JP2008100849A - Method for producing ferrous chloride solution - Google Patents
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- JP2008100849A JP2008100849A JP2006282250A JP2006282250A JP2008100849A JP 2008100849 A JP2008100849 A JP 2008100849A JP 2006282250 A JP2006282250 A JP 2006282250A JP 2006282250 A JP2006282250 A JP 2006282250A JP 2008100849 A JP2008100849 A JP 2008100849A
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- ferrous chloride
- chloride solution
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- 229960002089 ferrous chloride Drugs 0.000 title claims abstract description 117
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 title claims abstract description 117
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 66
- 239000011347 resin Substances 0.000 claims abstract description 66
- 239000013522 chelant Substances 0.000 claims abstract description 62
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 57
- 229910052738 indium Inorganic materials 0.000 claims abstract description 42
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical group [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000012535 impurity Substances 0.000 claims abstract description 25
- 229920000768 polyamine Polymers 0.000 claims abstract description 25
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 23
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- MBBZMMPHUWSWHV-BDVNFPICSA-N N-methylglucamine Chemical group CNC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO MBBZMMPHUWSWHV-BDVNFPICSA-N 0.000 claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 49
- 239000007788 liquid Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 229920001429 chelating resin Polymers 0.000 claims description 14
- 238000011069 regeneration method Methods 0.000 claims description 8
- 230000001172 regenerating effect Effects 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000005530 etching Methods 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 15
- 239000002699 waste material Substances 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 89
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 25
- 229910052759 nickel Inorganic materials 0.000 description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 12
- 229910052718 tin Inorganic materials 0.000 description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 10
- 229910052804 chromium Inorganic materials 0.000 description 10
- 239000011651 chromium Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 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
- 150000002500 ions Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 239000011135 tin Substances 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003957 anion exchange resin Substances 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000009616 inductively coupled plasma Methods 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
- 239000011259 mixed solution Substances 0.000 description 2
- 150000004880 oxines Chemical group 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000758 substrate 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
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 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
- 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
- 238000004140 cleaning Methods 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
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000010438 heat treatment Methods 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
- 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
- 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
- 239000005011 phenolic resin Substances 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
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- -1 that is Chemical compound 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Landscapes
- 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、ニッケル共存下で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、及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, in this case, it is necessary to coexist with 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４）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５）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 4). 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 the chelate resin, the ionic valence having two or more kinds of the above. Japanese Patent Application Laid-Open No. 62-176914 (Patent Document 5) 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キレート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 a chelate resin regenerated by a simple technique.
本発明者らは、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高純度の塩化第一鉄を得る方法を鋭意検討した結果、ポリアミン基またはN−メチルグルカミン基を有するキレート樹脂を用いることにより解決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＞粗塩化第一鉄液中の重金属不純物をポリアミン基またはN−メチルグルカミン基を有するキレート樹脂により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＞前記粗塩化第一鉄液の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ポリアミン基またはN−メチルグルカミン基を有するキレート樹脂から水、希塩化第一鉄液および／または希塩酸を用いて重金属を除去する、ポリアミン基またはN−メチルグルカミン基を有するキレート樹脂の再生方法であり、
＜５＞請求項４記載の再生方法を用いて再生したポリアミン基またはN−メチルグルカミン基を有するキレート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製造した塩化第二鉄である。
The present inventors removed heavy metals from crude ferrous chloride liquid (for example, obtained by treating ferric chloride etching waste liquid such as ITO material with iron material, etc.) to obtain high-purity ferrous chloride. As a result of intensive studies on a method for obtaining the above, it has been found that the problem can be solved by using a chelate resin having a polyamine group or an N-methylglucamine group, and the present invention has been completed. That is, specifically,
<1> A method for producing a ferrous chloride solution, wherein heavy metal impurities in the crude ferrous chloride solution are removed by a chelate resin having a polyamine group or an N-methylglucamine group,
<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> removing heavy metals from water, dilute ferrous chloride solution and / or dilute hydrochloric acid from a chelating resin having a polyamine group or N-methylglucamine group adsorbed with heavy metal impurities in the crude ferrous chloride solution. A method for regenerating a chelate resin having a polyamine group or an N-methylglucamine group,
<5> Manufacture of the ferrous chloride liquid as described in any one of said 1-3 using the chelating resin which has the polyamine group or N-methylglucamine group regenerated using the reproduction | regeneration method of Claim 4. Is the way
<6> Ferric chloride produced 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のイオンを含有する塩化第一鉄溶液であり、この水溶液に塩化第二鉄を含んでいても良い。粗塩化第一鉄液に含まれる重金属のイオンとしては、インジウム、ニッケル、クロムおよび／またはスズ等であればより良く、インジウムおよび／またはスズであれば更に良い。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のイオン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 is a ferrous chloride solution containing heavy metal ions such as indium, nickel, chromium, molybdenum, tin, zinc, and / or copper. It may contain iron. The heavy metal ions contained in the crude ferrous chloride solution are better if they are indium, nickel, chromium, and / or tin, and more preferably if they are indium and / or tin. In the manufacturing method of the ferrous chloride liquid of this invention, it is preferable that the heavy metal ions contained in the crude ferrous chloride liquid can be efficiently removed.
本発明において該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ＩＴＯが薄膜として形成したものに対し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、鉄材を加えて行ったものが好ましい。 In the present invention, particularly preferable as the crude ferrous chloride liquid is a waste liquid after etching with ITO etching liquid on a glass material or the like formed on the surface of ITO as a thin film. The ferric chloride contained in may be converted to ferrous chloride. The conversion from ferric chloride to ferrous chloride is preferably performed by adding an iron material.
本発明においてポリアミン基またはN−メチルグルカミン基を有するキレート樹脂とは、ポリスチレン、ポリスチレン−ジビニルベンゼン共重合体またはフェノール樹脂等に官能基としてポリアミン基またはN−メチルグルカミン基を有するものである。このポリアミン基とは、アルキレンアミン基を有するもので、−ＣＨ2ＮＨ（ＣＨ2ＣＨ2ＮＨ）nＨ基（ｎは１以上の整数）で表されるものが挙げられる。 In the present invention, the chelate resin having a polyamine group or N-methylglucamine group is one having a polyamine group or N-methylglucamine group as a functional group in polystyrene, polystyrene-divinylbenzene copolymer, phenol resin or the like. . This polyamine group has an alkyleneamine group and includes those represented by —CH 2 NH (CH 2 CH 2 NH) n H groups (n is an integer of 1 or more).
本発明においてポリアミン基を有するキレート樹脂としては、ダイヤイオンＣＲ２０（商品名、三菱化学株式会社製）やダイヤイオンＷＡ２０（商品名、三菱化学株式会社製）等が挙げられる。 Examples of the chelate resin having a polyamine group in the present invention include Diaion CR20 (trade name, manufactured by Mitsubishi Chemical Corporation), Diaion WA20 (trade name, manufactured by Mitsubishi Chemical Corporation), and the like.
本発明においてN−メチルグルカミン基を有するキレート樹脂としては、ダイヤイオンＣＲＢ０２（商品名、三菱化学株式会社製）、アンバーライトＩＲＡ７４３（商品名、Rohm & Haas社製）やユニセレックＵＲ−３５００Ｓ（商品名、ユニチカ(株)製）等を挙げることができる。 In the present invention, as a chelating resin having an N-methylglucamine group, Diaion CRB02 (trade name, manufactured by Mitsubishi Chemical Corporation), Amberlite IRA743 (trade name, manufactured by Rohm & Haas) or Uniselec UR-3500S (commodity) Name, manufactured by Unitika Ltd.).
本発明において用いるキレート樹脂としては、ポリアミン基を有するキレート樹脂がより重金属を除去できるので好ましい。 As the chelate resin used in the present invention, a chelate resin having a polyamine group is preferable because heavy metals can be removed more.
本発明における該粗塩化第一鉄液は、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 crude ferrous chloride solution in the present invention has a ferrous chloride content of preferably 10 to 48%, more preferably 25 to 48%, still more preferably 30 to 42%, and most preferably 33 to 39%. preferable. 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.
本発明における該粗塩化第一鉄液は、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。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 still more preferably 1% or less. 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以下であり、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 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.
該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。
粗塩化第一鉄液のｐＨが２超えて５以下の範囲では、インジウム以外のニッケル、クロム、モリブデン、錫および／または銅等のイオンが該キレート樹脂に吸着される。このため、まず粗塩化第一鉄液のｐＨを２超えで５以下の範囲に調製して、該キレート樹脂への吸着処理を行い、その後、酸を加えてｐＨを−１．５〜２の範囲に調製する事によって、インジウムを分離しながら不純物を含まない高度に精製された塩化第一鉄液を得ることもできる。
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 range where the pH of the crude ferrous chloride solution exceeds 2 and is 5 or less, ions such as nickel, chromium, molybdenum, tin and / or copper other than indium are adsorbed on the chelate resin. For this reason, first, the pH of the crude ferrous chloride solution is adjusted to a range of 2 to 5 and subjected to adsorption treatment on the chelate resin, and then an acid is added to adjust the pH to -1.5 to 2. By adjusting to the range, highly purified ferrous chloride liquid containing no impurities can be obtained while separating indium.
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該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／または銅等のイオンは、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。 Ions such as nickel, chromium, molybdenum, zinc, tin and / or copper in the crude ferrous chloride solution in the production method of the present invention are 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、高い方が良いが、０．２％以下が好ましく、好ましくは５０〜１５００ｐｐｍ、更に好ましくは１５０〜１５００ｐｐｍ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 is preferably high, but is preferably 0.2% or less, preferably 50-1500 ppm, and more preferably 150-1500 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、該キレート樹脂の使用量は、該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、該キレート樹脂からの溶出液中の重金属含有量をモニターして該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 chelate resin used may be determined by the heavy metal content in the crude ferrous chloride solution. For example, the amount of the crude ferrous chloride solution may be determined by monitoring the heavy metal content in the eluate from the chelate resin.
本発明の製造方法において、該粗塩化第一鉄液と該キレート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＝０．１〜５［１／ｈ］、更に好ましくはＳＶ＝０．２〜３［１／ｈ］、特に好ましくはＳＶ＝０．３〜２［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 chelate resin is, for example, a superficial velocity (hereinafter referred to as SV) when adsorbed in a packed tower, and SV = 0.1 to 5 [1 / h], more preferably SV = 0.2 to 3 [1 / h], particularly preferably by contacting at SV = 0.3 to 2 [1 / h], heavy metals can be adsorbed efficiently. it can. 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６０℃程度であり、好ましくは５℃から５０℃であり、より好ましくは１０℃から４５℃である。該キレート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 60 ° C, preferably 5 ° C to 50 ° C, more preferably 10 ° C to 45 ° C. It is preferable that the contact temperature with the chelate resin is within 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キレート樹脂と０℃から６０℃の間の温度で１時間接触させる流速で流して重金属を除去して、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キレート樹脂とをバッチで０℃から６０℃の間の温度で例えば２時間接触させて重金属を除去して、高純度塩化第一鉄液を製造することができる。 For example, a high purity ferrous chloride solution is produced by removing heavy metals by flowing at a flow rate at which the crude ferrous chloride solution is brought into contact with the chelating resin packed in a column at a temperature between 0 ° C. and 60 ° C. for 1 hour. can do. Alternatively, the crude ferrous chloride solution and the chelate resin are contacted in batches at a temperature between 0 ° C. and 60 ° C., for example, for 2 hours to remove heavy metals to produce a high purity ferrous chloride solution. it can.
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キレート樹脂は、再生して本発明の製造方法に用いるキレート樹脂として再利用することができる。
当該キレート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、当該キレート樹脂の再生方法としては、水で処理するもの、水で処理した後に希塩化第一鉄液によるもの、水で処理した後に希塩酸によるもの、水で処理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、キレート樹脂の再生方法としては、水で処理するもの、水で処理した後に希塩化第一鉄液によるもの、水で処理した後に希塩酸によるもの、または水で処理した後に希塩化第一鉄液と希塩酸との混合液によるが好ましく、水で処理するものがより好ましい。なお、希塩酸とは、濃度３％未満の溶液であることが好ましいものとして例示できる。また、希塩化第一鉄液とは、濃度３％未満の酸性水溶液であることが好ましいものとして例示できる。
In the production method of the present invention, the chelate resin used for removing heavy metals and / or indium can be regenerated and reused as the chelate resin used in the production method of the present invention.
A known method can be used as a method for regenerating the chelate resin. For example, the chelating resin can be regenerated by treating with water, treating with water and using dilute ferrous chloride solution, treating with water and using dilute hydrochloric acid, treating with water and dilute ferrous chloride. Examples thereof include a liquid mixture of a liquid and dilute hydrochloric acid, a dilute ferrous chloride liquid, a dilute ferrous chloride liquid and dilute hydrochloric acid, a dilute hydrochloric acid, and the like. In the production method of the present invention, the chelate resin is regenerated by treating with water, treating with water and then using diluted ferrous chloride solution, treating with water and then using diluted hydrochloric acid, or after treating with water. It is preferably based on a mixed solution of dilute ferrous chloride solution and dilute hydrochloric acid, and more preferably treated with water. The dilute hydrochloric acid can be exemplified as a preferable solution having a concentration of less than 3%. Further, the diluted ferrous chloride solution can be exemplified as a preferable acidic aqueous solution having a concentration of less than 3%.
本発明の製造方法において上記記載の水、希塩酸、または希塩化第一鉄液の使用量は、当該キレート樹脂が再生できれば如何様な量でも良い。例えば当該キレート樹脂（体積）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キレート樹脂の再生は、０〜６０℃であり、１０〜５０℃が好ましい。
In the production method of the present invention, the amount of water, dilute hydrochloric acid, or dilute ferrous chloride solution described above may be any amount as long as the chelate resin can be regenerated. For example, the amount is 1.2 to 10 times the amount of the chelate resin (volume).
In the production method of the present invention, regeneration of the chelate resin is 0 to 60 ° C, preferably 10 to 50 ° C.
また、粗塩化第一鉄液中のインジウムを吸着させたキレート樹脂から、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もできる。 Further, an indium compound can be produced by eluting indium from a chelate resin adsorbed with indium in a crude ferrous chloride solution using water and / or dilute ferrous chloride aqueous solution and / or dilute hydrochloric acid. .
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キレート樹脂は、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 chelate resin used for removing 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ポリアミン基またはN−メチルグルカミン基を有するキレート樹脂から重金属を水を用いて除去する、ポリアミン基またはN−メチルグルカミン基を有するキレート樹脂の再生方法。
粗塩化第一鉄液中の重金属不純物が吸着したポリアミン基を有するキレート樹脂から重金属を水を用いて除去する、ポリアミン基を有するキレート樹脂の再生方法。
粗塩化第一鉄液中の重金属不純物が吸着したポリアミン基またはN−メチルグルカミン基を有するキレート樹脂から重金属を水を用いて再生したポリアミン基またはN−メチルグルカミン基を有するキレート樹脂を用いて、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ポリアミン基を有するキレート樹脂から重金属を水を用いて再生したポリアミン基を有するキレート樹脂を用いて、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ポリアミン基またはN−メチルグルカミン基を有するキレート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 The polyamine group or N-methylglucamine group is removed from the chelate resin having a polyamine group or N-methylglucamine group adsorbed with heavy metal impurities in the crude ferrous chloride solution using water. Regeneration method of chelate resin.
A method for regenerating a chelate resin having a polyamine group, wherein heavy metal is removed from the chelate resin having a polyamine group adsorbed with heavy metal impurities in a crude ferrous chloride solution using water.
Using a chelating resin having a polyamine group or N-methylglucamine group obtained by regenerating heavy metal from water using a chelating resin having a polyamine group or N-methylglucamine group adsorbed with heavy metal impurities in the crude ferrous chloride solution And a method for producing a ferrous chloride solution for removing heavy metal impurities in the crude ferrous chloride solution.
Removal of heavy metal impurities in crude ferrous chloride solution using a chelating resin with polyamine groups obtained by regenerating heavy metals with water from a chelating resin with polyamine groups adsorbed by heavy metal impurities in the crude ferrous chloride solution A method for producing ferrous chloride liquid.
A method for producing a ferrous chloride solution, wherein heavy metal impurities in a crude ferrous chloride solution having a pH of -1.5 to 2 or less are removed by a chelate resin having a polyamine group or an N-methylglucamine group.
Ferric chloride produced by chlorinating ferrous chloride obtained by the method for producing ferrous chloride of the present invention.
＜実施例＞
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。
<Example>
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.
１）塩酸と４２度ボーメの塩化第二鉄液とを重量比で１：１に混合した液で、４５℃にてＩＴＯの薄膜を含むガラス基盤をエッチングした廃液を用いた。このエッチング廃液に鉄板を加え、８０℃にて４時間加熱を行った。放冷後、残留した鉄材を除き、ｐＨ測定器においてｐＨが−０．５６になるように３５％塩酸を用いて粗塩化第一鉄液を調製した。
２）粗塩化第一鉄液中の重金属等の分析を実施した結果、塩化第一鉄を３５．８７％、塩化第二鉄を０．０３％、遊離塩酸を０．１２％、インジウムを１６３ｐｐｍ、スズを１ｐｐｍ、ニッケルを５６ｐｐｍ、およびクロムを２９ｐｐｍ、含有していた。
３）充填塔にキレート樹脂として、ポリアミン基を有するキレート樹脂（三菱化学株式会社製ダイヤイオンＣＲ−２０（商品名））を充填し、ＳＶ＝１［１／ｈ］、ＬＶ＝２０［ｃｍ／ｈ］の条件で上記粗塩化第一鉄液を通液した。
４）キレート樹脂充填塔からの流出液について重金属分析を行い、表１に結果を記載した。この結果から、当該キレート樹脂は、１．７ｇ−Ｉｎ／Ｌ−キレート樹脂の吸着能力があった。
５）粗塩化第一鉄液を通液したキレート樹脂充填塔に対してＳＶ＝４［１／ｈ］、ＬＶ＝８０［ｃｍ／ｈ］の条件で水を流した。充填したキレート樹脂量の約１．６７倍毎に通過液を回収（溶出液）し、これら溶出液中の重金属分析を行った。この重金属分析の結果を表２に記載した。
６）前記５）の操作後、更にキレート樹脂量の１０倍量の水でキレート樹脂を水洗した。
７）その後、２０％塩酸を加え、キレート樹脂量の約１．６７倍毎に通過液を回収（溶出液）し、これら溶出液中の重金属分析を行ったが金属溶出が認められなかった。そこで更にキレート樹脂充填塔を８０℃に加熱しながら２０％塩酸を通液し、この通過液中の重金属分析を実施し表３に記載した。
1) A waste solution obtained by etching a glass substrate including an ITO thin film at 45 ° C. was used in a mixture of hydrochloric acid and ferric chloride solution of 42 ° Baume in a weight ratio of 1: 1. An iron plate was added to this etching waste liquid and heated at 80 ° C. for 4 hours. After standing to cool, the remaining iron material was removed, and a crude ferrous chloride solution was prepared using 35% hydrochloric acid so that the pH was -0.56 in a pH meter.
2) As a result of analysis of heavy metals, etc. in crude ferrous chloride solution, 35.87% ferrous chloride, 0.03% ferric chloride, 0.12% free hydrochloric acid, 163 ppm indium 1 ppm of tin, 56 ppm of nickel, and 29 ppm of chromium.
3) A chelating resin having a polyamine group (Diaion CR-20 (trade name) manufactured by Mitsubishi Chemical Corporation) is packed as a chelating resin in the packed tower, and SV = 1 [1 / h], LV = 20 [cm / The crude ferrous chloride solution was passed under the conditions of h].
4) Heavy metal analysis was performed on the effluent from the chelate resin packed tower, and the results are shown in Table 1. From this result, the chelate resin was capable of adsorbing 1.7 g-In / L-chelate resin.
5) Water was allowed to flow under conditions of SV = 4 [1 / h] and LV = 80 [cm / h] through the chelate resin packed tower through which the crude ferrous chloride solution was passed. The passing solution was collected (eluent) every 1.67 times the amount of the chelating resin filled, and heavy metals in the eluate were analyzed. The results of heavy metal analysis are listed in Table 2.
6) After the operation of 5), the chelate resin was further washed with 10 times the amount of the chelate resin.
7) Thereafter, 20% hydrochloric acid was added, and the passing liquid was collected (eluent) every 1.67 times the amount of the chelate resin, and heavy metal analysis was performed in these eluates, but metal elution was not observed. Therefore, 20% hydrochloric acid was passed through the chelate resin packed tower while heating to 80 ° C., and heavy metals were analyzed in the passed liquid and listed in Table 3.
○インジウム、ニッケル、クロムおよび錫の分析方法
採取した試料を適宜超純水で希釈し、２０％塩酸を全体の５％量加えメスアップにて正確に希釈した。各成分を標準添加法にて誘導結合型プラズマ発光分析装置（ＩＣＰ）にて、予め共存する他成分の干渉を受けないことが判明している波長にて濃度測定を行った。
○ Analytical method of indium, nickel, chromium and tin The collected sample was appropriately diluted with ultrapure water, and 20% hydrochloric acid was added in an amount of 5% of the whole and diluted accurately with a mess-up. The concentration of each component was measured by a standard addition method using an inductively coupled plasma emission spectrometer (ICP) at a wavelength that was previously known to be free from interference from other components that coexist.
＜比較例１＞
アミノリン酸系のキレート樹脂（ランクセンス株式会社製のレバチットモノプラスＴＰ２６０（商品名））を用いた以外は、実施例１とほぼ同様に実施した。
１）塩酸と４２度ボーメの塩化第二鉄液とを重量比で１：１に混合した液で、４５℃にてＩＴＯの薄膜を含むガラス基盤をエッチングした廃液を用いた。このエッチング後の液に鉄板を加え、８０℃にて４時間加熱を行った。放冷後、残留した鉄材を除き、ｐＨ測定器においてｐＨが−０．５３になるように３５％塩酸を用いて粗塩化第一鉄液を調製した。
２）粗塩化第一鉄液中の重金属等の分析を実施した結果、塩化第一鉄を３１．８８％、塩化第二鉄を０．００％、遊離塩酸を０．３０％、インジウムを１２１ｐｐｍ、スズを１ｐｐｍ、ニッケルを２０ｐｐｍ、およびクロムを２９ｐｐｍを含有していた。
３）充填塔にキレート樹脂として、レバチットモノプラスＴＰ２６０を充填し、ＳＶ＝１［１／ｈ］、ＬＶ＝２０［ｃｍ／ｈ］の条件で上記粗塩化第一鉄液を通液した。
４）キレート樹脂充填塔からの流出液の重金属分析を行い、表１に結果を記載した。この結果から、当該キレート樹脂は、０．６ｇ−Ｉｎ／Ｌ−キレート樹脂の吸着能力であった。
５）粗塩化第一鉄液を通液したキレート樹脂充填塔に対してＳＶ＝４［１／ｈ］、ＬＶ＝８０［ｃｍ／ｈ］の条件で水を加えた。充填したキレート樹脂量の約１．６７倍毎に液を回収（溶出液）し、これら溶出液中の重金属分析を行い、表２に結果を記載した。
６）５）の操作後、更にキレート樹脂量の１０倍量の水でキレート樹脂を水洗した。
７）その後２０％塩酸を加え、キレート樹脂量の約１．６７倍毎に液を回収（溶出液）し、これら溶出液中の重金属分析を行い、表３に結果を記載した。
<Comparative Example 1>
The test was carried out in substantially the same manner as in Example 1 except that an aminophosphate-based chelate resin (Lebatit Monoplus TP260 (trade name) manufactured by Ranksense Co., Ltd.) was used.
1) A waste solution obtained by etching a glass substrate including an ITO thin film at 45 ° C. was used in a mixture of hydrochloric acid and ferric chloride solution of 42 ° Baume in a weight ratio of 1: 1. An iron plate was added to the liquid after this etching and heated at 80 ° C. for 4 hours. After allowing to cool, the remaining iron material was removed, and a crude ferrous chloride solution was prepared using 35% hydrochloric acid so that the pH was -0.53 in a pH meter.
2) As a result of analysis of heavy metals, etc. in crude ferrous chloride solution, 31.88% ferrous chloride, 0.00% ferric chloride, 0.30% free hydrochloric acid, 121ppm indium Contained 1 ppm tin, 20 ppm nickel, and 29 ppm chromium.
3) The packed tower was filled with Lebachit Monoplus TP260 as a chelate resin, and the above-mentioned crude ferrous chloride solution was passed under the conditions of SV = 1 [1 / h] and LV = 20 [cm / h].
4) Heavy metal analysis of the effluent from the chelate resin packed tower was performed and the results are shown in Table 1. From this result, the chelate resin was capable of adsorbing 0.6 g-In / L-chelate resin.
5) Water was added under conditions of SV = 4 [1 / h] and LV = 80 [cm / h] to the chelate resin packed tower through which the crude ferrous chloride solution was passed. Liquids were collected (eluate) every 1.67 times the amount of filled chelate resin, heavy metals in these eluates were analyzed, and the results are shown in Table 2.
6) After the operation of 5), the chelate resin was further washed with 10 times the amount of the chelate resin.
7) Thereafter, 20% hydrochloric acid was added, and the liquid was collected (eluent) every 1.67 times the amount of the chelate resin. Heavy metals were analyzed in these eluates, and the results are shown in Table 3.
以上の様に、実施例１と比較例１ともに塩化第一鉄液中からインジウムを吸着することができるが、比較例１ではキレート樹脂からインジウムを外すのに大量の酸が必要である。しかし実施例１では、水でキレート樹脂からインジウムを外すことができることから、簡単に再生することができる。 As described above, both Example 1 and Comparative Example 1 can adsorb indium from the ferrous chloride solution, but Comparative Example 1 requires a large amount of acid to remove indium from the chelate resin. However, in Example 1, since indium can be removed from the chelate resin with water, it can be easily regenerated.
表１は、キレート樹脂充填塔からの経過時間ごとの溶出液中の重金属濃度変化を示す。初期濃度を１００としたときの溶出液中の各金属種の変化を示す表である。
表２は、水洗浄によって各回収された溶出液の分析結果を示すものである。単位はｐｐｍ。
表３は、水洗後の樹脂に対して酸洗浄することによって回収された溶出液の分析結果を示すものである。単位はｐｐｍ。
Table 1 shows the heavy metal concentration change in the eluate for each elapsed time from the chelate resin packed tower. It is a table | surface which shows the change of each metal seed | species in an eluate when an initial concentration is set to 100.
Table 2 shows the analysis results of the eluates collected by water washing. The unit is ppm.
Table 3 shows the analysis results of the eluate recovered by acid cleaning of the resin after washing with water. The unit is ppm.
比較例１におけるインジウム、ニッケルおよびクロムの溶出液量中の値は、カラム中に残存していた物からのものと考えられる（なお、このｐＨ条件では、ニッケルおよびクロムの大半が吸着しないと考えられる）。 The values in the eluate amounts of indium, nickel and chromium in Comparative Example 1 are considered to be from those remaining in the column (note that most of nickel and chromium are not adsorbed under this pH condition). ).
実施例１−６）の水洗したＣＲ−２０を用いた以外は、実施例１とほぼ同様に粗塩化第一鉄液（ｐＨは、−０．６）を処理した。この結果、実施例１と同様の結果か得られた。
このことから、水で再生したキレート樹脂を用いても粗塩化第一鉄液から塩化第一鉄液を製造できることが分かった。
The crude ferrous chloride solution (pH is -0.6) was treated in substantially the same manner as in Example 1 except that CR-20 washed with water in Example 1-6) was used. As a result, the same results as in Example 1 were obtained.
From this, it was found that a ferrous chloride solution can be produced from a crude ferrous chloride solution using a chelate resin regenerated with water.
ダイヤイオンＣＲＢ０２（三菱化学株式会社製）を用いた以外は、実施例１とほぼ同様に粗塩化第一鉄液（ｐＨは、−０．６）を処理した結果、インジウムの除去および該キレート樹脂が再生できた。 Except for using Diaion CRB02 (manufactured by Mitsubishi Chemical Corporation), as a result of treating the crude ferrous chloride solution (pH is -0.6) in substantially the same manner as in Example 1, the removal of indium and the chelate resin Was able to play.
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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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58172256A (en) * | 1982-03-30 | 1983-10-11 | 住友化学工業株式会社 | Recovery of indium |
| JPS6019087A (en) * | 1983-07-12 | 1985-01-31 | Toyo Soda Mfg Co Ltd | Removal of heavy metal in aqueous iron salt solution |
| JPS62176914A (en) * | 1986-01-29 | 1987-08-03 | Sumitomo Chem Co Ltd | Recovery of rare metal |
| JP2003266065A (en) * | 2002-03-18 | 2003-09-24 | Toagosei Co Ltd | Removing method and recovering method for cobalt and/ or zinc in iron chloride solution |
| JP2004075463A (en) * | 2002-08-19 | 2004-03-11 | Toagosei Co Ltd | Method for removing and recovering indium from indium-containing ferric chloride etchant waste |
| JP2005238181A (en) * | 2004-02-27 | 2005-09-08 | Nippon Steel Corp | Method for treating wastewater to recover valuable metal and plating solution manufacturing method |
| JP2007332006A (en) * | 2006-06-19 | 2007-12-27 | Sharp Corp | Regeneration treatment method and regeneration treatment apparatus for indium- and/or tin-containing iron chloride solution |
-
2006
- 2006-10-17 JP JP2006282250A patent/JP4745936B2/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58172256A (en) * | 1982-03-30 | 1983-10-11 | 住友化学工業株式会社 | Recovery of indium |
| JPS6019087A (en) * | 1983-07-12 | 1985-01-31 | Toyo Soda Mfg Co Ltd | Removal of heavy metal in aqueous iron salt solution |
| JPS62176914A (en) * | 1986-01-29 | 1987-08-03 | Sumitomo Chem Co Ltd | Recovery of rare metal |
| JP2003266065A (en) * | 2002-03-18 | 2003-09-24 | Toagosei Co Ltd | Removing method and recovering method for cobalt and/ or zinc in iron chloride solution |
| JP2004075463A (en) * | 2002-08-19 | 2004-03-11 | Toagosei Co Ltd | Method for removing and recovering indium from indium-containing ferric chloride etchant waste |
| JP2005238181A (en) * | 2004-02-27 | 2005-09-08 | Nippon Steel Corp | Method for treating wastewater to recover valuable metal and plating solution manufacturing method |
| JP2007332006A (en) * | 2006-06-19 | 2007-12-27 | Sharp Corp | Regeneration treatment method and regeneration treatment apparatus for indium- and/or tin-containing iron chloride solution |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109110969A (en) * | 2018-09-13 | 2019-01-01 | 上海离原环境科技有限公司 | A kind of uranium ore waste water plasma body cooperative method of disposal and system |
| CN109110969B (en) * | 2018-09-13 | 2021-06-25 | 上海离原环境科技有限公司 | Uranium ore wastewater plasma co-processing method and system |
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