WO2013006995A1 - 去除助溶剂中铁离子的方法 - Google Patents

去除助溶剂中铁离子的方法 Download PDF

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Publication number
WO2013006995A1
WO2013006995A1 PCT/CN2011/001509 CN2011001509W WO2013006995A1 WO 2013006995 A1 WO2013006995 A1 WO 2013006995A1 CN 2011001509 W CN2011001509 W CN 2011001509W WO 2013006995 A1 WO2013006995 A1 WO 2013006995A1
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WIPO (PCT)
Prior art keywords
iron
solvent
solubility promoter
iron ions
tank
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PCT/CN2011/001509
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English (en)
French (fr)
Inventor
欧建宗
Original Assignee
Ou Chien-Tsung
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Publication date
Priority claimed from CN201110192391.8A external-priority patent/CN102465330B/zh
Application filed by Ou Chien-Tsung filed Critical Ou Chien-Tsung
Priority to US14/232,049 priority Critical patent/US20140158544A1/en
Priority to GB1400362.8A priority patent/GB2510705A/en
Publication of WO2013006995A1 publication Critical patent/WO2013006995A1/zh

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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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/30—Fluxes or coverings on molten baths
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/16—Regeneration of process solutions
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel

Definitions

  • This method relates to a method for removing iron ions in a co-solvent, in particular, injecting a highly oxidizing gas without affecting the concentration of zinc chloride and ammonium chloride in the co-solvent and causing iron ions to form iron oxide and precipitate.
  • wetting with a co-solvent to wet the surface of the iron object is a common pre-treatment in the general galvanizing process, thereby facilitating the formation of a high-quality zinc-iron alloy layer with high corrosion resistance in subsequent galvanizing treatment. In turn, the iron objects are protected.
  • the surface of the iron object is partially dissolved in the co-solvent, and in the subsequent galvanizing treatment, the zinc liquid is caused to produce zinc dross, resulting in poor quality of the zinc-iron alloy layer of the iron object and reducing corrosion resistance. Therefore, in the prior art, it is often necessary to test the iron ion content of the co-solvent and filter it out, and the conventional practice of the conventional industry is to add hydrogen peroxide in the co-solvent to precipitate and react the iron ions, and then filter to remove the oxidation. Iron, to achieve the purpose of removing iron ions in the cosolvent.
  • the main object of the present invention is to provide a method for removing iron ions in a co-solvent, which is subjected to a wetting treatment on the surface of the iron object to facilitate the formation of a zinc-plated layer after subsequent galvanization, the method comprising: zinc chloride and chlorination Ammonium and adding solvent to prepare a cosolvent in the treatment tank; soaking the iron object in the treatment tank to dissolve the iron on the surface of the iron object in the cosolvent; adding the high oxidizing gas to the treatment tank a solvent to oxidize iron ions in the co-solvent to form insoluble iron oxide and precipitate; extract the co-solvent from the treatment tank and filter with a multi-layer filter - precipitating iron oxide; and refluxing the filtered co-solvent to the treatment tank, and repeating the soaking treatment of the above-mentioned iron object.
  • the method of the present invention can continuously remove the iron ions generated by the immersion of the iron object in the co-solvent, and maintain the concentration of zinc chloride and ammonium chloride in the co-solvent without supplementing the zinc chloride and
  • FIG. 0 is a schematic view showing the operation of the method for removing iron ions in a co-solvent according to the present invention
  • FIG. 2 is a schematic view showing the system for removing iron ions in a co-solvent according to the present invention.
  • Fig. 1 and Fig. 2 are respectively schematic diagrams showing the operation flow of the method for removing iron ions in a cosolvent according to the present invention.
  • the method of the present invention first begins with step S10, and a first co-solvent F1 is prepared in the configuration 10 with zinc chloride and ammonium chloride and a solvent is added, and is sent to the treatment tank 20.
  • the above first solubilizer F1 can be prepared by using a stirring device to increase the dissolution rate of zinc chloride and ammonium chloride, wherein the stirring device can include a plurality of stirring rods or a plurality of stirring blades, and the stirring device can be made of plastic or ceramic material. Composition. The mixing ratio by weight of zinc chloride and ammonium chloride may be between 1: 1.05 and 1: 1.55.
  • the solvent can be deionized water or pure water.
  • configuration tank 10 as the processing tank 20
  • the above-described arrangement tank 10 and treatment tank 20 may be the same tank body.
  • step S20 the iron object 30 is immersed in the first auxiliary solvent F1 included in the treatment tank 20, so that part of the iron on the surface of the iron object 30 is dissolved in the first auxiliary solvent F1 to form iron ions, and further The wetting effect on the surface of the iron object 30 is achieved.
  • a high oxidizing gas GG is added to the first co-solvent F1. containing iron ions to cause an oxidation reaction between the iron ions in the first co-solvent F1 and the highly oxidizing gas G.
  • the insoluble iron oxide is precipitated, thereby forming a second cosolvent containing the iron oxide precipitate.
  • the high oxidizing gas G may include nitrogen dioxide, nitrogen trioxide, high purity oxygen or ozone, wherein the high purity oxygen may be The oxygen purity is higher than 50%, and the highly oxidizing gas G can be injected into the bottom of the treatment tank 20 in a bubble rising manner to react with the iron ions.
  • a mixing device such as a stirring bar may be utilized to enhance the oxidation reaction rate of iron ions.
  • step S40 a pumping motor (not shown) may be used to extract the second solubilizer F2 in the treatment tank 20, and the multi-layer screen 40 is utilized to filter out the oxidation in the second solubilizer F2.
  • step S50 the process proceeds to step S50, and the filtered third solubilizer F3 is returned to the treatment tank 20, and the process returns to step S20 to repeat the above-described iron object soaking treatment.
  • the above described invention is characterized by that.
  • the concentration of zinc chloride and ammonium chloride in the co-solvent can be maintained without the need to supplement zinc chloride and ammonium chloride to ensure the wetting of the surface of the iron object, which is suitable for use in the subsequent galvanizing process, helping The zinc-iron reacts to form a corrosion-resistant zinc-bismuth alloy layer to achieve the purpose of protecting the iron object. . '

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Coating With Molten Metal (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

一种去除助溶剂中铁离子的方法，用以润湿铁材对象的表面。所述方法包括：以溶剂、氯化锌及氯化铵在配置槽中配置助溶剂并送至处理槽；浸泡铁材对象于助溶剂中以溶出表面的部分铁并产生润湿作用；加入高氧化性气体以氧化助溶剂中的铁离子，形成氧化铁沉淀；抽取出助溶剂并利用多层滤网过滤出已沉淀的氧化铁；以及将过滤后的助溶剂回流至处理槽中，并重复上述的铁材对象浸泡处理过程，以持续去除铁材对象浸泡处理中所产生的铁离子。

Description

去除助溶剂中铁离子的方法 技术领域
本^:明涉及一种去除助溶剂中铁离子的方法， 尤其是注入高氧化性 气体而不影响助溶剂中氯化锌及氯化铵的浓度并使铁离子形成氧化铁而 沉淀。、 背景技术
利用助溶剂进行润湿处理以润湿铁材对象的表面， 是一般镀锌过程 中常用的前处理， 藉以方便在后续的镀锌处理、中形成具高度耐蚀性的高 质量锌铁合金层， 进而保护铁材物件。
' 在润湿处理中， 铁材对象的表面会部分溶于助溶剂， 而在后续的镀 锌处理中使锌液产生锌渣， 导致铁材对象的锌铁合金层质量不良， 降低 防蚀性。 因此， 在现有技术中， 常须检验助溶剂的铁离子含量并加以过 滤清除， 而一般传统业者的实际作法是添加双氧水 ¾助溶剂中， 使铁离 子反应而沉淀， 再进行过滤以去除氧化铁， 而达到去除助溶剂中铁离子 的目的。
然而， 上述的铁离子去除效率只有 40%至 60%之间， 且助溶剂中的 氯化锌及氯化铰浓度会因加入水溶液的双氧水而大幅度降低， 所以必须 添加大量的氯化锌及氯化铵以维持铁材对象的润湿作用'， 因而增加处理 成本。 因此， 需要一种不影响氯化辞及氯化铵浓度以去除助溶剂中铁离 子的方法， 藉以解决土述现有技术的问题。 发明内容
本发明的主要目的在于提供一种去除助溶剂中铁离子的方法， 对铁 材对象的表面进行润湿处理以方便后续镀锌处理吋锌层的形成， 该方法 包括： 以氯化锌及氯化铵并添加溶剂而在处理槽中配制助溶剂； 将铁材 对象浸泡于处理槽 Ψ的助溶剂以使铁材对象表面的铁溶于助溶剂中； 加 入高氧化性气体于处理槽中的助溶剂， 以使助溶剂中的铁离子氧化而形 成不溶性的氧化铁并沉淀； 抽出处理槽中的助溶剂并利用多层滤网过滤 - 出己沉淀的氧化铁； 以及将过滤后的助溶剂回流至处理槽中， 并重复上 述铁材对象的浸泡处理。
由于本发明的方法可持续去除助溶剂中因铁材对象浸泡所产生的铁 离子， 并且可维持助溶剂中氯化锌及氯化铵的浓度而不需补充氯化锌及
5 氯化铵， 因而能确保对铁材对象表面所产生的润湿作用， 非常适合用于 后续的镀锌过程， 可帮助锌铁反应进行而形成具耐蚀性的锌铁合金层， 进而保护铁材物件。 附图说明
0 图 1为本发明去除助溶剂中铁离子的方法的操作流程示意图； 以及 图 2为本发明去除助溶剂中铁离子的方法的***示意图。 具体实施方式
以下配合说明书附图对本发明的实施方式做更详细的说明， 以使本5. 领^技术人员在研读本说明书后能据以实施。
参考图 1及图 2，图 1和图 2分别为本发明去除助溶剂中铁_离子的方 法的操作流程示意图 ¾***示意图。。如图 1及图 2所示， 本发明的方法 ' 首先由步骤 S10开始， 以氯化锌及氯化铵并添加溶剂而在配置 10中配 制第一助溶剂 F1 , 并传送至处理槽 20。
0 上述第一助溶剂 F1的配制可利用搅拌装置以提高氯化锌及氯化铵的 溶解 ¾率， 其中搅拌装置可包括多个搅拌棒或多个搅拌叶片， 且搅拌装 置可由塑料或陶瓷材料构成。 氯化锌及氯化铵的混合重量比可为 1 : 1.05 至 1 : 1.55之间。 溶剂可为去离子水或纯水。
要注意的是， 本发明的另一实施例可使用配置槽 10当作处理槽 20，5 也即上述的配置槽 10及处理槽 20可为同一槽体。
接着进入步骤 S20,将铁材对象 30浸泡于处理槽 20所包含的第一助 溶剂 F1中， 以使铁材对象 30的表面的部分铁溶于第一助溶剂 F1中而形 成铁离子， 进而达到对铁材对象 30的表面的润湿作用。
在步骤 S30中，在含有铁离子的第一助溶剂 F1.中加入高氧化性气体0 G, 以使得第一助溶剂 F1中的铁离子与高氧化性气体 G产生氧化反应而 形 不溶性的氧化铁并沉淀， 进而形成包含氧化铁沉淀物的第二助溶剂 高氧化性气体 G可包括二氧化氮、 三氧化氮、 .高纯度氧气或臭氧， ., 其中高纯度氧气可为氧气纯度高于 50%， 且高氧化性气体 G可经由处理 槽 20的底部以气泡上升的方式注入而与铁离子反应。 此外， 可利用混合 装置 (图未示出)， 比如搅拌棒， 以加强铁离子的氧化反应速率。
- 然后在步骤 S40中， .可藉抽水马达 (图未示出）以抽取出处理槽 20中 的第二助溶剂 F2， 并利用多层滤网 40以过滤出第二助溶剂 F2中的氧化 铁沉、 物， 并产生不含氧化铁沉淀物或包含低氧化铁含量的第三助溶剂 F3 o
最后进入步骤 S50, 将过滤后的第三助溶剂 F3回流至处理槽 20中， 并回到步骤 S20以重复上述的铁材对象浸泡处理。
上述本发明的特点在于，。可维持助溶剂中氯化锌及氯化铵的浓度而 不需补充氯化锌及氯化铵 能确保对铁材对象表面的润湿作用， 很适合 应用于后续的镀锌过程中， 帮助进行锌铁反应以形成具耐蚀—性的锌铢合 金层， 而达到保护铁材对象的目的。 . '
以上所述者仅为用以解释本发明的较佳实施例， 并非企图据以对本 发明做任何形式上的限制， 因此， 凡有在相同的发明精神下所作有关本 -发明的任何修饰或变更， 皆仍应包括在本发明意图保护的范畴。

Claims

权利要求
1.一种去除助溶剂中铁离子的方祛， 其特征在于， 包括以下步骤： 以氯化锌及氯化铵并添加 剂而在一配制槽中配制一第一助溶剂， 并传送至一处理槽；
将铁材对象浸泡于该第一助溶剂中， 使得该铁材对象的表面的部分 铢溶于该第一助溶剂 而形成铁离子， 以润湿该铁材对象的表面；
加入高氧化性气体于该处理槽的第一助瘠剂中， 以使得该第一助溶 剂中的铁离子氧化而形成不溶性的氧化铁并沉淀， 进而形成包含氧化铁 的一第二助溶剂；
抽取出该第二助溶剂， 并利用多层滤网以过滤出该第二助溶剂中已 沉淀的氧化铁， 并产生不含氧化铁或包含低氧化铁含量的一第三助溶剂; 以及
将该第三助溶剂回流至该处理槽中， 并重复另一铁材对象的上述浸 泡处理， '藉以持续去除因铁材对象浸袍所产生的铁离子。
2:如权利要求 1所述的方法，其特征在于， 该助溶剂中的氯化锌及氯 化铵的混合重量比为 1 : 1.05至 1 : 1.55之间， 且该溶剂为去离子水或纯 水。
,
3.如权利要求 1所述的方法，其特征在于，该配制槽当作该处理槽使 用。
4.如权^要求 1所述的方法，其特征在于， 该高氧化性气体包括二氧 化氮、 三氧化氮、 高纯度氧气及臭氧的其中之一， 且该高纯度氧气为氧 气纯度高于 50%的气体。
PCT/CN2011/001509 2010-11-18 2011-09-06 去除助溶剂中铁离子的方法 WO2013006995A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US14/232,049 US20140158544A1 (en) 2010-11-18 2011-09-06 Method for removing iron ions from galvanizing flux solution
GB1400362.8A GB2510705A (en) 2011-07-11 2011-09-06 Method for removing iron ions in solubility promoter

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201110192391.8A CN102465330B (zh) 2010-11-18 2011-07-11 去除助溶剂中铁离子的方法
CN201110192391.8 2011-07-11

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1974834A (zh) * 2006-12-01 2007-06-06 华南理工大学 用于热镀锌生产线的助镀液综合处理方法及装置
CN101100762A (zh) * 2007-07-19 2008-01-09 青岛大学 氯化物镀锌溶液再生处理剂及溶液再生处理方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1974834A (zh) * 2006-12-01 2007-06-06 华南理工大学 用于热镀锌生产线的助镀液综合处理方法及装置
CN101100762A (zh) * 2007-07-19 2008-01-09 青岛大学 氯化物镀锌溶液再生处理剂及溶液再生处理方法

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