CN102203324B - 用含三价铁离子的酸性酸洗溶液酸洗硅钢的方法 - Google Patents
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Abstract
为了以连续的方式酸洗电工钢而设计的酸洗方法,包括将带材浸入至少一个酸洗槽中。该酸洗槽包含HCl、Fe2+、Fe3+和低浓度HF的混合物。在离开最后的酸洗槽时,可对带材进行刷洗或洗涤以疏松任何残余的氧化皮从而形成干净的带材。
Description
相关申请的交叉引用
本申请特此要求2008年11月14日提交的相同标题的序列号为61/114,660的临时申请的权益,通过引用将其公开以其全文并入本文。
背景
含硅的电工钢为低碳(约0.1%或更低)的特种钢,其通常含有约0.5%至约3.5%的硅。这些钢包括晶粒取向和非取向的钢。含硅的电工钢的热加工可导致在钢带材表面上形成氧化物。这些氧化物主要包含铁、硅和其它相关金属,在冷轧和其它随后的加工之前必须将这些氧化物脱除。传统地,通过最初的机械处理如喷砂,然后进行化学处理如采用硝酸或者硝酸与盐酸和氢氟酸组合进行酸洗,从而脱除这些氧化物。
由于使用氢氟酸的成本,期望有一种减少所使用的酸量的酸洗硅钢的方法。
简单概述
酸洗钢的方法,包含采用HCl、Fe2+、Fe3+和低浓度HF的混合物处理钢。
附图的简要描述
图1是酸洗硅钢的三槽式装置的示意图,其中在前两个槽中连续产生三价铁离子。
图2是酸洗硅钢的三槽式装置的示意图,其中在全部三个槽中连续产生三价铁离子。
具体描述
在Si钢的酸洗中,铁(Fe)和Si的氧化物都必须被脱除。最初的机械处理如喷砂脱除了大部分表面氧化物。随后,来自酸洗溶液的酸性化学物可溶解残留的固守(entrenched)氧化物。酸例如HCl、硝酸(HNO3)和/或硫酸(H2SO4)起到优选溶解富Fe氧化物的作用,然而,HF可起到溶解富Si氧化物的作用。在以前的方法中,为了使得酸洗反应在经济上有利的速率下,所需HF的浓度通常大于3%,优选大于5%。HF是非常昂贵的化学物。所描述的方法通过利用Fe3+额外的酸洗能力积极地侵蚀富Si氧化物周围的Fe因而从Si钢的基底金属中释放/提升该氧化物来降低所需HF的浓度,而无对生产速率的负面影响。
该方法使用三价铁(Fe3+)的氧化力侵蚀基底金属。三价铁来源的一个例子是加入酸洗槽中的FeCl3。只要恒定供应的Fe3+是可获得的,基底金属的侵蚀就将进行。通过化学氧化剂如过氧化氢或任何其它氧化剂的使用可将所得的二价铁(Fe2+)氧化回三价铁(Fe3+)。此外,向酸洗槽添加盐酸(HCl)以维持氯离子(Cl-)的供应以及合适的pH值。通过氢氟酸(HF)可促进氧化物的脱除,该氢氟酸对通过包含铁橄榄石(FeSiO3)、富硅氧化物(SiO2)或两者的氧化皮层的化学研磨是有用的。
氢氟酸也帮助溶解硅酸盐并且防止在酸洗液中沉淀硅酸。在硅钢的酸洗过程中,通过暴露于盐酸,在酸洗期间脱除的硅可形成硅酸。硅酸可形成胶状的块,其可损坏酸洗的钢和酸洗槽。低浓度HF的使用帮助防止硅酸的形成。
氧化物的性质和从基底金属脱除它们的处理取决于基底金属的合金组成。碳钢(无显著性份数的合金添加物)形成富Fe的氧化物并且是在基底金属表面外的。这些氧化物通过大多数酸例如HCl、HNO3或H2SO4甚至不使用机械预处理如喷砂就可容易地溶解。不锈钢是富铬(Cr)的并且当被加热时它们形成富Cr的氧化物。富Cr的氧化物对大多数酸的侵蚀是相对耐受/钝性的。这需要酸例如HNO3和HF的结合使用来完全脱除氧化物。HF的功能是使保护性富Cr氧化物去钝化然后允许氧化性酸例如HNO3来溶解贫Cr的基底金属。当遇到具有名义(nominal)Cr含量的基底金属时,基底金属上因酸所致的化学侵蚀是自限性的。
在热加工例如退火后的硅钢上的氧化物的物理性质取决于钢中Si的含量。较高的Si(>2%)钢倾向于形成基底金属较外部的氧化物。较低的Si(<2%)钢倾向于形成基底金属表面下的氧化物。采用喷砂和酸洗的结合来脱除外部的氧化物是相对容易的。表面下的氧化物更难脱除,这是因为其镶嵌的性质。
在以前的方法中,例如在US 6,599,371中,可在钢上喷洒H2O2。部分H2O2将Fe2+转化为Fe3+,其余分解而没有任何有用的作用。所得的Fe3+立即与基底金属反应而转化为Fe2+,因而在槽中没有大量的Fe3+。所描述的方法在槽中需要至少约2%的Fe3+。
铁氧化皮和金属铁被HCl溶解:
FeO(方铁矿)+2HCl→FeCl2+H2O
Fe2O3(磁铁矿)+8HCl→FeCl2+2FeCl3+4H2O
Fe2O3(赤铁矿)+6HCl→2FeCl3+3H2O
Fe0(金属铁)+2HCl→FeCl2+H2
三价铁(Fe3+)可提供酸洗速率的增长,这是因为其在热力学上更有效。三价铁的酸洗引起金属铁溶解并在溶液中产生二价铁而不形成氢气(H2)。
2FeCl3+Fe0→3FeCl2
该方法包含至少一个酸洗槽,并且可包含两个或三个酸洗槽。在该方法中可以有额外的槽用于冲洗或清洗钢或者用于其它的原因。可以对槽进行加热或冷却以维持所需的温度。在一个实施方案中,这些槽在约160°F至约180°F之间。这些槽可以都在不同的温度或者相同的温度下。
在一个实施方案中,这些槽包含HCl、Fe2+和Fe3+的混合物。三价铁的来源可以是FeCl3,或者一些其它的三价铁来源。铁可以以二价铁氧化态提供并且被氧化以产生三价铁。二价铁的来源可以是FeCl2,或者金属铁,包括硅钢本身。可以以不同的氧化态提供铁并将其氧化或还原以产生二价铁。在一个实施方案中,二价铁来源于已被酸洗过程还原的三价铁。在一个实施方案中,三价铁来源于酸洗过程产生的二价铁氧化。
在一个实施方案中,在任何槽中的三价铁的数量为约2%至约8%,或约4%。二价铁的数量可为至多约6%,或约4%。在每个槽中三价铁和二价铁的数量可以是不同或相同的。在一个实施方案中,槽中铁离子的总数量可不超过约10%。
在一个实施方案中,在任何槽中HCl的数量为约6%至约15%,或约10%。在每个槽中HCl的数量可以是不同或相同的。
在一个实施方案中,在任何槽中HF的数量可为至多3%,0.5至2%,1至2%,或约1.5%。在每个槽中HF的数量可以是不同或相同的。
在一个实施方案中,过氧化氢或其它氧化剂可用于将二价铁离子氧化成三价铁离子,其起到酸洗剂的作用。方程1显示了该氧化过程。
2FeCl2+2HCl+H2O2→2FeCl3+2H2O (方程1)
在一个实施方案中,用来将二价铁离子氧化成三价铁离子的氧化剂可以是过氧化物,例如过氧化氢;过氧化物酸,例如过硫酸;氯盐,例如NaClO2和NaClO3;或高锰酸盐。氧化剂可直接添加至任何槽中,或者可以在混合物再循环到一个或多个其它槽时将其添加。
通过经其鼓入空气或通过其它的搅拌方法可搅拌槽。搅拌方法是现有技术中所熟知的。
以百分比测量的材料的数量是重量/体积百分比。
虽然本公开通过描述多个实施方案已经得到说明,并且虽然说明性的实施方案已经得到相当详细地描述,但是申请人并不意图将所附的权利要求的范围限定或以任何方式限制于这些细节。其它的优点和改进对于那些本领域技术人员可以容易地理解。
实施例
实施例1-三价铁的酸洗
将硅钢(1.6%Si)切割成1”×2”尺寸的样品试样。该钢在切割成试样之前进行退火和喷砂。每一个试样都浸入每个烧杯18秒以模仿连续的酸洗线处理。在将这些试样浸入每个烧杯之间,将试样浸入中间烧杯3秒以模仿喷洒。每一个方案都重复三次并且计算和外推了每吨的平均重量损失。表1显示了用于金属试样的酸洗条件和相应的金属损失。
表1:金属试样的酸洗处理和相应的金属损失
实施例2
对热轧硅钢(1.8%Si和3.25%Si,在试验A中),(1.8%Si、3%Si和3.25%Si,在试验B中)和(3%Si,在试验C中)在连续的酸洗线上于三种场合下进行试验加工。在三个槽中酸洗该硅钢。每一个槽中装有表2中显示的试剂。
表2:酸洗槽装填体积
在最初的设置后,通过所需化学物的滴流和允许这些槽的溢出来维持槽浓度。在槽3中仅HCl的浓度是通过添加额外的HCl来控制的。槽3中的任何其它化合物均不被监控。维持每个槽的温度。表3显示了试验期间的平均条件。从化学使用数据和酸洗流体分析计算了因酸洗所致的平均金属损失。
表3:试验期间的平均槽条件
实施例3
在连续的退火和酸洗线上加工具有不同水平Si的热轧硅钢。在三个槽中酸洗硅钢。表4显示了在每个槽中用于每种Si钢的酸洗化学物质。通过所需化学物的滴流和允许酸洗流体从槽1到槽2到槽3级流(cascade)并随后使流体再循环至槽1中来维持槽的浓度。在再循环管中注入受控数量的过氧化氢以将二价铁转化为三价铁离子。表4显示了在加工期间用于槽1和槽2的平均条件。
表4:加工期间平均槽条件
Claims (13)
1.一种酸洗硅钢的方法,其包括采用包含HCl、HF、Fe3+和Fe2+的混合物处理硅钢;其中HF的浓度低于3%;并且其中Fe3+的浓度不低于2%。
2.根据权利要求1的方法,其中Fe3+的浓度为2%至8%。
3.根据权利要求1的方法,其中HCl的浓度为6%至15%。
4.根据权利要求1的方法,其中HF的浓度为1至2%。
5.根据权利要求1的方法,其中HF的浓度为约1.5%。
6.根据权利要求1的方法,其中Fe2+的浓度低于6%。
7.根据权利要求1的方法,其中不将过氧化氢喷洒到钢上。
8.根据权利要求1的方法,其中以连续的方式酸洗钢。
9.根据权利要求1的方法,其中混合物的温度不低于140°F。
10.根据权利要求1的方法,其中混合物的温度不低于150°F。
11.根据权利要求1的方法,其中硅钢包含少于2%的硅。
12.根据权利要求1的方法,其中硅钢包含约3%的硅。
13.用于含硅的电工钢的酸洗方法,其包括步骤:将待处理的材料放置于酸洗槽中,所述酸洗槽含有包含Fe3+、HF和HCl的混合物,并维持在165°F至180°F范围的温度下;其中搅拌该槽,向混合物连续或周期地供给氧化剂、HF和HCl。
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