CN1084801C - 酸洗钢片、尤其是不锈钢薄板带的方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 45
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- 239000010959 steel Substances 0.000 title claims abstract description 37
- 230000008569 process Effects 0.000 title claims abstract description 23
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- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001447 ferric ion Inorganic materials 0.000 claims abstract description 5
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 5
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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
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- 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
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- C23G1/086—Iron or steel solutions containing HF
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Abstract
本发明涉及一种酸洗钢片特别是不锈钢薄板带的方法,包括使用一种含盐酸及二价铁离子和三价铁离子的水溶液,为保持pH值低于1的盐酸水溶液的恒定的酸洗能力,将Fe3+离子的浓度维持在1克/升~300克/升之间,所采用的手段是氧合在酸洗过程中生成的Fe2+离子的再氧化方法,氧化还原电位保持在0-800毫伏之间,所测量的电位是放置于溶液中的铂电极和参比电极Ag/AgCl电极之间的电位。
Description
本发明涉及一种酸洗钢片的方法,更具体地,涉及到酸洗不锈钢薄板带的方法。
日本专利昭56-171638公开了一种去除钢丝氧化皮的方法,其中,钢丝在盐酸液中酸洗20-40分钟,酸洗液中含10-20%重量浓度的盐酸。为促进酸洗过程,对酸洗液的浓度进行了调整。然而,可以理解的是过量浓溶液会产生酸雾,并需要增大设备规格,同时也提高成本。根据这份文献提出的现有技术,一定量的FeCl2与一定量的FeCl3一同加入,其中FeCl2的浓度可以多到产生饱和的程度,这样在酸洗过程中Fe3+/Fe2+的氧化还原电位被测量。通过用喷嘴加入FeCl3而调整电位。酸洗过程在于HCl溶解铁基体并释放出氢气。
在这份文献中还提到,基于盐酸的酸洗液通常导致钢铁针孔类型的腐蚀。
一种酸洗液是公知的,如日本专利平2-205692中公开的酸洗不锈钢液,其中经热轧或退火的产品在含Fe3+和Fe2+离子的硫酸溶液中酸洗,所述的溶液含有至少10克/升的铁,通过向溶液中通气进行酸洗,所用空气以每升溶液至少100毫升/分的速率鼓风。
在这种类型的酸液中,送入空气仅仅起到搅拌作用,因为公知的是在硫酸介质中,由于铁的氧化电位使得仅用空气的简单搅拌是不能够将Fe2+离子氧化成Fe3+离子。
另外,与专利EP0236354相关的实用新型证书No.FR2551465中公开了一种连续酸洗不锈钢带的方法,其中应用一种含铁离子的主要成分为氢氟酸的酸洗液,酸洗钢板的过程为:通过喷入空气或加入另一种氧化剂来氧化酸洗液以保持三价铁的含量至少为15克/升,同时保持所述酸液的氧化还原(REDOX)电位在0至800mV范围内。
这些文献都认为空气起到将Fe2+离子氧化成Fe3+离子的氧化作用,发生酸洗反应但不释放出氢气。
在酸洗不锈钢技术领域有大量文献记载酸洗方法,为了避免常规用的硝酸,这些酸洗液由两种或三种前述酸的混合液组成,因为硝酸具有产生这类酸的NOx型污染衍生物的缺陷。
在连续生产线上制造钢、尤其是不锈钢的轧制薄板带的生产中,薄板带连续地经过以下步骤:
机械处理,如在拉伸状态下矫平或喷丸处理;
初级酸洗,
形变加工,如轧制、退火处理;
二次酸洗;
最终加工,如“表皮光轧”型的冷轧。
在钢酸洗处理过程中采取了大幅度的减速操作以避免在生产线的各种装置之间出现钢带的堆积和聚集。这种生产线具有减少半成品的处理和减少存放量的优点。
在这种生产线上存在酸洗,尤其是在必须短时间内酸洗的问题,为的是避免在连续带钢生产线中设置的各种装置之间产生被处理带钢的堆积和集聚的现象。
考虑到酸洗的最主要的准则,设计出了许多关于酸洗方法的技术方案,其中的酸洗准则是酸洗速率和钢带必须与酸洗溶液接触的最短时间。
本发明的目的是提出一种酸洗方法,该方法可以在极短的时间周期内有效地酸洗钢片尤其是不锈钢带,酸洗时间可与制造薄片材或薄板带材的生产线上规定的时间周期相适应。
本发明还提供了一种酸洗钢片特别是不锈钢薄板带的方法。它包括使用一种含盐酸及二价铁离子和三价铁离子的水溶液,为保持pH值低于1的盐酸水溶液的恒定的酸洗能力,将Fe3+离子的浓度维持在1克/升~300克/升之间,所采用的手段是氧合在酸洗过程中生成的Fe2+离子的再氧化方法,氧化还原电位保持在0-800毫伏之间,所测量的电位是放置于溶液中的铂电极和参比电极Ag/AgCl电极之间的电位。
本发明的其它特征是:
通过氧合作用使Fe2+离子再氧化的过程是通过对酸洗溶液通气来进行的。
完成对酸洗液通气的过程可采用以下方式:在露天中泵入和排出溶液、鼓泡、搅拌、喷射含氧气成份的气体,在含空气的腔体内喷淋酸洗液。
通过加入选自过氧化物和/或过酸盐,优选过氧化氢H2O2和/或高锰酸钾KMnO4这类物质于其中完成再氧化过程。
处理液中的盐酸浓度优选在35克/升和250克/升之间。
处理液的使用温度为10℃~95℃之间,优选为65℃~85℃。
待处理钢片在施用溶液前被加热。
对带钢施用溶液的时间不超过2分钟。
通过加入一种化合物和/或一种氧化气体使氧化还原电位调整在0-800毫伏之间,优选为400-600毫伏之间。
本发明还涉及将根据本发明的酸洗方法应用在加速酸洗钢片的领域中,尤其是应用在连续生产钢带的生产线的整套装置中酸洗不锈钢带的情况下。
本发明还涉及用于制备轧制钢带尤其是不锈钢带的连续生产线,其中钢带连续进行下述步骤:
机械处理,如在拉伸状态下的矫平和/或喷丸处理;
初级酸洗;
形变加工,如轧制、退火处理;
二次酸洗;
最终加工,如“表皮光轧”型的冷轧。
至少一个酸洗步骤采用含有盐酸和二价铁和三价铁离子的酸洗水溶液,为保持pH值低于1的盐酸水溶液的恒定的酸洗能力,将Fe3+离子的浓度维持在1克/升~300克/升之间,所采用的手段是氧合在酸洗过程中生成的Fe2+离子的再氧化方法,氧化还原电位保持在0-800毫伏之间,所测量的电位是放置于溶液中的铂电极和参比电极Ag/AgCl电极之间的电位。
下面的说明将对本发明进一步解释。
在各种已知的酸洗方法中,基于盐酸的酸洗液被认为会在酸洗钢片的表面产生腐蚀,这种腐蚀是针孔型的腐蚀。
非污染酸洗方法优选使用含有不同浓度的硫酸和氢氟酸的溶液,其以单独方式或结合方式使用。
为了达到对不锈钢带的快速酸洗,对各种酸洗液进行测试,这样经酸洗后的钢带可以连续的方式使用在成套设备中,该设备包括制造钢带的生产线,在所说生产线中处于对钢改性处理装置之间的酸洗设备,其中的改性处理如使用拉伸的矫平和冷轧工艺。
酸洗试验优选采用单酸进行以避免形成不溶性复合化合物,则溶液可用来再循环,如再用于酸洗。
在一比较实验中,酸洗液中含有硫酸、氢氟酸或盐酸,结果发现浓溶液中的盐酸对于酸洗速度具有惊人的效果。
下面进行比较:
硫酸酸洗水溶液A,当量浓度为FN,相当于酸浓度196克/升,含有总铁量60克/升。
氢氟酸酸洗水溶液B,当量浓度4N,相当于酸浓度80克/升,含有总铁量60克/升。
盐酸酸洗水溶液C,当量浓度为4N,相当于酸浓度146克/升,并含有总铁量60克/升。
就酸洗效果方面,对这些酸洗液进行测试,并结合考虑通过调整氧化还原电位得到的最佳效果,而氧化还原电位与使用的各种酸浓度相对应。在溶液中停滞的时间适宜于钢的成份和要去除的氧化物种类。
在对盐酸的水溶液进行酸洗试验时,氧化还原电位相对于参比电极Ag/AgCl保持为460毫伏,通过喷射空气和另外供入过氧化氢使得电位维持恒定。
下表中给出了各种牌号钢的酸洗速率,以每平方米上每秒钟材料损失量(单位克)为计算单位。
钢牌号 溶液A 溶液B 溶液C
(本发明)
AISI 304 0.41;0.37 0.42;0.37 0.59
0.28;0.27 0.31;0.27 0.63;0.56
AISI 316L 0.31 0.40 0.53
AISI 430 0.46;0.46 0.92;0.90 1.6;1.1
AISI 430 Ti 0.65;0.67 1.01;0.99 1.5;1.8
AISI 409 0.55;0.58 0.93;0.96 1.3;1.6
结果,在盐酸溶液中酸洗对于酸洗速率有显著地提高。此外,还发现对于确定的酸洗时间来说,氧化物的痕迹经过盐酸溶液酸洗后明显地降低。
另外,用盐酸溶液酸洗的钢带表面呈白色外观,无针孔;而用硫酸水溶液酸洗的钢带表面呈发黑色外观。
经过这种明显的比较之后,为确定各种参数以使酸洗溶液最优化而进行各种试验。
改变盐酸浓度
用当量浓度在3N和5N之间的盐酸水溶液C进行酸洗试验,此浓度相当于酸浓度在108克/升至180克/升之间,含总铁量为60克/升。
在这些酸洗试验中,将相对参比电极Ag/AgCl电极的氧化还原电位固定为460毫伏,通过注入空气和另外供给过氧化氢来维持电位恒定,溶液温度保持在80℃。
在这些条件下,酸洗速率随酸浓度的增加而提高,其数值可达到高于对比溶液A或B的二至三倍。
为了达到这样的酸洗效果,对根据本发明的溶液氧化还原电位应控制,这种控制是通过除了充入空气之外还尤其另外供给过氧化氢,这样可维持高的腐蚀程度和在轧制生产线上连续地用酸溶液对钢带进行处理。
改变总铁含量
用盐酸酸洗水溶液C进行酸洗试验,其酸当量浓度为4N,相当于酸浓度为146克/升,和含有30克/升至250克/升的总铁量。
对于铁浓度约为250克/升来说,铁量为酸溶液中溶解的极限量。
在用该盐酸溶液的酸洗试验中,将相对于参比电极Ag/AgCl电极的氧化还原电位固定在460毫伏,通过充入空气和另外供给过氧化氢来维持电位恒定,溶液温度维持在80℃。
在这些条件下,酸洗速率随着铁浓度的增加而提高,其数值达到高于用常规酸洗液A或B获得的数值的三倍。
改变温度
酸洗溶液温度可以从10℃~95℃之间,优选在65℃~85℃之间改变。酸洗速率随温度提高而增大。低于70℃,酸洗速率随温度提高适度地提高,当温度达到70℃~80℃时,酸洗速率提高约20%。虽然高于某一温度会产生稍许的挥发,但是可以设计成在整套装置采用封闭腔体环境,这样可使用高于85℃温度的溶液,再相接一个用于冷凝溶液的装置使其返回后再利用。
为了从温度效应中获益,可将钢片或钢带加热以弥补热惯性影响。
改变氧化还原电位(REDOX)
测量氧化还原电位是在工业生产设备中控制溶液酸洗质量的手段,目的是使酸洗速率最优化,并用恒定的酸洗能力来保持恒定的质量。
当氧化还原电位从400毫伏上升至600毫伏时,酸洗速率从30%提高到50%。
酸洗速率可通过向本发明的盐酸中加入一定量的另一种酸来调整,例如氢氟酸,其比低于40克/升。
Claims (10)
1、一种酸洗不锈钢带的方法,该方法包括使用一种含盐酸及二价铁离子和三价铁离子的水溶液,为保持pH值低于1的盐酸水溶液的恒定的酸洗能力,将Fe3+离子的浓度维持在1克/升~300克/升之间,所采用的手段是氧合在酸洗过程中生成的Fe2+离子的再氧化方法,氧化还原电位保持在400-600毫伏之间,所测量的电位是放置于溶液中的铂电极和参比电极Ag/AgCl电极之间的电位。
2、根据权利要求1的方法,其中用氧合反应再将Fe2+离子氧化的步骤是向酸洗溶液中通入空气来进行的。
3、根据权利要求1或2的方法,其中完成对酸洗液通气的过程可选用下列手段:在露天中泵入或排出溶液、鼓泡、搅拌、喷射含氧气成份的气体,以及在含空气的腔体内喷淋酸洗液。
4、根据权利要求1的方法,其中再氧化步骤是通过加入选自过氧化物和/或过酸盐、优选的是过氧化氢H2O2和高锰酸钾KMnO4这类化合物于其中来完成的。
5、根据权利要求1的方法,其中溶液为含盐酸浓度在35克/升至250克/升范围之间。
6、根据权利要求1的方法,其中的处理溶液的使用温度在10℃~95℃之间,优选在65℃-85℃之间。
7、根据权利要求1的方法,其中的待处理钢片在使用酸洗液之前被加热。
8、根据权利要求1的方法,其中的对钢带施用溶液的时间低于2分钟。
9、将权利要求1至8的任一项的酸洗方法应用到加速酸洗钢片的领域中,特别是应用在连续制造带材生产线的成套设备中酸洗不锈钢带。
10、一种制造轧制钢带,特别是轧制不锈钢带材的连续生产线,使用根据权利要求1至9的任一项酸洗方法,其中钢带依次进行下面步骤:
机械处理,如在拉伸状态下的矫平和/或喷丸处理;
初级酸洗;
形变加工,如轧制、退火处理;
二次酸洗;
最终加工,如“表皮光轧”型的冷轧,
其中至少一个酸洗步骤采用含有盐酸和二价铁及三价铁离子的水溶液,为维持pH值低于1的盐酸水溶液的恒定的酸洗能力,将Fe3+离子浓度保持在1克/升~300克/升之间,所采用的手段是氧合在酸洗过程中生成的Fe2+离子的再氧化方法,氧化还原电位保持在400-600毫伏之间,所测量的电位是放置于溶液中的铂电极和参比电极Ag/AgCl之间的电位。
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FR9602405 | 1996-02-27 | ||
FR9602405A FR2745301B1 (fr) | 1996-02-27 | 1996-02-27 | Procede de decapage d'une piece en acier et notamment d'une bande de tole en acier inoxydable |
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EP (1) | EP0792949B1 (zh) |
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CN (1) | CN1084801C (zh) |
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CA (1) | CA2198631C (zh) |
DE (1) | DE69704732T2 (zh) |
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FR (1) | FR2745301B1 (zh) |
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EP0792949B1 (fr) | 2001-05-09 |
KR970062075A (ko) | 1997-09-12 |
KR100448972B1 (ko) | 2004-12-08 |
CA2198631C (fr) | 2004-08-31 |
CN1168823A (zh) | 1997-12-31 |
TW517099B (en) | 2003-01-11 |
JP4186131B2 (ja) | 2008-11-26 |
AU1488497A (en) | 1997-09-11 |
DE69704732T2 (de) | 2001-09-13 |
AU711782B2 (en) | 1999-10-21 |
ZA971647B (en) | 1998-08-26 |
FR2745301A1 (fr) | 1997-08-29 |
ES2156344T3 (es) | 2001-06-16 |
FR2745301B1 (fr) | 1998-04-03 |
US5992196A (en) | 1999-11-30 |
JPH101791A (ja) | 1998-01-06 |
US5851304A (en) | 1998-12-22 |
MX9701425A (es) | 1998-03-31 |
DE69704732D1 (de) | 2001-06-13 |
ATE201057T1 (de) | 2001-05-15 |
CA2198631A1 (fr) | 1997-08-27 |
BR9701076A (pt) | 1998-09-01 |
EP0792949A1 (fr) | 1997-09-03 |
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