JP5996771B2 - High purity In and its manufacturing method - Google Patents
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- 238000004519 manufacturing process Methods 0.000 title claims description 41
- 238000000746 purification Methods 0.000 claims description 67
- 239000012535 impurity Substances 0.000 claims description 40
- 238000005868 electrolysis reaction Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 31
- 239000008151 electrolyte solution Substances 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 238000005266 casting Methods 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 230000035699 permeability Effects 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 3
- 238000001514 detection method Methods 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- 239000000460 chlorine Substances 0.000 description 12
- 239000011701 zinc Substances 0.000 description 12
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 10
- 239000004744 fabric Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 238000007670 refining Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 6
- 239000003957 anion exchange resin Substances 0.000 description 6
- 238000007667 floating Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- IDCBOTIENDVCBQ-UHFFFAOYSA-N TEPP Chemical compound CCOP(=O)(OCC)OP(=O)(OCC)OCC IDCBOTIENDVCBQ-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B58/00—Obtaining gallium or indium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
本発明は、リン化インジウム（ＩｎＰ）の原料として特に有用である８Ｎ以上の純度を持つ高純度インジウム（Ｉｎ）及びそれを製造する方法を提供するものであり、さらに従来技術よりも安価に製造することができるという特徴を持つ電解精製による高純度Ｉｎの製造方法に関する。 The present invention provides a high-purity indium (In) having a purity of 8N or more that is particularly useful as a raw material for indium phosphide (InP), and a method for producing the same, and is manufactured at a lower cost than the prior art. The present invention relates to a method for producing high-purity In by electrolytic purification, which has a feature that it can be performed.
一般に、３−５族化合物半導体の１つであるＩｎＰのような化合物半導体単結晶の製造には、高純度の原料が使用されており、高純度のＩｎの製造方法には、蒸留、ゾーン精製等の乾式法により、４Ｎから６Ｎ以上に精製され、特許文献としては以下が挙げられる。
下記特許文献１には、１２５０℃で蒸留することが、特許文献２には、ベーキング後にゾーンメルトすることが、特許文献３には、塩素ガスと反応させて蒸留し、塩化Ｉｎを蒸留水と不均化反応させることが、特殊な例として特許文献４に蒸留したＩｎを連続して鋳造する方法が記載されている。Generally, high-purity raw materials are used for the production of a compound semiconductor single crystal such as InP, which is one of Group 3-5 compound semiconductors. Distillation and zone purification are used for the production of high-purity In. It is refine | purified from 4N to 6N or more by dry methods, such as the following, and the following is mentioned as patent documents.
In Patent Document 1 below, it is distilled at 1250 ° C., in Patent Document 2 it is zone-melted after baking, and in Patent Document 3, it is distilled by reacting with chlorine gas, and In chloride is distilled with distilled water. As a special example of disproportionation reaction, Patent Document 4 describes a method of continuously casting In distilled.
一方、湿式精製における従来技術を見ると、特許文献５にＩｎの精製方法が記載されている。その具体的内容は、次の通りである。
Ｃｄを１０ｐｐｍ未満、かつＴｌを１ｐｐｍ未満含有する粗Ｉｎを原料として、これをアノードとして塩酸浴でＩｎ濃度：１００〜３００ｇ／Ｌ、ｐＨ：０．５〜２、電流密度：０．５〜２Ａ／ｄｍ２で電解精製を行っている。
隔膜によって陽極室と陰極室を分けて電解精製を行い、電解後は陽極室の電解液を抜き取って濾過後、陰イオン交換樹脂と接触させることにより浄液を行っている。更に電流密度 ０．３〜２．５Ａ／ｄｍ２での電解により電解液中のＩｎより貴な不純物を除去し、これを陰極室に供給して電解精製を行っている。On the other hand, looking at the prior art in wet refining, Patent Document 5 describes a method for purifying In. The specific contents are as follows.
Crude In containing less than 10 ppm of Cd and less than 1 ppm of Tl is used as a raw material, and this is used as an anode in a hydrochloric acid bath. In concentration: 100 to 300 g / L, pH: 0.5 to 2, Current density: 0.5 to 2 A Electrolytic purification is performed at / dm 2 .
The anode chamber and the cathode chamber are separated by a diaphragm and subjected to electrolytic purification. After electrolysis, the electrolyte solution in the anode chamber is extracted, filtered, and then contacted with an anion exchange resin for purification. Further, noble impurities are removed from In in the electrolytic solution by electrolysis at a current density of 0.3 to 2.5 A / dm 2 , and this is supplied to the cathode chamber for electrolytic purification.
隔膜の材質としては、例として綿等の天然繊維、ポリエチレン、ポリプロピレン、ポリエステル等の合成繊維の織布、不織布が挙げられ、充分に小さな通孔を有するものが好ましいとされ、実施例ではテトロン濾布が使用されている。
フィルターについては、濾過ができれば良いという程度で、実施例ではカートリッジフィルターを使用している。
しかし、この特許文献５は、高価な陰イオン交換樹脂を使用しなければならないという問題及び電解液の浄液のため、不純物を除去する電解を行う必要があるという問題がある。Examples of the material of the diaphragm include natural fibers such as cotton, and woven and non-woven fabrics of synthetic fibers such as polyethylene, polypropylene, and polyester, and those having sufficiently small holes are preferred. Cloth is used.
Regarding the filter, a cartridge filter is used in the embodiment as long as it can be filtered.
However, this Patent Document 5 has a problem that it is necessary to use an expensive anion exchange resin and a problem that it is necessary to perform electrolysis to remove impurities for the purification of the electrolytic solution.
下記特許文献６は、Ｉｎの精製方法の記載がある。これは、前記特許文献５の改良版と考えられる。実施例では４〜５Ｎの純度であるが、特許文献５よりも不純物の多い粗Ｉｎを原料として、これをアノードとして塩酸浴でＩｎ濃度：１００〜２００ｇ／Ｌ、ｐＨ：１．５〜２．５、電流密度：０．５〜２Ａ／ｄｍ２で電解精製を行っている。Patent Document 6 below describes a method for purifying In. This is considered an improved version of the above-mentioned Patent Document 5. In Examples, the purity is 4 to 5N, but crude In, which has more impurities than Patent Document 5, is used as a raw material, and this is used as an anode, with an In concentration of 100 to 200 g / L, pH: 1.5 to 2.2. 5. Electrolytic purification is performed at a current density of 0.5 to 2 A / dm 2 .
隔膜によって陽極室と陰極室を分けて電解精製を行い、電解後は陽極室の電解液を抜き取り、陰イオン交換樹脂と接触させることにより浄液を行っている。更に電流密度：０．３〜２．５Ａ／ｄｍ２での電解、及び金属Ｉｎと電解液を接触することにより、電解液中のＩｎより貴な不純物を除去し、これを陰極室に供給して電解精製を行っている。また、セラミックフィルター等を使用した隔膜電解により、Ｉｎイオンを電解液に補給する方法も記載されている。The anode chamber and the cathode chamber are separated by a diaphragm and subjected to electrolytic purification. After the electrolysis, the electrolyte solution in the anode chamber is extracted and brought into contact with an anion exchange resin for purification. Furthermore, by removing the current density from 0.3 to 2.5 A / dm 2 and contacting the metal In with the electrolyte, impurities more noble than In in the electrolyte are removed and supplied to the cathode chamber. Electrolytic purification is performed. In addition, a method of supplying In ions to the electrolytic solution by diaphragm electrolysis using a ceramic filter or the like is also described.
隔膜の材質としては、例として綿等の天然繊維、ポリエチレン、ポリプロピレン、ポリエステル等の合成繊維の織布、不織布が挙げられ、充分に小さな通孔を有するものが好ましいとなっている。実施例ではテトロン濾布を使用している。
濾過については必要に応じて行うこともできるという程度で、実施例ではカートリッジフィルターを使用している。
しかし、この特許文献６は、特許文献５と同様に、高価な陰イオン交換樹脂を使用しなければならないという問題及び電解液の浄液のため不純物を除去する電解を行う必要があるという問題がある。Examples of the material of the diaphragm include natural fibers such as cotton, and woven fabrics and nonwoven fabrics of synthetic fibers such as polyethylene, polypropylene, and polyester, and those having sufficiently small through holes are preferable. In the examples, Tetron filter cloth is used.
In the embodiment, a cartridge filter is used so that the filtration can be performed as necessary.
However, as in Patent Document 5, this Patent Document 6 has a problem that an expensive anion exchange resin must be used and a problem that it is necessary to perform electrolysis to remove impurities for cleaning the electrolytic solution. is there.
下記特許文献７には、高純度金属Ｉｎとその製造方法及び用途の記載がある。具体的内容は、次の通りである。
２段階の電解精製を行い、２段目の電解精製で得られた電析Ｉｎを鋳造する際に不活性ガスを吹き込むことで残留揮発分を除去することにより精製を行っている。この特許文献７の達成純度は「６Ｎ水準」であるとしている。Patent Document 7 below describes high-purity metal In, a method for producing the same, and uses. The specific contents are as follows.
Purification is performed by removing residual volatiles by blowing an inert gas when casting the electrodeposited In obtained by the second stage of electrolytic purification. The achieved purity of Patent Document 7 is assumed to be “6N level”.
電解は塩酸浴でも硫酸浴でも良く、Ｉｎ濃度：２０〜８０ｇ／Ｌ、ｐＨ：１．０〜２．５が好ましいとなっており、隔膜は使用していない。第１電解と第２電解の合計電流密度が１００〜５００Ａ／ｍ２（１〜５Ａ／ｄｍ２）であること、第１電解よりも第２電解の電流密度を低くしている。鋳造時にフラックスとして水酸化Ｎａ、または水酸化Ｎａと硝酸Ｎａの混合物を添加してＣｌを０．０３ｐｐｍ以下、Ｓを０．０１ｐｐｍ以下としている。The electrolysis may be a hydrochloric acid bath or a sulfuric acid bath. In concentration is preferably 20 to 80 g / L, and pH is preferably 1.0 to 2.5, and no diaphragm is used. The total current density of the first electrolysis and the second electrolysis is 100 to 500 A / m 2 (1 to 5 A / dm 2 ), and the current density of the second electrolysis is made lower than that of the first electrolysis. At the time of casting, Na hydroxide or a mixture of Na hydroxide and nitrate is added as a flux so that Cl is 0.03 ppm or less and S is 0.01 ppm or less.
実施例１は不活性ガス吹き込みなし、実施例２は不活性ガス吹き込み、実施例３〜５はフラックスを使用して不活性ガスを吹き込んだ結果である。この特許文献７は、２段階での電解のためコスト高になるという問題があり、また１段目と２段目の間にアノード作製のための鋳造を行う必要があり、工程が複雑になるという問題がある。 Example 1 is the result of blowing inert gas, Example 2 is blowing inert gas, and Examples 3 to 5 are the results of blowing inert gas using a flux. This patent document 7 has a problem of high cost due to electrolysis in two stages, and it is necessary to perform casting for producing an anode between the first stage and the second stage, and the process becomes complicated. There is a problem.
特許文献８には、Ｉｎの精製方法において、陽極室から電解液を抜き取り、ろ過後、この電解液を陰イオン交換樹脂と接触させる工程、電解質が隔膜により陽極室と陰極室に隔てられた電解浄液槽の陰極室に供給して電解液を浄液する工程からなる精製方法が記載されている。この場合も、高価な陰イオン交換樹脂を使用しなければならないという問題及び電解液の浄液のため不純物を除去する電解を行う必要があるという問題がある。そして、達成している純度は６Ｎレベルに過ぎない。 In Patent Document 8, in the purification method of In, an electrolytic solution is extracted from the anode chamber, and after filtration, the electrolytic solution is contacted with an anion exchange resin, and the electrolyte is separated into an anode chamber and a cathode chamber by a diaphragm. A purification method comprising a step of supplying an electrolyte solution to a cathode chamber of a liquid tank and purifying an electrolyte is described. Also in this case, there is a problem that an expensive anion exchange resin must be used and a problem that it is necessary to perform electrolysis to remove impurities for the purification of the electrolytic solution. And the purity achieved is only 6N level.
特許文献９には、Ｉｎ含有物を塩酸で溶解し、この溶解液にアルカリを加えてｐＨが０.５〜４の範囲内の所定の値になるように中和し、溶解液中の所定の金属イオンを水酸化物として析出させて除去し、次いで、これに硫化水素ガスを吹き込み、次工程の電解に有害な金属イオンを硫化物として析出除去した後、この溶解液を電解元液としてＩｎメタルを電解精製する。 In Patent Document 9, an In-containing material is dissolved with hydrochloric acid, and an alkali is added to the solution to neutralize the solution to a predetermined value within a range of 0.5 to 4, and a predetermined solution in the solution is obtained. Then, the metal ions are precipitated and removed as hydroxides, and then hydrogen sulfide gas is blown into the metal ions, and the metal ions harmful to the electrolysis in the next step are precipitated and removed as sulfides. In metal is electrolytically purified.
この方法によって、ＩＴＯターゲット屑から純度９９.９９９％以上のＩｎを回収できるとする記載がある。しかし、この場合は、５Ｎレベルの純度を有するＩｎの回収方法に過ぎない。 There is a description that it is possible to recover 99.999% or more of In from ITO target waste by this method. However, in this case, it is only a recovery method of In having a purity level of 5N.
特許文献１０には、後述する本願発明で使用する高純度炭酸ストロンチウム（ＳｒＣＯ３）の製造方法が開示されているので、参考までに掲示する。Patent Document 10 discloses a method for producing high-purity strontium carbonate (SrCO 3 ) used in the present invention, which will be described later.
本発明は、特にＩｎＰの原料として有用である８Ｎ以上の純度を持つ高純度Ｉｎ及びそれを製造する方法を提供することを課題とし、さらに従来技術よりも安価に製造することができる電解精製による製造方法を提供することを課題とする。ＩｎＧａＮ、ＡｌＩｎＧａＰなどのＬＥＤ用のＩｎの需要が伸びていくという可能性があり、今後大量にかつ安価に製造することが要求されるが、本願発明はこれに対応できる技術を提供する。 An object of the present invention is to provide a high-purity In having a purity of 8N or more that is particularly useful as a raw material for InP and a method for producing the same, and further by electrolytic purification that can be produced at a lower cost than the prior art It is an object to provide a manufacturing method. There is a possibility that the demand for In for LEDs such as InGaN and AlInGaP will increase, and it will be required to manufacture in large quantities at low cost in the future. The present invention provides a technology that can cope with this.
以上から、本出願は、次の発明を提供する。
尚、本発明において、ガス成分元素である炭素（Ｃ）、窒素（Ｎ）、酸素（Ｏ）を除き、各元素濃度の分析値は、ＧＤＭＳ（Glow Discharge Mass Spectrometry）法によって分析した値である。また本発明で使用する「ｐｐｍ」の単位表記は、「ｗｔｐｐｍ」を意味する。
１）電解により高純度Ｉｎを製造する方法であって、５Ｎ（９９．９９９％）のＩｎを原料とし、この原料を用いて電解精製する際に、電解液に、不純物の含有量がそれぞれ、Ｓｉ：０．５１ｐｐｍ以下、Ｓ：４．９ｐｐｍ以下、Ｃａ：５０ｐｐｍ以下、Ｆｅ：０．５ｐｐｍ未満、Ｎｉ：０．５ｐｐｍ未満、Ｐｂ：０．１ｐｐｍ未満であるＳｒＣＯ３を添加して電解液中のＰｂの含有量を低減させ、さらに、電着Ｉｎを陰極板から剥離してるつぼ内に収容し、大気中もしくは酸素含有雰囲気下でＩｎを溶解した後、溶湯を１〜５分間攪拌し、さらにこれを鋳造することを特徴とする高純度Ｉｎの製造方法。
２）アノード液（アノライト）とカソード液（カソライト）を５ｃｍ３／ｃｍ２ｓｅｃ以下の通気性をもつ隔膜で仕切り、カソードに接する電解液を予め０．５μｍ以下の細孔を持つフィルターで濾過し、精製することを特徴とする前記１）に記載の高純度Ｉｎの製造方法。
As described above, the present application provides the following inventions.
In the present invention, except for carbon (C), nitrogen (N), and oxygen (O), which are gas component elements, the analytical values of each element concentration are values analyzed by a GDMS (Glow Discharge Mass Spectrometry) method. . The unit notation of “ppm” used in the present invention means “wtppm”.
1) A method for producing high-purity In by electrolysis, in which 5N (99.999%) In is used as a raw material, and when electrolytic purification is performed using this raw material, the content of impurities in the electrolytic solution is SrCO 3 containing Si: 0.51 ppm or less, S: 4.9 ppm or less, Ca: 50 ppm or less, Fe: less than 0.5 ppm, Ni: less than 0.5 ppm, Pb: less than 0.1 ppm is added to the electrolyte. The Pb content is reduced, and the electrodeposited In is peeled from the cathode plate and accommodated in the crucible. After dissolving In in the atmosphere or in an oxygen-containing atmosphere, the molten metal is stirred for 1 to 5 minutes, Furthermore, this is cast, The manufacturing method of high purity In characterized by the above-mentioned.
2) Partition the anolyte (anolyte) and catholyte (catholyte) with a breathable diaphragm of 5 cm 3 / cm 2 sec or less, and filter the electrolyte in contact with the cathode through a filter with pores of 0.5 μm or less in advance. The method for producing high-purity In according to 1) above, wherein the method is purified.
３）電解精製による高純度Ｉｎの製造方法であって、アノード液（アノライト）とカソード液（カソライト）を、５ｃｍ３／ｃｍ２ｓｅｃ以下の通気性を持つ隔膜で仕切り、さらに、カソライトの一部を電解槽とは異なるカソライトタンクに取り出し、カソライトタンク中のカソライトに、不純物の含有量がそれぞれ、Ｓｉ：０．５１ｐｐｍ以下、Ｓ：４．９ｐｐｍ以下、Ｃａ：５０ｐｐｍ以下、Ｆｅ：０．５ｐｐｍ未満、Ｎｉ：０．５ｐｐｍ未満、Ｐｂ：０．１ｐｐｍ未満であるＳｒＣＯ３を添加することにより、カソライト中のＰｂをＰｂＣＯ２−Ｏ−ＣＯ２Ｓｒとして沈殿させた後、そのカソライトを細孔０．５μｍ以下のフィルターを通して濾過し、濾過後のカソライトを再びカソードボックスへ戻すように循環供給しながら電解精製し、電着Ｉｎを陰極板から剥離してるつぼ内に収容し、大気中もしくは酸素含有雰囲気下でＩｎを溶解した後、溶湯を１〜５分間攪拌し、さらにこれを鋳造することを特徴とする高純度Ｉｎの製造方法。 3) A method for producing high-purity In by electrolytic purification, in which an anolyte (anolyte) and a catholyte (catholyte) are partitioned by a gas-permeable diaphragm of 5 cm 3 / cm 2 sec or less, and a part of catholyte Was extracted into a catholyte tank different from the electrolytic cell, and the contents of impurities in the catholyte in the catholyte tank were Si: 0.51 ppm or less, S: 4.9 ppm or less, Ca: 50 ppm or less, and Fe: 0.8. By adding SrCO 3 less than 5 ppm, Ni: less than 0.5 ppm, and Pb: less than 0.1 ppm, Pb in the catholite was precipitated as PbCO 2 —O—CO 2 Sr, and then the catholite was reduced to pores. While filtering through a filter of 0.5 μm or less and circulatingly feeding the filtered catholyte back to the cathode box again It is depurified and electrodeposited In is peeled off from the cathode plate and accommodated in a crucible. After melting In in the air or in an oxygen-containing atmosphere, the molten metal is stirred for 1 to 5 minutes and then cast. A method for producing high-purity In, which is characterized.
４）電解液を硫酸とし、ｐＨ：０．５〜１．５で電解することを特徴とする前記１）〜３）のいずれか一項に記載の高純度Ｉｎの製造方法。
５）電流密度：1〜５Ａ／ｄｍ２で電解することを特徴とする前記１）〜４）のいずれか一項に記載の高純度Ｉｎの製造方法。
６）電解液中のＩｎ濃度：６５〜１２０ｇ／Ｌ、Ｃｌ濃度：１１〜１５ｇ／Ｌとして電解することを特徴とする前記１）〜５）のいずれか一項に記載の高純度Ｉｎの製造方法。
７）ＳｒＣＯ ３ を０．１〜２．０ｇ／Ｌ添加して精製することを特徴とする前記１〜６のいずれか一項に記載の高純度Ｉｎの製造方法。
８）前記１）〜７）のいずれか一項に記載の高純度Ｉｎの電解精製方法で製造された高純度Ｉｎを陰極板から剥離し、大気中もしくは酸素含有雰囲気下で鋳造する際、１７０〜１９０℃で鋳造することを特徴とする高純度Ｉｎの製造方法。
4) The method for producing high-purity In according to any one of 1) to 3) above, wherein the electrolytic solution is sulfuric acid and electrolysis is performed at a pH of 0.5 to 1.5.
5) Current density: 1-5 A / dm < 2 > electrolyzes, The manufacturing method of high purity In as described in any one of said 1) -4) characterized by the above-mentioned .
6) Production of high-purity In according to any one of 1) to 5) above, wherein electrolysis is performed with an In concentration in the electrolytic solution of 65 to 120 g / L and a Cl concentration of 11 to 15 g / L. Method.
7) The method for producing high-purity In according to any one of 1 to 6 above, wherein the purification is performed by adding 0.1 to 2.0 g / L of SrCO 3 .
8) When the high-purity In produced by the high-purity In electrolytic purification method according to any one of 1) to 7 ) above is peeled from the cathode plate and cast in the air or in an oxygen-containing atmosphere, 170 A method for producing high-purity In, characterized by casting at ˜190 ° C.
本願発明は、特にＩｎＰの原料として有用である８Ｎ以上の純度を持つ高純度Ｉｎ及びそれを製造する方法を提供することができる優れた効果を有する。また、本発明の電解精製による製造方法は、従来技術よりも安価に製造することができるという特徴を持つ。ＩｎＧａＮ、ＡｌＩｎＧａＰなどのＬＥＤ用のＩｎの需要が急速に伸びており、今後大量にかつ安価に製造することが要求されるが、本願発明はこれに対応できる技術を提供することができる。 The present invention has an excellent effect that can provide a high-purity In having a purity of 8N or more, which is particularly useful as a raw material for InP, and a method for producing the same. In addition, the production method by electrolytic purification of the present invention is characterized in that it can be produced at a lower cost than the prior art. The demand for In for LEDs such as InGaN and AlInGaP is growing rapidly, and it will be required to manufacture in large quantities at low cost in the future. The present invention can provide a technology that can cope with this.
本発明の理解を容易にするために、試験の内容を説明する。
これまで、ＩｎＰウェハーの原料であるＩｎは、例えば４ＮのＩｎをベーキング（１０００℃）及び蒸留（１０５０℃）で６Ｎとする乾式法により精製されていた。しかし、乾式法は設備コスト及び製造コストがかかり、８Ｎ以上の高純度Ｉｎを増産するには、ベーキング工程と蒸留工程を複数回繰り返す必要もあり、多額の設備投資が必要である。そこで、湿式精製でＩｎＰに使用可能な高純度Ｉｎが得られるかを検討した。
また、従来技術では、６Ｎ以上という記載はあっても、実際は６ＮレベルのＩｎしか達成しておらず、さらに高純度化が必要であった。本願発明は、目標純度は８Ｎ以上とし、硫酸浴での電解精製による試験を行った。In order to facilitate understanding of the present invention, the contents of the test will be described.
Until now, In, which is a raw material for InP wafers, has been purified by a dry method in which, for example, 4N of In is baked (1000 ° C.) and distilled (1050 ° C.) to 6N. However, the dry method requires equipment costs and manufacturing costs. In order to increase the production of high-purity In of 8N or more, it is necessary to repeat the baking process and the distillation process several times, which requires a large capital investment. Therefore, it was examined whether high-purity In that could be used for InP was obtained by wet purification.
In addition, in the prior art, even though there is a description of 6N or more, in reality, only 6N level In was achieved, and higher purity was required. In the present invention, the target purity was set to 8N or more, and the test was conducted by electrolytic purification in a sulfuric acid bath.
本発明の電解精製による高純度Ｉｎの製造は、図１に示すような装置を用いて行なう。図１について説明すると、電解槽（電槽）中に陰極板となるチタン（Ｔｉ）製の金属板が配置され、陽極には純度５ＮのＩｎのインゴットが設置されている。カソードとアノードとの間には、隔壁の役割をする濾布を備えたカソードボックスが配置され、両電極板が仕切られている。
ここで、該濾布の細孔の規格は通気性というＪＩＳ Ｌ １０９６で規格化されており、本発明では、１２４．５Ｐａにおいて、５ｃｍ３／ｃｍ２ｓｅｃ以下の通気性を有する濾布を使用して、アノライト中の浮遊物等の不純物がカソライト中に混同することを防いでいる。The production of high purity In by electrolytic purification of the present invention is performed using an apparatus as shown in FIG. Referring to FIG. 1, a titanium (Ti) metal plate serving as a cathode plate is disposed in an electrolytic cell (battery cell), and an In ingot of purity 5N is disposed on the anode. A cathode box having a filter cloth serving as a partition is disposed between the cathode and the anode, and both electrode plates are partitioned.
Here, the specification of the pores of the filter cloth is standardized by JIS L 1096, which is air permeability, and in the present invention, a filter cloth having an air permeability of 5 cm 3 / cm 2 sec or less is used at 124.5 Pa. Thus, impurities such as suspended matter in the anolite are prevented from being confused in the catholyte.
さらに、電解槽の外側に、カソライトタンクを配置し、カソードボックス内の電解液の一部をカソライトタンクに導入し、この中に高純度ＳｒＣＯ３を添加する。この処理を行うことによって、カソライト中に含有される鉛（Ｐｂ）をＰｂＣＯ２−Ｏ−ＣＯ２Ｓｒとしてカソライトタンクの底部に沈殿させ、Ｐｂを除去したカソライトを電槽内のカソードボックス内に戻すことで、Ｐｂ除去されたカソライトが循環して使用される。Further, a catholyte tank is arranged outside the electrolytic cell, and a part of the electrolyte solution in the cathode box is introduced into the catholyte tank, and high purity SrCO 3 is added thereto. By carrying out this treatment, lead (Pb) contained in the catholite is precipitated as PbCO 2 —O—CO 2 Sr at the bottom of the catholyte tank, and the catholite from which Pb has been removed is placed in the cathode box in the battery case. By returning, the Pb-removed catholyte is circulated and used.
ここで、カソライトタンク内でＰｂ除去されたカソライトは、０．５μｍ以下の細孔を持つフィルターで濾過され、精製されることで、カソードボックス内へのＰｂの混入を防いでいる。フィルターの細孔は、０．２μｍであることが、より好ましい。
原料となるＩｎは、５Ｎ（９９．９９９％）のＩｎをアノードとして使用する。５ＮレベルのＩｎは蒸留法を単独で用いることにより容易に製造でき、市販品の材料を使用できる。Here, the catholite from which Pb has been removed in the catholyte tank is filtered through a filter having pores of 0.5 μm or less and purified, thereby preventing Pb from being mixed into the cathode box. The pores of the filter are more preferably 0.2 μm.
As the raw material In, 5N (99.999%) In is used as the anode. 5N level In can be easily produced by using the distillation method alone, and commercially available materials can be used.
前記蒸留法を単独で用いることにより製造した５ＮのＩｎの主たる不純物は、Ｐｂ（鉛）、Ｚｎ（亜鉛）、Ｓｎ（錫）であり、特に、Ｐｂは１ｐｐｍ程度含有する。電解精製法で、Ｓｎ、Ｆｅ（鉄）、Ｎｉ（ニッケル）などの不純物は低減できるが、最も問題となるのは、Ｐｂの除去であり、このＰｂを簡便に除去することが大きな課題となる。８Ｎという純度の向上は、極めて難しく、従来技術では、前記純度まで達成できなかったのが実情である。 The main impurities of 5N In produced by using the distillation method alone are Pb (lead), Zn (zinc), and Sn (tin), and in particular, Pb contains about 1 ppm. Impurities such as Sn, Fe (iron), and Ni (nickel) can be reduced by the electrolytic purification method, but the most problematic is the removal of Pb, and the simple removal of Pb is a major issue. . It is extremely difficult to improve the purity of 8N, and it is the actual situation that the above-mentioned purity could not be achieved by the prior art.
本願発明では、電解精製工程において硫酸溶液を使用しており、前記蒸留法によって製造された５ＮのＩｎ原料中のＳ（硫黄）は、０．００５ｐｐｍであるが、電解精製後に０．０５ｐｐｍに増加し、８ＮのＩｎを製造するためには、電解精製後のＳ分の低減が必要となる。
さらに、Ｚｎについても、前記蒸留法で製造された５ＮのＩｎ原料中にはＺｎが０．１ｐｐｍ含有されており、電解精製後０．０５ｐｐｍに低減できているが、８ＮのＩｎを製造するためには、不純物の低減化と工程中の不純物の混入防止という、さらに厳しい条件下で低減する必要がある。In the present invention, a sulfuric acid solution is used in the electrolytic purification process, and S (sulfur) in the 5N In raw material produced by the distillation method is 0.005 ppm, but increases to 0.05 ppm after the electrolytic purification. However, in order to produce 8N In, it is necessary to reduce the S content after electrolytic purification.
Further, Zn was also contained in the 5N In raw material produced by the above-mentioned distillation method, and 0.1 ppm of Zn could be reduced to 0.05 ppm after electrolytic purification, but in order to produce 8N In. Therefore, it is necessary to reduce it under more severe conditions such as reduction of impurities and prevention of contamination of impurities during the process.
本発明の高純度Ｉｎの製造に際して、５Ｎ（９９．９９９％）のＩｎを使用し、かつ電解により精製しようとするものであるが、図１に示すような装置のカソライトタンク中の電解液に高純度ＳｒＣＯ３を添加してＰｂを低減させる。これが、本願発明の大きな特徴の一つである。基本は電解精製にあるので、乾式法による精製の１／５〜１／６のコストで達成できるという優れた生産性向上の利点がある。In the production of the high-purity In of the present invention, 5N (99.999%) In is to be purified by electrolysis. The electrolytic solution in the catholyte tank of the apparatus as shown in FIG. Pb is reduced by adding high-purity SrCO 3 . This is one of the major features of the present invention. Since the basis is electrolytic purification, there is an advantage of excellent productivity improvement that can be achieved at a cost of 1/5 to 1/6 of the purification by the dry method.
高純度ＳｒＣＯ３の作製について説明すると、まず、特級硝酸ストロンチウム（Ｓｒ（ＮＯ３）２）を純水に溶解し、その液に特級炭酸アンモニウムを１．４倍当量添加したものを用いる。その反応式を、下記に示す。
（Ｓｒ（ＮＯ３）２）＋（ＮＨ４）２ＣＯ３→ＳｒＣＯ３↓＋２ＮＨ４ＮＯ３
この反応により、難溶性のＳｒＣＯ３を沈殿させる。この後、さらに純度を上げるために、リパルプ洗浄を行い、次に固液分離のろ過を行い、これを乾燥させて、高純度のＳｒＣＯ３を作製する。
このＳｒＣＯ３の高純度化の技術は、上記特許文献１０（特開平９−７７５１６号公報）により作製することができる。The production of high-purity SrCO 3 will be described. First, a special grade strontium nitrate (Sr (NO 3 ) 2 ) is dissolved in pure water, and a special grade ammonium carbonate added with 1.4 times equivalent amount is used. The reaction formula is shown below.
(Sr (NO 3 ) 2 ) + (NH 4 ) 2 CO 3 → SrCO 3 ↓ + 2NH 4 NO 3
This reaction precipitates poorly soluble SrCO 3 . Thereafter, in order to further increase the purity, repulp washing is performed, followed by solid-liquid separation filtration, and this is dried to produce high-purity SrCO 3 .
The technique for increasing the purity of SrCO 3 can be produced by the above-mentioned Patent Document 10 (Japanese Patent Laid-Open No. 9-77516).
電解精製は硫酸溶液中で行ない、カソードの周囲を取り巻くように前記カソードボックスが配置され、カソードボックスはアノード板に対向する面に濾布を張り、アノライト中の浮遊物等の不純物がカソライト中に混同することを防ぐようにした。
この濾布は、上記の通り、通気性５ｃｍ３／ｃｍ２ｓｅｃ以下、さらに好ましくは１ｃｍ３／ｃｍ２ｓｅｃ以下のものを使用した。電解槽内にあり、カソードボックスの外側に、５ＮのＩｎを配置する。電解槽の外側には、カソライトタンクを配置し、カソードボックス内のカソライトの一部をカソライトタンクに導入し、この中に高純度ＳｒＣＯ３を添加する。Electrolytic purification is carried out in a sulfuric acid solution, and the cathode box is arranged so as to surround the cathode. The cathode box has a filter cloth on the surface facing the anode plate, and impurities such as suspended matter in the anolyte are contained in the catholyte. I tried to prevent confusion.
As described above, the filter cloth used had a breathability of 5 cm 3 / cm 2 sec or less, more preferably 1 cm 3 / cm 2 sec or less. In the electrolytic cell, 5N In is arranged outside the cathode box. A catholyte tank is disposed outside the electrolytic cell, and a portion of the catholyte in the cathode box is introduced into the catholyte tank, and high purity SrCO 3 is added thereto.
電解に際しては、電解液を硫酸とし、ｐＨ０．５〜１．５で電解する。ｐＨ０．５未満では水素発生により電流効率が低下し、ｐＨ１．５を超えると電解電圧が高くなるためである。
さらに、電流密度：1〜５Ａ／ｄｍ２で電解する。これは、1Ａ／ｄｍ２未満では生産性が悪く、５Ａ／ｄｍ２を超えると電解電圧が高くなるためである。またデンドライトが発生しやすく、電解精製においてはＩｎよりも貴な不純物がカソードに析出しやすいためである。In electrolysis, the electrolytic solution is sulfuric acid and electrolysis is performed at pH 0.5 to 1.5. If the pH is less than 0.5, the current efficiency decreases due to hydrogen generation, and if the pH exceeds 1.5, the electrolysis voltage increases.
Furthermore, the current density: electrolysis at 1-5A / dm 2. This poor productivity is less than 1A / dm 2, is because the the electrolysis voltage exceeds 5A / dm 2 becomes high. In addition, dendrites are easily generated, and impurities more precious than In are easily deposited on the cathode in electrolytic purification.
カソードに接する電解液（カソライト）中のＩｎ濃度：６５〜１２０ｇ／Ｌ、Ｃｌ濃度：１１〜１５ｇ／Ｌとして電解する。Ｉｎ濃度：６５ｇ／Ｌ未満では、特に電解精製では水素発生により電流効率が低下し、１２０ｇ／Ｌを超えると高価なＩｎの工程内在庫が増えるためである。
また、Ｃｌ濃度１１ｇ／Ｌ未満ではＩｎの電着がデンドライト状に析出して隔膜を破損し、Ｉｎの純度を８Ｎ以上にすることができなくなる。１５ｇ／Ｌを超えると、周辺機器の腐食を加速させるため好ましくない。８Ｎ以上の高純度化を達成し、かつ効率的なＩｎの高純度化のためには、Ｃｌ濃度：１１〜１５ｇ／Ｌとして電解することが必要である。Electrolysis is performed at an In concentration of 65 to 120 g / L and a Cl concentration of 11 to 15 g / L in the electrolyte solution (catholyte) in contact with the cathode. This is because, when the In concentration is less than 65 g / L, current efficiency decreases due to hydrogen generation particularly in electrolytic refining, and when it exceeds 120 g / L, the in-process inventory of expensive In increases.
On the other hand, if the Cl concentration is less than 11 g / L, the electrodeposition of In precipitates in a dendritic state and damages the diaphragm, so that the purity of In cannot be increased to 8N or more. If it exceeds 15 g / L, corrosion of peripheral equipment is accelerated, which is not preferable. In order to achieve a high purity of 8N or more and to efficiently purify In, it is necessary to perform electrolysis with a Cl concentration of 11 to 15 g / L.
高純度ＳｒＣＯ３については、０．１〜２．０ｇ／Ｌをカソライトタンク中のカソライトに添加して、ＰｂをＰｂＣＯ２−Ｏ−ＣＯ２Ｓｒとしてカソライトタンクの底部に沈殿させる。Ｐｂを沈殿させたカソライトタンク中のカソライトは、ＰｂＣＯ２−Ｏ−ＣＯ２Ｓｒを含まないように、細孔０．５μｍ以下のフィルターを通して、カソードボックス内の電解液中に戻すことで、カソライトが循環して使用される。For high purity SrCO 3 , 0.1-2.0 g / L is added to the catholite in the catholite tank to precipitate Pb as PbCO 2 —O—CO 2 Sr at the bottom of the catholite tank. The catholyte in the catholyte tank in which Pb is precipitated is returned to the electrolyte in the cathode box through a filter having a pore size of 0.5 μm or less so as not to contain PbCO 2 —O—CO 2 Sr. Is used cyclically.
以上の工程によって、カソライトタンク中のカソライトに高純度ＳｒＣＯ３を添加することにより、Ｐｂ２＋はＰｂＣＯ２−Ｏ−ＣＯ２Ｓｒとして析出させ、カソライトタンクの底部に沈殿するので、電解液中のＰｂが低減でき、電解精製されるＩｎからＰｂを除去することが可能となる。ＳｒＣＯ３の濃度０．１ｇ／Ｌ未満ではＰｂの除去効果が低減し、２．０ｇ／Ｌを超えるとフィルターが目詰まりし、フィルターの交換頻度が高くなる。By adding high-purity SrCO 3 to the catholyte in the catholite tank by the above steps, Pb 2+ is precipitated as PbCO 2 —O—CO 2 Sr, and is precipitated at the bottom of the catholyte tank. Pb can be reduced, and Pb can be removed from the electrolytically purified In. When the concentration of SrCO 3 is less than 0.1 g / L, the effect of removing Pb is reduced, and when it exceeds 2.0 g / L, the filter is clogged and the frequency of filter replacement is increased.
本願発明による電解精製を行うと、アノードとして使用する原料Ｉｎは電解液（アノライト）に溶解する。適正な電解条件では、Ｉｎよりも貴な不純物はカソードに電着せず、アノード表面に残るか、電解液中に微細な浮遊物として混入するが、浮遊物となった場合はカソードに電着するＩｎに混入する可能性がある。したがって、電解精製の場合は、充分に小さい細孔を持つ隔壁を、アノードとカソードの間に配置することが好ましい。 When the electrolytic purification according to the present invention is performed, the raw material In used as the anode is dissolved in the electrolytic solution (anolite). Under proper electrolysis conditions, impurities more precious than In do not electrodeposit on the cathode and remain on the anode surface or are mixed as fine floating substances in the electrolyte, but if they become floating substances, they are electrodeposited on the cathode. There is a possibility of mixing in In. Therefore, in the case of electrolytic purification, it is preferable to arrange a partition wall having sufficiently small pores between the anode and the cathode.
（電極反応）
カソード反応は、次の通りである。
Ｉｎ３＋＋３ｅ → Ｉｎ
濾布膜
Ｉｎ３＋（アノード室）→Ｉｎ３＋（カソード室）
アノード反応は、次の通りである。
Ｉｎ → Ｉｎ３＋＋３ｅ
（微量）Ｐｂ → Ｐｂ２＋＋２ｅ
（カソライトタンク）
Ｐｂ２＋＋ＳｒＣＯ２−Ｏ−ＣＯ２Ｓｒ→ＰｂＣＯ２−Ｏ−ＣＯ２Ｓｒ＋Ｓｒ２＋ (Electrode reaction)
The cathode reaction is as follows.
In 3+ + 3e → In
Filter cloth membrane In 3+ (anode chamber) → In 3+ (cathode chamber)
The anodic reaction is as follows.
In → In 3+ + 3e
(Trace) Pb → Pb 2+ + 2e
(Catholite tank)
Pb 2+ + SrCO 2 —O—CO 2 Sr → PbCO 2 —O—CO 2 Sr + Sr 2+
上記カソライトタンク内の反応に示すように、ＳｒＣＯ３の添加によりＰｂ２＋はＰｂＣＯ２−Ｏ−ＣＯ２Ｓｒとして析出するので、除去が可能となる。該Ｐｂを除去したカソライトは、細孔０．５μｍ以下のフィルターに通液してＰｂＣＯ２−Ｏ−ＣＯ２Ｓｒを濾過した後、再び、カソードボックスに戻し、Ｔｉ電極上にはカソライト中のＩｎが析出し、８Ｎ以上の純度を有するＩｎを得ることができる。As shown in the reaction in the catholyte tank, Pb 2+ precipitates as PbCO 2 —O—CO 2 Sr by the addition of SrCO 3 , and thus can be removed. The catholite from which Pb was removed was passed through a filter having a pore size of 0.5 μm or less to filter PbCO 2 —O—CO 2 Sr, and then returned to the cathode box again. And In having a purity of 8N or higher can be obtained.
本発明において、カソライトタンクへ導入する高純度ＳｒＣＯ３中の不純物は、Ｓｉ：０．５１ｐｐｍ以下、Ｓ：４．９ｐｐｍ以下、Ｃａ：５０ｐｐｍ以下、Ｆｅ＜０．５ｐｐｍ、Ｎｉ＜０．５ｐｐｍ、Ｐｂ＜０．１ｐｐｍを使用することができる。なお、ここで使用される高純度ＳｒＣＯ３中の不純物は、カソライト中で希釈されるので、実際にＩｎ中へ混入する量は、実施例に示すように、さらに低減される。
参考までに、市販の特級のＳｒＣＯ３の不純物は、Ｓｉ：８．４ｐｐｍ、Ｓ：２９０ｐｐｍ、Ｃａ：５００ｐｐｍ、Ｆｅ：６．５ｐｐｍ、Ｎｉ＜６ｐｐｍ、Ｐｂ＜０．１ｐｐｍであり、Ｐｂ以外の不純物濃度は、本願発明において使用する高純度ＳｒＣＯ３に比べて、およそ一桁以上高い。In the present invention, impurities in the high purity SrCO 3 introduced into the catholyte tank are Si: 0.51 ppm or less, S: 4.9 ppm or less, Ca: 50 ppm or less, Fe <0.5 ppm, Ni <0.5 ppm, Pb <0.1 ppm can be used. Since impurities in the high purity SrCO 3 used here are diluted in the catholyte, the amount actually mixed into In is further reduced as shown in the examples.
For reference, impurities of commercially available special grade SrCO 3 are Si: 8.4 ppm, S: 290 ppm, Ca: 500 ppm, Fe: 6.5 ppm, Ni <6 ppm, Pb <0.1 ppm, and impurities other than Pb The concentration is approximately one digit or more higher than the high purity SrCO 3 used in the present invention.
図１では、硫酸を使用した例を示しているが、塩酸浴での電解精製の場合、アノードからの塩素ガス発生を防ぎたいのであれば、特開平０８−０６０２６４号公報（特許３０８９５９５号公報）の電解採取によるＩｎの回収方法（日鉱金属）のようにアノードボックスを設置して、アノードを硫酸と接触させるとよい。 FIG. 1 shows an example in which sulfuric acid is used. However, in the case of electrolytic purification in a hydrochloric acid bath, if it is desired to prevent generation of chlorine gas from the anode, Japanese Patent Laid-Open No. 08-060264 (Japanese Patent No. 3089595). It is good to install an anode box like the collection | recovery method (Nikko metal) of In by electrowinning, and to make an anode contact with a sulfuric acid.
電解後、カソードから電析Ｉｎを剥離し、１７０〜１９０℃で溶解・鋳造してインゴットを作製する。この溶解・鋳造の際に、陰極板から剥離した電着Ｉｎをるつぼ内に収容し、大気中もしくは酸素含有雰囲気下でＩｎを溶解した後、溶湯を１〜５分間かけて充分に攪拌し、さらにこれを鋳造して、８Ｎ（９９．９９９９９９％）以上の高純度Ｉｎを得る。
前記大気中もしくは酸素含有雰囲気下で溶解することにより、Ｚｎ、Ｓ等の酸化物が形成され、固体（亜鉛酸化物）又は気体（硫黄酸化物）の状態で、Ｉｎ中から分離、除去することができる。なお、上記酸素含有ガスとしては、高純度アルゴンと高純度酸素の混合ガスや酸素富化空気等が使用できる。After electrolysis, electrodeposited In is peeled from the cathode, and melted and cast at 170 to 190 ° C. to produce an ingot. During this melting and casting, the electrodeposited In peeled off from the cathode plate was accommodated in a crucible, and after dissolving In in the atmosphere or in an oxygen-containing atmosphere, the molten metal was sufficiently stirred for 1 to 5 minutes, Further, this is cast to obtain high purity In of 8N (99.99999999%) or more.
By dissolving in the atmosphere or in an oxygen-containing atmosphere, oxides such as Zn and S are formed and separated and removed from In in a solid (zinc oxide) or gas (sulfur oxide) state. Can do. As the oxygen-containing gas, a mixed gas of high purity argon and high purity oxygen, oxygen-enriched air, or the like can be used.
上記の製造方法により、硫黄（Ｓ）の含有量を０．０１ｐｐｍ未満に、鉛（Ｐｂ）及び亜鉛（Ｚｎ）の含有量をＧＤＭＳ分析において検出限界値未満とし、さらに鉄（Ｆｅ）、錫（Ｓｎ）及びシリコン（Ｓｉ）の含有量もＧＤＭＳ分析において検出限界値未満とすることができ、８Ｎ（９９．９９９９９９％）以上の純度を有する高純度Ｉｎを得ることができる。 According to the above manufacturing method, the content of sulfur (S) is less than 0.01 ppm, the content of lead (Pb) and zinc (Zn) is less than the detection limit in GDMS analysis, and iron (Fe), tin ( The content of Sn) and silicon (Si) can also be made less than the detection limit value in the GDMS analysis, and high purity In having a purity of 8N (99.99999999%) or more can be obtained.
次に、本願発明の実施例及び比較例について説明する。
（実施例１）
実施例１として硫酸浴を用いた電解精製（図１に示す装置を使用）について説明する。カソードボックスで仕切られたアノライトとカソライトの間には、通気性５ｃｍ３／ｃｍ２ｓｅｃ以下の濾布が配置され、アノライト中に存在する浮遊物等の不純物がカソライト側へ混入することを防止した。なお、電解精製の条件については、カソライト中Ｉｎ濃度：８０ｇ／Ｌ、ｐＨ：１．２、高純度ＳｒＣＯ３：０．５ｇ／Ｌ、電流密度：３Ａ／ｄｍ２、カソライト中Ｃｌ濃度を１１ｇ／Ｌとした。Next, examples and comparative examples of the present invention will be described.
Example 1
As Example 1, electrolytic purification using a sulfuric acid bath (using the apparatus shown in FIG. 1) will be described. Between the anolyte and catholyte partitioned by the cathode box, a filter cloth with air permeability of 5 cm 3 / cm 2 sec or less is arranged to prevent impurities such as suspended solids existing in the anolyte from entering the catholyte side. . The conditions for electrolytic purification were as follows: In concentration in catholyte: 80 g / L, pH: 1.2, high-purity SrCO 3 : 0.5 g / L, current density: 3 A / dm 2 , and Cl concentration in catholite of 11 g / L L.
カソライトタンクへ添加した高純度ＳｒＣＯ３中に含まれる不純物の含有量は、Ｓｉ：０．５１ｐｐｍ、Ｓ：４．９ｐｐｍ、Ｃａ：５０ｐｐｍ、Ｆｅ＜０．５ｐｐｍ、Ｎｉ＜０．５ｐｐｍ、Ｐｂ＜０．１ｐｐｍであった。
この高純度ＳｒＣＯ３を使用して、カソライトタンク中のカソライトへ高純度ＳｒＣＯ３を０．５ｇ／Ｌの濃度となるように添加し、ＰｂをＰｂＣＯ２−Ｏ−ＣＯ２Ｓｒとして沈殿させ、細孔０．５μｍ以下のフィルターを通して濾過し、濾過後のカソライトを再びカソードボックスへ戻すように循環供給しながら、電解精製を実施した。電解精製後の電析したＩｎをカソードのＴｉ電極板から剥離し、不純物を分析した結果を表１に示す。The content of impurities contained in the high purity SrCO 3 added to the catholyte tank is as follows: Si: 0.51 ppm, S: 4.9 ppm, Ca: 50 ppm, Fe <0.5 ppm, Ni <0.5 ppm, Pb < It was 0.1 ppm.
Using this high-purity SrCO 3 , high-purity SrCO 3 was added to the catholyte in the catholyte tank to a concentration of 0.5 g / L, and Pb was precipitated as PbCO 2 —O—CO 2 Sr, The solution was filtered through a filter having a pore size of 0.5 μm or less, and electrolytic purification was performed while circulating and supplying the filtered catholyte back to the cathode box. Table 1 shows the results of separating the electrodeposited In after electrolytic purification from the cathode Ti electrode plate and analyzing impurities.
その結果、電解精製後のＩｎ中の不純物は、Ｐｂ：０．００５ｐｐｍ未満（検出限界値未満）に低減でき、Ｓｎ：０．０１ｐｐｍ未満（検出限界値未満）、Ｎｉ：０．００６ｐｐｍ、Ｆｅ：０．００１ｐｐｍに低減できた。また、Ｚｎも０．０５ｐｐｍに低減できたが、この含有量では、８Ｎの純度を達成できるものではなく、さらに、Ｓは蒸留法で製造した５ＮのＩｎ原料中では０．００５ｐｐｍであったが、電解精製後では電解液中の硫酸からのＳ分が混入して０．０５ｐｐｍに増加し、８ＮのＩｎを製造するためには、低減しなくてはならないことになる。 As a result, impurities in In after electrolytic purification can be reduced to Pb: less than 0.005 ppm (less than detection limit value), Sn: less than 0.01 ppm (less than detection limit value), Ni: 0.006 ppm, Fe: It was reduced to 0.001 ppm. Further, Zn could be reduced to 0.05 ppm, but at this content, purity of 8N could not be achieved, and S was 0.005 ppm in the 5N In raw material produced by the distillation method. After electrolytic purification, S content from sulfuric acid in the electrolytic solution is mixed and increased to 0.05 ppm, and in order to produce 8N In, it must be reduced.
次に、電解精製後の電析したＩｎをカソード板から剥離し、これをるつぼ内に収容し、大気中でＩｎを１８０℃で溶解した後、溶湯を３分間攪拌し、さらにこれを大気中で鋳造した。
その結果、鋳造後のＩｎ中の不純物は、表１に示すように、Ｐｂについては、電解精製後の含有量が維持され、０．００５ｐｐｍ未満（検出限界値未満）となっており、またＳは０．００８ｐｐｍとなり、電解精製後に０．０５ｐｐｍに増加したが、鋳造工程によって大気中酸素と反応して酸化物を形成し、硫黄酸化物の気体状態となり、溶解しているＩｎから分離、除去されたことで低減した。Next, the electrodeposited In after electrolytic purification is peeled off from the cathode plate, accommodated in a crucible, and In is melted in the atmosphere at 180 ° C., then the molten metal is stirred for 3 minutes, and this is further dissolved in the atmosphere. Casted with.
As a result, as shown in Table 1, the impurities in In after casting are maintained in the content after electrolytic purification for Pb, being less than 0.005 ppm (less than the detection limit value), and S Became 0.008ppm and increased to 0.05ppm after electrolytic refining, but it reacted with atmospheric oxygen to form oxides by the casting process to form a sulfur oxide gas, which was separated from dissolved In and removed. Was reduced.
さらに、鋳造工程後のＺｎは０．００１ｐｐｍ未満（検出限界値未満）となっているが、電解精製後には０．０５ｐｐｍ含有していたが、鋳造工程によって大気中酸素と反応して酸化物（スラグ）を形成して個体（浮遊物）の状態となり、鋳型に溶湯を流し込む際に鋳型に浮遊物が入らないようにして、Ｉｎから分離、除去され、検出限界値未満まで低減した。その他、電解精製後に、僅かではあるが、ある程度の含有量を示していたＮａ、Ｃａ、Ｆｅ、Ｎｉについては、ＧＤＭＳの検出限界値未満にまで低減した。 Furthermore, Zn after the casting process is less than 0.001 ppm (less than the detection limit value), but was 0.05 ppm after electrolytic purification, but it reacted with oxygen in the atmosphere by the casting process to produce an oxide ( The slag was formed into a solid (floating matter) state, and when the molten metal was poured into the mold, it was separated and removed from In, so that the floating material did not enter the mold, and reduced to below the detection limit value. In addition, Na, Ca, Fe, and Ni, which showed a slight content after electrolytic purification, were reduced to less than the detection limit value of GDMS.
また、本実施例１では、上記以外の不純物として、Ｌｉ、Ｂｅ、Ｂ、Ｆ、Ｍｇ、Ａｌ、Ｐ、Ｃｌ、Ｋ、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｃｏ、Ｃｕ、Ｇａ、Ｇｅ、Ａｓ、Ｓｅ、Ｂｒ、Ｒｂ、Ｓｒ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｃｄ、Ｓｂ、Ｔｅ、Ｉ、Ｃｓ、Ｂａ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ、Ｈｆ、Ｔａ、Ｗ、Ｒｅ、Ｏｓ、Ｉｒ、Ｐｔ、Ａｕ、Ｈｇ、Ｔｌ、Ｂｉ、Ｔｈ、Ｕの元素の含有濃度は、ＧＤＭＳの検出限界値未満なので、これらの元素は除く。以下の実施例においても、同様である。
以上の実施例の結果から明らかなように、電解精製および鋳造処理によって、いずれも不純物は低減し、特にＰｂ、Ｚｎ、Ｓ、Ｆｅ、Ｓｎ、Ｓｉの不純物の極限までの低減ができ、８Ｎ純度のＩｎが製造できた。また、歩留りは９８％以上であった。In Example 1, as impurities other than the above, Li, Be, B, F, Mg, Al, P, Cl, K, Sc, Ti, V, Cr, Mn, Co, Cu, Ga, Ge, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Sb, Te, I, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Bi, Th, and U are contained in GDMS. These elements are excluded because they are below the detection limit. The same applies to the following embodiments.
As is clear from the results of the above examples, the impurities are reduced by electrolytic refining and casting treatment, and in particular, the impurities of Pb, Zn, S, Fe, Sn, Si can be reduced to the limit, and the purity of 8N In could be produced. The yield was 98% or more.
（比較例１）
次に、比較例１として、上記実施例１において、カソライトタンク内の電解液中へ高純度ＳｒＣＯ３を添加する工程を無くし、電解液中のＣｌ濃度を８ｇ／Ｌとした。それ以外は、全て実施例１と同様の条件でＩｎの電解精製を行った。
また、溶湯の鋳造時に実施例では大気中で溶湯をるつぼ内で撹拌して、溶湯中の不純物の酸化を促進させる工程を設けたが、この比較例１では、溶湯の撹拌工程を設けることなく、１７０℃の溶湯温度で鋳造した。
この結果を表２に示す。比較例１の条件で電解精製し、鋳造されたＩｎ中には、Ｐｂが０．５ｐｐｍ、Ｓ：０．０３ｐｐｍ、Ｚｎ：０．０２ｐｐｍ含有しており、８Ｎの純度を達成することはできなかった。
その他の不純物については、実施例１と同等の含有量に低減できていた。すなわち、Ｎａ：０．００１ｐｐｍ、Ｓｉ：＜０．００５ｐｐｍ（検出限界値未満）、Ｃａ：＜０．００５ｐｐｍ（検出限界値未満）、Ｆｅ：０．００１ｐｐｍ、Ｎｉ：０．００１ｐｐｍ、Ｓｎ＜０．０１ｐｐｍ（検出限界値未満）であった。
(Comparative Example 1)
Next, as Comparative Example 1, in Example 1 above, the step of adding high-purity SrCO 3 into the electrolytic solution in the catholyte tank was eliminated, and the Cl concentration in the electrolytic solution was 8 g / L. Other than that, electrolytic purification of In was performed under the same conditions as in Example 1.
In addition, in the embodiment, a step of stirring the molten metal in the crucible in the atmosphere at the time of casting the molten metal to promote the oxidation of impurities in the molten metal was provided. In Comparative Example 1, a molten metal stirring step was not provided. And cast at a molten metal temperature of 170 ° C.
The results are shown in Table 2. In the In purified by electrolytic purification under the conditions of Comparative Example 1, Pb contained 0.5 ppm, S: 0.03 ppm, Zn: 0.02 ppm, and a purity of 8N could not be achieved. It was.
About other impurities, it was able to be reduced to content equivalent to Example 1. FIG. That is, Na: 0.001 ppm, Si: <0.005 ppm (less than detection limit value), Ca: <0.005 ppm (less than detection limit value) , Fe: 0.001 ppm, Ni: 0.001 ppm, Sn <0. It was 01 ppm (below the detection limit).
（実施例２）
実施例２として、カソライトタンク中への高純度ＳｒＣＯ３の添加濃度を０．１ｇ／Ｌとし、カソライト中のＩｎ濃度：６５ｇ／Ｌ、ｐＨ：０．５、電流密度：１Ａ／ｄｍ２、カソライト中Ｃｌ濃度を１３ｇ／Ｌとした。実施例１との電解精製条件との大きな相違点は、カソライト中の高純度ＳｒＣＯ３の添加濃度を実施例１よりも低濃度とし、電解液中のＣｌ濃度を１１ｇ／Ｌから１３ｇ／Ｌへと高くした点にある。(Example 2)
As Example 2, the concentration of high-purity SrCO 3 added to the catholyte tank was 0.1 g / L, the In concentration in the catholyte was 65 g / L, the pH was 0.5, the current density was 1 A / dm 2 , The concentration of Cl in catholyte was 13 g / L. The major difference from the electrolytic purification conditions of Example 1 is that the concentration of high-purity SrCO 3 in the catholyte is lower than that in Example 1, and the Cl concentration in the electrolytic solution is changed from 11 g / L to 13 g / L. It is in the point raised.
カソライトタンクへ添加した高純度ＳｒＣＯ３の不純物の含有量は、Ｓｉ：０．５１ｐｐｍ、Ｓ：４．９ｐｐｍ、Ｃａ：５０ｐｐｍ、Ｆｅ＜０．５ｐｐｍ、Ｎｉ＜０．５ｐｐｍ、Ｐｂ＜０．１ｐｐｍであった。
上記の条件で電解精製を行い、電解精製で電析したＩｎをカソード板から剥離し、これをるつぼ内に収容し、大気中でＩｎを１７０℃で溶解した後、溶湯を３分間攪拌し、さらにこれを大気中で鋳造した。この結果を、表３に示す。The content of impurities of high purity SrCO 3 added to the catholyte tank is Si: 0.51 ppm, S: 4.9 ppm, Ca: 50 ppm, Fe <0.5 ppm, Ni <0.5 ppm, Pb <0.1 ppm. Met.
Performing electrolytic purification under the above conditions, peeling In deposited by electrolytic purification from the cathode plate, placing this in a crucible, melting In at 170 ° C. in the atmosphere, stirring the molten metal for 3 minutes, Further, this was cast in the atmosphere. The results are shown in Table 3.
この結果、鋳造後のＩｎ中の不純物は、表３に示すように、Ｐｂについては、電解精製後の含有量が維持され、０．００５ｐｐｍ未満（検出限界未満）となっており、またＳは電解精製後に０．０５ｐｐｍに増加したが、鋳造工程によって大気中の酸素と反応して硫黄酸化物の気体となり、溶解しているＩｎから分離、除去され、０．００７ｐｐｍに低減した。 As a result, as shown in Table 3, the impurities in In after casting were maintained in the content after electrolytic purification for Pb, being less than 0.005 ppm (less than the detection limit), and S is Although it increased to 0.05 ppm after electrolytic purification, it reacted with oxygen in the atmosphere by the casting process to become a sulfur oxide gas, which was separated and removed from dissolved In and reduced to 0.007 ppm.
さらに、Ｚｎは電解精製後に０．０５ｐｐｍ含有していたが、鋳造工程によって大気中の酸素と反応して酸化物（スラグ）を形成し、個体（浮遊物）の状態となり、鋳型に溶湯を流し込む際に鋳型に浮遊物が入らないようにして、Ｉｎから分離、除去され、０．００１ｐｐｍ未満（検出限界値未満）まで低減した。その他、電解精製後に、僅かではあるが、ある程度の含有量を示していたＮａ、Ｃａ、Ｆｅ、Ｎｉについては、ＧＤＭＳの検出限界値未満にまで低減した。
以上により、８Ｎの純度を有するＩｎが製造できた。また、歩留りは９８％以上であった。Furthermore, although Zn was contained at 0.05 ppm after electrolytic purification, it reacted with oxygen in the atmosphere by the casting process to form an oxide (slag), becoming a solid (floating matter), and pouring the molten metal into the mold At this time, it was separated and removed from In, preventing suspended matter from entering the mold, and reduced to less than 0.001 ppm (less than the detection limit). In addition, Na, Ca, Fe, and Ni, which showed a slight content after electrolytic purification, were reduced to less than the detection limit value of GDMS.
Thus, In having a purity of 8N could be produced. The yield was 98% or more.
（実施例３）
実施例３として、カソライトタンク中への高純度ＳｒＣＯ３の添加濃度を２．０ｇ／Ｌとし、カソライト中のＩｎ濃度：１２０ｇ／Ｌ、ｐＨ：１．５、電流密度：５Ａ／ｄｍ２、カソライト中Ｃｌ濃度を１５ｇ／Ｌとした。実施例１、２との電解精製条件との大きな相違点は、カソライト中の高純度ＳｒＣＯ３の添加濃度を実施例１、２よりも高濃度とし、電解液中のＣｌ濃度を１５ｇ／Ｌと高くした点にある。(Example 3)
As Example 3, the addition concentration of high-purity SrCO 3 into the catholyte tank was set to 2.0 g / L, the In concentration in the catholite: 120 g / L, pH: 1.5, current density: 5 A / dm 2 , The concentration of Cl in catholyte was 15 g / L. The major difference between the electrolytic purification conditions of Examples 1 and 2 is that the concentration of high-purity SrCO 3 in the catholyte is higher than that of Examples 1 and 2, and the Cl concentration in the electrolytic solution is 15 g / L. It is in the point raised.
カソライトタンクへ添加した高純度ＳｒＣＯ３中に含有されている不純物は、Ｓｉ：０．５１ｐｐｍ、Ｓ：４．９ｐｐｍ、Ｃａ：５０ｐｐｍ、Ｆｅ＜０．５ｐｐｍ、Ｎｉ＜０．５ｐｐｍ、Ｐｂ＜０．１ｐｐｍであった。
上記の条件で電解精製を行い、電解精製で電析したＩｎをカソード板から剥離し、これをるつぼ内に収容し、大気中でＩｎを１９０℃で溶解した後、溶湯を３分間攪拌し、さらにこれを大気中で鋳造した。この結果（Ｉｎ中の不純物濃度の結果）を表４に示す。Impurities contained in the high purity SrCO 3 added to the catholyte tank are Si: 0.51 ppm, S: 4.9 ppm, Ca: 50 ppm, Fe <0.5 ppm, Ni <0.5 ppm, Pb <0. 0.1 ppm.
Performing electrolytic purification under the above conditions, peeling In deposited by electrolytic purification from the cathode plate, storing this in a crucible, dissolving In at 190 ° C. in the atmosphere, stirring the molten metal for 3 minutes, Further, this was cast in the atmosphere. The results (results of impurity concentration in In) are shown in Table 4.
この結果、鋳造後のＩｎ中の不純物は、表４に示すように、Ｐｂについては、電解精製後の含有量が維持され、０．００５ｐｐｍ未満（検出限界未満）となっており、またＳは電解精製後に０．０５ｐｐｍに増加したが、鋳造工程によって大気中の酸素と反応して硫黄酸化物の気体となり、溶解しているＩｎから分離、除去され、０．００６ｐｐｍに低減した。 As a result, as shown in Table 4, the impurities in In after casting are Pb, the content after electrolytic purification is maintained, being less than 0.005 ppm (less than the detection limit), and S is Although it increased to 0.05 ppm after electrolytic refining, it reacted with oxygen in the atmosphere by the casting process to become a sulfur oxide gas, which was separated and removed from dissolved In and reduced to 0.006 ppm.
さらに、Ｚｎは電解精製後に０．０５ｐｐｍ含有していたが、鋳造工程によって大気中の酸素と反応して酸化物（スラグ）を形成し、個体（浮遊物）の状態となり、溶解しているＩｎから分離、除去され、０．００１ｐｐｍ未満（検出限界値未満）まで低減した。その他、電解精製後に、僅かではあるが、ある程度の含有量を示していたＮａ、Ｃａ、Ｆｅ、Ｎｉについては、ＧＤＭＳの検出限界値未満にまで低減した。
以上により、８Ｎの純度を有するＩｎが製造できた。また、歩留りは９８％以上であった。Furthermore, Zn was contained at 0.05 ppm after electrolytic refining, but it reacted with oxygen in the atmosphere by the casting process to form an oxide (slag), becoming a solid (floating matter) state, and dissolved In And reduced to less than 0.001 ppm (less than the detection limit). In addition, Na, Ca, Fe, and Ni, which showed a slight content after electrolytic purification, were reduced to less than the detection limit value of GDMS.
Thus, In having a purity of 8N could be produced. The yield was 98% or more.
（比較例２）
次に、比較例２は、上記実施例１の内容の多くを前提とするが、カソライトタンク内の電解液中へＳｒＣＯ３を添加する際に、従来の市販品である特級のＳｒＣＯ３を添加した場合である。他は、実施例１同条件とした。ここで使用したＳｒＣＯ３中の不純物濃度は、Ｓｉ：８．４ｐｐｍ、Ｓ：２９０ｐｐｍ、Ｃａ：５００ｐｐｍ、Ｆｅ：６．５ｐｐｍ、Ｎｉ：４．６ｐｐｍ、Ｐｂ＜０．１ｐｐｍであり、Ｐｂ以外の不純物濃度は、本願発明において使用する高純度ＳｒＣＯ３に比べて、およそ一桁以上高いものである。(Comparative Example 2)
Next, Comparative Example 2 presupposes much of the contents of Example 1 above, but when adding SrCO 3 into the electrolyte solution in the catholyte tank, special grade SrCO 3 which is a conventional commercial product is added. This is the case when it is added. Other conditions were the same as in Example 1. The impurity concentration in SrCO 3 used here is Si: 8.4 ppm, S: 290 ppm, Ca: 500 ppm, Fe: 6.5 ppm, Ni: 4.6 ppm, Pb <0.1 ppm, and impurities other than Pb The concentration is approximately one digit higher than that of the high purity SrCO 3 used in the present invention.
上記の条件でＩｎの電解精製を行った結果を、表５に示す。比較例２の条件で精製されたＩｎ中には、Ｐｂが０．００５ｐｐｍ、Ｃａ＜０．００５ｐｐｍ（検出限界値未満）、Ｚｎ＜０．００１ｐｐｍ未満（検出限界値未満）であったが、Ｎａ：０．００２ｐｐｍ、Ｓｉ：０．０３ｐｐｍ、Ｓ：０．０１ｐｐｍ、Ｆｅ：０．００２ｐｐｍ、Ｎｉ：０．００２ｐｐｍであり、全体的に不純物が多くなり、本願発明で企図する８Ｎ（９９．９９９９９９％）の純度を達成することはできなかった。 Table 5 shows the results of electrolytic purification of In under the above conditions. In In purified in the conditions of Comparative Example 2, Pb was 0.005 ppm, Ca <0.005 ppm (less than detection limit value), Zn <0.001 ppm (less than detection limit value), : 0.002 ppm, Si: 0.03 ppm, S: 0.01 ppm, Fe: 0.002 ppm, Ni: 0.002 ppm, and as a whole, the amount of impurities increased, and 8N (99.99999999%) contemplated by the present invention. ) Purity could not be achieved.
本発明は、硫黄（Ｓ）の含有量が０．０１ｐｐｍ未満である８Ｎ（９９．９９９９９９％）以上の高純度インジウム（Ｉｎ）であり、鉛（Ｐｂ）及び亜鉛（Ｚｎ）の含有量がＧＤＭＳ分析において検出限界値未満である８Ｎ（９９．９９９９９９％）以上の高純度Ｉｎ、さらには鉄（Ｆｅ）、錫（Ｓｎ）及びシリコン（Ｓｉ）の含有量がＧＤＭＳ分析において検出限界値未満である８Ｎ（９９．９９９９９９％）以上の高純度Ｉｎと、その製造方法を提供するものである。ＩｎＧａＮ、ＡｌＩｎＧａＰなどのＬＥＤ用のＩｎ需要が伸びていくという可能性があり、今後大量にかつ安価に製造することが要求されるが、本願発明はこれに対応できる技術を提供する。さらに、乾式精製法に比べて、効果な設備費を必要とせず、またランニングコストも低減できるので、コスト低減を図ることができるという効果を有する。 The present invention is high-purity indium (In) of 8N (99.99999999%) or more with a sulfur (S) content of less than 0.01 ppm, and a lead (Pb) and zinc (Zn) content of GDMS. High purity In of 8N (99.99999999%) or more, which is less than the detection limit in the analysis, and also the content of iron (Fe), tin (Sn), and silicon (Si) are less than the detection limit in the GDMS analysis The present invention provides a high-purity In of 8N (99.99999999%) or more and a method for producing the same. There is a possibility that In demand for LEDs such as InGaN and AlInGaP will increase, and it will be required to manufacture in large quantities at low cost in the future. The present invention provides a technology that can cope with this. Furthermore, compared with the dry refining method, an effective equipment cost is not required, and the running cost can be reduced, so that the cost can be reduced.
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| JP6471072B2 (en) * | 2015-09-15 | 2019-02-13 | Ｊｘ金属株式会社 | Low alpha ray high purity zinc and method for producing low alpha ray high purity zinc |
| JP7128075B2 (en) * | 2018-10-05 | 2022-08-30 | 株式会社アルバック | Metal hydroxide production apparatus and production method |
| CN110257648B (en) * | 2019-07-05 | 2021-07-06 | 上海大学 | Device and method for preparing ultra-high-purity indium |
| CN116287792B (en) * | 2023-03-14 | 2024-09-17 | 武汉拓材科技有限公司 | Device for preparing high-purity indium by zone melting method |
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| JPH10121163A (en) * | 1996-10-16 | 1998-05-12 | Dowa Mining Co Ltd | Method and device for producing high-purity indium |
| JP2005179778A (en) * | 2003-11-28 | 2005-07-07 | Mitsubishi Materials Corp | High purity metal indium, and its production method and use |
| JP2006283192A (en) * | 2006-07-12 | 2006-10-19 | Dowa Mining Co Ltd | High-purity indium |
| JP2009242911A (en) * | 2008-03-31 | 2009-10-22 | Dowa Metals & Mining Co Ltd | Method for producing indium metal |
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| JP2004043946A (en) * | 2002-05-21 | 2004-02-12 | Nikko Materials Co Ltd | Method and device for manufacturing high purity metal |
| JP5283403B2 (en) * | 2008-03-12 | 2013-09-04 | Ｄｏｗａメタルマイン株式会社 | Indium recovery method |
| JP5711073B2 (en) * | 2011-08-05 | 2015-04-30 | Jx日鉱日石金属株式会社 | Method for purifying indium or indium alloy |
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| JPH10121163A (en) * | 1996-10-16 | 1998-05-12 | Dowa Mining Co Ltd | Method and device for producing high-purity indium |
| JP2005179778A (en) * | 2003-11-28 | 2005-07-07 | Mitsubishi Materials Corp | High purity metal indium, and its production method and use |
| JP2006283192A (en) * | 2006-07-12 | 2006-10-19 | Dowa Mining Co Ltd | High-purity indium |
| JP2009242911A (en) * | 2008-03-31 | 2009-10-22 | Dowa Metals & Mining Co Ltd | Method for producing indium metal |
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| JPN6015050430; Ｓｅｒｇｅｙ Ｖ．Ｋｏｖａｌｅｖｓｋｙ， Ｉｒｉｎａ Ｒ．Ｓｈｅｌｐａｋｏｖａ: 'Ｈｉｇｈ-Ｐｕｒｉｔｙ Ｚｉｎｃ， Ｃａｄｍｉｕｍ， Ｔｅｌｌｕｒｉｕｍ， Ｉｎｄｉｕｍ ａｎｄ Ｇ' Ｃｈｅｍｉｓｔｒｙ ｆｏｒ Ｓｕｓｔａｉｎａｂｌｅ Ｄｅｖｅｌｏｐｍｅｎｔ 第８号, 2000, ｐ８５〜８７ * |
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| WO2015064201A1 (en) | 2015-05-07 |
| JP2016216828A (en) | 2016-12-22 |
| JPWO2015064201A1 (en) | 2017-03-09 |
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