange membrane performance recovery method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5215422A (en) * | 1975-07-29 | 1977-02-05 | Ebara Udylite Kk | Method of and device for renewing pickling bath of copperrzinc alloy products |
| JPS5851908A (en) * | 1981-09-25 | 1983-03-26 | Tokuyama Soda Co Ltd | Recovery of acid by diffusion dialysis |
| JPS5858112A (en) * | 1981-10-03 | 1983-04-06 | Tokuyama Soda Co Ltd | Recovery of acid |
-
1982
- 1982-04-30 JP JP57074318A patent/JPS58193378A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58193378A (en) | 1983-11-11 |
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