JPS58110682A - Pickling method for stainless steel with suppressed generation of nox - Google Patents
Pickling method for stainless steel with suppressed generation of noxInfo
- Publication number
- JPS58110682A JPS58110682A JP21062881A JP21062881A JPS58110682A JP S58110682 A JPS58110682 A JP S58110682A JP 21062881 A JP21062881 A JP 21062881A JP 21062881 A JP21062881 A JP 21062881A JP S58110682 A JPS58110682 A JP S58110682A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- nitric acid
- nox
- pickling
- hydrogen peroxide
- 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
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
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
- C23G1/086—Iron or steel solutions containing HF
-
- 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
- C23G1/10—Other heavy metals
- C23G1/103—Other heavy metals copper or alloys of copper
Abstract
Description
【発明の詳細な説明】
本発明はステンレス鋼の酸洗方法、さらに詳しくは、硝
酸と弗化水素酸の混合水溶液（以上、硝弗酸と称する）
Ｋ添加されたスルファミン酸の窒素酸化物（以下、ＮＯ
ｘと称する）発生抑制効果が低丁ないし消滅した状態の
酸洗浴に硝酸を投入する際、高濃度のＫｈｃ発生および
それに伴う酸洗浴の突部を防止ｒる方法に関するもので
ある。Detailed Description of the Invention The present invention relates to a method for pickling stainless steel, and more specifically, a mixed aqueous solution of nitric acid and hydrofluoric acid (hereinafter referred to as nitric-fluoric acid).
K-doped sulfamic acid nitrogen oxide (hereinafter referred to as NO
This invention relates to a method for preventing the generation of a high concentration of Khc and the resulting protrusions in the pickling bath when nitric acid is introduced into a pickling bath in which the generation suppressing effect (referred to as x) is low or has disappeared.
ステンレス鋼板を熱間圧延あるいは焼鈍した際に生成さ
れた酸化スケールは、ショットプラストあるいは溶融ア
ルカリ塩等による前処理後、硝弗酸に浸漬してその地峡
の溶解とともに除去される。Oxidized scale generated when hot rolling or annealing a stainless steel plate is removed by dissolving the isthmus by immersing it in nitric-fluoric acid after pretreatment with shot blast or molten alkali salt.
この酸洗におけるアノードおよびカソード反応は主にそ
れぞれ次式〇示される。The anode and cathode reactions in this pickling are mainly represented by the following formulas.
Ｆｅ −＊ Ｆｅ”＋３ｅ ・
”（１）ＮＯｓ−＋ ３Ｈ” ＋ ２ｅ −ＨＮＯｔ＋
Ｈ２Ｏ・”１２）カソード反応で生成された亜硝酸は
酸液中に数−までは蓄積されるが、酸洗溶解量の増加と
ともにやがで過飽和となった亜硝酸は次の（３）式の反
応に従い、−酸化窒素および二酸化ｆｆｌ素ブスに分解
され、酸洗槽から排出される。Fe−*Fe”+3e・
"(1) NOs-+ 3H" + 2e -HNOt+
H2O・”12) Nitrous acid generated in the cathode reaction accumulates in the acid solution up to a few points, but as the amount dissolved in pickling increases, the nitrite becomes supersaturated and is expressed by the following equation (3). According to the reaction, it is decomposed into nitrogen oxide and ffl dioxide, which are discharged from the pickling tank.
２ＨＮＯｔ−ＮＯ十ＮＯ，＋ Ｈ２Ｏ・・・（３）酸洗
槽から排出さルる有害なＮＯｘは公害の原因となるので
、ＮＯｘを含む排ガスを脱硝装置で浄化するか、あるい
は酸洗時硝弗酸液に予めスルファミノ酸を添加しＣＮＯ
ｘ発生量を抑制する方法が採用されている。ところが、
第１表に示されるように、ＮＯｘ処理後の残留ＮＯｘ量
は排がス脱硝装置による処理（おいては、ステンレス鋼
（被酸洗材）の種類によって脱硝能力が十分とはいえな
い。一方、硝弗酸液にスルファミノ酸を添加することに
より動発生量を抑制する方法では第１表から明らかな如
く、ステンレス鋼の種類に関係なく絶大な効果があるが
、この方法においては長期間使用してスルファミノ酸の
添加積算量が増してくると、酸洗されたステンレス鋼の
表面光沢が悪化してくる問題点を有している。このため
、スルファミノ酸添加によるＮＯｘ抑制法はＮＯｘ発生
量の多い酸洗時や社会的な要請で勤発生量を一時的によ
り以上抑制しなければならない場合等に応急的に用いる
Ｄが有効である。2HNOt - NO + H2O... (3) Harmful NOx discharged from the pickling tank causes pollution, so the exhaust gas containing NOx should be purified with a denitrification device, or the Sulfamino acid is added to the hydrofluoric acid solution in advance and CNO
A method has been adopted to suppress the amount of x generated. However,
As shown in Table 1, the amount of residual NOx after NOx treatment is determined by the treatment with exhaust gas denitrification equipment (in which case the denitrification ability may not be sufficient depending on the type of stainless steel (material to be pickled). As is clear from Table 1, the method of suppressing the amount of dynamic generation by adding sulfamino acid to the nitric-fluoric acid solution is extremely effective regardless of the type of stainless steel. As the cumulative amount of sulfamino acid added increases, the surface gloss of pickled stainless steel deteriorates.For this reason, the NOx suppression method by adding sulfamino acid has the problem of reducing the amount of NOx generated. D is effective when used as an emergency, such as when pickling with a large amount of water or when the amount of work must be temporarily suppressed due to social demands.
しかしながら、硝弗酸液にＮＯｘ発生抑制効果をもつス
ルファミン酸を添加してステンレス鋼を酸洗し、スルフ
ァ２ン酸が有効に作用している状態Ｘから移行したスル
ファミノ酸の効力が低下ないしは消滅した状ｌＩＹで硝
酸を投入しようとすると、ｓ１図に示す如く、硝酸の投
入と同時に高濃度の廟がスが発生し、かつその急激なガ
ス化反応により酸浴の突部が起り、槽外にオーバーフロ
ーしたり、酸ミストが飛散する等の危険があり、このた
めスルファミノ酸の添加された酸液なそのままにしてス
ルファミノ酸くよる廟発生抑制法から排ガス脱硝法への
変更ができなかった。However, when stainless steel is pickled by adding sulfamic acid, which has the effect of suppressing NOx generation, to a nitric-fluoric acid solution, the effectiveness of sulfamino acid, which has moved from state X where sulfanoic acid is effectively acting, decreases or disappears. When trying to introduce nitric acid into the tank, as shown in Figure s1, a high concentration of gas is generated at the same time as the nitric acid is added, and the rapid gasification reaction causes a protrusion in the acid bath, causing a drop outside the tank. There was a risk of overflow or scattering of acid mist, and for this reason, it was not possible to change from the sulfamino acid-based method of suppressing mausoleum generation to the exhaust gas denitrification method by leaving the acid solution with sulfamino acid added as is.
酸液の突部なしに硝酸を添加するくは、従来経験りから
スルファミン酸を添加した酸液はその全量を一旦廃棄し
、新しく硝弗酸液を建浴し直すか、あるいは硝酸を２０
−以下に希釈し徐々に投入する方法が採られている。し
かしながら、酸液な全量更新することは酸液の損失が甚
しく、又希釈した硝酸を投入する方法では酸＃［が薄く
なり、新酸の補充を必要とし、一方酸液が過剰となる等
の欠点がある。In order to add nitric acid without any acid solution protrusions, we have learned from past experience that the entire amount of acid solution to which sulfamic acid has been added should be discarded and a new nitric-fluoric acid solution should be prepared, or nitric acid should be added to the bath for 20 minutes.
-The method used is to dilute it to the following amount and gradually introduce it. However, replacing the entire amount of acid solution results in a significant loss of acid solution, and the method of adding diluted nitric acid dilutes the acid and requires replenishment of new acid, while the acid solution becomes excessive. There are drawbacks.
硝酸投入前のｍａ中には第１鉄イオンと第２鉄イオンが
共存するが、硝酸投入によりＮＯｘが異常発生したあと
では殆んど７４２鉄イオンＫｆ化していることから、Ｎ
Ｏｘの異常発生現象が硝酸による鉄イオンの酸化反応と
慴妥しＣいると考え、硝酸に各樵薬剤を添加ｒる実験を
重ねた結果、少量の過酸化水素を硝酸に添加しておけば
ＮＯｘの著しい発生や酸浴の突部が抑制されることを見
い出した。Ferrous ions and ferric ions coexist in ma before nitric acid injection, but after NOx is abnormally generated due to nitric acid injection, most of the 742 iron ions are converted to Kf.
We believe that the phenomenon of abnormal Ox generation is related to the oxidation reaction of iron ions caused by nitric acid, and as a result of repeated experiments in which various woodcutter chemicals were added to nitric acid, we found that if a small amount of hydrogen peroxide was added to nitric acid, It has been found that significant generation of NOx and protrusions in the acid bath are suppressed.
第２図は、硝酸に過酸化水素（１００チ純分換算）を０
．１〜５点綾チの範囲で種々変化させて添加した後、ス
ルファミノ酸のＫ）ｘ発生抑制効果の低ｆした一定の硝
弗酸液く投入し、酸洗槽から排出されるＮＯｘ ３１を
連続的に記録した結果ケ示したものである。第２図から
、硝酸に添加する過酸化水素が０．５重量−未満では酸
洗浴に投入時のＮＯｘの異常発生を完全に防止できない
が、０．５重Ｉｌ−以上であればＮＯｘ Ｊ） ４常発
生に対して抑制効果があり、安全に硝酸を投入できるこ
とが判明した。Figure 2 shows the amount of hydrogen peroxide (100% pure equivalent) added to nitric acid.
．． After adding various amounts in the range of 1 to 5 points, a certain amount of nitric fluoride acid solution with a low effect of suppressing the generation of K)x of sulfamino acid was added, and NO This shows the results of continuous recording. From Figure 2, if the amount of hydrogen peroxide added to nitric acid is less than 0.5 weight, it is not possible to completely prevent the abnormal generation of NOx when it is added to the pickling bath, but if it is 0.5 weight or more, NOx J) It has been found that nitric acid can be safely injected, with the effect of suppressing the occurrence of 4 regular occurrences.
本発明は以上の知見に基づくものであり、そのｇ！ｄと
するところは、硝弗酸に廟の発生を抑制する効果をもつ
スルファミン酸を添加してステンレス鋼を酸洗し、スル
ファミノ酸の効力が低ドないしは完全（消滅した状況下
で、酸濃度調整のために投入される硝酸の中に過酸化水
素を０．５重量−以上添加したことにある。The present invention is based on the above findings, and the g! d is obtained by pickling stainless steel by adding sulfamic acid, which has the effect of suppressing the formation of mausoleum, to nitric-fluoric acid. The reason is that more than 0.5 weight of hydrogen peroxide was added to the nitric acid used for adjustment.
不発＠によれば、ＮＯｘの発生を抑制するスルファミン
酸を添加した硝弗酸をその効力が低下した後も酸液なそ
の塘ま使用できることから、排ガス脱硝法から一時的く
スルファミン酸によるＮＯｘ発生抑制法の採用が可能と
なり、ひいてはステンレス鋼酸洗におゆるＮＯｘ公害の
低減に大きく寄与することができる。According to Fufu@, nitrofluoric acid added with sulfamic acid, which suppresses NOx generation, can be used as an acid solution even after its effectiveness has decreased, so NOx generation due to sulfamic acid can be temporarily prevented from exhaust gas denitrification method. It becomes possible to adopt a suppression method, which in turn can greatly contribute to reducing NOx pollution caused by pickling stainless steel.
本発明における過酸化水素の作用圧ついては次のように
考えられる。スルファミノ酸を含む硝弗酸中でのステン
レス鋼酸洗時の化学反応としては、次式に示すようにス
ルファミノ酸は亜硝酸と反応して硝酸となり、その結果
地鉄の溶解反応で第１鉄と第２鉄が生成される。The working pressure of hydrogen peroxide in the present invention can be considered as follows. The chemical reaction during pickling of stainless steel in nitric-fluoric acid containing sulfamino acid is as shown in the following equation: sulfamino acid reacts with nitrous acid to become nitric acid, and as a result, ferrous iron is dissolved in the dissolution reaction of the base iron. and ferric iron is generated.
ＮＨ，８０畠Ｈ→對０．→迅８０４ ＋ Ｎｔ ｔ ＋
Ｈ！Ｏ・・・（４）５Ｆｅ ＋ １８）ｆＮＯｓ ＋
Ｈｓ ＳＯａ →４Ｆｅ （ＮＯｓ ）ｓ ＋Ｆｅ５Ｏ
ｉ ＋ ６ＨＮＯ＊ ＋ ６１４．Ｏ＋ Ｈａ ””
＋５）ステンレス鋼の酸洗溶解量が増大し、やがてスル
ファミノ酸が消耗されると、酸洗浴内には亜硝酸が蓄積
濃化されてくる。このような状況Ｆで硝酸を投入すると
、次の６）式に示すように第１鉄が第２鉄に酸化される
と同時に水素ガスが生成され、そして亜硝酸はその水素
によって瞬時に１７）式に従って分解され、一時的に多
量のＮＯｘを発生する。NH, 80 Hatake H→對0. →Jun804 + Nt t +
H! O...(4)5Fe + 18)fNOs +
Hs SOa →4Fe (NOs )s +Fe5O
i + 6HNO* + 614. O+ Ha ””
+5) As the amount of stainless steel dissolved in pickling increases and sulfamino acid is eventually consumed, nitrous acid accumulates and becomes concentrated in the pickling bath. When nitric acid is added in such a situation F, ferrous iron is oxidized to ferric iron as shown in the following equation 6), and at the same time hydrogen gas is generated, and nitrite is instantly converted to 17) by the hydrogen. It is decomposed according to the formula and temporarily generates a large amount of NOx.
６ＦｅＳＯ４＋６ＨＮ）３−２Ｆｅｌ （８０４）３
十２Ｆｅ（ＮＯｘ）ｓ ＋ ３Ｈ２・・・、６）４ＨＮ
Ｏ，＋Ｉ（、→ ３＆０＋３ＮＯ＋ＦＫ）ｔ
・・・（力しかし、この際硝酸に過酸化水素を添加
しておくと、１８）弐に示すように硝酸が第１鉄と反応
しても水素がスが生成されないので、亜硝酸の分解反応
が生起せず、ＮＯｘの異常発生に対して抑制効果を発揮
する。6FeSO4+6HN)3-2Fel (804)3
12Fe(NOx)s + 3H2..., 6) 4HN
O, +I(, → 3&0+3NO+FK)t
(However, if hydrogen peroxide is added to nitric acid at this time, as shown in 18) 2, even if nitric acid reacts with ferrous iron, hydrogen will not be produced, so the decomposition of nitrous acid will be No reaction occurs, and it exerts a suppressive effect on abnormal NOx generation.
６ＦｅＳＯ４＋ ６ＨＮＯ３＋ ３＆ ０！ −４２Ｆ
ｅｔ （ＳＯ４）ｓ ＋ ２Ｆｅ（ＮＯｓλ＋６Ｈ，Ｏ
−（８）なお、過酸化水素は予め硝酸に添加しておくこ
とが肝要Ｃあり、例えば過酸化水素を先ず酸洗浴に投入
した後硝ＷＲｆｔ投入しても、悶りの異常発生に対して
全く有効でないばかりか、過酸化水素投入時に酸液が激
しく突弗し、重大な危険が伴うので注意が必要である。6FeSO4+ 6HNO3+ 3&0! -42F
et (SO4)s + 2Fe(NOsλ+6H,O
-(8) It is important to add hydrogen peroxide to nitric acid in advance.For example, even if hydrogen peroxide is first added to the pickling bath and then nitric acid WRft is added, it will prevent the abnormal occurrence of writhing. Not only is it not effective at all, but the acid solution splashes violently when hydrogen peroxide is added, creating a serious danger, so care must be taken.
本発ＬｊｌＪＫｊＬ５いて用いる過酸化水素の純度は特
に高純度である必要がなく、工業薬品純度程度のものＱ
良く、又その濃度についても通常市販されている艮ρ１
分が３０〜９０重量％程度のものをそのまま使用するか
、あるいは適宜水で希釈したものでも効果に大差がない
。要するに、実質的Ｋ Ｈｓ Ｏｘ分として０．５重量
−以上の過酸化水素が硝酸〈均一に温合されていれば良
い。しかし、過酸化水素水を不必要に硝１１に添加する
ことは徒らにコスト上昇を招くので、最大でＨ，ｌｔと
して５重量−程度とするのが好ましい。酸濃度調整のた
めに投入される硝酸は酸洗液の濃度を不必要に希釈せず
、−；１
力木発明の効果としてＮｏｗの異常発生を抑制するとい
う点から高濃度の物Ｃ良く、ＨＮＯ３として９８重量−
１！度の発煙硝酸等が使用できる。The purity of the hydrogen peroxide used in the present invention does not need to be particularly high; it can be at the level of industrial chemical purity.
It is good and its concentration is usually commercially available.
There is no significant difference in effectiveness even if the composition is used as it is or diluted with water as appropriate. In short, it is sufficient if 0.5 weight or more of hydrogen peroxide is heated uniformly with nitric acid as a substantial K Hs Ox content. However, unnecessary addition of hydrogen peroxide solution to the nitric acid 11 unnecessarily increases the cost, so it is preferable to set the hydrogen peroxide solution to a maximum of about 5% by weight in terms of H,lt. The nitric acid added to adjust the acid concentration does not unnecessarily dilute the concentration of the pickling solution, and -; 98 weight as HNO3-
1! degree of fuming nitric acid, etc. can be used.
以下、本発明？実施例２挙げて具体的に説明する。Is this invention the following? This will be specifically explained using Example 2.
次に示す組成、温度の酸洗液を調合し、焼鈍後ショット
プラストで予備脱スケールされたステンレス鋼熱延板を
酸洗処理した。A pickling solution having the composition and temperature shown below was prepared, and a hot rolled stainless steel plate that had been annealed and preliminary descaled using shot blasting was pickled.
酸洗液 弗化水素酸（）ＩＦ’） １．５〜２，
０重量％硝酸（ＨＮＯｓ ） １２〜１６
重量％スルフアミ／酸（鵬５ＯａＨ） ３重量
嗟液温 ５５〜６０゛Ｃ
酸洗槽の上部にはツー−を設け、酸洗時Ｊｃ４！ボンデ
で槽内の排ガスケ大量の空気とともに秋引し、その一部
を採取してＮＯ＋ｃ発生量を測定した。酸洗中、弗化水
素酸および硝酸の濃度が上記範囲内圧管理されるように
適宜酸液の分析および新酸の補給を行った。ただし、ス
ルファミン酸は酸洗途中での追加は一切行わなかった。Pickling liquid Hydrofluoric acid ()IF') 1.5~2,
0wt% nitric acid (HNOs) 12-16
Weight% sulfuric acid/acid (Peng 5OaH) 3 weight/liquid temperature 55~60°C Two pipes are provided at the top of the pickling tank, and Jc4! The exhaust gas in the tank was evacuated together with a large amount of air using a bonder, and a portion of it was collected to measure the amount of NO+C generated. During pickling, the acid solution was analyzed and new acid was replenished as appropriate so that the concentrations of hydrofluoric acid and nitric acid were controlled within the above range. However, sulfamic acid was not added at all during pickling.
酸洗中のＮＯｘがスの発生状況は第３図に示す如く、酸
洗量の比較的少ない間はスルファミノ酸の効力忙よりＫ
）ｘは殆んど検出されないが、スルファミノ酸が消耗さ
れると、漸次廟が検出されるようになり、さらに酸洗量
を増していくと種ｉ発生量は高濃度のほぼ一定した値を
示すようＫなる。第３図のＡ、Ｂ。The generation of NOx during pickling is as shown in Figure 3, when the amount of pickling is relatively small, the effectiveness of sulfamino acid is
) x is hardly detected, but as the sulfamino acid is depleted, it gradually becomes detected, and as the amount of pickling is further increased, the amount of species i generated reaches a nearly constant value at a high concentration. As shown, it becomes K. A and B in Figure 3.
Ｃの各点における酸液を採取し、直ちに酸洗処理を開始
すると同時に第２表に示す条件の硝酸＆ 一定量投入し
、その際の障発生量および酸浴の突部状況を調べた。そ
の結果は、第２表に示す如く、本発ｄＡ〈おけるように
０．５重量−以上の過酸化水素？添加した硝酸の場合に
は投入による廟がスの発生が殆んどなく、かつ酸浴の突
棒現象も全く見られなかった。しかし、過酸化水素を添
加しても０．５重量−未溝の場合は第２表のＮｏ、 １
４．１５．１７．１８の如く、砲発生量の著しい増力ａ
および酸浴の突弗な防止できなかった。The acid solution at each point C was collected, and at the same time the pickling process was started, a certain amount of nitric acid was added under the conditions shown in Table 2, and the amount of damage and the condition of protrusions in the acid bath were investigated. The results are shown in Table 2, as shown in Table 2, 0.5% by weight or more of hydrogen peroxide? In the case of added nitric acid, there was almost no generation of soot due to addition, and no acid bath protrusion phenomenon was observed at all. However, even if hydrogen peroxide is added, if there is no groove by 0.5 weight, No. 1 in Table 2.
As shown in 4.15.17.18, a significant increase in the amount of gunfire a
and acid baths could not be prevented.
本発明方法は、ステンレス鋼以外の例えば鋼、アルミ÷
クム等の非鉄材料および各種合金鋼にあっても硝ａｔ含
有する酸液中で脱スケールあるいは化学研磨する場合に
広く適用することができる。The method of the present invention applies to materials other than stainless steel, such as steel, aluminum ÷
It can be widely applied to descaling or chemically polishing non-ferrous materials such as cum and various alloy steels in an acid solution containing nitric acid.
第１図はスルファミノ酸含有硝弗酸液が老化した状態で
硝酸を投入した時のＮＯｘ発生状況を示すグラフ、第２
図は同様な酸液に種々の量の過酸化水素を添加した硝酸
を投入した時のＮＯｘ発生状況を示すグラフ、第３図は
スルファミン酸の消耗とともにステンレス鋼酸洗時の動
発生量が変化する状況を示すグラフである。
特許出願人 川崎製鉄株式会社 、−代理人弁理士
渡 辺 望 稔（□′了−１′、夕ぜ７・′
滅１図
経時変化（釦−諸）Figure 1 is a graph showing the NOx generation situation when nitric acid is added to an aged sulfamino acid-containing nitrofluoric acid solution.
The figure is a graph showing the NOx generation situation when nitric acid with various amounts of hydrogen peroxide added to the same acid solution. Figure 3 shows the change in the amount of dynamic generation during stainless steel pickling as sulfamic acid is consumed. This is a graph showing a situation in which Patent applicant: Kawasaki Steel Corporation, -Representative patent attorney
Minoru Watanabe (□'Ryo-1', Evening 7/' Mei-1 Diagram change over time (buttons - miscellaneous)
Claims (1)
ンを添加してステンレス鋼な酸洗するに際し、前記スル
ファミノ酸の効力が低ドないしは完全に消滅した状況下
で、硝酸を追加投入する場合、過酸化水素を０．５重量
−以上温顔した硝酸を使用することを特徴とする種＼発
生を抑制したステンレス鋼の酸洗方法。[Claims] When pickling stainless steel by adding sulfamine, which has the effect of suppressing the generation of nitrogen oxides (NCNC), to a mixed acid of nitric acid and hydrofluoric acid, the effectiveness of the sulfamino acid is low. A method for pickling stainless steel that suppresses the generation of seeds, characterized by using nitric acid warmed by 0.5 weight or more of hydrogen peroxide when adding nitric acid in a situation where nitric acid has completely disappeared. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21062881A JPS602392B2 (en) | 1981-12-25 | 1981-12-25 | Pickling method for stainless steel that suppresses NOx generation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21062881A JPS602392B2 (en) | 1981-12-25 | 1981-12-25 | Pickling method for stainless steel that suppresses NOx generation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58110682A true JPS58110682A (en) | 1983-07-01 |
| JPS602392B2 JPS602392B2 (en) | 1985-01-21 |
Family
ID=16592467
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21062881A Expired JPS602392B2 (en) | 1981-12-25 | 1981-12-25 | Pickling method for stainless steel that suppresses NOx generation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS602392B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4103598A1 (en) * | 1990-03-14 | 1991-09-19 | Mannesmann Ag | Alloy pickling in mixed acid bath - using nitrogen oxide(s) emission measurement to control amidosulphonic acid addn. |
| EP0626469A1 (en) * | 1993-05-24 | 1994-11-30 | MANNESMANN Aktiengesellschaft | Tickling process for high-alloyed workpieces |
| US5843240A (en) * | 1995-10-18 | 1998-12-01 | Novamax Itb S.R.L. | Process for stainless steel pickling and passivation without using nitric acid |
| US6068001A (en) * | 1995-10-18 | 2000-05-30 | Novamax Itb S.R.L. | Process for stainless steel pickling and passivation without using nitric acid |
| EP3255179A1 (en) * | 2016-06-08 | 2017-12-13 | United Technologies Corporation | Removing material with nitric acid and hydrogen peroxide solution |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6206382B2 (en) * | 2014-11-28 | 2017-10-04 | 住友金属鉱山株式会社 | Method for producing indium hydroxide powder |
-
1981
- 1981-12-25 JP JP21062881A patent/JPS602392B2/en not_active Expired
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4103598A1 (en) * | 1990-03-14 | 1991-09-19 | Mannesmann Ag | Alloy pickling in mixed acid bath - using nitrogen oxide(s) emission measurement to control amidosulphonic acid addn. |
| DE4103598C2 (en) * | 1990-03-14 | 1992-05-21 | Mannesmann Ag, 4000 Duesseldorf, De | |
| EP0626469A1 (en) * | 1993-05-24 | 1994-11-30 | MANNESMANN Aktiengesellschaft | Tickling process for high-alloyed workpieces |
| US5843240A (en) * | 1995-10-18 | 1998-12-01 | Novamax Itb S.R.L. | Process for stainless steel pickling and passivation without using nitric acid |
| US6068001A (en) * | 1995-10-18 | 2000-05-30 | Novamax Itb S.R.L. | Process for stainless steel pickling and passivation without using nitric acid |
| EP3255179A1 (en) * | 2016-06-08 | 2017-12-13 | United Technologies Corporation | Removing material with nitric acid and hydrogen peroxide solution |
| US10316414B2 (en) | 2016-06-08 | 2019-06-11 | United Technologies Corporation | Removing material with nitric acid and hydrogen peroxide solution |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS602392B2 (en) | 1985-01-21 |
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