JP2008100126A - Manufacturing method of ferrous chloride solution - Google Patents
Manufacturing method of ferrous chloride solution Download PDFInfo
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- JP2008100126A JP2008100126A JP2006282264A JP2006282264A JP2008100126A JP 2008100126 A JP2008100126 A JP 2008100126A JP 2006282264 A JP2006282264 A JP 2006282264A JP 2006282264 A JP2006282264 A JP 2006282264A JP 2008100126 A JP2008100126 A JP 2008100126A
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- ferrous chloride
- chloride solution
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- 229960002089 ferrous chloride Drugs 0.000 title claims abstract description 113
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 title claims abstract description 113
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 45
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 41
- 229910052738 indium Inorganic materials 0.000 claims abstract description 39
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000012535 impurity Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 125000001302 tertiary amino group Chemical group 0.000 claims abstract description 21
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 20
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 20
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 20
- 125000000524 functional group Chemical group 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000011069 regeneration method Methods 0.000 claims description 11
- 230000001172 regenerating effect Effects 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 14
- 238000005530 etching Methods 0.000 abstract description 12
- 239000002699 waste material Substances 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 85
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 239000011347 resin Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 229910052742 iron Inorganic materials 0.000 description 13
- 238000005406 washing Methods 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 230000008929 regeneration Effects 0.000 description 7
- 229910052718 tin Inorganic materials 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000013522 chelant Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 229920001429 chelating resin Polymers 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 150000004880 oxines Chemical group 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- -1 that is Chemical compound 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000006294 amino alkylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical class NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002472 indium compounds Chemical class 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000003544 oxime group Chemical group 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- Treatment Of Water By Ion Exchange (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
この発明は、粗塩化第一鉄液中に存在する重金属類を効果的に除去して塩化第一鉄液を製造する方法に関するものである。 The present invention relates to a method for producing a ferrous chloride solution by effectively removing heavy metals present in a crude ferrous chloride solution.
液晶モニターやプラズマモニター等に、透明電極としてＩＴＯ（インジウム・錫・酸化物）材やＩＺＯ（インジウム・亜鉛・酸化物）材が多く用いられている。この透明電極は、一般的にガラス材等の表面にＩＴＯまたはＩＺＯが薄膜として形成され、これを用いて電極回路を形成する。この回路形成のためフォトエッチング等が使用され、特にＩＴＯ材では、エッチング剤として塩化第二鉄と塩酸の混合液や王水等が多く用いられている。そしてエッチング剤は高速エッチングや微細回路パターン形成に必要な高エッチファクターを得るために塩化第二鉄と塩酸の混合液が使われる事が多い。
このエッチングにより、エッチング廃液には、ＩＴＯ材に由来するインジウムと錫が含まれるが、特にインジウムは資源量が少ないことから、過去多くの回収方法が提案されている。塩化鉄からのインジウム回収として特開２００４−７５４６３号公報（特許文献１）に、ニッケル共存下、鉄粉でインジウムと錫とを除去及び回収する方法が開示されている。しかし、本件は高価なニッケルを共存させる必要があること、および回収されたインジウム以外の成分、即ち鉄やニッケルの含有量が高く、インジウムを高濃度で回収することが難しかった。
An ITO (indium / tin / oxide) material or an IZO (indium / zinc / oxide) material is often used as a transparent electrode in a liquid crystal monitor or a plasma monitor. This transparent electrode is generally formed of ITO or IZO as a thin film on the surface of a glass material or the like, and an electrode circuit is formed using this. Photoetching or the like is used to form this circuit, and in particular for ITO materials, a mixed solution of ferric chloride and hydrochloric acid, aqua regia, and the like are often used as an etching agent. As the etchant, a mixture of ferric chloride and hydrochloric acid is often used to obtain a high etch factor necessary for high-speed etching and fine circuit pattern formation.
Due to this etching, the etching waste liquid contains indium and tin derived from the ITO material. In particular, since indium has a small amount of resources, many recovery methods have been proposed in the past. As a method for recovering indium from iron chloride, Japanese Patent Application Laid-Open No. 2004-75463 (Patent Document 1) discloses a method for removing and recovering indium and tin with iron powder in the presence of nickel. However, this case requires the coexistence of expensive nickel, and the content of components other than recovered indium, that is, iron and nickel, is high, and it is difficult to recover indium at a high concentration.
イオン交換樹脂やキレート樹脂により不純物を除去および回収する方法も多く提案されている。例えば、特開２００３−２６６０６５号公報（特許文献２）では、塩化第二鉄液中に含まれるコバルトおよび／または亜鉛を、除去および回収するために、該液に鉄板等を加え一旦塩化第一鉄に還元して、更に濃度調整を行って前記樹脂に吸着／脱着させることにより、塩化鉄液からの不純物除去（その後塩素等によって塩化第一鉄は塩化第二鉄に酸化して再生）および不純物液からの金属類の回収が開示されている。 Many methods for removing and recovering impurities using ion exchange resins or chelate resins have been proposed. For example, in Japanese Patent Application Laid-Open No. 2003-266065 (Patent Document 2), in order to remove and recover cobalt and / or zinc contained in a ferric chloride solution, an iron plate or the like is added to the solution once to obtain first chloride. Reduction to iron, further concentration adjustment and adsorption / desorption to the resin, removal of impurities from the iron chloride solution (then ferrous chloride is oxidized to ferric chloride and regenerated by chlorine etc.) and Recovery of metals from impurity liquids is disclosed.
特開昭６０−１９０８７号公報（特許文献３）では、塩化第一鉄や塩化第二鉄などの水溶液中からエチレンイミン重合体を母体とするアミノ基−ＮＨＲ−（Ｒ：水素原子または炭素数１０以下のアルキルアミノ基）を有するキレート樹脂または弱塩基性陰イオン交換樹脂を用いてクロム、ニッケル、亜鉛、鉛、銅、水銀などの重金属除去方法が開示されている。 In JP-A-60-19087 (Patent Document 3), an amino group -NHR- (R: hydrogen atom or carbon number) based on an ethyleneimine polymer from an aqueous solution such as ferrous chloride or ferric chloride. A method for removing heavy metals such as chromium, nickel, zinc, lead, copper, and mercury using a chelate resin or a weakly basic anion exchange resin having 10 or less alkylamino groups) is disclosed.
オキシム基、アミノアルキレンリン酸基、オキシン基、ジチオカルバミン酸基および前記官能基の金属塩から選ばれた少なくとも一種の官能基を有するキレート樹脂と、インジウムを含有する溶液を接触させて、インジウムを回収する方法が特開昭５８−１７２２５６（特許文献３）に開示されている。このインジウムを含有する溶液は、海水または亜鉛、鉛を精製する際の副産物の硫酸浸出液である。
２種以上のイオン価を有する金属のイオンが共存するインジウム等の希有金属含有水溶液をキレート樹脂と接触させて選択的に希有金属を吸着し回収する方法において、上記２種以上のイオン価を有する金属のイオンを最も低いイオン価として行なうことを特徴とする希有金属の回収方法が特開昭６２−１７６９１４（特許文献４）に開示されている。このキレート樹脂としては、分子中に＝ＮＯＨ、−Ｐ+（Ｒ）3、−ＰＯ（ＯＲ）2、−ＰＨ（ＯＲ）3、−ＳＲ、−Ｎ（Ｒ）2またはオキシン基（但し、上式中Ｒは水素、フェニル基、アルキル基またはアルケニル基を示し、２個以上の場合は同一または異なっていてもよい。）で表わされる官能基もしくはその無機塩から選ばれる少なくとも一種の基を有するものである。
Indium is recovered by bringing a chelate resin having at least one functional group selected from an oxime group, an aminoalkylene phosphate group, an oxine group, a dithiocarbamic acid group and a metal salt of the functional group into contact with a solution containing indium. This method is disclosed in Japanese Patent Laid-Open No. 58-172256 (Patent Document 3). This solution containing indium is a sulfuric acid leaching solution of by-products when purifying seawater, zinc, or lead.
In the method of selectively adsorbing and recovering a rare metal by bringing a rare metal-containing aqueous solution such as indium coexisting with ions of a metal having two or more kinds of ionic valence into contact with a chelate resin, the ionic valence having two or more kinds Japanese Patent Application Laid-Open No. 62-176914 (Patent Document 4) discloses a rare metal recovery method characterized by performing metal ions at the lowest ionic value. As this chelate resin, = NOH, -P + (R) 3 , -PO (OR) 2 , -PH (OR) 3 , -SR, -N (R) 2 or an oxine group (provided that In the formula, R represents hydrogen, a phenyl group, an alkyl group or an alkenyl group, and in the case of two or more, they may have the same or different functional group) or at least one group selected from inorganic salts thereof. Is.
ＩＴＯを有するＬＣＤ廃パネルを塩酸で処理して得たインジウム含有塩酸溶液を第４級アンモニウム基または第３級アミノ基を有する陰イオン交換樹脂に接触させてインジウムを吸着させ、この陰イオン交換樹脂からインジウムを回収することが報告されている（非特許文献１参照）。 An indium-containing hydrochloric acid solution obtained by treating a waste LCD panel with ITO with hydrochloric acid is brought into contact with an anion exchange resin having a quaternary ammonium group or a tertiary amino group to adsorb indium, and the anion exchange resin It has been reported that indium is recovered from (see Non-Patent Document 1).
本発明の課題は、重金属不純物を含有する粗塩化第一鉄液中の重金属を簡単な手段で低レベルまで除去して高純度の塩化第一鉄液を得る方法を提供するものである。また、簡単な手法で再生した陰イオン交換樹脂を用いて高純度の塩化第一鉄液を得る方法を提供することである。 An object of the present invention is to provide a method for obtaining a high-purity ferrous chloride solution by removing heavy metals in a crude ferrous chloride solution containing heavy metal impurities to a low level by simple means. Another object of the present invention is to provide a method for obtaining a high purity ferrous chloride solution using an anion exchange resin regenerated by a simple technique.
本発明者は、粗塩化第一鉄液（例えば、ＩＴＯ材等の塩化第二鉄によるエッチング廃液を鉄材等で処理して得たもの）から重金属を除去して再生する方法を鋭意検討した結果、官能基として第３級アミノ基または第４級アンモニウム基を有する陰イオン交換樹脂を用いることにより塩化第一鉄液を得ることができることを見出し本発明を完成させたのである。即ち、具体的には、
＜１＞官能基として第３級アミノ基または第４級アンモニウム基を有する陰イオン交換樹脂を用いて粗塩化第一鉄液中の重金属不純物を除去することを特徴とする塩化第一鉄液の製造方法であり、
＜２＞前記重金属不純物がインジウムである前記１に記載の塩化第一鉄液の製造方法であり、
＜３＞粗塩化第一鉄液のｐＨが２以下である前記１または２に記載の塩化第一鉄液の製造方法であり、
＜４＞粗塩化第一鉄液中の重金属不純物が吸着した官能基として第３級アミノ基または第４級アンモニウム基を有する陰イオン交換樹脂から水、希塩酸および／または希塩化第一鉄液を用いて重金属を除去する、官能基として第３級アミノ基または第４級アンモニウム基を有する陰イオン交換樹脂の再生方法であり、
＜５＞前記４記載の再生方法により再生した官能基として第３級アミノ基または第４級アンモニウム基を有する陰イオン交換樹脂を使用する前記１〜３のいずれか１つに記載の塩化第一鉄液の製造方法であり、
＜６＞前記１、２、３、または５のいずれか１つに記載の塩化第一鉄液の製造方法により得た塩化第一鉄を酸化して得た塩化第二鉄である。
As a result of earnest examination of a method for removing heavy metals from a crude ferrous chloride solution (for example, obtained by treating an etching waste solution of ferric chloride such as an ITO material with an iron material, etc.). The present inventors have found that a ferrous chloride solution can be obtained by using an anion exchange resin having a tertiary amino group or a quaternary ammonium group as a functional group. That is, specifically,
<1> A ferrous chloride solution characterized by removing heavy metal impurities in a crude ferrous chloride solution using an anion exchange resin having a tertiary amino group or a quaternary ammonium group as a functional group Manufacturing method,
<2> The method for producing a ferrous chloride liquid according to 1 above, wherein the heavy metal impurity is indium.
<3> The method for producing a ferrous chloride solution according to 1 or 2, wherein the pH of the crude ferrous chloride solution is 2 or less,
<4> Water, dilute hydrochloric acid and / or dilute ferrous chloride solution from an anion exchange resin having a tertiary amino group or a quaternary ammonium group as a functional group to which heavy metal impurities in the crude ferrous chloride solution are adsorbed. A method for regenerating an anion exchange resin having a tertiary amino group or a quaternary ammonium group as a functional group, wherein the heavy metal is removed using
<5> The first chloride as described in any one of 1 to 3 above, wherein an anion exchange resin having a tertiary amino group or a quaternary ammonium group is used as a functional group regenerated by the regeneration method described in 4 above. A method for producing an iron liquid,
<6> Ferric chloride obtained by oxidizing ferrous chloride obtained by the method for producing ferrous chloride liquid according to any one of 1, 2, 3, or 5.
本発明の塩化第一鉄液の製造方法により、粗塩化第一鉄液を複雑な希釈やｐＨ調整することなく重金属不純物を除去できることから、高純度の塩化第一鉄液を容易に得ることができる。このことから、この高純度の塩化第一鉄液からエッチング等に使用できる塩化第二鉄を簡単に得ることができる。 The method for producing ferrous chloride solution of the present invention can remove heavy metal impurities without complicated dilution or pH adjustment of the crude ferrous chloride solution, so that a high-purity ferrous chloride solution can be easily obtained. it can. Therefore, ferric chloride that can be used for etching or the like can be easily obtained from this high-purity ferrous chloride solution.
以下、本発明を詳細に説明する。なお、「％」は特に明記しない限り「重量％」を示し、「ｐｐｍ」は特に明記しない限り「重量ｐｐｍ」を示す。
塩化第二鉄系でのＩＴＯエッチング液は、一般に塩酸と混合されており、このものが市場で多く流通している。例えば、ＩＴＯエッチング液は、３５％塩酸と４０〜５０度ボーメの塩化第二鉄液とを３：１〜１：１０の重量比で混合したものであり、多用されているものは、３：２〜１：２の範囲のものである。
The present invention will be described in detail below. Note that “%” indicates “% by weight” unless otherwise specified, and “ppm” indicates “weight ppm” unless otherwise specified.
Ferric chloride ITO etching solution is generally mixed with hydrochloric acid, and this is widely distributed in the market. For example, an ITO etching solution is a mixture of 35% hydrochloric acid and 40-50 degree Baume ferric chloride solution in a weight ratio of 3: 1 to 1:10. The range of 2 to 1: 2.
本発明において粗塩化第一鉄液とは、インジウム、ニッケル、クロム、モリブデン、スズ、亜鉛、および／または銅等の重金属を含有する塩化第一鉄溶液あでる。粗塩化第一鉄液に含まれる重金属としては、インジウム、ニッケルおよび／またはスズ等であればより良く、インジウムおよび／またはニッケルであれば更に良い。本発明の塩化第一鉄液の製造方法において、粗塩化第一鉄液中に含まれる重金属がこれらであると効率よく除去でき好ましい。 In the present invention, the crude ferrous chloride solution refers to a ferrous chloride solution containing heavy metals such as indium, nickel, chromium, molybdenum, tin, zinc, and / or copper. The heavy metal contained in the crude ferrous chloride solution is better if it is indium, nickel, and / or tin, and more preferably if it is indium and / or nickel. In the manufacturing method of the ferrous chloride liquid of this invention, it is preferable that the heavy metals contained in the crude ferrous chloride liquid can be efficiently removed.
本発明において粗塩化第一鉄液として特に好ましいものは、ガラス材等の表面にあるＩＴＯ材等に対しＩＴＯエッチング液を用いてエッチングを施した後の廃液であり、この溶液中に含まれる塩化第二鉄を塩化第一鉄に変換したものでも良い。この塩化第二鉄から塩化第一鉄への変換は、電解又は、鉄材を加えて行ったものが好ましい。 Particularly preferred as the ferrous chloride liquid in the present invention is a waste liquid after etching with ITO etching liquid on the ITO material on the surface of the glass material or the like, and the chloride contained in this solution. What converted ferric iron into ferrous chloride may be used. The conversion from ferric chloride to ferrous chloride is preferably performed by electrolysis or by adding an iron material.
本発明において官能基として第３級アミノ基または第４級アンモニウム基を有する陰イオン交換樹脂としては、Ａｍｂｅｒｌｉｔｅ−ＩＲＡ９６ＳＢ（商品名、Rohm & Haas社製）、Ｄｏｗｅｘ−３（商品名、Dow Chemical社製）、Ａｍｂｅｒｌｉｔｅ−ＩＲＡ４００（商品名、Rohm & Haas社製）、Ａｍｂｅｒｌｉｔｅ−ＩＲＡ４１０（商品名、Rohm & Haas社製）、Ｄｏｗｅｘ−１（商品名、Dow Chemical社製）、Ｄｏｗｅｘ−２（商品名、Dow Chemical社製）などがある。
本発明の製造方法において用いる陰イオン交換樹脂としては、第３級アミノ基を有する陰イオン交換樹脂がより重金属を除去できおよび再生できるので好ましい。
Examples of the anion exchange resin having a tertiary amino group or a quaternary ammonium group as a functional group in the present invention include Amberlite-IRA96SB (trade name, manufactured by Rohm & Haas), Dowex-3 (trade name, Dow Chemical). Amberlite-IRA400 (trade name, manufactured by Rohm & Haas), Amberlite-IRA410 (trade name, manufactured by Rohm & Haas), Dowex-1 (trade name, manufactured by Dow Chemical), Dowex-2 (trade name) , Manufactured by Dow Chemical).
As the anion exchange resin used in the production method of the present invention, an anion exchange resin having a tertiary amino group is preferable because it can remove and regenerate heavy metals.
本発明における粗塩化第一鉄液は、塩化第一鉄の含有量として、１０〜４８％が好ましく、２５〜４８％がより好ましく、３０〜４２％が更に好ましく、３３〜３９％が最も好ましい。塩化第一鉄の含有量が１０％未満の粗塩化第一鉄液であっても本発明の製造方法を適用できるが、得られた塩化第一鉄液は、濃度を上げて製品にする必要があるため製造効率が悪いので好ましくない。 The content of ferrous chloride in the present invention is preferably 10 to 48%, more preferably 25 to 48%, still more preferably 30 to 42%, and most preferably 33 to 39% as the content of ferrous chloride. . Although the production method of the present invention can be applied even to a crude ferrous chloride solution having a ferrous chloride content of less than 10%, it is necessary to increase the concentration of the obtained ferrous chloride solution into a product. This is not preferable because the production efficiency is poor.
本発明における粗塩化第一鉄液は、塩化第二鉄の含有量が５％以下であり、３％以下が好ましく、２％以下がより好ましく、１％以下が更に好ましい。粗塩化第一鉄液に塩化第二鉄を含む場合は、塩化第二鉄の含有量が０．０１％以上が好ましく、０．０５％以上がより好ましい。当該粗塩化第一鉄液中の塩化第二鉄の含有量がこの濃度であると、重金属不純物の除去を効率よくできるので好ましい。なお、粗塩化第一鉄液中の塩化第二鉄含有量は、鉄を用いて還元して塩化第一鉄とすることができる。 The crude ferrous chloride solution in the present invention has a ferric chloride content of 5% or less, preferably 3% or less, more preferably 2% or less, and even more preferably 1% or less. When ferric chloride is contained in the crude ferrous chloride solution, the ferric chloride content is preferably 0.01% or more, and more preferably 0.05% or more. It is preferable that the content of ferric chloride in the crude ferrous chloride solution is at this concentration, because heavy metal impurities can be efficiently removed. The ferric chloride content in the crude ferrous chloride solution can be reduced to ferrous chloride by using iron.
本発明において用いる粗塩化第一鉄液は、ｐＨ測定器を用いて測定した場合、粗塩化第一鉄液のｐＨは、２以下が好ましく、１以下がより好ましく、０以下が更に好ましい。また、ｐＨが−１．５以上が好ましく、−１．３以上がより好ましく、−１以上が更に好ましい。本発明においてｐＨがこの範囲であると、粗塩化第一鉄液中から効率よく重金属不純物を除去することができるので好ましい。 When the crude ferrous chloride solution used in the present invention is measured using a pH meter, the pH of the crude ferrous chloride solution is preferably 2 or less, more preferably 1 or less, and even more preferably 0 or less. Moreover, -1.5 or more is preferable, -1.3 or more is more preferable, and -1 or more is still more preferable. In the present invention, it is preferable that the pH is within this range because heavy metal impurities can be efficiently removed from the crude ferrous chloride solution.
粗塩化第一鉄液中の塩酸濃度は、０〜５％がより好ましく、０．１〜２％が更に好ましく、０．２〜１％が特に好ましい。本発明において塩酸濃度がこの範囲であると、粗塩化第一鉄液中から効率よく重金属不純物を除去することができるので好ましい。
本発明の製造方法において、ｐＨが−２まで測定できるｐＨ測定器を用いて、粗塩化第一鉄液のｐＨを測定することが、製造の効率面から好ましい。
The hydrochloric acid concentration in the crude ferrous chloride solution is more preferably 0 to 5%, further preferably 0.1 to 2%, and particularly preferably 0.2 to 1%. In the present invention, the hydrochloric acid concentration within this range is preferable because heavy metal impurities can be efficiently removed from the crude ferrous chloride solution.
In the production method of the present invention, it is preferable from the viewpoint of production efficiency to measure the pH of the crude ferrous chloride solution using a pH measuring device capable of measuring pH to −2.
本発明の製造方法における粗塩化第一鉄液中のニッケル、クロム、モリブデン、亜鉛、錫および／または銅等は２００ｐｐｍ以下が好ましく、より好ましくは１００ｐｐｍ以下であり、１ｐｐｍ以上が好ましい。これらの不純物がこの濃度であると、本発明の製造方法により純度の高い塩化第一鉄水溶液を得ることができ好ましい。 In the production method of the present invention, nickel, chromium, molybdenum, zinc, tin, and / or copper in the crude ferrous chloride solution is preferably 200 ppm or less, more preferably 100 ppm or less, and preferably 1 ppm or more. It is preferable that these impurities have this concentration because a high-purity ferrous chloride aqueous solution can be obtained by the production method of the present invention.
本発明の製造方法における粗塩化第一鉄液中のインジウムの濃度は、溶解していれば如何様な濃度でも良いが、０．２％以下がより好ましく、更に好ましくは５０〜１５００ｐｐｍである。インジウムの濃度が上記範囲であると、本発明の製造方法により純度の高い塩化第一鉄水溶液と脱着液での高濃度インジウム液を得ることができ好ましい。 The concentration of indium in the crude ferrous chloride solution in the production method of the present invention may be any concentration as long as it is dissolved, but is preferably 0.2% or less, more preferably 50 to 1500 ppm. It is preferable that the concentration of indium is in the above range because a high-concentration ferrous chloride aqueous solution and a high-concentration indium solution in a desorption solution can be obtained by the production method of the present invention.
本発明において、該陰イオン交換樹脂の使用量は、粗塩化第一鉄液中の重金属の含有量により決定すればよい。例えば、該陰イオン交換樹脂からの溶出液中の重金属含有量をモニターして粗塩化第一鉄液の処理量を決めてもよい。 In the present invention, the amount of the anion exchange resin used may be determined by the content of heavy metal in the crude ferrous chloride solution. For example, the amount of crude ferrous chloride solution may be determined by monitoring the heavy metal content in the eluate from the anion exchange resin.
本発明の製造方法において、粗塩化第一鉄液と該陰イオン交換樹脂との処理時間は、例えば充填塔で吸着させる場合は空塔速度（以下ＳＶと表記）で、ＳＶ＝０．１〜２０［１／ｈ］、更に好ましくはＳＶ＝０．２〜１０［１／ｈ］、特に好ましくはＳＶ＝０．３〜５［１／ｈ］で接触させることにより効率良く重金属を吸着する事ができる。この範囲であると効率良く重金属を除去することができることから好ましい。 In the production method of the present invention, the treatment time of the crude ferrous chloride solution and the anion exchange resin is, for example, a superficial velocity (hereinafter referred to as SV) when adsorbed in a packed tower, and SV = 0.1 20 [1 / h], more preferably SV = 0.2 to 10 [1 / h], and particularly preferably SV = 0.3 to 5 [1 / h] to contact heavy metal efficiently. Can do. This range is preferable because heavy metals can be efficiently removed.
本発明の製造方法において、操作温度は０℃から８０℃程度であり、好ましくは５℃から６０℃であり、より好ましくは１０℃から５０℃である。該陰イオン交換樹脂との接触温度がこの範囲であると粗塩化第一鉄液中の重金属を効率よく除去することができるので好ましい。 In the production method of the present invention, the operating temperature is about 0 ° C to 80 ° C, preferably 5 ° C to 60 ° C, more preferably 10 ° C to 50 ° C. It is preferable that the contact temperature with the anion exchange resin be in this range because heavy metals in the crude ferrous chloride solution can be efficiently removed.
例えば、粗塩化第一鉄液をカラムにつめた該陰イオン交換樹脂と０℃から８０℃の間の温度で１時間接触させる流速で流して重金属イオンを除去して、高純度塩化第一鉄液を製造することができる。または、粗塩化第一鉄液と該陰イオン交換樹脂とをバッチで０℃から８０℃の間の温度で例えば２時間接触させて重金属イオンを除去して、高純度塩化第一鉄液を製造することができる。 For example, high-purity ferrous chloride is removed by flowing heavy iron ions at a flow rate at which the crude ferrous chloride solution is brought into contact with the anion exchange resin packed in a column at a temperature between 0 ° C. and 80 ° C. for 1 hour. A liquid can be produced. Alternatively, the crude ferrous chloride solution and the anion exchange resin are contacted in batches at a temperature between 0 ° C. and 80 ° C. for 2 hours, for example, to remove heavy metal ions to produce a high purity ferrous chloride solution. can do.
本発明の製造方法を用いて製造した高純度塩化第一鉄液は、用途により濃度を調整して使用することができる。
本発明の製造方法を用いて製造した高純度塩化第一鉄液は、塩素等を用いて酸化して高純度塩化第二鉄として使用することができる。
The high-purity ferrous chloride liquid produced using the production method of the present invention can be used after adjusting the concentration depending on the application.
The high-purity ferrous chloride liquid produced using the production method of the present invention can be used as high-purity ferric chloride by oxidation with chlorine or the like.
本発明の製造方法において、重金属および／またはインジウムの除去に使用した陰イオン交換樹脂は、再生して本発明の製造方法に用いる陰イオン交換樹脂として再利用することができる。
当該陰イオン交換樹脂の再生方法としては、公知の方法を用いることができる。例えば、当該陰イオン交換樹脂の再生方法としては、水洗によるもの、水洗した後に希塩化第一鉄液によるもの、水洗した後に希塩酸によるもの、水洗した後に希塩化第一鉄液と希塩酸との混合液によるもの、希塩化第一鉄液によるもの、希塩化第一鉄液と希塩酸との混合液によるもの、および希塩酸によるものなどを挙げることができる。本発明の製造方法においては、水洗によるもの、水洗した後に希塩化第一鉄液によるもの、水洗した後に希塩酸によるもの、または水洗した後に希塩化第一鉄液と希塩酸との混合液による陰イオン交換樹脂の再生方法が好ましい。なお、希塩化第一鉄液の濃度は、１０％未満の液であることが好ましく、５％以下がより好ましく、２％以下のものが更に好ましいものとして例示できる。また、希塩酸の濃度は、１０％以下の液であることが好ましく、５％以下がより好ましく、２％以下のものが更に好ましいものとして例示できる。
In the production method of the present invention, the anion exchange resin used for removing heavy metals and / or indium can be recycled and reused as the anion exchange resin used in the production method of the present invention.
A known method can be used as a method for regenerating the anion exchange resin. For example, as a method for regenerating the anion exchange resin, washing with water, washing with water and dilute ferrous chloride, washing with dilute hydrochloric acid, washing with dilute ferrous chloride and dilute hydrochloric acid after washing Examples thereof include a liquid, a diluted ferrous chloride liquid, a mixed liquid of diluted ferrous chloride and dilute hydrochloric acid, and a dilute hydrochloric acid. In the production method of the present invention, anion by washing with water, washing with water after dilute ferrous chloride, washing with water and dilute hydrochloric acid, or washing with water and a mixture of dilute ferrous chloride and dilute hydrochloric acid A method for regenerating the exchange resin is preferred. The concentration of dilute ferrous chloride solution is preferably less than 10%, more preferably 5% or less, and even more preferably 2% or less. The concentration of dilute hydrochloric acid is preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less.
本発明の製造方法において上記記載の水または水溶液の使用量は、当該陰イオン交換樹脂が再生できれば如何様な量でも良い。例えば当該陰イオン交換樹脂量に対して１．２〜１０倍量が挙げられる。
本発明の製造方法において当該陰イオン交換樹脂の再生は、０〜８０℃であり、１０〜６０℃が好ましい。
In the production method of the present invention, the amount of water or aqueous solution described above may be any amount as long as the anion exchange resin can be regenerated. For example, the amount is 1.2 to 10 times the amount of the anion exchange resin.
In the production method of the present invention, regeneration of the anion exchange resin is 0 to 80 ° C, preferably 10 to 60 ° C.
また、粗塩化第一鉄液中のインジウムを吸着させた陰イオン交換樹脂から、水および／または希塩化第一鉄水溶液および／または希塩酸を用いてインジウムを溶出させて、インジウム化合物を製造することができる。 In addition, an indium compound is produced by eluting indium from water and / or dilute ferrous chloride aqueous solution and / or dilute hydrochloric acid from an anion exchange resin adsorbing indium in the crude ferrous chloride solution. Can do.
また、本再生方法にて樹脂の再生を繰り返していると、インジウムより吸着性の高い鉄（III）やニッケル等の重金属類が樹脂内に留まり、吸着能力が低下する場合がある。この様な場合、例えば３〜２０％の塩酸等の酸性液にて重金属類を脱離させ、その後水洗等にて、同様に再生を行うことによりインジウム等の吸着力を再生する事ができる。即ち、本発明の製造方法において重金属および／またはインジウムの除去に使用した該陰イオン交換樹脂は、上記記載の方法により再生することができる。 In addition, when the regeneration of the resin is repeated by this regeneration method, heavy metals such as iron (III) and nickel having a higher adsorptivity than indium may remain in the resin and the adsorption capacity may be reduced. In such a case, the adsorptive power of indium and the like can be regenerated by desorbing heavy metals with an acidic solution such as 3 to 20% hydrochloric acid and then performing similar regeneration by washing with water or the like. That is, the anion exchange resin used for the removal of heavy metals and / or indium in the production method of the present invention can be regenerated by the method described above.
○実施態様
粗塩化第一鉄液中の重金属不純物が吸着した官能基として第３級アミノ基または第４級アンモニウム基を有する陰イオン交換樹脂を水を用いて重金属を除去する、官能基として第３級アミノ基または第４級アンモニウム基を有する陰イオン交換樹脂の再生方法。
粗塩化第一鉄液中の重金属不純物が吸着した官能基として第３級アミノ基を有する陰イオン交換樹脂を水を用いて重金属を除去する、官能基として第３級アミノ基を有する陰イオン交換樹脂の再生方法。
粗塩化第一鉄液中の重金属不純物が吸着した官能基として第３級アミノ基または第４級アンモニウム基を有する陰イオン交換樹脂を水を用いて再生した当該陰イオン交換樹脂を用いて、粗塩化第一鉄液中の重金属不純物を除去する塩化第一鉄液の製造方法。
粗塩化第一鉄液中の重金属不純物が吸着した官能基として第３級アミノ基を有する陰イオン交換樹脂を水を用いて再生した当該陰イオン交換樹脂を用いて、粗塩化第一鉄液中の重金属不純物を除去する塩化第一鉄液の製造方法。
ｐＨが−１．５〜２以下である粗塩化第一鉄液中の重金属不純物を官能基として第３級アミノ基または第４級アンモニウム基を有する陰イオン交換樹脂により除去する塩化第一鉄液の製造方法。
本発明の塩化第一鉄の製造方法で得た塩化第一鉄を、塩素酸化して製造した塩化第二鉄。
Embodiment An anion exchange resin having a tertiary amino group or a quaternary ammonium group as a functional group adsorbed with heavy metal impurities in the crude ferrous chloride solution is removed with heavy water to remove the heavy metal. A method for regenerating an anion exchange resin having a tertiary amino group or a quaternary ammonium group.
Anion exchange resin having a tertiary amino group as a functional group adsorbed with heavy metal impurities in a crude ferrous chloride solution is removed using water to remove the heavy metal, and an anion exchange having a tertiary amino group as a functional group Resin regeneration method.
The anion exchange resin having a tertiary amino group or a quaternary ammonium group as a functional group adsorbed with heavy metal impurities in the crude ferrous chloride solution is regenerated using water, and the A method for producing a ferrous chloride solution, which removes heavy metal impurities in the ferrous chloride solution.
In the crude ferrous chloride solution, the anion exchange resin having a tertiary amino group as a functional group adsorbed with heavy metal impurities in the crude ferrous chloride solution is regenerated with water. A method for producing ferrous chloride solution that removes heavy metal impurities.
A ferrous chloride solution for removing heavy metal impurities in a crude ferrous chloride solution having a pH of -1.5 to 2 or less with an anion exchange resin having a tertiary amino group or a quaternary ammonium group as a functional group. Manufacturing method.
Ferric chloride produced by chlorinating ferrous chloride obtained by the method for producing ferrous chloride of the present invention.
以下具体例を実施例にて説明するが、本発明はこれらの実施例だけにとどまるものではない。なお、％は重量％を、ｐｐｍは重量ｐｐｍを表す。 Specific examples will be described below with reference to examples, but the present invention is not limited to these examples. In addition,% represents weight% and ppm represents weight ppm.
インジウムを９８ｐｐｍ含む粗塩化第一鉄液（ＦｅＣｌ2濃度：３４％、ｐＨは−０．１であった）をアンバーライトＩＲＡ９６ＳＢ（商品名、Ｃｌ型、第３級アミノ基を有する陰イオン交換樹脂）を充填した樹脂層高さ６０ｃｍのカラム（４０℃に保温）に、ＳＶ＝１ｈｒ-1で流し、塩化第一鉄液を製造した。なお１時間ごとに塩化第一鉄液の通過液を集め、それらのインジウム含有量を測定し（ＩＣＰ発光分光分析による。なお、試料液に鉄を含んでいることからインジウムの検出限界が悪くなっている。）、結果を表１に記載した。 Crude ferrous chloride solution containing 98 ppm of indium (FeCl 2 concentration: 34%, pH was −0.1) and Amberlite IRA 96SB (trade name, Cl type, anion exchange resin having tertiary amino group) ) Packed in a column with a resin layer height of 60 cm (insulated at 40 ° C.) at SV = 1 hr −1 to produce a ferrous chloride solution. In addition, the passing liquid of ferrous chloride solution is collected every hour and the indium content thereof is measured (by ICP emission spectroscopic analysis. In addition, since the sample solution contains iron, the detection limit of indium deteriorates. The results are shown in Table 1.
インジウムを１００ｐｐｍ含む粗塩化第一鉄液（ＦｅＣｌ2濃度：３４％、ｐＨは−０．１であった）をアンバーライトＩＲＡ４００（商品名、Ｃｌ型、第４級アンモニウム基を有する陰イオン交換樹脂）を充填した樹脂層高さ６０ｃｍのカラム（４０℃に保温）に、ＳＶ＝２ｈｒ-1で流し、塩化第一鉄液を製造した。なお１時間ごとに塩化第一鉄液の通過液を集め、インジウム含有量を測定し、結果を表２に記載した。 Crude ferrous chloride solution containing 100 ppm of indium (FeCl 2 concentration: 34%, pH was −0.1) and Amberlite IRA400 (trade name, Cl type, anion exchange resin having a quaternary ammonium group) ) Packed in a resin layer with a height of 60 cm (insulated at 40 ° C.) at SV = 2 hr −1 to produce a ferrous chloride solution. In addition, the passage liquid of the ferrous chloride liquid was collected every 1 hour, indium content was measured, and the result was described in Table 2.
実施例１において使用したアンバーライトＩＲＡ９６ＳＢ（商品名）を水を流して再生した（４０℃、ＳＶ＝１ｈｒ-1）。この再生した樹脂に再度粗塩化第一鉄液を通液して塩化第一鉄液を製造した。なお、水での再生状況（１時間ごとに再生液を集め、この中のインジウム含有量を測定した）を表３に記載した。 Amberlite IRA96SB (trade name) used in Example 1 was regenerated by flowing water (40 ° C., SV = 1 hr −1 ). A crude ferrous chloride solution was again passed through the regenerated resin to produce a ferrous chloride solution. In addition, Table 3 shows the state of regeneration with water (collecting the regenerated solution every hour and measuring the indium content therein).
実施例２において使用したアンバーライトＩＲＡ４００（商品名）を水で流して再生した（４０℃、ＳＶ＝４ｈｒ-1）。この再生した樹脂に再度粗塩化第一鉄液を通液して塩化第一鉄液を製造した。なお、水での再生状況（１時間ごとに再生液を集め、この中のインジウム含有量を測定した）を表４に記載した。 Amberlite IRA400 (trade name) used in Example 2 was regenerated by flushing with water (40 ° C., SV = 4 hr −1 ). A crude ferrous chloride solution was again passed through the regenerated resin to produce a ferrous chloride solution. In addition, Table 4 shows the state of regeneration with water (collecting the regeneration solution every hour and measuring the indium content therein).
３価の鉄を４００ｐｐｍ含有する粗塩化第一鉄液を用いた以外は、実施例１と同様に操作して塩化第一鉄液を製造した。この結果、６時間通液してもＩｎ濃度は２０ｐｐｍ以下であった。 A ferrous chloride solution was produced in the same manner as in Example 1 except that a crude ferrous chloride solution containing 400 ppm of trivalent iron was used. As a result, the In concentration was 20 ppm or less even after passing through for 6 hours.
３価の鉄を０．４％含有する粗塩化第一鉄液を用いた以外は、実施例１と同様に操作して塩化第一鉄液を製造した。この結果、６時間通液してもＩｎ濃度は２０ｐｐｍ以下であった。 A ferrous chloride solution was produced in the same manner as in Example 1 except that a crude ferrous chloride solution containing 0.4% of trivalent iron was used. As a result, the In concentration was 20 ppm or less even after passing through for 6 hours.
３価の鉄を０．８％含有する粗塩化第一鉄液を用いた以外は、実施例１と同様に操作して塩化第一鉄液を製造した。この結果、４時間通液してもＩｎ濃度は２０ｐｐｍ以下であった。 A ferrous chloride solution was produced in the same manner as in Example 1 except that a crude ferrous chloride solution containing 0.8% of trivalent iron was used. As a result, the In concentration was 20 ppm or less even after passing through for 4 hours.
水の替わりに２％塩酸または５％塩酸を用いた以外は実施例３と同様に処理した。この結果を表５に記載した。 The treatment was performed in the same manner as in Example 3 except that 2% hydrochloric acid or 5% hydrochloric acid was used instead of water. The results are shown in Table 5.
本発明の製造方法は、液晶モニターやプラズマモニター等に透明電極として使用されているＩＴＯ（インジウム・錫・酸化物）材やＩＺＯ（インジウム・亜鉛・酸化物）材のエッチングに使用した塩化第二鉄系溶液等の再生に適用することができる。 The manufacturing method of the present invention is a second chloride used for etching an ITO (indium / tin / oxide) material or an IZO (indium / zinc / oxide) material used as a transparent electrode in a liquid crystal monitor or a plasma monitor. It can be applied to the regeneration of iron-based solutions and the like.
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