JP7594930B2 - Method for separating As and Sb - Google Patents
Method for separating As and Sb Download PDFInfo
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- JP7594930B2 JP7594930B2 JP2021022307A JP2021022307A JP7594930B2 JP 7594930 B2 JP7594930 B2 JP 7594930B2 JP 2021022307 A JP2021022307 A JP 2021022307A JP 2021022307 A JP2021022307 A JP 2021022307A JP 7594930 B2 JP7594930 B2 JP 7594930B2
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- 238000000034 method Methods 0.000 title claims description 49
- 229910052787 antimony Inorganic materials 0.000 title claims description 41
- 229910052785 arsenic Inorganic materials 0.000 title claims description 39
- 238000006386 neutralization reaction Methods 0.000 claims description 44
- 238000011946 reduction process Methods 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 description 156
- 239000010949 copper Substances 0.000 description 62
- 238000002203 pretreatment Methods 0.000 description 48
- 239000007788 liquid Substances 0.000 description 23
- 238000000926 separation method Methods 0.000 description 23
- 238000003723 Smelting Methods 0.000 description 10
- 229910052797 bismuth Inorganic materials 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- GCPXMJHSNVMWNM-UHFFFAOYSA-N arsenous acid Chemical compound O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 3
- 229940000488 arsenic acid Drugs 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 150000001621 bismuth Chemical class 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 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
- 230000008021 deposition Effects 0.000 description 1
- WUOBERCRSABHOT-UHFFFAOYSA-N diantimony Chemical compound [Sb]#[Sb] WUOBERCRSABHOT-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Description
本発明は、ＡｓとＳｂとの分離方法に関し、特に、金属製錬で生じる溶液に対するＡｓとＳｂとの分離方法に関する。 The present invention relates to a method for separating As and Sb, and in particular, to a method for separating As and Sb from a solution produced during metal smelting.
特許文献１には、アンチモンを含有するヒ酸水溶液に二酸化硫黄ガスを吹き込み、ヒ素とアンチモンを還元して、亜ヒ酸（Ａｓ２Ｏ３）と三酸化二アンチモン（Ｓｂ２Ｏ３）を含有する析出物を得る工程（Ａ）、及び前記析出物を７０～１００℃の温度を有する温水中に添加し、該析出物中の亜ヒ酸を溶解して、亜ヒ酸水溶液とアンチモンを含有する未溶解残渣を得る工程（Ｂ）を含むことを特徴とするヒ酸水溶液中のヒ素とアンチモンの分離方法が記載されている。 Patent Document 1 describes a method for separating arsenic and antimony in an aqueous arsenic acid solution, which comprises the steps of: (A) blowing sulfur dioxide gas into an aqueous arsenic acid solution containing antimony to reduce the arsenic and antimony and obtain a precipitate containing arsenous acid (As 2 O 3 ) and diantimony trioxide (Sb 2 O 3 ); and (B) adding the precipitate to warm water having a temperature of 70 to 100° C. to dissolve the arsenous acid in the precipitate and obtain an aqueous arsenous acid solution and an undissolved residue containing antimony.
特許文献２には、ビスマスを含有する酸性溶液を中和処理してビスマス塩を沈澱させ、該沈澱の溶解液を還元してビスマスを共存金属から分離回収する方法であって、中和処理を常温で二段階に行い、第一中和処理においてビスマス含有溶液のｐＨを６０分以上かけて０.５～１.５に調整して該ｐＨ域で沈澱する共存金属を沈澱化し、該沈澱を濾別した後に、第二中和処理において濾液のｐＨを２～３に調整してビスマスを含む沈澱を生成させ、このビスマス含有沈澱を回収して塩酸に溶解し、該溶解液を鉄還元して析出した金属ビスマスを回収することを特徴とするビスマスの回収方法が記載されている。 Patent Document 2 describes a method for recovering bismuth by neutralizing an acidic solution containing bismuth to precipitate bismuth salts, reducing the solution of the precipitates, and separating and recovering bismuth from coexisting metals, in which the neutralization is carried out in two stages at room temperature, and in the first neutralization step, the pH of the bismuth-containing solution is adjusted to 0.5 to 1.5 over 60 minutes or more to precipitate the coexisting metals that precipitate in that pH range, and after filtering out the precipitate, in the second neutralization step, the pH of the filtrate is adjusted to 2 to 3 to generate a precipitate containing bismuth, and this bismuth-containing precipitate is recovered and dissolved in hydrochloric acid, and the solution is reduced with iron to recover the precipitated metallic bismuth.
特許文献１に記載の内容だと、析出物中にＡｓとＳｂとが混在するため、ＡｓとＳｂとを分離する工程が別途必要になる。特許文献２に記載の内容は、そもそもビスマスの回収方法が主旨である。 In the case of the method described in Patent Document 1, As and Sb are mixed in the precipitate, so a separate process is required to separate As and Sb. The content of Patent Document 2 is primarily a method for recovering bismuth.
本発明の目的は、ＡｓとＳｂとのうちＳｂを選択的に析出させてＡｓとＳｂとを分離することにある。 The object of the present invention is to separate As and Sb by selectively precipitating Sb from As.
本発明の第１の態様は、
Ｃｕ、Ａｓ、Ｓｂを含有し、溶解したＳｂの濃度が１．０ｇ／Ｌ以上であり、濃度比Ｃｕ／Ａｓが０．１０以上、且つ、濃度比Ｃｕ／Ｓｂが０．１０以上である溶液からＳｂを析出させるＳｂ析出工程を有し、
Ｓｂ析出工程は、Ｓｂ還元工程と中和工程をこの順で有し、
中和工程開始時のＯＲＰ（３．３Ｍ ＫＣｌ－Ａｇ／ＡｇＣｌ）は７０～２１０ｍＶである、ＡｓとＳｂとの分離方法である。
The first aspect of the present invention is a method for producing a cellular membrane comprising the steps of:
The method includes a step of precipitating Sb from a solution containing Cu, As, and Sb, the solution having a concentration of dissolved Sb of 1.0 g/L or more, a concentration ratio of Cu/As of 0.10 or more, and a concentration ratio of Cu/Sb of 0.10 or more,
The Sb precipitation step includes an Sb reduction step and a neutralization step in this order,
The ORP (3.3M KCl-Ag/AgCl) at the start of the neutralization process is 70 to 210 mV. This is a method for separating As and Sb.
本発明の第２の態様は、第１の態様において、
前記溶液は、Ｓｂ還元工程開始時の溶液である。
A second aspect of the present invention is a method for producing a composition comprising the steps of:
This solution is the solution at the start of the Sb reduction process.
本発明の第３の態様は、第２の態様において、
Ｓｂ還元工程前にＣｕ源添加工程を含む。
A third aspect of the present invention is the method according to the second aspect,
A Cu source addition step is included before the Sb reduction step.
本発明の第４の態様は、第１～第３のいずれかの態様において、
中和工程開始時のｐＨは０．９～３．０である。
A fourth aspect of the present invention is a method for producing a composition according to any one of the first to third aspects,
The pH at the start of the neutralization step is 0.9 to 3.0.
本発明の第５の態様は、第１～第４のいずれかの態様において、
中和工程終了時のＯＲＰは１３０～３５０ｍＶである。
A fifth aspect of the present invention is a method for producing a composition comprising the steps of:
The ORP at the end of the neutralization step is 130 to 350 mV.
本発明の第６の態様は、第１～第５のいずれかの態様において、
Ｓｂ還元工程開始時のｐＨは０．５～２．０である。
A sixth aspect of the present invention is a method for producing a composition comprising the steps of:
The pH at the start of the Sb reduction step is 0.5 to 2.0.
本発明の第７の態様は、第１～第６のいずれかの態様において、
Ｓｂ還元工程開始時のＯＲＰは１００～７００ｍＶである。
A seventh aspect of the present invention is a method for producing a composition according to any one of the first to sixth aspects,
The ORP at the start of the Sb reduction step is 100 to 700 mV.
本発明によれば、ＡｓとＳｂとのうちＳｂを選択的に析出させてＡｓとＳｂとを分離できる。 According to the present invention, As and Sb can be separated by selectively precipitating Sb out of As and Sb.
本実施形態は、ＡｓとＳｂとの分離方法に関する。本明細書における「～」は所定の数値以上かつ所定の数値以下を指す。本実施形態における「Ａｓ」「Ｓｂ」等の元素記号は、金属単体又はイオンを指す。以降、濃度比はｗｔ比を意味し、％はｗｔ％を意味する。 This embodiment relates to a method for separating As and Sb. In this specification, "~" indicates a value equal to or greater than a specified value and equal to or less than a specified value. In this embodiment, element symbols such as "As" and "Sb" indicate metal elements or ions. Hereinafter, concentration ratio means wt ratio, and % means wt%.
本実施形態での処理対象となる溶液は、例えば、金属製錬（特に亜鉛製錬）で生じる溶液である。「ＡｓとＳｂとを分離する」とは、具体的には溶液中からＳｂを析出させる一方でＡｓは溶液中に残存させることを意味する。 The solution to be treated in this embodiment is, for example, a solution produced during metal smelting (particularly zinc smelting). "Separating As and Sb" specifically means precipitating Sb from the solution while leaving As in the solution.
本実施形態では、溶液中からＳｂを析出させるＳｂ析出工程を行う。Ｓｂ析出工程は、溶液中においてＳｂを還元する還元工程と、還元工程後の溶液を中和することにより還元後のＳｂを析出させる中和工程とをこの順で有する。以降、還元工程開始前の溶液を処理前溶液とも言い、還元工程開始後ないし中和工程終了前の溶液を処理中溶液とも言い、中和工程終了後の溶液を処理後溶液とも言う。 In this embodiment, an Sb precipitation process is performed to precipitate Sb from the solution. The Sb precipitation process includes, in this order, a reduction process to reduce Sb in the solution, and a neutralization process to neutralize the solution after the reduction process to precipitate reduced Sb. Hereinafter, the solution before the start of the reduction process is also referred to as the pre-treatment solution, the solution after the start of the reduction process or before the end of the neutralization process is also referred to as the in-treatment solution, and the solution after the end of the neutralization process is also referred to as the post-treatment solution.
［態様１］
本態様では、処理前溶液中にＣｕを予め存在させる場合を例示する。
[Aspect 1]
In this embodiment, a case where Cu is previously present in the pre-treatment solution is exemplified.
本態様における処理前溶液は、以下の特徴を有するのがよい。
・Ｃｕ、Ａｓ、Ｓｂを含有する。
・溶解したＳｂの濃度が１．０ｇ／Ｌ以上である。
・濃度比Ｃｕ／Ａｓが０．１０以上、且つ、濃度比Ｃｕ／Ｓｂが０．１０以上である。
The pre-treatment solution in this embodiment should have the following characteristics:
-Contains Cu, As, and Sb.
- The concentration of dissolved Sb is 1.0 g/L or more.
The concentration ratio Cu/As is 0.10 or more, and the concentration ratio Cu/Sb is 0.10 or more.
処理前溶液中におけるＣｕ、Ａｓ、Ｓｂは、好適にはいずれもイオン化（錯イオン含む）して溶液中に溶解している。 The Cu, As, and Sb in the pre-treatment solution are preferably all ionized (including complex ions) and dissolved in the solution.
処理前溶液中に溶解したＳｂの濃度が１．０ｇ／Ｌ以上であり、特許文献２に記載のビスマスの回収を前提とした溶液と本実施形態の処理前溶液とは異なる。 The concentration of Sb dissolved in the pre-treatment solution is 1.0 g/L or more, and the pre-treatment solution of this embodiment is different from the solution described in Patent Document 2, which is intended for the recovery of bismuth.
処理前溶液中に溶解したＳｂの濃度の下限は１．５ｇ／Ｌ、２．０ｇ／Ｌであってもよい。該濃度の上限は２０ｇ／Ｌ、１５ｇ／Ｌ、１０ｇ／Ｌであってもよい。 The lower limit of the concentration of Sb dissolved in the pre-treatment solution may be 1.5 g/L or 2.0 g/L. The upper limit of the concentration may be 20 g/L, 15 g/L, or 10 g/L.
処理前溶液中に溶解したＡｓの濃度には限定は無いが、該濃度の下限は１ｇ／Ｌ、１０ｇ／Ｌ、２０ｇ／Ｌであってもよい。該濃度の上限は２００ｇ／Ｌ、１００ｇ／Ｌであってもよい。 There is no limit to the concentration of As dissolved in the pre-treatment solution, but the lower limit of the concentration may be 1 g/L, 10 g/L, or 20 g/L. The upper limit of the concentration may be 200 g/L or 100 g/L.
処理前溶液中に溶解したＣｕの濃度には限定は無いが、該濃度の下限は１０ｇ／Ｌ、２０ｇ／Ｌ、２５ｇ／Ｌであってもよい。該濃度の上限は１５０ｇ／Ｌ、１００ｇ／Ｌ、８０ｇ／Ｌであってもよい。 There is no limit to the concentration of Cu dissolved in the pre-treatment solution, but the lower limit of the concentration may be 10 g/L, 20 g/L, or 25 g/L. The upper limit of the concentration may be 150 g/L, 100 g/L, or 80 g/L.
但し、処理前溶液中の濃度比Ｃｕ／Ａｓが０．１０以上、且つ、濃度比Ｃｕ／Ｓｂが０．１０以上とする。 However, the concentration ratio Cu/As in the pre-treatment solution must be 0.10 or more, and the concentration ratio Cu/Sb must be 0.10 or more.
処理前溶液中の濃度比Ｃｕ／Ａｓの下限は１、３、５であってもよい。濃度比Ｃｕ／Ａｓの上限は５０、３０であってもよい。 The lower limit of the Cu/As concentration ratio in the pre-treatment solution may be 1, 3, or 5. The upper limit of the Cu/As concentration ratio may be 50 or 30.
処理前溶液中の濃度比Ｃｕ／Ｓｂの下限は０．３、０．５であってもよい。濃度比Ｃｕ／Ｓｂの上限は５、３、２であってもよい。 The lower limit of the concentration ratio Cu/Sb in the pre-treatment solution may be 0.3 or 0.5. The upper limit of the concentration ratio Cu/Sb may be 5, 3, or 2.
処理前溶液中の濃度比Ａｓ／Ｓｂの下限は０．１、１、５であってもよい。濃度比Ａｓ／Ｓｂの上限は５０、３０、２０であってもよい。 The lower limit of the concentration ratio As/Sb in the pre-treatment solution may be 0.1, 1, or 5. The upper limit of the concentration ratio As/Sb may be 50, 30, or 20.
処理前溶液中の濃度比Ｃｕ／（Ｓｂ＋Ａｓ）の下限は０．１であってもよい。濃度比Ｃｕ／（Ｓｂ＋Ａｓ）の上限は５であってもよい。 The lower limit of the concentration ratio Cu/(Sb+As) in the pre-treatment solution may be 0.1. The upper limit of the concentration ratio Cu/(Sb+As) may be 5.
処理前溶液中のＡｓ、Ｓｂに関する上記濃度設定は、金属製錬（特に亜鉛製錬）で生じる溶液中のＡｓ、Ｓｂの濃度の値を包含する設定である。その一方、金属製錬（特に亜鉛製錬）で生じる溶液中において、処理前溶液中のＣｕに関する上記濃度設定を満たさない場合、処理前溶液に対して別途Ｃｕ源を添加してもよい（Ｃｕ源添加工程）。別途添加する際のＣｕ源としては水溶性のものが好ましく例えば硫酸銅（ＣｕＳＯ４）（水和物も使用可）が挙げられる。この場合、処理前溶液中にて２価の銅イオンが存在することになる。 The above-mentioned concentration settings for As and Sb in the pre-treatment solution include the concentration values of As and Sb in the solution produced in metal smelting (particularly zinc smelting). On the other hand, if the above-mentioned concentration setting for Cu in the pre-treatment solution is not satisfied in the solution produced in metal smelting (particularly zinc smelting), a Cu source may be added separately to the pre-treatment solution (Cu source addition step). The Cu source added separately is preferably water-soluble, for example, copper sulfate (CuSO 4 ) (hydrates can also be used). In this case, divalent copper ions will be present in the pre-treatment solution.
処理前溶液の組成の一例は以下のとおりである。
Ａｓ：０．２～１００ｇ／Ｌ
Ｓｂ：０．０５～１０ｇ／Ｌ
Ｃｕ：０．１～１００ｇ／Ｌ
上記以外の重金属（Ｃｄ，Ｃｏ，Ｎｉ，Ｐｂ，Ｚｎなど）：１ｇ／Ｌ以下
An example of the composition of the pre-treatment solution is as follows:
As: 0.2-100g/L
Sb: 0.05-10g/L
Cu: 0.1-100g/L
Heavy metals other than those mentioned above (Cd, Co, Ni, Pb, Zn, etc.): 1g/L or less
処理前溶液のｐＨの下限は０．５であってもよく、１．０を超えてもよい。処理前溶液のｐＨの上限は３．０、２．０であってもよい。この数値範囲が示すように、処理前溶液は酸性である。また、本明細書におけるｐＨの値は、変化が収まった状態（例えば１０分間での変化が０．１以内）での値である。処理前溶液のｐＨは、Ｓｂ還元工程開始時のｐＨと言い換えてもよい。 The lower limit of the pH of the pre-treatment solution may be 0.5 or may exceed 1.0. The upper limit of the pH of the pre-treatment solution may be 3.0 or 2.0. As these numerical ranges indicate, the pre-treatment solution is acidic. In addition, the pH value in this specification is the value in a state where the change has settled (for example, the change in 10 minutes is within 0.1). The pH of the pre-treatment solution may be rephrased as the pH at the start of the Sb reduction process.
本明細書でのＯＲＰ（３．３Ｍ ＫＣｌ－Ａｇ／ＡｇＣｌ）は、本発明では標準電極に対して＋１９９ｍＶ（ｖｓ．ＳＨＥ、２５℃）でいわゆる酸化還元電位（ｖｓＡｇ／ＡｇＣｌ）である。以降、ＯＲＰは同様の定義とする。また、本明細書におけるＯＲＰの値は、変化が収まった状態（例えば１０分間での変化が１０ｍＶ以内）での値である。処理前溶液のＯＲＰは、Ｓｂ還元工程開始時のＯＲＰと言い換えてもよい。 In this specification, ORP (3.3M KCl-Ag/AgCl) is +199 mV (vs. SHE, 25°C) against a standard electrode, which is the so-called oxidation-reduction potential (vs. Ag/AgCl). Hereinafter, ORP will have the same definition. In addition, the ORP value in this specification is the value in a state where the change has settled (for example, the change in 10 minutes is within 10 mV). The ORP of the pre-treatment solution may be rephrased as the ORP at the start of the Sb reduction process.
処理前溶液のＯＲＰの下限は１００ｍＶ、１５０ｍＶ、２００ｍＶであってもよい。処理前溶液のＯＲＰの上限は７００ｍＶ、６００ｍＶであってもよい。 The lower limit of the ORP of the pre-treatment solution may be 100 mV, 150 mV, or 200 mV. The upper limit of the ORP of the pre-treatment solution may be 700 mV or 600 mV.
処理前溶液に対してＳｂの還元工程を行う。具体的には、処理前溶液に対して還元剤を添加する。還元剤には限定は無いが、例えば二酸化硫黄（ＳＯ２）（ガスの吹き込みも利用可）、亜硫酸ナトリウム（ＮａＨＳＯ３）の少なくともいずれかが挙げられる。 The untreated solution is subjected to a reduction step of Sb. Specifically, a reducing agent is added to the untreated solution. The reducing agent is not limited, but may be at least one of sulfur dioxide (SO 2 ) (gas injection may also be used) and sodium sulfite (NaHSO 3 ).
Ｓｂの還元工程中の処理中溶液の温度は４０～９５℃であってもよい。Ｓｂの還元工程の反応時間は３０～１５０分であってもよい。 The temperature of the solution during the Sb reduction step may be 40 to 95°C. The reaction time of the Sb reduction step may be 30 to 150 minutes.
Ｓｂの還元工程後の処理中溶液のｐＨの下限は０．９、１．０、１．０超え、１．５、２．０であってもよい。Ｓｂの還元工程後の処理中溶液のｐＨの上限は３．０、２．５であってもよい。Ｓｂの還元工程後の処理中溶液のｐＨは、中和工程開始時のｐＨと言い換えてもよい。 The lower limit of the pH of the solution in process after the Sb reduction step may be 0.9, 1.0, more than 1.0, 1.5, or 2.0. The upper limit of the pH of the solution in process after the Sb reduction step may be 3.0 or 2.5. The pH of the solution in process after the Sb reduction step may be rephrased as the pH at the start of the neutralization step.
Ｓｂの還元工程後の処理中溶液のＯＲＰは７０～２１０ｍＶとする。これにより、中和工程後にＳｂを十分に析出できる。つまり、処理前溶液中に溶解しているＳｂの濃度に対する、中和工程後の処理後溶液中に溶解しているＳｂの濃度（析出したＳｂの分離後）の百分率を１００から引いた数値（脱Ｓｂ率）を向上できる。 The ORP of the solution being treated after the Sb reduction process is set to 70-210 mV. This allows sufficient Sb to precipitate after the neutralization process. In other words, it is possible to improve the value (Sb removal rate) obtained by subtracting the percentage of the concentration of Sb dissolved in the treated solution after the neutralization process (after separation of precipitated Sb) from 100 relative to the concentration of Sb dissolved in the pre-treatment solution.
Ｓｂの還元工程後の処理中溶液のＯＲＰの下限は１００ｍＶ、１１０ｍＶ、１３０ｍＶであってもよい。Ｓｂの還元工程後の処理中溶液のＯＲＰの上限は１９０ｍＶ、１７０ｍＶであってもよい。Ｓｂの還元工程後の処理中溶液のＯＲＰは、中和工程開始時のＯＲＰと言い換えてもよい。 The lower limit of the ORP of the solution being treated after the Sb reduction process may be 100 mV, 110 mV, or 130 mV. The upper limit of the ORP of the solution being treated after the Sb reduction process may be 190 mV or 170 mV. The ORP of the solution being treated after the Sb reduction process may be rephrased as the ORP at the start of the neutralization process.
なお、Ｓｂの還元工程後の処理中溶液中の濃度比Ｃｕ／Ａｓ、Ｃｕ／Ｓｂ、Ａｓ／Ｓｂ、Ｃｕ／（Ｓｂ＋Ａｓ）に関しては、本発明でのＳｂの還元工程ではＡｓもＳｂもほとんど析出しないうえ、処理中溶液に対しては固液分離工程を行っていないので、処理前溶液と同様の濃度比の規定を適用できる。 Regarding the concentration ratios Cu/As, Cu/Sb, As/Sb, and Cu/(Sb+As) in the solution being treated after the Sb reduction process, the same concentration ratios as in the solution before treatment can be applied because As and Sb are hardly precipitated in the Sb reduction process of the present invention and no solid-liquid separation process is performed on the solution being treated.
Ｓｂの還元工程前の処理前溶液中に溶解しているＡｓ、Ｓｂ、Ｃｕの濃度、及び、該処理前溶液中に溶解している各元素の濃度比Ｃｕ／Ａｓ、Ｃｕ／Ｓｂ、Ａｓ／Ｓｂ、Ｃｕ／（Ｓｂ＋Ａｓ）からの、Ｓｂの還元工程後の処理中溶液中に溶解している各元素の該濃度及び濃度比への減少率（特にＡｓの濃度の減少率）は２％以下、１％以下であってもよい。 The concentration of As, Sb, and Cu dissolved in the pre-treatment solution before the Sb reduction step, and the reduction rate from the concentration ratios of each element dissolved in the pre-treatment solution, Cu/As, Cu/Sb, As/Sb, and Cu/(Sb+As), to the concentration and concentration ratio of each element dissolved in the treatment solution after the Sb reduction step (particularly the reduction rate of the As concentration) may be 2% or less, 1% or less.
Ｓｂの還元工程後の処理中溶液に対して還元後のＳｂを析出させる中和工程を行う。還元工程後の処理中溶液のｐＨを増加できれば添加物に限定は無いが、例えばアルカリ（一例としては炭酸カルシウム（ＣａＣＯ３）及び水酸化ナトリウム（ＮａＯＨ）の少なくともいずれか）を添加してもよい。石膏（ＣａＳＯ４）も該添加物として挙げられる。 The solution in process after the Sb reduction step is subjected to a neutralization step to precipitate reduced Sb. There is no limitation on the additives as long as they can increase the pH of the solution in process after the reduction step, and for example, an alkali (one example being at least one of calcium carbonate (CaCO 3 ) and sodium hydroxide (NaOH)) may be added. Gypsum (CaSO 4 ) is also an example of such an additive.
中和工程中の処理中溶液の温度は４０～９５℃であってもよい。中和工程の反応時間は３０～１５０分であってもよい。 The temperature of the solution during the neutralization step may be 40 to 95°C. The reaction time of the neutralization step may be 30 to 150 minutes.
中和工程後の処理後溶液のｐＨは、還元工程後且つ中和工程前の処理中溶液のｐＨよりも増加していればよい。そのうえで、中和工程後の処理後溶液のｐＨの下限は２．５、３．０が好ましい。中和工程後の処理後溶液のｐＨの上限は４．０が好ましい。 The pH of the post-treatment solution after the neutralization step should be higher than the pH of the treatment solution after the reduction step and before the neutralization step. In addition, the lower limit of the pH of the post-treatment solution after the neutralization step is preferably 2.5 or 3.0. The upper limit of the pH of the post-treatment solution after the neutralization step is preferably 4.0.
中和工程後の処理後溶液のＯＲＰの下限は５０ｍＶ、８０ｍＶ、１００ｍＶ、１３０ｍＶであってもよい。中和工程後の処理後溶液のＯＲＰの上限は３５０ｍＶ、３００ｍＶ、２８０ｍＶであってもよい。 The lower limit of the ORP of the treated solution after the neutralization step may be 50 mV, 80 mV, 100 mV, or 130 mV. The upper limit of the ORP of the treated solution after the neutralization step may be 350 mV, 300 mV, or 280 mV.
中和工程後の処理後溶液の上記ｐＨ及びＯＲＰのいずれかの数値範囲ならば、Ｓｂを十分に析出でき且つＡｓは処理後溶液中に十分に残存可能となる。つまり、処理前溶液中に溶解しているＡｓの濃度に対する、中和工程後の処理後溶液中に溶解しているＡｓの濃度（析出したＡｓの分離後）の百分率を１００から引いた数値（脱Ａｓ率）は低く抑えつつ、脱Ｓｂ率を向上できる。 If the pH and ORP of the treated solution after the neutralization step are in any of the above numerical ranges, Sb can be sufficiently precipitated and As can be sufficiently left in the treated solution. In other words, the value obtained by subtracting the percentage of the As concentration (after separation of precipitated As) dissolved in the treated solution after the neutralization step relative to the As concentration dissolved in the pre-treatment solution from 100 (As removal rate) can be kept low, while the Sb removal rate can be improved.
処理後溶液に対して固液分離を行った後の固液分離後溶液中の脱Ａｓ率は３３％以下、２５％以下が好ましい。固液分離後溶液中の脱Ｓｂ率は７５％以上、８０％以上が好ましい。但し、脱Ａｓ率と脱Ｓｂ率との両方が適度に良好であるのが好ましい。そのため、（１００－脱Ａｓ率）×脱Ｓｂ率の値の下限が６６００、７０００、７５００、８０００であってもよい。 After the post-treatment solution is subjected to solid-liquid separation, the As depletion rate in the solution after solid-liquid separation is 33% or less, preferably 25% or less. The Sb depletion rate in the solution after solid-liquid separation is 75% or more, preferably 80% or more. However, it is preferable that both the As depletion rate and the Sb depletion rate are adequately good. Therefore, the lower limit of the value of (100 - As depletion rate) x Sb depletion rate may be 6600, 7000, 7500, or 8000.
処理後溶液に対して固液分離を行った後の固液分離後溶液中の脱Ｃｕ率は２５％以下、１５％以下であってもよい。また、処理後溶液に対して固液分離を行った後の固液分離後溶液中の脱（Ａｓ、Ｓｂ、Ｃｕ以外の重金属）率も２５％以下、１５％以下であってもよい。 The de-Cu rate in the solution after solid-liquid separation performed on the treated solution may be 25% or less, or 15% or less. In addition, the de-Cu rate (heavy metals other than As, Sb, and Cu) in the solution after solid-liquid separation performed on the treated solution may be 25% or less, or 15% or less.
処理後溶液に対して固液分離を行った後の固液分離後溶液中の濃度比Ｃｕ／Ａｓには限定は無いが、下限が０．２、０．６、１．０、１．４であってもよく、上限が２．０、１．６であってもよい。 There is no limitation on the concentration ratio Cu/As in the solution after solid-liquid separation of the treated solution, but the lower limit may be 0.2, 0.6, 1.0, or 1.4, and the upper limit may be 2.0 or 1.6.
処理後溶液に対して固液分離を行った後の固液分離後溶液中の濃度比Ｃｕ／Ｓｂには限定は無いが、下限が１０、６０であってもよく、上限が２００００、２０００、６００、２００、１００、７０であってもよい。 There is no limitation on the concentration ratio Cu/Sb in the solution after solid-liquid separation of the treated solution, but the lower limit may be 10 or 60, and the upper limit may be 20,000, 2,000, 600, 200, 100, or 70.
処理後溶液に対して固液分離を行った後の固液分離後溶液中の濃度比Ａｓ／Ｓｂには限定は無いが、下限が４０であってもよく、上限が２５０００、８００、６００であってもよい。 There is no limitation on the concentration ratio As/Sb in the solution after solid-liquid separation of the treated solution, but the lower limit may be 40 and the upper limit may be 25,000, 800, or 600.
還元工程及び中和工程において撹拌を行ってもよく、例えばスターラー又は傾斜パドル等を使用してもよい。 Stirring may be performed during the reduction and neutralization steps, for example using a stirrer or tilted paddle.
本態様では還元工程終了後に中和工程を開始しているが、本発明はそれに限定されない。例えば、還元工程終了直前に中和工程を開始してもよい。その場合、上記処理中溶液のｐＨ及びＯＲＰの規定は中和工程開始時のｐＨ及びＯＲＰの値に対して適用可能である。 In this embodiment, the neutralization step is started after the reduction step is completed, but the present invention is not limited thereto. For example, the neutralization step may be started immediately before the reduction step is completed. In that case, the above-mentioned specifications for the pH and ORP of the solution being treated are applicable to the pH and ORP values at the start of the neutralization step.
本態様に記載のＡｓとＳｂとの分離方法は、Ｓｂ及びＡｓの分離回収方法にも適用可能である。例えば、中和工程後に処理後溶液に対して固液分離工程を行い、固体（残渣）からＳｂを回収できる。つまり本発明は、Ｓｂ回収方法（Ｓｂ製造方法）としても成り立つ。なお、固液分離後溶液に残存したＡｓは、亜鉛製錬において使用される亜ヒ酸として活用してもよい。 The method for separating As and Sb described in this embodiment can also be applied to a method for separating and recovering Sb and As. For example, a solid-liquid separation process can be performed on the treated solution after the neutralization process, and Sb can be recovered from the solid (residue). In other words, the present invention can also be used as a method for recovering Sb (a method for producing Sb). In addition, the As remaining in the solution after solid-liquid separation can be used as arsenous acid used in zinc smelting.
本明細書における固液分離工程は公知の手法を用いてよく、例えばろ過、遠心分離等を使用すればよい。 The solid-liquid separation step in this specification may be carried out using a known method, such as filtration or centrifugation.
［態様２］
還元工程後且つ中和工程前の処理中溶液に対して上記Ｃｕ源を添加し、上記態様１での処理前溶液中のＣｕに関する上記濃度設定を満たすようにＣｕの濃度を設定してもよい。後掲の実施例５が態様２に該当する。
[Aspect 2]
The Cu source may be added to the in-process solution after the reduction step and before the neutralization step, and the Cu concentration may be set so as to satisfy the above-mentioned concentration setting for Cu in the pre-processing solution in the above-mentioned embodiment 1. Example 5 described later corresponds to embodiment 2.
本態様においては、処理前溶液においてＣｕを含有しない又は含有してもＣｕに関する上記濃度設定を満たさない。その代わり、還元工程後且つ中和工程前の処理中溶液において、処理前溶液でのＣｕに関する上記濃度設定を満たせばよい。それ以外の規定は、上記態様１と同様とすればよい。 In this embodiment, the pre-treatment solution does not contain Cu, or if it does contain Cu, it does not satisfy the above-mentioned concentration setting for Cu. Instead, the pre-treatment solution after the reduction step and before the neutralization step only needs to satisfy the above-mentioned concentration setting for Cu in the pre-treatment solution. Other regulations may be the same as those in embodiment 1 above.
本明細書においては態様１及び態様２を含む表現として以下の表現を用いている。
「Ｃｕ、Ａｓ、Ｓｂを含有し、溶解したＳｂの濃度が１．０ｇ／Ｌ以上であり、濃度比Ｃｕ／Ａｓが０．１０以上、且つ、濃度比Ｃｕ／Ｓｂが０．１０以上である溶液からＳｂを析出させるＳｂ析出工程を有し、
Ｓｂ析出工程は、Ｓｂ還元工程と中和工程をこの順で有し、
Ｓｂ還元工程終了時のＯＲＰ（３．３Ｍ ＫＣｌ－Ａｇ／ＡｇＣｌ）は７０～２１０ｍＶである、ＡｓとＳｂとの分離方法。」
上記表現は、Ｓｂ析出工程の対象となる溶液の規定を満たすのが、Ｓｂ還元工程前である場合も含むし、Ｓｂ還元工程後且つ中和工程前である場合も含む。
In this specification, the following expressions are used to include both aspect 1 and aspect 2.
"The method includes a step of precipitating Sb from a solution containing Cu, As, and Sb, the concentration of dissolved Sb being 1.0 g/L or more, the concentration ratio Cu/As being 0.10 or more, and the concentration ratio Cu/Sb being 0.10 or more,
The Sb precipitation step includes an Sb reduction step and a neutralization step in this order,
The ORP (3.3M KCl-Ag/AgCl) at the end of the Sb reduction step is 70-210 mV.
The above expression includes the case where the solution that is the target of the Sb deposition step satisfies the requirement before the Sb reduction step, and also includes the case where the solution satisfies the requirement after the Sb reduction step and before the neutralization step.
次に実施例を示し、本発明について具体的に説明する。本発明は、以下の実施例に限定されるものではない。なお、以下に記載のない内容は、本実施形態で述べた内容と同様とする。 The present invention will now be described in detail with reference to examples. The present invention is not limited to the following examples. Any content not described below is the same as that described in this embodiment.
＜実施例１＞
亜鉛製錬で生じた残渣を硫酸にて溶解し、処理前溶液Ｘを得た。処理前溶液Ｘの詳細は以下の通りである。実施例１以外の各例に関しては、後掲の表１に以下の内容を記載する。
・液量：４００ｍＬ
・Ａｓ濃度：２０ｇ／Ｌ
・Ｓｂ濃度：２．０ｇ／Ｌ
・Ｃｕ濃度：３３ｇ／Ｌ
・上記以外の重金属（Ｃｄ，Ｃｏ，Ｎｉ，Ｐｂ，Ｚｎなど）：１ｇ／Ｌ以下
・ｐＨ：０．６９
・ＯＲＰ（３．３Ｍ ＫＣｌ－Ａｇ／ＡｇＣｌ、以降記載を省略）：４３０ｍＶ
・濃度比Ｃｕ／Ａｓ：１．６
・濃度比Ｃｕ／Ｓｂ：１７
・濃度比Ａｓ／Ｓｂ：１０
本例では、処理前溶液ＸにおいてＣｕの濃度に関する規定（濃度比Ｃｕ／Ａｓが０．１０以上、且つ、濃度比Ｃｕ／Ｓｂが０．１０以上）が既に満たされていたため、Ｃｕ源の添加は行わなかった。
Example 1
Residues produced during zinc smelting were dissolved in sulfuric acid to obtain pre-treatment solution X. Details of pre-treatment solution X are as follows. For each example other than Example 1, the following details are shown in Table 1 below.
Volume: 400mL
・As concentration: 20g/L
・Sb concentration: 2.0g/L
・Cu concentration: 33g/L
Heavy metals other than those mentioned above (Cd, Co, Ni, Pb, Zn, etc.): 1g/L or less pH: 0.69
ORP (3.3M KCl-Ag/AgCl, omitted below): 430 mV
・Concentration ratio Cu/As: 1.6
・Concentration ratio Cu/Sb: 17
・Concentration ratio As/Sb: 10
In this example, since the pre-treatment solution X already satisfied the regulation regarding the Cu concentration (the concentration ratio Cu/As being 0.10 or more and the concentration ratio Cu/Sb being 0.10 or more), no Cu source was added.
本例の処理前溶液Ｘに対して還元工程を行った。具体的には、液温の設定値を６０℃とし、還元剤としてＮａＨＳＯ３を処理前溶液Ｘに所定量添加した。そして、３枚傾斜パドル（バッフル無し）にて１２０分間撹拌を行った。そして、還元工程後且つ中和工程前の処理中溶液を得た。処理中溶液の詳細は以下の通りである。実施例１以外の各例に関しては、後掲の表１に以下の内容を記載する。
・ｐＨ：１．６
・ＯＲＰ：１３７ｍＶ
A reduction process was carried out on the untreated solution X of this example. Specifically, the liquid temperature was set to 60°C, and a predetermined amount of NaHSO 3 was added as a reducing agent to the untreated solution X. Then, the solution was stirred for 120 minutes with a three-blade inclined paddle (without a baffle). Then, an in-process solution was obtained after the reduction process and before the neutralization process. Details of the in-process solution are as follows. For each example other than Example 1, the following details are listed in Table 1 below.
pH: 1.6
・ORP: 137mV
なお、処理中溶液中の濃度比Ｃｕ／Ａｓ、Ｃｕ／Ｓｂ、Ａｓ／Ｓｂ、Ｃｕ／（Ｓｂ＋Ａｓ）に関しては、本発明でのＳｂの還元工程ではＡｓもＳｂもほとんど析出しないうえ、処理中溶液に対しては固液分離工程を行っていないので、処理前溶液Ｘと同じ値であった。 Regarding the concentration ratios Cu/As, Cu/Sb, As/Sb, and Cu/(Sb+As) in the solution during treatment, since As and Sb are hardly precipitated in the Sb reduction process in the present invention and since no solid-liquid separation process is performed on the solution during treatment, the values were the same as those of solution X before treatment.
本例の処理中溶液に対して中和工程を行った。具体的には、液温を６０℃とし、中和剤としてＣａＣＯ３を処理中溶液に所定量添加した。そして、３枚傾斜パドル（バッフル無し）にて１２０分間撹拌を行った。そして、中和工程後の処理後溶液を得た。処理後溶液の詳細は以下の通りである。実施例１以外の各例に関しては、後掲の表１に以下の内容を記載する。
・ｐＨ：３．７
・ＯＲＰ：１４６ｍＶ
The neutralization process was carried out on the in-process solution of this example. Specifically, the liquid temperature was set to 60°C, and a predetermined amount of CaCO3 was added as a neutralizing agent to the in-process solution. Then, the solution was stirred for 120 minutes with a three-blade inclined paddle (without baffles). Then, a post-processed solution was obtained after the neutralization process. Details of the post-processed solution are as follows. For each example other than Example 1, the following contents are listed in Table 1 below.
pH: 3.7
・ORP: 146mV
処理後溶液に対してろ紙を用いて固液分離工程を行った。固液分離後溶液の詳細は以下の通りである。実施例１以外の各例に関しては、後掲の表２に以下の内容を記載する。
・脱Ａｓ率：２１％
・脱Ｓｂ率：９９％
・脱Ｃｕ率：５％
・濃度比Ｃｕ／Ａｓ：１．９
・濃度比Ｃｕ／Ｓｂ：１４１２
・濃度比Ａｓ／Ｓｂ：７２６
The treated solution was subjected to a solid-liquid separation step using filter paper. Details of the solution after solid-liquid separation are as follows. For each example other than Example 1, the following details are shown in Table 2 below.
・As free rate: 21%
Sb removal rate: 99%
Cu removal rate: 5%
・Concentration ratio Cu/As: 1.9
・Concentration ratio Cu/Sb: 1412
・Concentration ratio As/Sb: 726
＜実施例２～４＞
上記表１に記載のように実施例１から各設定を変更したうえで、各例を行った。固液分離後溶液の詳細は上記表２に記載した。
<Examples 2 to 4>
Each example was carried out after changing each setting from Example 1 as shown in Table 1. Details of the solution after solid-liquid separation are shown in Table 2.
＜実施例５＞
本例では、製錬残渣ではなく、試薬により処理前溶液Ｙを作製した。
Example 5
In this example, the pre-treatment solution Y was prepared using a reagent instead of a smelting residue.
具体的には、５０℃に加熱した１５０ｍＬの純水に０．７２ｇのＳｂ２Ｏ３を添加し、硫酸を添加し、ｐＨ１以下にした。そして、処理前溶液Ｙ中に溶解するＡｓの濃度が４０ｇ／Ｌ程度になるように６０％ヒ酸液を添加した。 Specifically, 0.72 g of Sb 2 O 3 was added to 150 mL of pure water heated to 50° C., and sulfuric acid was added to adjust the pH to 1 or less. Then, a 60% arsenic acid solution was added so that the concentration of As dissolved in the pre-treatment solution Y was about 40 g/L.
その後、更にＨ２Ｏ２を添加し、ＯＲＰを５３０ｍＶ程度へとし、１時間程度撹拌した。撹拌には恒温槽付きマグネチックスターラーを用いた。 Thereafter, H 2 O 2 was further added, the ORP was adjusted to about 530 mV, and stirring was performed for about 1 hour. A magnetic stirrer with a thermostatic bath was used for stirring.
撹拌後に得られた溶液を１５０ｍＬ測り取り、純水で２倍に希釈し、希釈液を６０℃に加熱し処理前溶液Ｙとした。（この溶液は、比較例1に係る処理前溶液でもある） After stirring, 150 mL of the solution obtained was measured and diluted 2-fold with pure water, and the diluted solution was heated to 60°C to obtain pre-treatment solution Y. (This solution is also the pre-treatment solution for Comparative Example 1.)
実施例５では、処理前溶液Ｙに対し、ＣｕＳＯ４（フレーク）を添加し、溶解させ、所定のＣｕ濃度の処理前溶液を作製した。 In Example 5, CuSO 4 (flakes) was added to and dissolved in pre-treatment solution Y to prepare a pre-treatment solution having a predetermined Cu concentration.
上記表１に記載のように実施例１から各設定を変更したうえで、各例を行った。固液分離後溶液の詳細は上記表２に記載した。 Each example was carried out after changing the settings from Example 1 as described in Table 1 above. Details of the solution after solid-liquid separation are described in Table 2 above.
＜実施例６＞
実施例６では処理前溶液Ｙを用いた。処理前溶液Ｙから始めて、Ｓｂの還元工程後且つ中和工程前の処理中溶液へと変化させ、ＣｕＳＯ４（フレーク）を添加し、溶解させ、所定のＣｕ濃度の処理中溶液を作製した。他、上記表１に記載のように実施例１から各設定を変更したうえで、各例を行った。固液分離後溶液の詳細は上記表２に記載した。
Example 6
In Example 6, pre-treatment solution Y was used. Starting from pre-treatment solution Y, the solution was changed to an in-treatment solution after the Sb reduction step and before the neutralization step, and CuSO 4 (flakes) was added and dissolved to prepare an in-treatment solution with a predetermined Cu concentration. In addition, each setting was changed from Example 1 as described in Table 1 above, and each example was performed. Details of the solution after solid-liquid separation are described in Table 2 above.
＜比較例１＞
比較例１では処理前溶液Ｙを用いた。他、上記表１に記載のように実施例１から各設定を変更したうえで、各例を行った。固液分離後溶液の詳細は上記表２に記載した。処理中溶液の銅濃度は、０ｇ/Ｌとしている。
<Comparative Example 1>
In Comparative Example 1, pre-treatment solution Y was used. Other than that, each setting was changed from Example 1 as shown in Table 1 above, and each example was carried out. Details of the solution after solid-liquid separation are shown in Table 2 above. The copper concentration of the solution during treatment was 0 g/L.
＜比較例２，３＞
上記表１に記載のように実施例１から各設定を変更したうえで、各例を行った。固液分離後溶液の詳細は上記表２に記載した。実施例１と同様の処理前溶液を用いた。
<Comparative Examples 2 and 3>
Each example was carried out after changing each setting from Example 1 as shown in Table 1. Details of the solution after solid-liquid separation are shown in Table 2. The same pre-treatment solution as in Example 1 was used.
＜比較例４＞
比較例４では処理前溶液Ｙを用いた。処理前溶液Ｙから始めて、Ｓｂの還元工程後且つ中和工程前の処理中溶液へと変化させ、ＣｕＳＯ４（フレーク）を添加し、溶解させ、所定のＣｕ濃度の処理中溶液を作製した。上記表１に記載のように実施例１から各設定を変更したうえで、各例を行った。固液分離後溶液の詳細は上記表２に記載した。
<Comparative Example 4>
In Comparative Example 4, pre-treatment solution Y was used. Starting from pre-treatment solution Y, the solution was changed to an in-treatment solution after the Sb reduction step and before the neutralization step, and CuSO 4 (flakes) was added and dissolved to prepare an in-treatment solution with a predetermined Cu concentration. Each example was carried out after changing each setting from Example 1 as shown in Table 1 above. Details of the solution after solid-liquid separation are shown in Table 2 above.
＜まとめ＞
各実施例では、低い脱Ａｓ率を示しつつも高い脱Ｓｂ率を達成できた。特に、中和工程後の処理後溶液のＯＲＰが８０～３５０ｍＶの範囲内にある実施例１～３、５では、低い脱Ａｓ率と高い脱Ｓｂ率をバランスよく発揮できた。
<Summary>
In each Example, a high Sb desorption rate was achieved while a low As desorption rate was shown. In particular, in Examples 1 to 3 and 5 in which the ORP of the treated solution after the neutralization step was within the range of 80 to 350 mV, a low As desorption rate and a high Sb desorption rate were achieved in a well-balanced manner.
Claims (7)
Ｓｂ析出工程は、Ｓｂ還元工程と中和工程をこの順で有し、
中和工程開始時のＯＲＰ（３．３Ｍ ＫＣｌ－Ａｇ／ＡｇＣｌ）は７０～２１０ｍＶである、ＡｓとＳｂとの分離方法。 The method includes a step of precipitating Sb from a solution containing Cu, As, and Sb, the solution having a concentration of dissolved Sb of 1.0 g/L or more, a concentration ratio of Cu/As of 0.10 or more, and a concentration ratio of Cu/Sb of 0.10 or more,
The Sb precipitation step includes an Sb reduction step and a neutralization step in this order,
A method for separating As and Sb, in which the ORP (3.3M KCl-Ag/AgCl) at the start of the neutralization process is 70 to 210 mV.
The method for separating As and Sb according to any one of claims 1 to 6, wherein the ORP at the start of the Sb reduction step is 100 to 700 mV.
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| JP2010059035A (en) | 2008-09-08 | 2010-03-18 | Sumitomo Metal Mining Co Ltd | Method for producing aqueous arsenous acid solution of high purity from copper removal slime |
| JP2012167334A (en) | 2011-02-15 | 2012-09-06 | Jx Nippon Mining & Metals Corp | METHOD OF RECOVERING Ir FROM PLATINUM GROUP-CONTAINING SOLUTION |
| WO2015113141A1 (en) | 2014-01-31 | 2015-08-06 | Goldcorp Inc. | Process for separation of at least one metal sulfide compristng arsenic and/or antimony from a mixed sulfide concentrate |
| CN109957660A (en) | 2017-12-26 | 2019-07-02 | 株洲冶炼集团股份有限公司 | A kind of process for isolating antimony arsenic from antimony arsenic smoke dust |
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