KR20050032201A - Process for acid pickling of stainless steel products - Google Patents

Process for acid pickling of stainless steel products Download PDF

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KR20050032201A
KR20050032201A KR1020030068220A KR20030068220A KR20050032201A KR 20050032201 A KR20050032201 A KR 20050032201A KR 1020030068220 A KR1020030068220 A KR 1020030068220A KR 20030068220 A KR20030068220 A KR 20030068220A KR 20050032201 A KR20050032201 A KR 20050032201A
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pickling
mixed
acid
tank
air
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KR1020030068220A
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Korean (ko)
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오복석
강승훈
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창원특수강주식회사
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    • 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
    • C23G1/081—Iron or steel solutions containing H2SO4
    • 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

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  • 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)

Abstract

To provide a method for pickling stainless steel capable of reducing consumption of hydrogen peroxide for oxidizing Fe^2+ into Fe^3+ in a pickling solution in which sulfuric acid and hydrofluoric acid are mixed. A method for pickling stainless steel comprises: a step of pickling stainless steel by putting stainless steel into a mixed acid tank containing a sulfuric acid-hydrofluoric acid mixed pickling solution comprising 50 to 120 g/L of sulfuric acid, 15 to 35 g/L of hydrofluoric acid and 5 g/L or more of Fe^3+; a step of transferring the mixed pickling solution into an aeration tank to which air is supplied when performing a pickling process in a mixed acid pickling tank; and a step of maintaining a Fe^3+ concentration in the mixed pickling solution of the mixed acid pickling tank to 5 g/L or more by circulating the Fe^3+ ions into the mixed acid pickling tank after oxidizing Fe^2+ ions in the mixed pickling solution into Fe^3+ ions by using air in the aeration tank.

Description

스테인레스강의 산세방법{PROCESS FOR ACID PICKLING OF STAINLESS STEEL PRODUCTS}PROCESS FOR ACID PICKLING OF STAINLESS STEEL PRODUCTS}

본 발명은 무질산 혼합산세액을 이용하는 스테인레스강의 산세방법에 관한 것으로, 보다 상세하게는 혼합산세액의 Fe3+ 이온 농도를 별도의 에어폭기조에서 공기에 의해 조절하여 순환함으로써 산화제인 과산화수소를 절감할 수 있는 산세방법에 관한 것이다.The present invention relates to a method for pickling stainless steel using a nitric acid-free pickling solution. More specifically, the concentration of Fe 3+ ions in the mixed pickling solution is controlled by air in a separate air aeration tank to reduce hydrogen peroxide as an oxidant. The pickling method that can be.

스테인레스강은 열간압연시 생성된 스케일이 소둔열처리과정에서 재산화되어 소재표면에 두껍고 치밀하게 형성된다. 스케일은 산세작업을 통해 제거한다. 스테인레스강의 산세처리에 대한 종래기술로는 대한민국 공개특허공보 1997-0043302호, 2000-0045517호가 있다. 대한민국 공개특허공보 1997-0043302호는 황-질산 혼산액에서 단독산세하는 기술이며, 대한민국 공개특허공보 2000-0045517호는 불산-질산의 혼산조에서 질산의 농도를 낮추어 산세하는 기술이다. 이들 기술은 기본적으로 혼합산세액으로 질산을 사용하므로, NOx의 독성 매연의 배출 및 폐액에서 질산염 이온의 고농도로 존재하므로 환경문제가 발생한다. In stainless steel, the scale produced during hot rolling is reoxidized during the annealing heat treatment to form thick and dense material on the surface of the material. The scale is removed by pickling. Conventional technologies for pickling treatment of stainless steel are Korean Patent Publication Nos. 1997-0043302 and 2000-0045517. Korean Unexamined Patent Publication No. 1997-0043302 is a technique for pickling alone in a sulfur-nitric acid mixed solution, and Korean Unexamined Patent Publication No. 2000-0045517 is a technique for lowering the concentration of nitric acid in a hydrofluoric acid-nitrate mixing tank. Since these technologies basically use nitric acid as a mixed pickling solution, environmental problems arise because there is a high concentration of nitrate ions in the waste gas and the emission of toxic fumes of NOx.

따라서, 무질산 혼합산세기술의 필요성이 대두되고 있다. 무질산 혼합산세액으로 불산-황산의 혼합산세액이 알려져 있다. 불산-황산의 혼합산세액에서 산화스케일을 제거할 때 산화력은 Fe3+ 이온 농도에 따라 결정되며 이때의 산세반응이 반응식 1에 나타나 있다.Therefore, there is a need for a mixed acid free pickling technique. A mixed pickling solution of hydrofluoric acid-sulfuric acid is known as a nitric acid free pickling solution. When the oxidative scale is removed from the mixed pickling solution of hydrofluoric acid-sulfuric acid, the oxidizing power is determined according to the Fe 3+ ion concentration, and the pickling reaction is shown in Scheme 1.

Fe3+ + Me0 = nFe2+ + Men+ Fe 3+ + Me 0 = nFe 2+ + Me n +

여기서, Me0= Fe, Cr, Ni Men+ = Fe2+, Ni2+, Cr 3+ Where Me 0 = Fe, Cr, Ni Me n + = Fe 2+ , Ni 2+ , Cr 3+

2Fe3+ + Fe = 3Fe 2+ 2Fe 3+ + Fe = 3Fe 2+

Fe2+ + H2SO₄= FeSO₄ + 2H+ Fe 2+ + H 2 SO ₄ = FeSO ₄ + 2H +

Ni2+ + H2SO₄ = NiSO₄ + 2H+ Ni 2+ + H 2 SO₄ = NiSO₄ + 2H +

Fe3+ + 3HF = FeF₃ + 3H+ Fe 3+ + 3HF = FeF₃ + 3H +

Cr3+ + 3HF = CrF₃ + 3H+ Cr 3+ + 3HF = CrF₃ + 3H +

상기 반응식에서 산세력을 결정하는 것은 Fe3+ 이온의 농도임을 알 수 있다.It can be seen that the pickling force in the reaction scheme is the concentration of Fe 3+ ions.

따라서, 혼합산세액에서 Fe3+ 이온농도를 높이거나 일정하게 유지하기 위해서는 산화제를 투입하여 산세 과정에서 생성하는 Fe2+ 이온을 지속적으로 산화시켜 Fe3+ 이온 농도를 조정하고 있다. 산화제로서는 과산화수소가 이용되고 있으며, 그 반응식은 다음과 같다.Therefore, in order to increase or maintain a constant Fe 3+ ion concentration in the mixed pickling solution, an oxidant is added to continuously oxidize Fe 2+ ions generated during the pickling process to adjust the Fe 3+ ion concentration. Hydrogen peroxide is used as an oxidizing agent, and the reaction formula is as follows.

Fe2+ + 1/2H2O2 + H+ ↔ Fe3+ + + 2H2OFe 2+ + 1 / 2H 2 O 2 + H + ↔ Fe 3+ + + 2H 2 O

이와 같이, 과산화수소를 투입하여 혼합산세액의 Fe2+ 이온을 산화시키는 방법은 산세액의 온도가 약 50℃ 내외에서 실시한다. 따라서, 산세작업조에 과산화수소수를 보충함에 따라 과산화수소의 분해열로 인하여 산세액의 온도상승이 일어나고 온도 상승에 따른 과산화수소수의 반응 효율이 감소하는 등 저효율의 연쇄 반응이 일어나는 구조로 과산화수소수의 사용량이 증가할 수 밖에 없다As described above, the method of oxidizing Fe 2+ ions in the mixed pickling solution by adding hydrogen peroxide is performed at about 50 ° C. Therefore, as hydrogen peroxide is added to the pickling tank, the temperature of the pickling solution increases due to the decomposition heat of hydrogen peroxide, and the reaction efficiency of the hydrogen peroxide solution decreases as the temperature rises. Have no choice but to

이에 따라 산액 냉각 장치를 산세작업조 내부나 외부에 설치하여 운용 하였으나 열교환기의 가격 및 내산성을 갖는 플라스틱류를 열교환기 재질로 선택할 수밖에 없는 특성으로 열교환 효율성이 낮아 고비용 저효율 구조를 갖고 이에 따른 추가적인 비용증가를 무시할수 없는 실정이었다.As a result, the acid-liquid cooling device was installed inside or outside the pickling tank and operated.However, the price of heat exchanger and plastics with acid resistance can be selected as the heat exchanger material. The increase could not be ignored.

본 발명은 황산-불산의 혼합산세액에서 Fe2+ 를 Fe3+ 산화시키는 과산화수소의 사용량을 절감할 수 있는 산세방법을 제공하는데 그 목적이 있다.An object of the present invention is to provide a pickling method that can reduce the amount of hydrogen peroxide used to oxidize Fe 2+ to Fe 3+ in a sulfuric acid-hydrofluoric acid pickling solution.

상기 목적을 달성하기 위한 본 발명의 산세방법은, 황산-불산의 혼합산세액이 수용된 혼합산세조에 스테인레스강을 인입하여 산세하는 단계,Pickling method of the present invention for achieving the above object, the step of pickling stainless steel in a mixed pickling bath containing a mixed pickling solution of sulfuric acid-hydrofluoric acid,

상기 혼합산세조의 산세과정에서 혼합산세액을 공기가 공급되는 에어폭기조로 이송하는 단계,Transferring the mixed pickling liquid to an air aeration tank to which air is supplied during the pickling process of the mixed pickling tank;

상기 에어폭기조에서 혼합산세액중의 Fe2+이온을 공기에 의해 Fe3+이온으로 산화한 후 상기 혼합산세조로 순환하여 혼합산세조의 혼합산세액중 Fe3+농도를 5g/ℓ이상으로 유지하는 단계를 포함하여 구성된다.Fe 2+ ions in the mixed pickling solution in the air aeration tank Oxidizing with Fe 3+ ions by air and circulating the mixed pickling tank to maintain the Fe 3+ concentration in the mixed pickling solution of the mixed pickling bath at 5 g / l or more.

이하, 본 발명을 상세히 설명한다. Hereinafter, the present invention will be described in detail.

본 발명에서는 혼합산세액에 공기를 공급하여 Fe2+ 이온을 Fe3+ 이온으로 산화시키는데, 이때의 반응식은 다음과 같다.In the present invention, air is supplied to the mixed pickling solution to oxidize Fe 2+ ions to Fe 3+ ions.

Fe2+ + 1/2O2 + 2H+ ↔ Fe3+ + H2OFe 2+ + 1 / 2O 2 + 2H + ↔ Fe 3+ + H 2 O

본 발명에서 공기에 의한 Fe2+ 이온의 산화는 혼산조에서 행하지 않고 별도의 에어폭기조에 행하는데 특징이 있다. 혼산조에 공기를 공급하여 Fe2+ 이온을 Fe3+ 이온으로 산화시키게 되면 발생되는 슬러지가 산세를 방해하는 문제가 있다. 또한, 산세반응에서는 산가스가 발생하며 이 산가스를 별도의 설비에서 중화하여 처리하게 되는데, 혼산조에 공기를 공급하게 되면 처리해야 할 산가스의 양이 증대되어 산가스 처리설비의 부하가 커지게 된다. 이러한 점을 고려하여 본 발명에서는 별도의 에어폭기조를 설치하고, 혼합산세액을 에어폭기조로 이송하여 Fe2+ 이온을 산화시키는 것이 바람직하다.In the present invention, the oxidation of Fe 2+ ions by air is characterized in that it is performed in a separate air aeration tank rather than in a mixed acid tank. When air is supplied to the mixed acid tank to oxidize Fe 2+ ions to Fe 3+ ions, there is a problem that sludge generated prevents pickling. In addition, the acid gas is generated in the pickling reaction, and the acid gas is neutralized and processed in a separate facility. You lose. In view of this point, in the present invention, it is preferable to install a separate air aeration tank, and to transfer the mixed pickling liquid to the air aeration tank to oxidize Fe 2+ ions.

도 1에는 혼산조와는 별도로 설치하는 에어폭기조의 일례가 제시되어 있으며, 이를 참고하여 본 발명의 산세방법을 설명한다. 1 shows an example of an air aeration tank installed separately from the mixed acid tank, and the pickling method of the present invention will be described with reference to this.

혼산조에는 황산, 불산, Fe3+이온으로 조성되는 혼합산세액이 수용되어 있다. 혼합산세액은 황산:50~120g/ℓ, 불산:15~35g/ℓ, Fe3+:5g/ℓ이상으로 조성되는 것을 사용할 수 있다. 상기 혼산조에 스테인레스강을 인입하여 산세를 행하는 과정에서 Fe3+이온의 농도가 관리범위인 5g/ℓ이하가 되면 혼합산세액을 에어폭기조로 이송한다. 에어폭기조에는 공기가 공급되어 지속적으로 Fe2+ 이온을 Fe3+이온으로 산화시키게 된다. 에어 폭기조는 도 1(b)에 나타난 바와 같이, 공기공급 파이프가 내부에 구비되어 있다.The mixed acid bath contains a mixed pickling solution composed of sulfuric acid, hydrofluoric acid, and Fe 3+ ions. The mixed pickling solution may be composed of sulfuric acid: 50-120 g / l, hydrofluoric acid: 15-35 g / l, Fe 3+ : 5 g / l or more. In the process of pickling stainless steel by introducing stainless steel into the mixed acid bath, when the concentration of Fe 3+ ions is 5 g / l or less, which is a management range, the mixed acid wash is transferred to the air aeration tank. Air is supplied to the air aeration tank to continuously oxidize Fe 2+ ions to Fe 3+ ions. As shown in FIG. 1 (b), the air aeration tank is provided with an air supply pipe therein.

에어폭기조에서 산화처리된 혼합산세액은 다시 혼산조로 순환한다. The mixed pickling liquid oxidized in the air aeration tank is circulated to the mixed acid tank again.

본 발명에 따라 혼합산세액을 산화처리하는 공정에서 과산화수소의 사용을 병행할 수 있다. 이 경우에는 과산화수소를 산화제로 사용하는 것에 비해 과산화수소의 사용량을 절감할 수 있는 것이다. 본 발명에 따라 혼합산세액에서 Fe2+ 이온의 산화제로서 공기와 함께 과산화수소를 사용하는 경우에는 혼산조의 혼합산세액에서 Fe3+이온이 Fe2+ 이온으로의 변화속도가 느려지며, 산세액의 온도 급상승이 방지되어 과산화수소의 반응효율이 향상된다.According to the present invention, the use of hydrogen peroxide in the step of oxidizing the mixed pickling liquor can be performed in parallel. In this case, the amount of hydrogen peroxide can be reduced compared to using hydrogen peroxide as the oxidizing agent. According to the present invention, when hydrogen peroxide is used together with air as an oxidant of Fe 2+ ions in the mixed pickling solution, the rate of change of Fe 3+ ions into Fe 2+ ions in the mixed pickling solution of the mixed acid bath is lowered. The sudden rise in temperature is prevented and the reaction efficiency of hydrogen peroxide is improved.

이하, 본 발명을 실시예를 통하여 보다 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.

[실시예 1]Example 1

에어폭기조에 혼합산세액을 공급하고 공기를 22.2m3/Hr 공급하여 시간에 따른 Fe3+의 생성량을 측정하고 그 결과를 도 2에 나타내었다.The mixed pickling liquid was supplied to the air aeration tank and air was supplied to 22.2m 3 / Hr to measure the amount of Fe 3+ produced over time, and the results are shown in FIG. 2.

도 2에서 알 수 있듯이, 에어폭기조의 혼합산세액에 공기를 공급하는 경우에 Fe3+의 생성량이 증가함을 알 수 있었다. 이와 같이, 혼합산세액의 Fe2+을 공기에 의해 Fe3+로 산화시킬 수 있음을 알 수 있었다. 도 2에서 공기의 공급시간과 Fe3+ 이온 농도 변화는 비례 관계에 있음을 알 수 있으며, 이를 회귀식으로 구하면 다음과 같다.As can be seen in Figure 2, when the air is supplied to the mixed pickling liquid in the air aeration tank it can be seen that the amount of Fe 3+ production increases. In this way, it was found that Fe 2+ in the mixed pickling solution could be oxidized to Fe 3+ by air. In FIG. 2, it can be seen that the supply time of air and the change in Fe 3+ ion concentration are proportional to each other.

[관계식 1] [Relationship 1]

Fe3+ 이온 농도 증가량 = 0.13t + CFe 3+ ion concentration increase = 0.13t + C

여기서, t는 공기공급시간, C는 최초의 Fe3+이온농도Where t is the air supply time and C is the initial Fe 3+ ion concentration

[실시예 2]Example 2

혼산조에 수용된 황산:50~120g/ℓ, 불산:15~35g/ℓ, Fe3+:5g/ℓ이상을 포함하고, 온도가 48~52℃의 혼산용액에서 STS304(Cr:18%, Ni:8%)강을 산세하는 공정에서, 혼합산세액을 에어폭기조로 이송하고 공기를 22.2m3/Hr을 공급하면서 Fe3+ 생성에 따른 과산화수소의 절감량을 구하고 그 결과를 표 1에 나타내었다.STS304 (Cr: 18%, Ni) containing 50 ~ 120g / l sulfuric acid, 15 ~ 35g / l hydrofluoric acid, Fe 3+ : 5g / l and mixed at 48 ~ 52 ℃ In the process of pickling steel, the mixed pickling liquid was transferred to an air aeration tank and air was supplied to 22.2m 3 / Hr to calculate the hydrogen peroxide reduction resulting from Fe 3+ formation.

구분division 과산화수소 반응효율Hydrogen Peroxide Reaction Efficiency 70%70% 80%80% 90%90% Fe+3 생성량Fe + 3 production amount 1 g/ℓ1 g / ℓ 0.87g0.87 g 0.77g0.77 g 0.68g0.68 g 2 g/ℓ2 g / ℓ 1.75g1.75 g 1.54g1.54 g 1.36g1.36 g 3 g/ℓ3 g / ℓ 2.62g2.62 g 2.31g2.31 g 2.04g2.04 g

표 1에 나타난 바와 같이, 과산화수소 반응효율이 70%의 경우에 Fe3+을 1g/ℓ을 생성하는데 과산화수소의 절감량은 0.87g이며, 과산화수소 반응효율이 90%의 경우에 Fe3+을 1g/ℓ을 생성하는데 과산화수소의 절감량은 0.67g인 것으로 확인되었다. 따라서, 과산화수소 반응효율이 낮을 수록 에어폭기를 병행한 경우에 과산화수소의 절감량은 커진다는 것을 알 수 있었다.As shown in Table 1, when hydrogen peroxide reaction efficiency is 70%, Fe 3+ is produced 1g / L, hydrogen peroxide reduction is 0.87g, and when hydrogen peroxide reaction efficiency is 90%, Fe 3+ is 1g / L. The amount of hydrogen peroxide saved was 0.67 g. Therefore, it was found that the lower the hydrogen peroxide reaction efficiency, the greater the amount of hydrogen peroxide saved when air aeration was combined.

상술한 바와 같이, 본 발명에 따르면 혼합산세액을 별도의 에어폭기조에서 공기에 의해 산화시키면 Fe3+ 농도 변화 속도가 느려지며 또한 산세액의 온도 급상승 방지에 따른 과산화수소 반응효율 향상으로 과산화수소수의 사용량을 줄일 수 있었고 또한 산세성에 영향이 큰 인자인 Fe3+ 이온 농도의 변화폭을 최소화 할 수 있어 일정한 생산성을 확보 할 수 있는 유용한 효과가 있다.As described above, according to the present invention, when the mixed pickling liquid is oxidized by air in a separate air aeration tank, the rate of change of Fe 3+ concentration is slowed, and the amount of hydrogen peroxide water used is improved by improving the hydrogen peroxide reaction efficiency by preventing the temperature rise of the pickling liquid. In addition, it is possible to minimize the change in Fe 3+ ion concentration, which is a factor affecting pickling, and thus has a useful effect of securing constant productivity.

도 1은 혼산조와 에어폭기조의 일례도이며, 1 is an example of a mixed acid tank and an air aeration tank.

도 2는 공기의 공급시간에 따른 Fe+3농도의 변화를 나타내는 그래프이다.2 is a graph showing a change in Fe +3 concentration with air supply time.

Claims (2)

황산-불산의 혼합산세액이 수용된 혼산조에 스테인레스강을 인입하여 산세하는 단계,Introducing and pickling stainless steel into a mixing tank containing a sulfuric acid-fluoric acid mixed acid solution; 상기 혼합산세조의 산세과정에서 혼합산세액을 공기가 공급되는 에어폭기조로 이송하는 단계,Transferring the mixed pickling liquid to an air aeration tank to which air is supplied during the pickling process of the mixed pickling tank; 상기 에어폭기조에서 혼합산세액중의 Fe2+이온을 공기에 의해 Fe3+이온으로 산화한 후 상기 혼합산세조로 순환하여 혼합산세조의 혼합산세액중 Fe3+농도를 5g/ℓ이상으로 유지하는 단계를 포함하여 이루어지는 스테인레스강의 산세방법.Fe 2+ ions in the mixed pickling solution in the air aeration tank And oxidizing Fe 3+ ions with air to circulate the mixed pickling tank to maintain the Fe 3+ concentration in the mixed pickling solution of the mixed pickling bath at 5 g / l or more. 제 1항에 있어서, 상기 황산-불산의 혼합산세액은 황산:50~120g/ℓ, 불산:15~35g/ℓ, Fe3+:5g/ℓ이상으로 조성되는 것을 특징으로 하는 스테인레스강의 산세방법.The method of claim 1, wherein the sulfuric acid-hydrofluoric acid mixed acid wash is composed of sulfuric acid: 50-120 g / l, hydrofluoric acid: 15-35 g / l, Fe 3+ : 5 g / l or more. .
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012091412A3 (en) * 2010-12-28 2012-10-04 주식회사 포스코 Eco-friendly high-speed pickling process for producing a low-chrome ferrite-based cold-rolled stainless steel sheet having superior surface quality
KR101853412B1 (en) * 2017-12-12 2018-04-30 임태균 System for treating steel pipes with an acid and method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012091412A3 (en) * 2010-12-28 2012-10-04 주식회사 포스코 Eco-friendly high-speed pickling process for producing a low-chrome ferrite-based cold-rolled stainless steel sheet having superior surface quality
KR101289147B1 (en) * 2010-12-28 2013-07-23 주식회사 포스코 Environmental-Friendly and High Speed Pickling Process for Ferritic Stainless Cold Strip with Good Surface Quality
KR101853412B1 (en) * 2017-12-12 2018-04-30 임태균 System for treating steel pipes with an acid and method thereof

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