JP2022155328A - Classification method of ruthenium and iridium - Google Patents
Classification method of ruthenium and iridium Download PDFInfo
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 104
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 104
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 50
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 136
- 239000000243 solution Substances 0.000 claims abstract description 105
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229910052742 iron Inorganic materials 0.000 claims abstract description 34
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 22
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims abstract description 22
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229940006280 thiosulfate ion Drugs 0.000 claims abstract description 10
- 229910052709 silver Inorganic materials 0.000 claims abstract description 9
- 239000004332 silver Substances 0.000 claims abstract description 9
- 235000019345 sodium thiosulphate Nutrition 0.000 claims abstract description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 41
- 239000010949 copper Substances 0.000 claims description 40
- 229910052802 copper Inorganic materials 0.000 claims description 39
- 239000002253 acid Substances 0.000 claims description 37
- -1 thiosulfate ions Chemical class 0.000 claims description 26
- 229910052785 arsenic Inorganic materials 0.000 claims description 25
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 12
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 claims description 11
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000013049 sediment Substances 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 239000003929 acidic solution Substances 0.000 abstract description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 28
- 229910052751 metal Inorganic materials 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000011669 selenium Substances 0.000 description 14
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 229910052711 selenium Inorganic materials 0.000 description 13
- 238000003723 Smelting Methods 0.000 description 11
- 229910052714 tellurium Inorganic materials 0.000 description 11
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 239000010953 base metal Substances 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000007670 refining Methods 0.000 description 6
- 238000000638 solvent extraction Methods 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000010970 precious metal Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- KZVBBTZJMSWGTK-UHFFFAOYSA-N 1-[2-(2-butoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOCCCC KZVBBTZJMSWGTK-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000011133 lead Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- CUGMJFZCCDSABL-UHFFFAOYSA-N arsenic(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[As+3].[As+3] CUGMJFZCCDSABL-UHFFFAOYSA-N 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- MKOYQDCOZXHZSO-UHFFFAOYSA-N [Cu].[Cu].[Cu].[As] Chemical compound [Cu].[Cu].[Cu].[As] MKOYQDCOZXHZSO-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- CABDFQZZWFMZOD-UHFFFAOYSA-N hydrogen peroxide;hydrochloride Chemical compound Cl.OO CABDFQZZWFMZOD-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- FPHQLDRCDMDGQW-UHFFFAOYSA-N iridium Chemical compound [Ir].[Ir] FPHQLDRCDMDGQW-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 102220013078 rs140245123 Human genes 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
Description
本発明は、ルテニウム及びイリジウムの分別方法に係る。 The present invention relates to a method for separating ruthenium and iridium.
銅乾式製錬では銅精鉱を熔解し、転炉、精製炉で９９％以上の粗銅とした後に電解精製工程において例えば純度９９．９９％以上の電気銅を生産する。近年では転炉においてリサイクル原料として電子部品由来の貴金属を含む金属屑が投入されており、銅以外の有価物は電解精製時にスライムとして沈殿する。 In copper pyrometallurgical refining, copper concentrate is melted, converted into blister copper of 99% or more in a converter and a refining furnace, and then refined copper having a purity of 99.99% or more is produced in an electrolytic refining process. In recent years, metal scraps containing precious metals derived from electronic components have been put into converters as recycled raw materials, and valuables other than copper precipitate as slime during electrolytic refining.
このスライムには貴金族類、希少金属、銅精鉱に含まれているセレンやテルルも同時に濃縮される。銅製錬副産物としてこれらの元素は個別に分離・回収される。 This slime is enriched with precious metals, rare metals, and selenium and tellurium contained in copper concentrates at the same time. These elements are separately separated and recovered as copper smelting by-products.
このスライムの処理には湿式製錬法が適用される場合が多い。例えば特許文献１においてはスライムを塩酸－過酸化水素により銀を回収し、溶解した金は溶媒抽出により回収した後に、その他の有価物を二酸化硫黄で順次還元回収する方法が開示されている。特許文献２には同様の方法で金銀を回収した後、二酸化硫黄で有価物を還元して沈殿せしめ、セレンのみを蒸留して除去して貴金属類を濃縮する方法が開示されている。
Hydrometallurgical methods are often applied to treat this slime. For example,
貴金属を回収した後の溶液には希少金属イオン、テルル、セレンが含まれておりさらにこれら有価物を回収することが必要である。回収方法としては還元剤により生じた沈殿を回収する方法、溶液ごと銅精鉱に混合しドライヤーで乾燥させて製錬炉に繰り返す方法が知られている。 The solution after recovering precious metals contains rare metal ions, tellurium, and selenium, and it is necessary to recover these valuables. Known recovery methods include a method of recovering precipitates produced by a reducing agent, and a method of mixing the whole solution with copper concentrate, drying it with a dryer, and repeating it in a smelting furnace.
とりわけ特許文献１に示されている、二酸化硫黄により生じた沈殿を回収する方法は、コストや製造規模の面で利点が多い。加えて各元素が順次沈殿することから分離精製にも効果がある。
In particular, the method of recovering precipitates caused by sulfur dioxide, which is disclosed in
二酸化硫黄を用いて有価物を回収する方法では、溶解後に順次有価物を還元して回収することができる。初めに白金、パラジウムが沈殿する。次にセレンが還元を受ける。イリジウム、ルテニウムは酸化還元電位が比較的低いので還元を受け難く、最後まで溶液に残留する。イリジウムについては、特許文献３に記載されているように、溶媒抽出により分離、濃縮後に焼成して回収する方法が広く知られる。また、特許文献４には、イリジウムを含む有機溶媒にマグネシウム、アルミニウム、亜鉛、鉄、錫及び鉛から選ばれた卑金属及び鉱酸を添加し貴金属を還元させて沈殿させる方法が開示されている。 In the method of recovering valuables using sulfur dioxide, valuables can be recovered by sequentially reducing them after dissolution. Platinum and palladium precipitate first. Selenium then undergoes reduction. Iridium and ruthenium have relatively low oxidation-reduction potentials, so they are difficult to be reduced and remain in the solution until the end. As for iridium, as described in Patent Document 3, a method of separating by solvent extraction, concentrating, and then calcining and recovering is widely known. Patent Document 4 discloses a method of adding a base metal selected from magnesium, aluminum, zinc, iron, tin and lead and a mineral acid to an organic solvent containing iridium to reduce and precipitate the noble metal.
銅電解澱物溶解液中のイリジウム濃度は１～７０ｍｇ／Ｌ程度である。イリジウムは高価な金属であるがこの程度の低濃度では溶媒抽出による製錬はコストに見合わない。他の金属との分離効率やストリップの効率も高くない。 The iridium concentration in the copper electrolytic precipitate solution is about 1 to 70 mg/L. Iridium is an expensive metal, but at concentrations this low, smelting by solvent extraction is not cost-effective. Separation efficiency from other metals and strip efficiency are not high either.
一方、ルテニウムを蒸留回収するにはＮａＢｒＯ3等の強力な酸化剤を使用する。酸化剤のコストも高く、本対象液のようなルテニウム濃度が５０～２００ｍｇ／Ｌ程度の希薄でかつ不純物の多い溶液からルテニウムを回収するには不向きな方法である。また四酸化ルテニウムは毒性が強く、過量の使用は安全性の面で問題がある。 On the other hand, to recover ruthenium by distillation, a strong oxidizing agent such as NaBrO 3 is used. The cost of the oxidizing agent is also high, and this method is not suitable for recovering ruthenium from a dilute solution with a ruthenium concentration of about 50 to 200 mg/L and containing many impurities, such as the subject solution. Also, ruthenium tetroxide is highly toxic, and its use in excess poses a safety problem.
亜鉛等の卑金属でセメンテーションする方法はイリジウムとルテニウムいずれにも有効な方法である。しかしながら、卑金属によるセメンテーションではイリジウムとルテニウムの分別回収は困難である。 Cementation with a base metal such as zinc is effective for both iridium and ruthenium. However, separate recovery of iridium and ruthenium is difficult with base metal cementation.
さらには、強酸条件下では水素が短時間に集中的に発生して吹きこぼれる、もしくは静電気等により発生した水素が爆発する問題がある。また、他にセメンテーションを受ける元素も混在するため反応効率が低い。銅製錬由来液にはヒ素も含まれており、卑金属を添加するとヒ素も沈殿する。 Furthermore, under strong acid conditions, hydrogen is generated intensively in a short period of time and is blown over, or the generated hydrogen explodes due to static electricity or the like. In addition, the reaction efficiency is low because other elements undergoing cementation are mixed. The liquid derived from copper smelting also contains arsenic, and arsenic also precipitates when base metals are added.
イリジウムやルテニウムはその水酸化物が沈殿することが知られている。しかしながら、同時に沈殿してしまい、分別回収はできない。一般的な問題として強酸を中和するのであれば、アルカリ試薬のコストが大きい。また、ナトリウムイオンやアルカリ土類金属イオンは酸性条件下でも水に難溶性の硫酸塩を沈殿する。過量のアルカリで中和した時にはこの難溶性硫酸塩が製造設備の配管内に沈着して閉塞を起こすことが予想される。 Iridium and ruthenium are known to precipitate their hydroxides. However, it precipitates at the same time and cannot be collected separately. As a general problem, the cost of alkaline reagents is high if strong acids are to be neutralized. In addition, sodium ions and alkaline earth metal ions precipitate sparingly water-soluble sulfates even under acidic conditions. When neutralized with an excessive amount of alkali, it is expected that this sparingly soluble sulfate deposits in the pipes of manufacturing equipment and clogs them.
強酸性溶液から安価に効率よく低濃度のイリジウムとルテニウム分別－沈殿回収する方法は知られていない。特にヒ素が共存する条件ではアルシンの発生懸念から取り得る手法は限定される。 A method for economically and efficiently fractionating and recovering low-concentration iridium and ruthenium from a strongly acidic solution by precipitation is not known. In particular, under conditions where arsenic coexists, possible methods are limited due to concerns about the generation of arsine.
本発明はこのような従来の事情を鑑み、ルテニウム及びイリジウムを含む塩酸酸性液からルテニウム及びイリジウムを効率的に分別する方法を提供する。対象液がヒ素も含むときには回収物へのヒ素の混入を抑制できる。特に銅製錬における電解精製工程で発生する電解澱物を酸化溶解して得られた塩酸酸性液は、本発明のルテニウム及びイリジウムを含む塩酸酸性液として好対象である。 In view of such conventional circumstances, the present invention provides a method for efficiently separating ruthenium and iridium from a hydrochloric acid acid solution containing ruthenium and iridium. When the target liquid also contains arsenic, it is possible to suppress contamination of the collected material with arsenic. In particular, the hydrochloric acid acid solution obtained by oxidizing and dissolving the electrolytic sediment generated in the electrolytic refining process in copper smelting is suitable as the hydrochloric acid acid solution containing ruthenium and iridium of the present invention.
上記課題は以下に特定される発明によって解決することができる。
［１］ルテニウム及びイリジウムを含む塩酸酸性液に対して、酸化還元電位を銀／塩化銀電極を基準電極として４８０ｍＶ未満に調整する工程と、下記（１）及び（２）の工程と、を有する、ルテニウム及びイリジウムの分別方法。
（１）前記酸化還元電位を調整した塩酸酸性液を３０～７０℃に調整し、鉄と反応させてルテニウムを沈殿させる工程、
（２）前記塩酸酸性液を７５℃以上に加温し、チオ硫酸ナトリウム塩もしくはチオ硫酸イオン含有溶液を、チオ硫酸ナトリウム５水和物に換算して１０ｇ／Ｌ以上になるよう添加してイリジウムを沈殿させる工程。
［２］前記塩酸酸性液の酸化還元電位を１００ｍＶ以上に維持して前記（１）の工程を実施した後に、前記（２）の工程を実施する、［１］に記載のルテニウム及びイリジウムの分別方法。
［３］前記（１）の工程で使用する鉄は表面の一部が銅で被覆されており、銅の含有率が２０～７０質量％である、［１］または［２］に記載のルテニウム及びイリジウムの分別方法。
［４］前記塩酸酸性液は更にヒ素を含有し、前記（１）の工程では、鉄をルテニウムに対し５～１０質量倍添加し、前記（２）の工程では、チオ硫酸ナトリウム塩もしくはチオ硫酸イオン含有溶液を添加してイリジウムを回収した後の液にヒ素を残す、［１］～［３］のいずれかに記載のルテニウム及びイリジウムの分別方法。
［５］前記塩酸酸性液は更にヒ素を含有し、前記（２）の工程で得た沈殿を、アルカリ性溶液と混合してヒ素の一部もしくは全部を除去する、［１］～［４］のいずれかに記載のルテニウム及びイリジウムの分別方法。
The above problems can be solved by the inventions specified below.
[1] Adjusting the oxidation-reduction potential of a hydrochloric acid acid solution containing ruthenium and iridium to less than 480 mV using a silver/silver chloride electrode as a reference electrode, and the following steps (1) and (2). , a method for separating ruthenium and iridium.
(1) a step of adjusting the oxidation-reduction potential-adjusted hydrochloric acid acid solution to 30 to 70° C. and reacting it with iron to precipitate ruthenium;
(2) The hydrochloric acid solution is heated to 75° C. or higher, and a sodium thiosulfate salt or a solution containing thiosulfate ions is added so as to be 10 g/L or more in terms of sodium thiosulfate pentahydrate. precipitating.
[2] Separation of ruthenium and iridium according to [1], wherein the step (2) is performed after the step (1) is performed while the oxidation-reduction potential of the hydrochloric acid acid solution is maintained at 100 mV or more. Method.
[3] The ruthenium according to [1] or [2], wherein the iron used in the step (1) is partially coated with copper and has a copper content of 20 to 70% by mass. and a method for separating iridium.
[4] The hydrochloric acid solution further contains arsenic, and in the step (1), iron is added by 5 to 10 times the mass of ruthenium, and in the step (2), sodium thiosulfate or thiosulfate The method for separating ruthenium and iridium according to any one of [1] to [3], wherein arsenic is left in the liquid after adding the ion-containing solution and recovering the iridium.
[5] The acid solution of hydrochloric acid further contains arsenic, and the precipitate obtained in the step (2) is mixed with an alkaline solution to remove part or all of the arsenic. A method for separating ruthenium and iridium according to any one of the above.
本発明の実施形態によれば、ルテニウム及びイリジウムを含む塩酸酸性液からルテニウム及びイリジウムを効率的に分別する方法を提供することができる。 According to embodiments of the present invention, it is possible to provide a method for efficiently separating ruthenium and iridium from a hydrochloric acid acid solution containing ruthenium and iridium.
以下、本発明のルテニウム及びイリジウムの分別方法の実施形態について説明するが、本発明は、これに限定されて解釈されるものではなく、本発明の範囲を逸脱しない限りにおいて、当業者の知識に基づいて、種々の変更、修正、改良を加え得るものである。 Hereinafter, embodiments of the method for separating ruthenium and iridium of the present invention will be described. Based on this, various changes, modifications and improvements may be made.
＜イリジウムの回収方法＞
本発明の実施形態に係るルテニウム及びイリジウムの分別方法は、ルテニウム及びイリジウムを含む塩酸酸性液に対して、酸化還元電位を銀／塩化銀電極を基準電極として４８０ｍＶ未満に調整する工程と、下記（１）及び（２）の工程と、を有する、ルテニウム及びイリジウムの分別方法である。
（１）酸化還元電位を調整した塩酸酸性液を３０～７０℃に調整し、鉄と反応させてルテニウムを沈殿させる工程、
（２）塩酸酸性液を７５℃以上に加温し、チオ硫酸ナトリウム塩もしくはチオ硫酸イオン含有溶液を、チオ硫酸ナトリウム５水和物に換算して１０ｇ／Ｌ以上になるよう添加してイリジウムを沈殿させる工程。
<Method of collecting iridium>
A method for separating ruthenium and iridium according to an embodiment of the present invention includes the steps of adjusting the oxidation-reduction potential of a hydrochloric acid acid solution containing ruthenium and iridium to less than 480 mV using a silver/silver chloride electrode as a reference electrode, and the following ( A method for separating ruthenium and iridium, comprising steps 1) and (2).
(1) A step of adjusting the oxidation-reduction potential-adjusted hydrochloric acid acid solution to 30 to 70° C. and reacting it with iron to precipitate ruthenium;
(2) An acid solution of hydrochloric acid is heated to 75°C or higher, and a sodium thiosulfate salt or a solution containing thiosulfate ions is added so as to be 10 g/L or more in terms of sodium thiosulfate pentahydrate to add iridium. Precipitating process.
本発明の実施形態に係るルテニウム及びイリジウムの分別方法において、処理対象となるイリジウムを含む塩酸酸性液は、どのような処理を経て得られたものであってもよいが、特に、銅製錬における電解精製工程で発生する電解澱物を酸化溶解して得られた塩酸酸性液は、本発明のイリジウムを含む塩酸酸性液として好対象である。また、非鉄金属製錬、とりわけ銅製錬の電解精製工程で生じる電解澱物は白金族元素がその他希少元素と共に濃縮される。希少元素は単独で製錬されることはなく、他金属の副産物として回収されるか廃触媒等のリサイクル原料から分離される。したがって、本発明の実施形態に係るルテニウム及びイリジウムの分別方法は、廃棄物からのリサイクルにも適用することができる。すなわち、当該廃棄物の処理工程で生じた、ルテニウム及びイリジウムを含む塩酸酸性液を対象とすることができる。 In the method for separating ruthenium and iridium according to the embodiment of the present invention, the hydrochloric acid acid solution containing iridium to be treated may be obtained through any treatment, but in particular, electrolysis in copper smelting A hydrochloric acid solution obtained by oxidizing and dissolving an electrolytic sediment generated in a refining process is suitable as the iridium-containing hydrochloric acid solution of the present invention. In addition, platinum group elements are concentrated together with other rare elements in the electrolytic sediment produced in the electrorefining process of non-ferrous metal smelting, especially copper smelting. Rare elements are not smelted by themselves, but are recovered as by-products of other metals or separated from recycled raw materials such as spent catalysts. Therefore, the method for separating ruthenium and iridium according to embodiments of the present invention can also be applied to recycling from waste. That is, the object can be a hydrochloric acid acid solution containing ruthenium and iridium generated in the waste treatment process.
本発明の実施形態に係るルテニウム及びイリジウムの分別方法において、処理対象となるイリジウムを含む塩酸酸性液は、所定の工程を経て得られた塩酸酸性液である場合、ルテニウム及びイリジウム（Ｉｒ）以外に種々の金属元素を含んでいる。 In the method for separating ruthenium and iridium according to the embodiment of the present invention, when the hydrochloric acid acid liquid containing iridium to be treated is a hydrochloric acid acid liquid obtained through a predetermined process, other than ruthenium and iridium (Ir) Contains various metal elements.
イリジウムを含む塩酸酸性液は、例えば、アルカリ金属、アルカリ土類金属、アンチモン（Ｓｂ）、ビスマス（Ｂｉ）等を含んでもよい。これらは、後述のチオ硫酸イオンと反応しないことから、特段の処理が不要である。また、イリジウムを含む塩酸酸性液は、ヒ素（Ａｓ）は、チオ硫酸イオンと比較的反応し難いものであり、含んでもよい。 The hydrochloric acid solution containing iridium may contain, for example, alkali metals, alkaline earth metals, antimony (Sb), bismuth (Bi), and the like. Since these do not react with thiosulfate ions, which will be described later, no special treatment is required. The iridium-containing hydrochloric acid solution may also contain arsenic (As), which is relatively difficult to react with thiosulfate ions.
セレン（Ｓｅ）、テルル（Ｔｅ）、銅（Ｃｕ）等は、イリジウムを含む塩酸酸性液に含まれていてもよいが、チオ硫酸イオンで還元されるため、詳しくは後述するが、事前にこれら金属の濃度を下げておく必要がある。 Selenium (Se), tellurium (Te), copper (Cu), and the like may be contained in the iridium-containing hydrochloric acid solution, but since they are reduced by thiosulfate ions, they are described in detail later. It is necessary to keep the metal concentration low.
鉄（Ｆｅ）は、２価であればチオ硫酸イオンと反応しないため、イリジウムを含む塩酸酸性液に含まれていてもよい。一方、３価であれば、チオ硫酸イオンと反応してしまうため、含まれていてもよいが、事前に２価に還元しておく必要がある。 Since iron (Fe) does not react with thiosulfate ions if it is divalent, it may be contained in the hydrochloric acid solution containing iridium. On the other hand, if it is trivalent, it reacts with thiosulfate ions, so it may be contained, but it is necessary to reduce it to divalent in advance.
一例として、銅製錬の銅電解精製工程由来の電解澱物からの、ルテニウム及びイリジウムを含む塩酸酸性液の作製方法を示す。まず、銅製錬の銅電解精製工程由来の電解澱物から硫酸により銅を溶解して除く。次に、濃塩酸と過酸化水素水を添加して溶解し、固液分離してＰＬＳ（浸出貴液）を得る。塩化物浴である浸出貴液（ＰＬＳ）には白金族元素、希少金属元素、カルコゲン元素、ヒ素、アンチモン等が分配する。 As an example, a method for producing a hydrochloric acid acid solution containing ruthenium and iridium from an electrolytic sediment derived from a copper electrorefining process in copper smelting will be described. First, copper is dissolved and removed with sulfuric acid from the electrolytic sediment derived from the copper electrorefining process of copper smelting. Next, concentrated hydrochloric acid and hydrogen peroxide water are added and dissolved, followed by solid-liquid separation to obtain PLS (precious leach liquor). Platinum group elements, rare metal elements, chalcogen elements, arsenic, antimony, etc. are distributed in the pregnant leach liquor (PLS), which is a chloride bath.
浸出貴液（ＰＬＳ）を一度冷却し、鉛やアンチモンといった卑金属類の塩化物を沈殿分離する。その後に溶媒抽出により金を有機相に分離する。金の抽出剤はジブチルカルビトール（ＤＢＣ）が広く使用されている。抽出液には、二酸化硫黄を吹き込むことで、白金やパラジウム等の貴金属とセレン、テルルを還元除去し、続いて固液分離することで、ルテニウム及びイリジウムを含む塩酸酸性液を作製することができる。 Precious leach liquor (PLS) is cooled once to precipitate and separate chlorides of base metals such as lead and antimony. The gold is then separated into the organic phase by solvent extraction. A widely used extractant for gold is dibutyl carbitol (DBC). Sulfur dioxide is blown into the extract to reduce and remove precious metals such as platinum and palladium, selenium, and tellurium, followed by solid-liquid separation to produce a hydrochloric acid solution containing ruthenium and iridium. .
本発明の実施形態に係るルテニウム及びイリジウムの分別方法では、ルテニウム及びイリジウムを含む塩酸酸性液に対して、二酸化硫黄、硫化水素、アルデヒド類等の還元剤を添加して酸化還元電位を銀／塩化銀電極を基準電極として４８０ｍＶ未満に調整する。これによって塩酸酸性液中に残る有価物としては、ルテニウム、イリジウム、アンチモン、ビスマス等が挙げられる。このうちルテニウムとイリジウムは付加価値が特に高く回収することが好ましい。還元後液には、ヒ素も０．５～３ｇ／Ｌ含まれているが、ヒ素は有価物回収時には混入を抑制したい。ルテニウム及びイリジウムも元素別に回収する方が好ましい。 In the method for separating ruthenium and iridium according to the embodiment of the present invention, a reducing agent such as sulfur dioxide, hydrogen sulfide, and aldehydes is added to a hydrochloric acid acid solution containing ruthenium and iridium to reduce the oxidation-reduction potential to silver/chloride. Adjust the silver electrode to less than 480 mV as a reference electrode. Ruthenium, iridium, antimony, bismuth and the like can be cited as valuables remaining in the hydrochloric acid acid solution. Of these, ruthenium and iridium have particularly high added value and are preferably recovered. Although the post-reduction solution also contains 0.5 to 3 g/L of arsenic, it is desired to suppress the contamination of arsenic when recovering valuable materials. Ruthenium and iridium are also preferably recovered by element.
還元後液からルテニウムを回収するには、金属によるセメンテーションが効果的である。ただし、塩酸酸性液にヒ素が含まれるのでアルシンの発生を抑制するため酸化還元電位が銀／塩化銀を基準にして－３８０ｍＶ以上の金属である必要がある。ルテニウムのセメンテーション条件に合致する金属は、鉄、ニッケル、銅等が挙げられる。 Metal cementation is effective for recovering ruthenium from the post-reduction solution. However, since arsenic is contained in the hydrochloric acid solution, the metal should have an oxidation-reduction potential of -380 mV or more based on silver/silver chloride in order to suppress the generation of arsine. Metals that meet the cementation requirements of ruthenium include iron, nickel, copper, and the like.
ルテニウムのセメンテーションに使用する金属の中で次の金属は問題がある。銅はヒ素もヒ化銅として沈殿させてしまい、鉛はルテニウムと未反応の鉛が酸溶解せず混入してしまい、ニッケルは高コストになる。しかしながら、鉄は反応時に水素が瞬間的に多量発生する問題はあるものの、塩酸酸性液の温度を３０～７０℃に調整し、添加量をルテニウムの５～１０質量倍にすれば大きな問題にはならない。さらには鉄を添加するとイリジウムは液温７０℃以下ではセメンテーションを受け難いので元素毎の分別回収が可能になる。 Among the metals used for ruthenium cementation, the following metals are problematic. In the case of copper, arsenic is also precipitated as copper arsenide, and in the case of lead, ruthenium and unreacted lead are mixed in without acid dissolution, and the cost of nickel increases. However, iron has the problem that a large amount of hydrogen is instantaneously generated during the reaction, but if the temperature of the hydrochloric acid solution is adjusted to 30 to 70° C. and the amount added is 5 to 10 times the mass of ruthenium, it will not be a big problem. not. Furthermore, when iron is added, iridium is less susceptible to cementation at a liquid temperature of 70° C. or less, so separate recovery of each element becomes possible.
添加する鉄の上限は特に限定されないが、試薬の節約の観点から、塩酸酸性液におけるイリジウムに対し、４００質量倍以下であることが好ましい。また、添加する鉄は、塩酸酸性液におけるイリジウムに対し、１００～２００質量倍であるのがより好ましい。 The upper limit of iron to be added is not particularly limited, but from the viewpoint of saving reagents, it is preferably 400 times by mass or less that of iridium in the hydrochloric acid acid solution. Further, the amount of iron to be added is more preferably 100 to 200 times the mass of iridium in the hydrochloric acid solution.
添加する鉄としては、鉄粉が、反応性が良く好適である。また、見かけ直径が数ｃｍに及ぶ鉄粒でも代用され得る。鉄の形状は特に制限されず、粉状、粒状、礫状、塊状、板状、線状等いずれの形でもよく、鉄の品位は特に制限はない。 As iron to be added, iron powder is suitable because of its high reactivity. Alternatively, iron grains with an apparent diameter of several centimeters may be used. The shape of the iron is not particularly limited, and may be powdery, granular, gravel, lumpy, plate-like, linear, or the like, and the grade of the iron is not particularly limited.
もしくは鉄板、鉄塊を設置した反応器に塩酸酸性液を通液してもよい。この時、反応器はバッチ式でなく、鉄を投入した容器に連続通液するタイプの反応器が好ましい。しかしながら、操作性と反応性との両面から鉄粉が好適である。本発明において、「鉄粉」とは、粒径としてＰ８０＜０．２ｍｍの鉄の粒子を指す。 Alternatively, a hydrochloric acid solution may be passed through a reactor in which an iron plate or an iron lump is installed. At this time, the reactor is not a batch type reactor, but a reactor of a type in which liquid is continuously passed through a vessel containing iron is preferred. However, iron powder is preferable in terms of both operability and reactivity. In the present invention, "iron powder" refers to iron particles having a particle size P80<0.2 mm.
鉄は塩酸酸性液に接触すると水素が発生する。水素は爆発性があるという問題がある。さらに鉄として鉄粉を使用するならば、表面積が大きいため短時間に大量に水素が発生して溶液が吹きこぼれる問題もある。そのため、特に鉄粉を使用する時、その投入量は１～１０ｇ／Ｌとする。一度に投入せずに複数回に分けて投入してもよい。 When iron comes into contact with a hydrochloric acid solution, hydrogen is generated. Hydrogen has the problem of being explosive. Furthermore, if iron powder is used as iron, there is a problem that a large amount of hydrogen is generated in a short time due to its large surface area, causing the solution to boil over. Therefore, especially when iron powder is used, the input amount is set to 1 to 10 g/L. You may divide into multiple times and may throw in without throwing in at once.
水素発生による吹きこぼれや爆発の危険を避ける方法として、表面の一部が銅で被覆された鉄粉（銅被覆鉄）を使用することも可能である。原理的には鉄と酸溶液の接触が制限されて水素発生は抑制される。徐々に銅が溶解した後、表面に現れる鉄とルテニウムとが反応する。銅品位が高すぎるとイリジウムとの反応が悪くなるおそれがあるため、表面を銅で被覆した鉄の銅の含有量は、好ましくは７０質量％以下、さらに好ましくは４０質量％以下である。また、銅被覆鉄は銅の含有率が２０～７０質量％に調整したものを用いると、反応速度とルテニウム選択性の面で効果が高い。この時の反応温度は４０℃～７０℃に調整するとより効果が高い。温度が高すぎると選択性が低下する。反対に低すぎると反応が遅い。 As a method of avoiding the danger of boiling over and explosion due to hydrogen generation, it is also possible to use iron powder whose surface is partly coated with copper (copper-coated iron). In principle, contact between the iron and the acid solution is restricted to suppress hydrogen generation. After gradual copper dissolution, the iron and ruthenium appearing on the surface react. If the copper grade is too high, the reaction with iridium may deteriorate, so the copper content of the iron whose surface is coated with copper is preferably 70% by mass or less, more preferably 40% by mass or less. Further, when the copper-coated iron is adjusted to have a copper content of 20 to 70% by mass, it is highly effective in terms of reaction rate and ruthenium selectivity. If the reaction temperature at this time is adjusted to 40.degree. C. to 70.degree. If the temperature is too high, the selectivity will decrease. Conversely, if it is too low, the reaction will be slow.
塩酸酸性液の酸化還元電位を１００ｍＶ以上に維持しながら、鉄と反応させてルテニウムを沈殿させた後に、チオ硫酸ナトリウム塩もしくはチオ硫酸イオン含有溶液によるイリジウムの沈殿反応を実施してもよい。塩酸酸性液の酸化還元電位を１００ｍＶ以上に維持しながら、鉄と反応させてルテニウムを沈殿させることで、溶液中のイリジウムの濃度を維持することができる。このため、イリジウムとルテニウムの個別分離が可能となる。 After precipitating ruthenium by reaction with iron while maintaining the oxidation-reduction potential of the hydrochloric acid acid solution at 100 mV or more, the precipitation reaction of iridium with a sodium thiosulfate salt or a solution containing thiosulfate ions may be carried out. The concentration of iridium in the solution can be maintained by reacting with iron and precipitating ruthenium while maintaining the oxidation-reduction potential of the hydrochloric acid acid solution at 100 mV or more. Therefore, separate separation of iridium and ruthenium is possible.
先に鉄粉でルテニウムを回収しても、先にチオ硫酸ナトリウム塩もしくはチオ硫酸イオン含有溶液でイリジウムを回収しても効果はある。ただし、先にチオ硫酸ナトリウム塩もしくはチオ硫酸イオン含有溶液でイリジウムを回収する場合は、セメンテーションによるルテニウムの還元効率が著しく低下し、セメンテーション用の金属使用量が増加する。そのため、効率的にルテニウムとイリジウムを回収するには、先にルテニウムをセメンテーションで回収し、沈殿を分離後にチオ硫酸ナトリウム塩もしくはチオ硫酸イオン含有溶液によりイリジウムを沈殿させることが好ましい。 It is effective to recover ruthenium with iron powder first, or recover iridium with sodium thiosulfate or a solution containing thiosulfate ions first. However, when iridium is first recovered with a sodium thiosulfate salt or a solution containing thiosulfate ions, the efficiency of reducing ruthenium by cementation is significantly lowered, and the amount of metal used for cementation is increased. Therefore, in order to efficiently recover ruthenium and iridium, it is preferable to first recover ruthenium by cementation, and after separating the precipitate, precipitate iridium with sodium thiosulfate or a solution containing thiosulfate ions.
塩酸酸性液が更にヒ素を含有する場合、鉄をルテニウムに対し５～１０質量倍添加してルテニウムを回収し、回収後の塩酸酸性液にチオ硫酸ナトリウム塩もしくはチオ硫酸イオン含有溶液を添加してイリジウムを回収し、回収後液にヒ素を残すことができる。ここで、塩酸酸性液中でチオ硫酸ナトリウム塩もしくはチオ硫酸イオン含有溶液とヒ素が反応して硫化ヒ素を沈殿することが知られている。イリジウムの沈殿には硫化ヒ素の混入が避けられないが、硫化ヒ素は水酸化ナトリウム水溶液等のアルカリ性溶液に溶けやすく、これによって容易にヒ素の一部または全部を除くことが可能である。 When the hydrochloric acid solution further contains arsenic, ruthenium is recovered by adding iron 5 to 10 times the weight of ruthenium, and sodium thiosulfate or a solution containing thiosulfate ions is added to the recovered hydrochloric acid solution. Iridium can be recovered, leaving arsenic in the recovered solution. Here, it is known that arsenic reacts with a sodium thiosulfate salt or a solution containing thiosulfate ions in an acid solution of hydrochloric acid to precipitate arsenic sulfide. Arsenic sulfide is inevitably included in iridium precipitation, but arsenic sulfide is easily dissolved in an alkaline solution such as an aqueous sodium hydroxide solution, so that part or all of the arsenic can be easily removed.
チオ硫酸ナトリウム塩もしくはチオ硫酸イオン含有溶液でイリジウムを沈殿させる工程では、塩酸酸性液を７５℃以上に加温し、チオ硫酸ナトリウム塩もしくはチオ硫酸イオン含有溶液を、チオ硫酸ナトリウム５水和物に換算して１０ｇ／Ｌ以上になるよう添加してイリジウムを沈殿させる。イリジウムは塩酸酸性液中に塩化物錯イオンとして残留しているため、当該塩酸酸性液からイリジウムを効率的に沈殿させるために、塩酸酸性液を７５℃以上に加温してチオ硫酸イオンを添加して沈殿させる。 In the step of precipitating iridium with a sodium thiosulfate salt or a solution containing thiosulfate ions, the hydrochloric acid solution is heated to 75° C. or higher to convert the sodium thiosulfate salt or thiosulfate ion-containing solution into sodium thiosulfate pentahydrate. Iridium is precipitated by adding so that the converted amount becomes 10 g/L or more. Since iridium remains in the hydrochloric acid solution as a chloride complex ion, in order to efficiently precipitate iridium from the hydrochloric acid solution, the hydrochloric acid solution is heated to 75°C or higher and thiosulfate ions are added. to precipitate.
代表的なチオ硫酸イオン源としては、市販のチオ硫酸ナトリウム５水和物が挙げられる。チオ硫酸ナトリウム塩の固体で添加してもよいし、チオ硫酸イオン含有溶液で添加してもよい。チオ硫酸イオン源は、これら以外にも、亜硫酸と元素硫黄をアルカリ溶液中で加熱すれば得ることができるが、コストや取り扱い安さの面から、特に固体塩が有利である。特に、チオ硫酸ナトリウム５水和物は毒性も低く、チオ硫酸イオン源として最も好適である。 Representative sources of thiosulfate ions include commercially available sodium thiosulfate pentahydrate. It may be added as a solid sodium thiosulfate salt or as a solution containing thiosulfate ions. The thiosulfate ion source can also be obtained by heating sulfurous acid and elemental sulfur in an alkaline solution, but solid salts are particularly advantageous in terms of cost and ease of handling. In particular, sodium thiosulfate pentahydrate has low toxicity and is most suitable as a thiosulfate ion source.
イリジウムは塩酸酸性液中では塩化物錯体となっている。銅の殿物処理工程では二酸化硫黄で還元処理されているのでイリジウムの価数は三価以下であると想定される。チオ硫酸イオンは硫黄－硫黄結合が単結合であるとされており、硫黄元素上に負電荷が局在している。硫黄は軟らかい元素であり、上述のように、価数が三価以下のイリジウムも軟らかいイオンであるため、互いに親和性が高い。 Iridium forms a chloride complex in the acid solution of hydrochloric acid. In the copper precipitate treatment step, the iridium is assumed to have a valence of three or less because it is reduced with sulfur dioxide. A thiosulfate ion is considered to have a single sulfur-sulfur bond, and a negative charge is localized on the sulfur element. Sulfur is a soft element, and as described above, iridium, which has a valence of three or less, is also a soft ion, so they have a high affinity with each other.
塩酸酸性液は、７５℃以上に加温し、チオ硫酸イオンを添加して沈殿させる。塩酸酸性液を７５℃以上に加温した状態でチオ硫酸イオンを添加すると、沈殿反応が進み、イリジウムを効率的に沈殿させることができる。塩酸酸性液の加温温度が７５℃未満であると、沈殿反応の速度が鈍化するおそれがある。塩酸酸性液の加温温度は、好ましくは８０℃以上である。塩酸酸性液の加温温度の上限は特に限定されないが、１００℃以下であってもよい。 The hydrochloric acid solution is heated to 75° C. or higher, and thiosulfate ions are added for precipitation. When thiosulfate ions are added to the hydrochloric acid solution heated to 75° C. or higher, the precipitation reaction proceeds and iridium can be precipitated efficiently. If the heating temperature of the hydrochloric acid solution is lower than 75°C, the speed of the precipitation reaction may slow down. The heating temperature of the hydrochloric acid solution is preferably 80° C. or higher. The upper limit of the heating temperature of the hydrochloric acid solution is not particularly limited, but may be 100° C. or lower.
チオ硫酸ナトリウム塩もしくはチオ硫酸イオン含有溶液は、チオ硫酸ナトリウム５水和物に換算して１０ｇ／Ｌ以上になるように、イリジウムを含む塩酸酸性液に添加することが好ましい。チオ硫酸ナトリウム塩もしくはチオ硫酸イオン含有溶液を、チオ硫酸ナトリウム５水和物に換算して１０ｇ／Ｌ以上になるように添加することで、チオ硫酸イオンがより有効に機能し、沈殿反応がより良好に進む。チオ硫酸ナトリウム塩もしくはチオ硫酸イオン含有溶液は、チオ硫酸ナトリウム５水和物に換算して１５ｇ／Ｌ以上になるように、イリジウムを含む塩酸酸性液に添加することがより好ましく、２０ｇ／Ｌ以上になるように、イリジウムを含む塩酸酸性液に添加することがより好ましい。また、チオ硫酸ナトリウム塩もしくはチオ硫酸イオン含有溶液は、多すぎると酸分解時に生じる硫黄が混入するおそれがあるため、チオ硫酸ナトリウム５水和物に換算して３０ｇ／Ｌ以下になるように、イリジウムを含む塩酸酸性液に添加することが好ましい。 The sodium thiosulfate salt or thiosulfate ion-containing solution is preferably added to the iridium-containing hydrochloric acid solution so that the amount is 10 g/L or more in terms of sodium thiosulfate pentahydrate. By adding a sodium thiosulfate salt or a solution containing thiosulfate ions in an amount of 10 g/L or more in terms of sodium thiosulfate pentahydrate, the thiosulfate ions function more effectively and the precipitation reaction becomes more efficient. proceed well. The sodium thiosulfate salt or thiosulfate ion-containing solution is added to the hydrochloric acid solution containing iridium in an amount of 15 g/L or more in terms of sodium thiosulfate pentahydrate, more preferably 20 g/L or more. It is more preferable to add to the hydrochloric acid solution containing iridium so that In addition, if the amount of sodium thiosulfate salt or thiosulfate ion-containing solution is too large, there is a risk of contamination with sulfur generated during acid decomposition. It is preferably added to a hydrochloric acid solution containing iridium.
チオ硫酸イオンは酸性条件下では硫黄と亜硫酸イオンに分解する平衡がある。さらには酸化性物質があればこれと反応するし、銅等の一部の遷移金属イオンは硫化物を作って沈殿する。そのため、予め二酸化硫黄によりその他の夾雑元素を沈殿させておくことが好ましい。その他の夾雑元素とは、例えばセレン及びテルルである。このような観点から、イリジウムを含む塩酸酸性液が、セレン及びテルルのうちの少なくとも一種を含む場合、イリジウムを含む塩酸酸性液に、予め二酸化硫黄または二酸化硫黄の水溶液を添加して、セレン及びテルルの合計濃度を１００ｍｇ／Ｌ以下に調整しておくことが好ましい。そして、チオ硫酸ナトリウム塩またはチオ硫酸イオン含有溶液を、セレン及びテルルの合計濃度を調整したイリジウムを含む塩酸酸性液に添加することが好ましい。当該セレン及びテルルの合計濃度を予め５０ｍｇ／Ｌ以下に調整しておくことがより好ましく、１０ｍｇ／Ｌ以下に調整しておくことが更により好ましい。 Thiosulfate ions have an equilibrium to decompose into sulfur and sulfite ions under acidic conditions. Furthermore, if there is an oxidizing substance, it reacts with it, and some transition metal ions such as copper form sulfide and precipitate. Therefore, it is preferable to precipitate other contaminant elements with sulfur dioxide in advance. Other contaminants are, for example, selenium and tellurium. From this point of view, when the iridium-containing hydrochloric acid acid liquid contains at least one of selenium and tellurium, sulfur dioxide or an aqueous solution of sulfur dioxide is added in advance to the iridium-containing hydrochloric acid acid liquid to obtain selenium and tellurium. is preferably adjusted to 100 mg/L or less. Then, it is preferable to add the thiosulfate sodium salt or the thiosulfate ion-containing solution to the hydrochloric acid solution containing iridium with the total concentration of selenium and tellurium adjusted. It is more preferable to previously adjust the total concentration of selenium and tellurium to 50 mg/L or less, and even more preferably to 10 mg/L or less.
沈殿したイリジウム含有物は、固液分離後に公知の方法でイリジウムとその他夾雑物を分離する。例えば、酸化溶解後にイリジウムを溶媒抽出で分離回収する方法が挙げられる。この酸化溶解液では、イリジウムは十分濃縮されており、公知の溶媒抽出での回収が可能である。 The precipitated iridium-containing material is separated into iridium and other contaminants by a known method after solid-liquid separation. For example, there is a method of separating and recovering iridium by solvent extraction after oxidation and dissolution. In this oxidized solution, the iridium is sufficiently concentrated to allow recovery by known solvent extractions.
以下、実施例により本発明をさらに具体的に説明する。ただし、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these.
（実験例１）
銅製錬の銅電解精製工程由来の電解澱物から硫酸により銅を溶解して除いた。濃塩酸と６０％過酸化水素水を添加して溶解し、固液分離してＰＬＳ（浸出貴液）を得た。ＰＬＳを６℃まで冷却して卑金属分を沈殿除去した。酸濃度を２Ｎ以上に調整しＤＢＣ（ジブチルカルビトール）とＰＬＳを混合して金を抽出した。金抽出後のＰＬＳを７０℃に加温し、二酸化硫黄を吹き込んで貴金属とセレン、テルルを還元除去した。これを固液分離し、イリジウムを含む塩酸酸性液を得た。この時の酸化還元電位は４５０ｍＶであった。
(Experimental example 1)
Copper was dissolved and removed with sulfuric acid from the electrolytic sediment derived from the copper electrorefining process of copper smelting. Concentrated hydrochloric acid and 60% aqueous hydrogen peroxide were added to dissolve the solution, followed by solid-liquid separation to obtain PLS (leaching solution). The PLS was cooled to 6° C. to precipitate and remove base metals. Gold was extracted by adjusting the acid concentration to 2N or more and mixing DBC (dibutyl carbitol) and PLS. The PLS after the gold extraction was heated to 70° C., and sulfur dioxide was blown into the PLS to reduce and remove the noble metals, selenium, and tellurium. This was subjected to solid-liquid separation to obtain a hydrochloric acid acid solution containing iridium. The oxidation-reduction potential at this time was 450 mV.
二酸化硫黄還元後液を２００ｍＬ分取し、表１の条件１～６に示す各温度に加熱した。二酸化硫黄還元後液のイリジウム濃度は２６ｍｇ／Ｌ、ルテニウム濃度は１３０ｍｇ／Ｌであった。二酸化硫黄還元後液はその他の元素としてヒ素を１．５ｇ／Ｌ、セレンを６ｍｇ／Ｌ、テルルを１８ｍｇ／Ｌ含有していた。表１に示す量の鉄粉（Ｐ８０＝１５０～２００μｍ）、もしくはチオ硫酸ナトリウム５水和物を添加して攪拌した。
所定時間後に反応を停止し、沈殿を固液分離した。ろ過後、溶液の各種元素濃度を定量した。これを一段目還元と称す。
次に、ろ液を再度所定温度に加熱して表１の二段目還元に示される試薬を添加した。銅被覆鉄は常温の硫酸銅溶液に鉄粉を浸して洗浄して調製した。銅含有量が３０質量％と６０質量％の２種類を調製して使用した。
所定時間後に反応を停止し再度固液分離した。
試薬はすべて和光純薬工業社製の特級グレードを使用した。溶液中の元素濃度の定量は溶液２ｍＬを分取して５０ｍＬに規正後、ＩＣＰ－ＯＥＳ（セイコー社製ＳＰＳ３１００）により濃度を定量した。沈殿物の溶解液は１００ｍＬに規正してその濃度を決定した。評価結果を表２に示す。
200 mL of the post-reduction solution of sulfur dioxide was taken and heated to each temperature shown in
After a predetermined time, the reaction was stopped and the precipitate was solid-liquid separated. After filtration, the concentrations of various elements in the solution were quantified. This is called first-stage reduction.
Next, the filtrate was heated again to a predetermined temperature and the reagents shown in Table 1 for the second stage reduction were added. Copper-coated iron was prepared by immersing iron powder in a copper sulfate solution at room temperature and washing it. Two types with a copper content of 30% by mass and 60% by mass were prepared and used.
After a predetermined time, the reaction was stopped and solid-liquid separation was performed again.
All the reagents used were special grades manufactured by Wako Pure Chemical Industries, Ltd. 2 mL of the solution was aliquoted and adjusted to 50 mL, and then the concentration was quantified by ICP-OES (SPS3100 manufactured by Seiko). The precipitate solution was adjusted to 100 mL to determine its concentration. Table 2 shows the evaluation results.
表２の結果から、鉄粉もしくは銅被覆鉄を添加して、５０～８０℃に加温することでルテニウムを選択的に還元できることが分かる。その添加量は鉄に換算して０．２ｇ以上、すなわちルテニウムの８質量倍以上で効果があり、１０質量倍以上でさらに効果が高かった。 From the results in Table 2, it can be seen that ruthenium can be selectively reduced by adding iron powder or copper-coated iron and heating to 50 to 80°C. The addition amount of 0.2 g or more in terms of iron, that is, 8 times or more by mass of ruthenium is effective, and 10 times or more by mass of ruthenium is more effective.
ルテニウムを還元後、固液分離して溶液にチオ硫酸ナトリウムをチオ硫酸ナトリウム５水和物に換算して１０ｇ／Ｌ以上になるよう添加して７５℃以上に加温すると、ヒ素の混入を抑制してイリジウムを沈殿させることができた。 After reducing the ruthenium, solid-liquid separation is performed, and sodium thiosulfate is added to the solution so that the amount of sodium thiosulfate pentahydrate is 10 g/L or more, and the solution is heated to 75°C or more to suppress arsenic contamination. was able to precipitate iridium.
実験例１の条件５と条件６に見られるように、チオ硫酸ナトリウムを先に添加してイリジウムを回収し、後から鉄粉を添加すると、ルテニウムに対する効果も残留イリジウムの回収効果も減殺される。 As seen in conditions 5 and 6 of Experimental Example 1, when sodium thiosulfate is added first to recover iridium and iron powder is added afterwards, both the effect on ruthenium and the effect on recovery of residual iridium are reduced. .
（実験例２）
実験例１と同じ方法で調整したイリジウム含有液を３００ｍＬ分取し６０℃に加熱した。イリジウム濃度は２５ｍｇ／Ｌ、ルテニウム濃度は７７ｍｇ／Ｌ、酸化還元電位は４５５ｍＶであった。最初に鉄粉０．１ｇを添加した時を０分とし、鉄粉を１５分ごとに０．１ｇずつ添加した。鉄粉を添加する直前に酸化還元電位を測定し、成分分析用のサンプルを２ｍＬ採取した。分析方法は実験例１に準じる。酸化還元電位（ＯＲＰ）とイリジウム濃度並びにルテニウム濃度の関係を図１に示す。
(Experimental example 2)
300 mL of an iridium-containing liquid prepared in the same manner as in Experimental Example 1 was taken and heated to 60°C. The iridium concentration was 25 mg/L, the ruthenium concentration was 77 mg/L, and the redox potential was 455 mV. The time when 0.1 g of iron powder was first added was taken as 0 minute, and 0.1 g of iron powder was added every 15 minutes. The oxidation-reduction potential was measured immediately before adding the iron powder, and 2 mL of a sample for component analysis was collected. The analysis method conforms to Experimental Example 1. FIG. 1 shows the relationship between oxidation-reduction potential (ORP), iridium concentration, and ruthenium concentration.
反応中はルテニウムが液中に１０ｍｇ／Ｌ以上残っていればイリジウムの濃度はほとんど変化せず、その時の酸化還元電位は９０ｍＶ以上を維持していた。さらには溶液の酸化還元電位が１００ｍＶ未満となった図１の経過時間３０分～６５分、１２０分以降の区間を除くと、部分的にも大きくイリジウムの濃度が低下することはなかった。このため、イリジウムの濃度を維持するためには、酸化還元電位を１００ｍＶ以上に維持することが好ましいことがわかる。 During the reaction, if 10 mg/L or more of ruthenium remained in the liquid, the concentration of iridium hardly changed, and the oxidation-reduction potential at that time was maintained at 90 mV or more. Furthermore, the concentration of iridium did not decrease significantly even partially except for the sections from 30 minutes to 65 minutes and after 120 minutes in FIG. 1 where the oxidation-reduction potential of the solution was less than 100 mV. Therefore, in order to maintain the concentration of iridium, it is preferable to maintain the oxidation-reduction potential at 100 mV or more.
Claims (5)
（１）前記酸化還元電位を調整した塩酸酸性液を３０～７０℃に調整し、鉄と反応させてルテニウムを沈殿させる工程、
（２）前記塩酸酸性液を７５℃以上に加温し、チオ硫酸ナトリウム塩もしくはチオ硫酸イオン含有溶液を、チオ硫酸ナトリウム５水和物に換算して１０ｇ／Ｌ以上になるよう添加してイリジウムを沈殿させる工程。 Ruthenium and iridium, comprising a step of adjusting the oxidation-reduction potential of a hydrochloric acid acid solution containing ruthenium and iridium to less than 480 mV using a silver/silver chloride electrode as a reference electrode, and the following steps (1) and (2). Separation method of iridium.
(1) a step of adjusting the oxidation-reduction potential-adjusted hydrochloric acid acid solution to 30 to 70° C. and reacting it with iron to precipitate ruthenium;
(2) The hydrochloric acid solution is heated to 75° C. or higher, and a sodium thiosulfate salt or a solution containing thiosulfate ions is added so as to be 10 g/L or more in terms of sodium thiosulfate pentahydrate. precipitating.
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