JP2008013838A - Method for pickling metallic material - Google Patents
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- JP2008013838A JP2008013838A JP2006188929A JP2006188929A JP2008013838A JP 2008013838 A JP2008013838 A JP 2008013838A JP 2006188929 A JP2006188929 A JP 2006188929A JP 2006188929 A JP2006188929 A JP 2006188929A JP 2008013838 A JP2008013838 A JP 2008013838A
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- carbon dioxide
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- 238000005554 pickling Methods 0.000 title claims abstract description 77
- 239000007769 metal material Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000243 solution Substances 0.000 claims abstract description 42
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 28
- 238000005260 corrosion Methods 0.000 claims abstract description 22
- 230000007797 corrosion Effects 0.000 claims abstract description 22
- 239000003112 inhibitor Substances 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 9
- 239000010959 steel Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 6
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 4
- 230000005587 bubbling Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 abstract 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 229910001447 ferric ion Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 229910001448 ferrous ion Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
Description
本発明は、金属材料の酸洗方法に関する。 The present invention relates to a pickling method for metal materials.
熱間圧延処理、熱処理などが施された金属材料の表面には、一般にミルスケールと呼ばれる酸化物皮膜が形成されている。また、ボイラー、熱交換器などを構成する金属材料の表面にも、スケールと呼ばれる酸化物皮膜が形成される。 An oxide film generally called a mill scale is formed on the surface of a metal material that has been subjected to hot rolling treatment, heat treatment, or the like. In addition, an oxide film called a scale is also formed on the surface of a metal material constituting a boiler, a heat exchanger, or the like.
かかる酸化物皮膜を除去するために、塩酸、硫酸などの酸を含む酸洗液を金属材料表面に接触させることにより酸化物皮膜を溶解して除去する、いわゆる酸洗が広く行われている。 In order to remove the oxide film, so-called pickling is widely performed in which the oxide film is dissolved and removed by bringing a pickling solution containing an acid such as hydrochloric acid or sulfuric acid into contact with the surface of the metal material.
金属材料の酸洗は速やかに行われることが好ましい。速やかに酸洗しうる方法としては、特許文献１〔特開昭６２−２４３７８８号公報〕に記載されるように、酸洗液を空気でバブリングしながら金属材料の表面に接触させる方法が挙げられる。 The pickling of the metal material is preferably performed promptly. Examples of a method capable of prompt pickling include a method of bringing the pickling solution into contact with the surface of the metal material while bubbling with air, as described in Patent Document 1 (Japanese Patent Laid-Open No. 62-243788). .
しかし、空気をバブリングさせる従来の酸洗方法では、表面の酸化物皮膜を越えて金属材料が溶解してしまう腐食と呼ばれる現象が起こることがあった。 However, in the conventional pickling method in which air is bubbled, a phenomenon called corrosion in which the metal material dissolves beyond the oxide film on the surface may occur.
そこで本発明者らは、金属材料の腐食を防止しつつ、速やかに酸洗しうる方法を開発するべく鋭意検討した結果、本発明に至った。 Thus, the present inventors have intensively studied to develop a method capable of pickling quickly while preventing corrosion of the metal material, and as a result, have reached the present invention.
すなわち本発明は、酸洗液を炭酸ガスでバブリングながら金属材料の表面に接触させることを特徴とする前記金属材料の酸洗方法を提供するものである。 That is, the present invention provides a pickling method for a metal material, wherein the pickling solution is brought into contact with the surface of the metal material while bubbling with carbon dioxide gas.
本発明の酸洗方法によれば、金属材料を腐食させることなく、酸化物皮膜を除去することができる。 According to the pickling method of the present invention, the oxide film can be removed without corroding the metal material.
本発明の方法により酸先しうる金属材料として代表的には、鉄、鋼、合金鋼（特殊鋼）、鋳鉄などの鉄鋼材料が挙げらる。熱間圧延処理、熱処理などが施された鉄鋼材料の表面には通常、ミルスケールと呼ばれる酸化物〔Ｆｅ2Ｏ3〕の皮膜が形成されていることから、本発明の方法は、かかる熱間圧延処理、熱処理などが施された鉄鋼材料の酸洗に好ましく適用される。 Typical examples of the metal material that can be acidified by the method of the present invention include steel materials such as iron, steel, alloy steel (special steel), and cast iron. Since a film of an oxide [Fe 2 O 3 ] called a mill scale is usually formed on the surface of a steel material subjected to hot rolling treatment, heat treatment, etc., the method of the present invention performs such hot It is preferably applied to pickling of steel materials that have been subjected to rolling treatment, heat treatment, and the like.
酸洗液としては、通常の酸洗に用いられると同様の酸の水溶液を用いることができ、代表的には塩化水素〔ＨＣｌ〕、硫酸〔Ｈ2ＳＯ4〕などの無機酸の水溶液が挙げられる。無機酸水溶液における酸濃度は通常１０ｇ／Ｌ〜５００ｇ／Ｌであり、好ましくは酸として塩化水素を単独で用いる場合には２０ｇ／Ｌ〜２００ｇ／Ｌ、硫酸を単独で用いる場合には５０ｇ／Ｌ〜３００ｇ／Ｌである。 As the pickling solution, an aqueous solution of an acid similar to that used in ordinary pickling can be used. Typically, an aqueous solution of an inorganic acid such as hydrogen chloride [HCl] or sulfuric acid [H 2 SO 4 ] is used. It is done. The acid concentration in the inorganic acid aqueous solution is usually 10 g / L to 500 g / L, preferably 20 g / L to 200 g / L when hydrogen chloride is used alone as the acid, and 50 g / L when sulfuric acid is used alone. -300 g / L.
酸洗液は、酸洗により金属材料から溶出した金属成分を含有していてもよい。例えば鉄鋼材料を酸洗する場合には、酸洗液中に２価の第一鉄イオン〔Ｆｅ2+〕、３価の第二鉄イオン〔Ｆｅ3+〕などとして鉄分が含有される。酸洗液中に含有し得る第一鉄イオンの濃度は通常２００ｇ／Ｌ以下であり、第二鉄イオンの濃度は通常５ｇ／Ｌ以下である。 The pickling solution may contain a metal component eluted from the metal material by pickling. For example, when pickling steel materials, the pickling solution contains iron as divalent ferrous ions [Fe 2+ ], trivalent ferric ions [Fe 3+ ], and the like. The concentration of ferrous ions that can be contained in the pickling solution is usually 200 g / L or less, and the concentration of ferric ions is usually 5 g / L or less.
酸洗液は酸洗腐食抑制剤を含有することが好ましい。酸洗腐食抑制剤は、酸化皮膜を越えて金属材料が浸食されることを抑制するために添加される添加剤であり、これを含有することで、金属材料の腐食をより一層、防止することができる。酸先腐食抑制剤としては、例えば朝日化学工業(株)から市販されている「イビットＮｏ．７１０Ｎ」、「イビットＮｏ．６２０ＬＴ２」「ニューハイパーＤＳ−２Ｋ」、「ニューハイパーＤＳ−Ｈ」、「ニューハイパーＤＳ−１Ｎ」など、スギムラ化学工業(株)から市販されている「ヒビロンＡ−５」、「スーパーヒビロンＹＡ−９」などが挙げられる。酸洗液における酸洗腐食防止剤の濃度は通常０．０２ｇ／Ｌ〜１０ｇ／Ｌである。 The pickling solution preferably contains a pickling corrosion inhibitor. The pickling corrosion inhibitor is an additive added to prevent the metal material from being eroded beyond the oxide film, and by containing this, the corrosion of the metal material can be further prevented. Can do. As an acid corrosion inhibitor, for example, “Ibit No. 710N”, “Ibit No. 620LT2”, “New Hyper DS-2K”, “New Hyper DS-H”, “Asahi Chemical Industry Co., Ltd.”, “ “Hyperon A-5”, “Super Hibiron YA-9” and the like, which are commercially available from Sugimura Chemical Co., Ltd., such as “New Hyper DS-1N”. The concentration of the pickling corrosion inhibitor in the pickling solution is usually 0.02 g / L to 10 g / L.
酸洗液にバブリングする炭酸ガスは、二酸化炭素濃度１００容量％の純炭酸ガスが好ましいが、窒素ガス、アルゴンガスなどの不活性ガスを含んでいてもよい。 The carbon dioxide gas that is bubbled into the pickling solution is preferably pure carbon dioxide having a carbon dioxide concentration of 100% by volume, but may contain an inert gas such as nitrogen gas or argon gas.
酸洗液のバブリングは通常、酸洗液中に炭酸ガスを吹き込むことにより行われる。炭酸ガスの吹込量は、酸洗液中でバブリングし得る量であればよく、静止状態の酸洗液１Ｌあたり０．０５Ｌ／分〜２Ｌ／分（大気圧換算）の吹込量で吹き込むことにより酸洗液を十分に撹拌しながらバブリングすることが好ましい。 Bubbling of the pickling solution is usually performed by blowing carbon dioxide into the pickling solution. The amount of carbon dioxide blown may be an amount that can be bubbled in the pickling solution, and is blown at a rate of 0.05 L / min to 2 L / min (at atmospheric pressure) per liter of pickling solution in a stationary state. It is preferable that the pickling solution is bubbled with sufficient stirring.
酸洗液と金属材料の表面との接触は通常、酸洗液中に金属材料を浸漬することにより行われ、炭酸ガスは通常、浸漬された金属材料よりも下側から酸洗液中に吹き込まれる。金属材料は回分式で浸漬してもよいし、連続式で浸漬してもよい。また、炭酸ガスを酸洗液にバブリングしながら金属材料を浸漬してもよいし、酸洗液中に金属材料を浸漬したのちに炭酸ガスのバブリングを開始してもよい。 Contact between the pickling solution and the surface of the metal material is usually performed by immersing the metal material in the pickling solution, and carbon dioxide gas is usually blown into the pickling solution from below the immersed metal material. It is. The metal material may be immersed in a batch system or in a continuous system. Further, the metal material may be immersed while bubbling carbon dioxide in the pickling solution, or bubbling of carbon dioxide gas may be started after the metal material is immersed in the pickling solution.
酸洗温度は、通常５０℃以上沸騰温度以下、好ましくは１００℃以下である。 The pickling temperature is usually 50 ° C. or higher and the boiling temperature or lower, preferably 100 ° C. or lower.
金属材料を酸洗液中に浸漬することにより、金属材料の表面に酸洗液が接触し、表面の酸化物皮膜が溶出する。このとき、酸洗液は炭酸ガスでバブリングされているので、酸化物皮膜が速やかに溶出し、また、金属材料が腐食されることがない。 By immersing the metal material in the pickling solution, the pickling solution comes into contact with the surface of the metal material, and the oxide film on the surface is eluted. At this time, since the pickling solution is bubbled with carbon dioxide, the oxide film is eluted quickly and the metal material is not corroded.
酸洗後の金属材料は通常、酸洗液から金属材料を引き上げ、水洗し、乾燥される。 The metal material after pickling is usually pulled from the pickling solution, washed with water, and dried.
以下、実施例により本発明をより詳細に説明するが、本発明は、かかる実施例により限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by this Example.
なお、酸洗液の第二鉄イオン濃度は、以下の方法で定量した。
ホールピペットにより酸洗液１ｍＬを秤取し、（１＋２）硫酸〔９８％硫酸１容量部を純水２容量部で希釈した硫酸〕５ｍＬを加え、さらに２Ｎヨウ化カリウム水溶液〔ヨウ化カリウム濃度２モル／Ｌの水溶液〕５ｍＬを加えて５分間静置し、次いで純水１００ｍＬを加えた後、１／１００Ｎチオ硫酸カリウム水溶液〔チオ硫酸カリウム濃度０．０１モル／Ｌの水溶液〕で滴定することにより第二鉄イオン濃度を求めた。滴定は、チオ硫酸ナトリウム水溶液を滴下することにより、溶液のが淡黄色となった時点で、デンプン指示薬３ｍＬを加え、その後、更に滴下を続け、溶液の色が無色となった時点を終点とした。
In addition, the ferric ion concentration of the pickling solution was quantified by the following method.
Pick up 1 mL of pickling solution with a whole pipette, add 5 mL of (1 + 2) sulfuric acid [sulfuric acid obtained by diluting 1 part by volume of 98% sulfuric acid with 2 parts by volume of pure water], and then add 2N potassium iodide aqueous solution [potassium iodide concentration 2 5 mol / L aqueous solution], add 5 mL, let stand for 5 minutes, add 100 mL of pure water, and then titrate with 1 / 100N potassium thiosulfate aqueous solution (aqueous solution with a potassium thiosulfate concentration of 0.01 mol / L). Was used to determine the ferric ion concentration. The titration was performed by adding 3 mL of a starch indicator when the aqueous solution of sodium thiosulfate was added dropwise, and when the solution became pale yellow, and then dropping was continued until the color of the solution became colorless. .
実施例１
表面にミルスケールが形成された熱間圧延鋼板〔縦３０ｍｍ、横３０ｍｍ、厚さ３ｍｍの矩形状、表面積（Ｓ）は２１６０ｍｍ2＝２．１６ｃｍ2〕を試験片とし、その四辺をそれぞれ端から５ｍｍ幅で保護テープ〔日東電工(株)製「ニトフロンテープ」〕により保護した。
Example 1
A hot-rolled steel sheet (30 mm long, 30 mm wide, 3 mm thick, with a surface area (S) of 2160 mm 2 = 2.16 cm 2 ) having a mill scale formed on the surface is used as a test piece, and each of the four sides from each end. It was protected with a protective tape (“Nitoflon Tape” manufactured by Nitto Denko Corporation) with a width of 5 mm.
水に塩化水素〔ＨＣｌ〕１００ｇ、第一鉄イオン７０ｇ、第二鉄イオン１ｇおよび酸洗腐食抑制剤〔朝日化学工業(株)製「イビットＤＳ−２Ｋ」〕０．２ｇを含む酸洗液１Ｌを準備した。この酸洗液を酸洗槽に入れ、８５℃に加熱し、同温度を維持したまま酸洗槽の底部から純炭酸ガスを吹き込み量１００ｍＬ／分で８時間吹き込みバブリングさせた。試験片を浸漬する直前の酸洗液の第二鉄イオン濃度は１．４ｇ／Ｌであった。 1 L pickling solution containing 100 g of hydrogen chloride [HCl], 70 g of ferrous ions, 1 g of ferric ions, and 0.2 g of pickling corrosion inhibitor ["Ibit DS-2K" manufactured by Asahi Chemical Industry Co., Ltd.] Prepared. This pickling solution was put into a pickling bath and heated to 85 ° C., and pure carbon dioxide gas was blown from the bottom of the pickling bath at a rate of 100 mL / min for 8 hours while maintaining the same temperature. The ferric ion concentration of the pickling solution just before the test piece was immersed was 1.4 g / L.
その後、同温度、同吹き込み量で純炭酸ガスをバブリングさせながら、上記の試験片を酸洗液に浸漬したところ、ミルスケールの除去が進行した。試験片を酸洗液に浸漬してから、ミルスケールが完全に除去されたことが目視により確認されるまでに要した時間〔脱スケール時間〕は３３．０秒であった。 Thereafter, when the above test piece was immersed in the pickling solution while bubbling pure carbon dioxide gas at the same temperature and the same blowing amount, removal of the mill scale proceeded. The time [descaling time] required from when the test piece was immersed in the pickling solution until it was visually confirmed that the mill scale was completely removed was 33.0 seconds.
ミルスケールが完全に除去されたことを確認した後、直ちに試験片を酸洗液から引き上げ、冷水洗浄、温水洗浄、温風乾燥を行い、その後、試験片表面の白色度を分光光度計〔ミノルタ(株)製「ＣＭ−５０８ｃ」〕によりＬ値として測定したところ、６２であった。 After confirming that the mill scale has been completely removed, immediately pull up the test piece from the pickling solution, wash with cold water, wash with hot water, and dry with hot air, and then measure the whiteness of the test piece surface with a spectrophotometer [Minolta It was 62 when measured as L value by "CM-508c" manufactured by Co., Ltd.].
次いで、この試験片の質量〔Ｍ0(ｍｇ)〕を測定したのち、再び上記と同じ温度および吹込量で純炭酸ガスをバブリングした状態の上記酸洗液に浸漬時間〔ｔ〕５分で浸漬し、その後、冷水洗浄、温水洗浄、温風乾燥を行い、再び質量〔Ｍ(ｍｇ)〕を測定し、浸漬時間〔ｔ＝５分〕および試験片の表面積（Ｓ＝２．１６ｃｍ2）から式（１）
腐食速度＝（Ｍ0−Ｍ）／Ｓ／ｔ〔ｍｇ／ｃｍ2／分〕・・・（１）
により腐食速度を求めたところ、０．４２ｍｇ／ｃｍ2／分であった。
結果を第１表にまとめて示す。
Next, after measuring the mass [M 0 (mg)] of the test piece, it was immersed again in the pickling solution in a state where pure carbon dioxide gas was bubbled at the same temperature and blowing amount as described above for an immersion time [t] of 5 minutes. After that, washing with cold water, washing with warm water and drying with warm air were performed, and the mass [M (mg)] was measured again, and the immersion time [t = 5 minutes] and the surface area of the test piece (S = 2.16 cm 2 ) Formula (1)
Corrosion rate = (M 0 −M) / S / t [mg / cm 2 / min] (1)
The corrosion rate was determined by the above and found to be 0.42 mg / cm 2 / min.
The results are summarized in Table 1.
比較例１
純炭酸ガスに代えて空気を吹き込んだ以外は実施例１と同様に操作した。結果を第１表に示す。
Comparative Example 1
The same operation as in Example 1 was performed except that air was blown in place of pure carbon dioxide. The results are shown in Table 1.
比較例２
純炭酸ガスを吹き込まなかった以外は実施例１と同様に操作した。結果を第１表に示す。
Comparative Example 2
The same operation as in Example 1 was performed except that pure carbon dioxide gas was not blown. The results are shown in Table 1.
第 １ 表
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
ガス 吹込量 Fe3+ 脱スケール時間 白色度 腐食速度
(mL／分) (g/L) （秒） (mg/cm2/分)
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
実施例１ 純炭酸ガス 100 1.4 33.0 62 0.42
─────────────────────────────────────
比較例１ 空気 100 5.0 34.2 62 0.80
比較例２ − − 1.9 40.7 61 0.33
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
酸：塩化水素〔ＨＣｌ〕（１００ｇ／Ｌ）
酸洗腐食防止剤：イビットＤＳ−２Ｋ（０．２ｇ／Ｌ）
Table 1
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Gas blow rate Fe 3+ descaling time Whiteness Corrosion rate
(mL / min) (g / L) (sec) (mg / cm 2 / min)
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example 1 Pure carbon dioxide 100 1.4 33.0 62 0.42
─────────────────────────────────────
Comparative Example 1 Air 100 5.0 34.2 62 0.80
Comparative Example 2 − − 1.9 40.7 61 0.33
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Acid: Hydrogen chloride [HCl] (100 g / L)
Pickling corrosion inhibitor: Ibit DS-2K (0.2 g / L)
実施例２〜実施例６
酸洗腐食抑制剤〔イビットＤＳ−２Ｋ〕に代えて酸洗腐食抑制剤〔朝日化学工業(株)製「ニューハイパーＤＳ−２Ｋ」〕０．２ｇを用い、純炭酸ガスの吹込量を２０ｍＬ／分〔実施例２〕、５０ｍＬ／分〔実施例３〕、１００ｍＬ／分〔実施例４〕、３００ｍＬ／分〔実施例５〕、５００ｍＬ／分〔実施例６〕とした以外は実施例１と同様に操作した。結果を第２表に示す。
Example 2 to Example 6
In place of the pickling corrosion inhibitor [Ibit DS-2K], 0.2 g of pickling corrosion inhibitor ["New Hyper DS-2K" manufactured by Asahi Chemical Industry Co., Ltd.] was used, and the injection amount of pure carbon dioxide gas was 20 mL / Example 1 with the exception of min [Example 2], 50 mL / min [Example 3], 100 mL / min [Example 4], 300 mL / min [Example 5], 500 mL / min [Example 6]. The same operation was performed. The results are shown in Table 2.
比較例３
純炭酸ガスを吹き込まなかった以外は実施例２と同様に操作した。結果を第２表に示す。
Comparative Example 3
The same operation as in Example 2 was performed except that pure carbon dioxide gas was not blown. The results are shown in Table 2.
第 ２ 表
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
ガス 吹込量 Fe3+ 脱スケール時間 白色度 腐食速度
(mL／分) (g/L) （秒） (mg/cm2/分)
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
実施例２ 純炭酸ガス 20 1.7 27.2 61 0.32
実施例３ 純炭酸ガス 50 1.7 25.4 61 0.32
実施例４ 純炭酸ガス 100 1.7 23.5 61 0.33
実施例５ 純炭酸ガス 300 1.7 18.7 61 0.34
実施例６ 純炭酸ガス 500 1.7 16.2 61 0.35
─────────────────────────────────────
比較例３ − − 1.7 30.9 61 0.33
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
酸：塩化水素〔ＨＣｌ〕（１００ｇ／Ｌ）
酸洗腐食防止剤：ニューハイパーＤＳ−２Ｋ（０．２ｇ／Ｌ）
Table 2
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Gas blow rate Fe 3+ descaling time Whiteness Corrosion rate
(mL / min) (g / L) (sec) (mg / cm 2 / min)
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example 2 Pure carbon dioxide 20 1.7 27.2 61 0.32
Example 3 Pure carbon dioxide 50 1.7 25.4 61 0.32
Example 4 Pure carbon dioxide 100 1.7 23.5 61 0.33
Example 5 Pure carbon dioxide 300 1.7 18.7 61 0.34
Example 6 Pure carbon dioxide 500 1.7 16.2 61 0.35
─────────────────────────────────────
Comparative Example 3 − − 1.7 30.9 61 0.33
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Acid: Hydrogen chloride [HCl] (100 g / L)
Pickling corrosion inhibitor: New Hyper DS-2K (0.2 g / L)
実施例７
酸洗液として、水に硫酸〔Ｈ2ＳＯ4〕３００ｇ、第一鉄イオン６０ｇ、第二鉄イオン１ｇおよび酸洗腐食抑制剤〔朝日化学工業(株)製「イビットＮｏ．６００ＬＴ２」〕０．７ｇを含む酸洗液１Ｌを準備した。この酸洗液を９５℃に加熱し、同温度を維持したまま純炭酸ガスを吹込量１００ｍＬ／分で５分間吹き込みバブリングさせた。その後、実施例１と同様に操作した。結果を第３表に示す。
Example 7
As the pickling solution, 300 g of sulfuric acid [H 2 SO 4 ], 60 g of ferrous ions, 1 g of ferric ions and a pickling corrosion inhibitor [“Ibit No. 600LT2” manufactured by Asahi Chemical Industry Co., Ltd.] 1 L of pickling solution containing 7 g was prepared. The pickling solution was heated to 95 ° C., and pure carbon dioxide gas was bubbled for 5 minutes at a blowing rate of 100 mL / min while maintaining the same temperature. Thereafter, the same operation as in Example 1 was performed. The results are shown in Table 3.
比較例４
純炭酸ガスを吹き込まなかった以外は実施例７と同様に操作した。結果を第３表に示す。
Comparative Example 4
The same operation as in Example 7 was performed except that pure carbon dioxide gas was not blown. The results are shown in Table 3.
第 ３ 表
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
ガス 吹込量 Fe3+ 脱スケール時間 白色度 腐食速度
(mL／分) (g/L) （秒） (mg/cm2/分)
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
実施例７ 純炭酸ガス 100 1.7 78.0 57 0.28
─────────────────────────────────────
比較例４ − − 1.6 91.0 56 0.24
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
酸：硫酸〔Ｈ2ＳＯ4〕（３００ｇ／Ｌ）
酸洗腐食防止剤：イビットＮｏ．６００ＬＴ２（０．７ｇ／Ｌ）
Table 3
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Gas blow rate Fe 3+ descaling time Whiteness Corrosion rate
(mL / min) (g / L) (sec) (mg / cm 2 / min)
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Example 7 Pure carbon dioxide 100 1.7 78.0 57 0.28
─────────────────────────────────────
Comparative Example 4 − − 1.6 91.0 56 0.24
━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
Acid: Sulfuric acid [H 2 SO 4 ] (300 g / L)
Pickling corrosion inhibitor: Ibit No. 600LT2 (0.7g / L)
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| CN104451739A (en) * | 2014-11-25 | 2015-03-25 | 三达奥克化学股份有限公司 | Environment-friendly security cleaning agent for large-scale cast iron machine tool body before spaying and coating and preparation method |
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| CN104451739A (en) * | 2014-11-25 | 2015-03-25 | 三达奥克化学股份有限公司 | Environment-friendly security cleaning agent for large-scale cast iron machine tool body before spaying and coating and preparation method |
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