JP2021520291A - 低金属濃度の工業廃水から金属を回収する方法 - Google Patents
低金属濃度の工業廃水から金属を回収する方法 Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 103
- 239000002184 metal Substances 0.000 title claims abstract description 103
- 239000010842 industrial wastewater Substances 0.000 title claims abstract description 50
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- 229910052733 gallium Inorganic materials 0.000 claims description 31
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- -1 ferrous metals Chemical class 0.000 claims description 13
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- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 19
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- 239000005725 8-Hydroxyquinoline Substances 0.000 description 3
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
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- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 description 1
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
- C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/18—Removal of treatment agents after treatment
-
- 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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- Health & Medical Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
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- Manufacture And Refinement Of Metals (AREA)
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Abstract
Description
A:シデロホアを工業廃水に加えることによる、回収すべき金属の金属イオンの錯化、
B:金属シデロホア錯体の分離、
C:金属シデロホア錯体からの金属の放出、
D:金属の分離、
E:シデロホアの回収、及び
F:シデロホアの分離、
を含む、前記方法である。
a. Fe(III)−シデロホア錯体に還元剤を添加することによって行われ、それにより、Fe(III)がFe(II)に還元され、このFe(II)が脱錯化され、最後にFe(II)としてフリーな状態で存在する、
b. a.に記載の還元剤の添加及びキレート剤の添加による形成したFe(II)の追加的な錯化によって行われ、それにより、溶液中のFe(II)が結合され、そして脱錯化の平衡が、より高い収率の方向にシフトされる、または
c. Fe(III)をシデロホアと競合して錯化する過剰のキレート剤の添加によって、行われる。
・固定相抽出
・析出
・濾過及び/またはナノ濾過
・キャリア材料上へのシデロホアの不動化
・発泡と泡の収集による金属−シデロホア錯体の濃縮
・並びに、上記の方法の組み合わせ。
・クロマトグラフィ法
・析出
・濾過及び/またはナノ濾過
・キャリア材料上へのシデロホアの不動化
・発泡と泡の収集による金属−シデロホア錯体の濃縮、並びに
・上記の方法の組み合わせ。
・キャリア材料上へのシデロホアの不動化と、濾過及び/またはナノ濾過との組み合わせ、及び
・析出と、濾過及び/またはナノ濾過との組み合わせ。
DFO−Eを使用した、低Ga濃度(4mg/L)の工業廃水のための方法の説明:
低Ga濃度の工業廃水1.95mLに、デフェロキサミンEの2mM溶液0.05mLを加え、そして得られた溶液を15分間、室温で攪拌する。この溶液100μLを、溶剤流速を0.8mL/分として商業的に入手可能なクロマトグラフィカラムであるZORBAX Eclipse XDB−C18(4.6×150mm、5μm)中にポンプ輸送する。作業温度は25℃である。溶剤としては10mM KH2PO4(溶剤A)及びアセトニトリル(HPLCグレード、溶剤B)を勾配モードで利用する。プロセスコストを低減するためには、勾配モードにおいて溶剤Aを比較的低い濃度で使用することもでき、具体的には1mM H3PO4を使用できる。溶剤Bの割合は、10分間のうちに10%から15%に高める。溶離の後には、90%の10mM KH2PO4及び10%のアセトニトリルからなる溶剤混合物を用いた20分間の平衡相が続く。
0.087mMのインジウムを含む工業廃水1.91mLに、デフェロキサミンEの2mM溶液0.09mLを加え、そして得られた溶液を15分間、室温で攪拌する。この溶液100μLをクロマトグラフィカラムに供給する。残りのステップは、DFO−Eを使用した低Ga濃度についての上記の実験と同様に行う。インジウム含有工業廃水の場合は、以下の他の汚染元素がイオン形態で含まれていた: Na、K、Ca、Mg、P、S、Si、Zn及びPb。
全プロセスの類似の実験を、Ga濃度が40mg/Lの工業廃水試料1.6mLを用いて行う。この溶液に、0.4mLの2mM水性デフェロキサミン−E溶液を加える。上記のプロセスの全てのステップを同様に使用する。唯一の違いは、使用した試薬の量にある:41.6μLの1mM Fe3+溶液及びその後に、28μLのNa2SO3の10mM溶液を使用する。
及び
DFO−Bを使用した、比較的高いGa濃度(40mg/L)の工業廃水のための方法の説明:
比較的高いGa濃度の工業廃水、並びに低Ga濃度の工業廃水からのガリウムの回収は、上記の方法に類似して、デフェロキサミン−Eの代わりにデフェロキサミン−Bを使用して行う。全てのプロセスステップを、収集される画分は除き同様に使用する。Ga−デフェロキサミン−B錯体及びFe−デフェロキサミン−B錯体のどちらも、8〜10分間ではなく、4.5〜6.5分間の溶離時間で集められる。
M=mol/L。
DFO−Eを使用した、低Ga濃度(4mg/L)の工業廃水のための方法の説明
低Ga濃度(4mg/L)の工業廃水1.95mLに、デフェロキサミン−Eの2mM溶液0.05mLを加え、そして得られた溶液を15分間、室温で攪拌する。この溶液100μLを、溶剤流速を0.8mL/分として商業的に入手可能なクロマトグラフィカラムであるZORBAX Eclipse XDB−C18(4.6×150mm、5μm)中にポンプ輸送する。作業温度は25℃である。溶剤としては10mM KH2PO4(溶剤A)及びアセトニトリル(HPLCグレード、溶剤B)を勾配モードで利用する。溶剤Bの割合は、10分間のうちに10%から15%に高める。溶離の後には、90%の10mM KH2PO4及び10%のアセトニトリルからなる溶剤混合物を用いた20分間の平衡相が続く。
逆相クロマトグラフィ樹脂を使用した、負荷の最大化及び溶剤損失の最小化のための最適化されたクロマトグラフィ樹脂
Ga−シデロホア錯体の分離または精製のための最適化されたクロマトグラフィ樹脂の探索では、以下の最適化を行った。
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Claims (12)
- 工業廃水から非鉄金属を回収する方法であって、
A:シデロホアを工業廃水に加えることによる、回収すべき金属の錯化、
B:金属シデロホア錯体の分離、
C:金属シデロホア錯体からの金属の放出、
D:金属の分離、
E:シデロホアの回収、及び
F:シデロホアの分離、
を含む、前記方法。 - 請求項1に記載の方法であって、
C:Fe(III)イオンの添加及びFe(III)−シデロホア錯体の形成による金属−シデロホア錯体からの金属の放出を行い、及び
E:還元剤の及び/またはキレート剤の添加によるシデロホアの回収を行う、
前記方法。 - 前記還元剤が、H2SO3、アスコルビン酸及びそれらの塩から選択される、請求項2に記載の方法。
- 請求項1に記載の方法であって、
C: キレート剤の添加による金属−シデロホア錯体からの金属の放出を行い、それによって、金属−キレート剤錯体が形成する、
前記方法。 - 前記金属が金属−キレート剤錯体として分離される、請求項4に記載の方法。
- 前記金属が、Ga、In、Sc、Pu、Co、Ge、V、Al、Mn、Th、Ti、Zr、Hf、Nb、Ta、Mo、Bk、Eu、Dy、Pa、Gd、Yb、Ce、La、Rh、Tl、Bi及びPdから選択される、請求項1〜5のいずれか一つに記載の方法。
- 前記シデロホアが、デフェロキサミン及び脂肪酸含有シデロホア及びそれらの塩から選択される、請求項1〜6のいずれか一つに記載の方法。
- 前記シデロホアが、デフェロキサミンB(DFO−B)、デフェロキサミンE(DFO−E)、マリノバクチン、アクアケリン、アンフィバクチン、オクロバクチン及びシネコバクチン及びそれらの塩から選択される、請求項7に記載の方法。
- 分離ステップB、D及びFのうちの少なくとも一つにおいて、分離のための方法が、
・クロマトグラフィ法、
・固定相抽出、
・析出、
・濾過及び/またはナノ濾過、
・キャリア材料上へのシデロホアの不動化、
・発泡と泡の収集による金属−シデロホア錯体の濃縮、
・並びに、上記の方法の組み合わせ、
から選択される、請求項1〜8のいずれか一つに記載の方法。 - 温度が一貫して10℃と50℃との間である、請求項1〜9のいずれか一つに記載の方法。
- 請求項1〜10のいずれか一つに記載の方法における工業廃水からの非鉄金属の回収のための、シデロホアの使用。
- 前記非鉄金属が、Ga、In、Sc、Pu、Co、Ge、V、Al、Mn、Th、Ti、Zr、Hf、Nb、Ta、Mo、Bk、Eu、Dy、Pa、Gd、Yb、Ce、La、Rh、Tl、Bi及びPdから選択される、請求項11に記載の使用。
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