JP5544153B2 - Electrolytic extraction of zinc - Google Patents
Electrolytic extraction of zinc Download PDFInfo
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- JP5544153B2 JP5544153B2 JP2009277394A JP2009277394A JP5544153B2 JP 5544153 B2 JP5544153 B2 JP 5544153B2 JP 2009277394 A JP2009277394 A JP 2009277394A JP 2009277394 A JP2009277394 A JP 2009277394A JP 5544153 B2 JP5544153 B2 JP 5544153B2
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- 239000011701 zinc Substances 0.000 title claims description 90
- 229910052725 zinc Inorganic materials 0.000 title claims description 73
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 72
- 238000000605 extraction Methods 0.000 title 1
- 239000008151 electrolyte solution Substances 0.000 claims description 86
- 239000007864 aqueous solution Substances 0.000 claims description 57
- 229910052712 strontium Inorganic materials 0.000 claims description 46
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 43
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 42
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 42
- 238000005363 electrowinning Methods 0.000 claims description 38
- 229910001427 strontium ion Inorganic materials 0.000 claims description 38
- 239000003792 electrolyte Substances 0.000 claims description 30
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 26
- 238000005868 electrolysis reaction Methods 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000007664 blowing Methods 0.000 claims description 20
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 12
- 229960001763 zinc sulfate Drugs 0.000 claims description 12
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 12
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 11
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 11
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 9
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 description 44
- 239000000243 solution Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004070 electrodeposition Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 150000003437 strontium Chemical class 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- FCRMJSYZVAIBRC-UHFFFAOYSA-N 1,2,4,5-tetraoxane-3,6-dione Chemical compound O=C1OOC(=O)OO1 FCRMJSYZVAIBRC-UHFFFAOYSA-N 0.000 description 1
- NEAPKZHDYMQZCB-UHFFFAOYSA-N N-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]ethyl]-2-oxo-3H-1,3-benzoxazole-6-carboxamide Chemical compound C1CN(CCN1CCNC(=O)C2=CC3=C(C=C2)NC(=O)O3)C4=CN=C(N=C4)NC5CC6=CC=CC=C6C5 NEAPKZHDYMQZCB-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- HFNQLYDPNAZRCH-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O.OC(O)=O HFNQLYDPNAZRCH-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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Classifications
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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
Description
本発明は、亜鉛の電解採取方法に関し、特に、鉛を含むアノードを使用して硫酸亜鉛を含む電解液から亜鉛を電解採取する方法に関する。 The present invention relates to a method for electrowinning zinc, and more particularly, to a method for electrowinning zinc from an electrolyte containing zinc sulfate using an anode containing lead.
従来、アノードとして硫酸に不溶な鉛板または鉛−銀合金板を使用して、硫酸亜鉛を含む電解液から亜鉛をカソード上に析出または付着させて、亜鉛を電解採取する方法が知られている。 2. Description of the Related Art Conventionally, there has been known a method of electrolytically collecting zinc by using a lead plate or a lead-silver alloy plate insoluble in sulfuric acid as an anode, and depositing or depositing zinc on an anode from an electrolyte containing zinc sulfate. .
しかし、このような亜鉛の電解採取方法では、アノードから電解液中に少量の鉛イオンが移行して、その一部がカソード上に析出または付着して電着亜鉛に混入する。 However, in such a zinc electrowinning method, a small amount of lead ions migrates from the anode into the electrolytic solution, and some of them are deposited or deposited on the cathode and mixed into the electrodeposited zinc.
このような電着亜鉛中に混入する鉛の量を低減させるために、電解液に炭酸ストロンチウムなどの添加剤を少量添加して、電解液中の鉛イオンなどを吸着させて除去する方法が知られている（例えば、特許文献１参照）。また、アノードとして鉛を含まないＤＳＥ電極（寸法安定電極）を使用して、高純度亜鉛を電解採取する方法も知られている（例えば、特許文献２参照）。 In order to reduce the amount of lead mixed in such electrodeposited zinc, a method is known in which a small amount of an additive such as strontium carbonate is added to the electrolytic solution to adsorb and remove lead ions and the like in the electrolytic solution. (For example, refer to Patent Document 1). In addition, a method of electrolytically collecting high-purity zinc using a DSE electrode (dimension stable electrode) that does not contain lead as an anode is also known (see, for example, Patent Document 2).
しかし、電解液に炭酸ストロンチウムを添加する方法では、炭酸ストロンチウムの水への溶解度が非常に低いため、電解液中にストロンチウムを均一に分散させることができず、カソード上の電着亜鉛中の鉛の品位をさらに低減させるのは困難である。また、比較的高価なＤＳＥ電極を使用せずに、安価な鉛板や（１〜３質量％の銀を含む）鉛−銀合金板を使用して、カソード上の電着亜鉛中の鉛の品位をさらに低減させることが望まれている。 However, in the method of adding strontium carbonate to the electrolyte, the solubility of strontium carbonate in water is very low, so strontium cannot be uniformly dispersed in the electrolyte and lead in the electrodeposited zinc on the cathode It is difficult to further reduce the quality. Moreover, without using a relatively expensive DSE electrode, an inexpensive lead plate or a lead-silver alloy plate (containing 1 to 3% by mass of silver) can be used. It is desired to further reduce the quality.
したがって、本発明は、このような従来の問題点に鑑み、鉛の品位が極めて低い亜鉛を安価に電解採取することができる、亜鉛の電解採取方法を提供することを目的とする。 Therefore, in view of such a conventional problem, an object of the present invention is to provide a zinc electrowinning method capable of electrowinning zinc with extremely low lead quality at low cost.
本発明者らは、上記課題を解決するために鋭意研究した結果、鉛を含むアノードを使用して硫酸亜鉛を含む電解液から亜鉛を電解採取する方法において、ストロンチウムイオンを含む水溶液を電解液に添加した後に亜鉛の電解採取を行うことにより、鉛の品位が極めて低い亜鉛を安価に電解採取することができることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the present inventors have found that an aqueous solution containing strontium ions is used as an electrolytic solution in a method of electrowinning zinc from an electrolytic solution containing zinc sulfate using an anode containing lead. By performing electrowinning of zinc after the addition, it has been found that zinc with extremely low lead quality can be electrowinned at low cost, and the present invention has been completed.
すなわち、本発明による亜鉛の電解採取方法は、鉛を含むアノードを使用して、硫酸亜鉛を含む電解液から亜鉛を電解採取する方法において、ストロンチウムイオンを含む水溶液を電解液に添加した後に亜鉛の電解採取を行うことを特徴とする。この亜鉛の電解採取方法において、ストロンチウムイオンを含む水溶液が、水に二酸化硫黄ガスを吹き込み且つ炭酸ストロンチウムを添加することによって、炭酸ストロンチウムを溶解させた水溶液であるのが好ましい。あるいは、ストロンチウムイオンを含む水溶液が、水に二酸化硫黄ガスを吹き込み且つ過剰の炭酸ストロンチウムを添加することによって、炭酸ストロンチウムの一部を溶解させるとともに残りを懸濁させた懸濁液でもよい。あるいは、ストロンチウムイオンを含む水溶液が、水に硫化水素ガスを吹き込み且つ水酸化ストロンチウムを添加することによって、水酸化ストロンチウムを溶解させた水溶液でもよい。また、電解採取後の電解液中の全ストロンチウム濃度が５０ｍｇ／Ｌ以上であるのが好ましい。 That is, the zinc electrowinning method according to the present invention is a method of electrowinning zinc from an electrolyte containing zinc sulfate using an anode containing lead, and after adding an aqueous solution containing strontium ions to the electrolyte, Electrolytic collection is performed. In this zinc electrowinning method, the aqueous solution containing strontium ions is preferably an aqueous solution in which strontium carbonate is dissolved by blowing sulfur dioxide gas into water and adding strontium carbonate. Alternatively, the aqueous solution containing strontium ions may be a suspension in which a part of strontium carbonate is dissolved and the rest is suspended by blowing sulfur dioxide gas into water and adding excess strontium carbonate. Alternatively, the aqueous solution containing strontium ions may be an aqueous solution in which strontium hydroxide is dissolved by blowing hydrogen sulfide gas into water and adding strontium hydroxide. Moreover, it is preferable that the total strontium concentration in the electrolytic solution after electrolytic collection is 50 mg / L or more.
また、本発明による亜鉛の電解採取用電解液は、硫酸亜鉛とストロンチウムイオンを含む電解液において、ストロンチウムイオン濃度が１６ｍｇ／Ｌより高いことを特徴とする。この亜鉛の電解採取用電解液において、全ストロンチウム濃度が５０ｍｇ／Ｌ以上であるのが好ましい。 Moreover, the electrolytic solution for electrowinning zinc according to the present invention is characterized in that the concentration of strontium ions is higher than 16 mg / L in an electrolytic solution containing zinc sulfate and strontium ions. In the electrolytic solution for zinc electrowinning, the total strontium concentration is preferably 50 mg / L or more.
本発明によれば、鉛の品位が極めて低い亜鉛を安価に電解採取することができる。 According to the present invention, zinc with extremely low lead quality can be electrolytically collected at low cost.
本発明による亜鉛の電解採取方法の実施の形態では、鉛を含むアノードを使用して、硫酸亜鉛を含む電解液から亜鉛を電解採取する方法において、ストロンチウムイオンを含む水溶液を電解液に添加した後に亜鉛の電解採取を行う。 In an embodiment of the zinc electrowinning method according to the present invention, in the method of electrowinning zinc from an electrolyte containing zinc sulfate using an anode containing lead, an aqueous solution containing strontium ions is added to the electrolyte. Perform zinc electrowinning.
本実施の形態の亜鉛の電解採取方法では、水に二酸化硫黄ガスを吹き込み且つ炭酸ストロンチウムを添加して、炭酸ストロンチウムを溶解させることによって、ストロンチウムイオンを含む水溶液を作製することができる。例えば、純水に二酸化硫黄ガスを吹き込みながら炭酸ストロンチウム粉末を添加したり、純水に炭酸ストロンチウムを添加して二酸化硫黄ガスを吹き込むことによって、炭酸ストロンチウムを溶解させて、ストロンチウムイオンを含む水溶液（炭酸ストロンチウムが過剰の二酸化硫黄ガスに溶解した水溶液）を作製することができる。 In the zinc electrowinning method of this embodiment, an aqueous solution containing strontium ions can be prepared by blowing sulfur dioxide gas into water and adding strontium carbonate to dissolve strontium carbonate. For example, by adding strontium carbonate powder while blowing sulfur dioxide gas into pure water, or adding strontium carbonate to pure water and blowing sulfur dioxide gas, strontium carbonate is dissolved and an aqueous solution containing strontium ions (carbonic acid carbonate). An aqueous solution in which strontium is dissolved in an excess of sulfur dioxide gas can be produced.
なお、炭酸ストロンチウム粉末は、二酸化硫黄ガスを吹き込んでｐＨが（例えば１．５程度まで）下がったことを確認した後に添加するのが好ましい。このように純水に二酸化硫黄ガスを吹き込みながら炭酸ストロンチウム粉末を添加して、炭酸ストロンチウムを溶解させることによって、ストロンチウムイオン（Ｓｒ２＋）濃度が２．６〜２．８ｇ／Ｌの高濃度のストロンチウムイオンを含む水溶液を作製することができる。 The strontium carbonate powder is preferably added after it is confirmed that the pH has dropped (for example, to about 1.5) by blowing in sulfur dioxide gas. By adding strontium carbonate powder while blowing sulfur dioxide gas into pure water and dissolving strontium carbonate in this way, strontium ions (Sr 2+ ) concentration of 2.6 to 2.8 g / L high concentration strontium An aqueous solution containing ions can be prepared.
一方、硫酸亜鉛を含む電解液として亜鉛製錬工程で得られた電解尾液を用意し、それぞれ１８０ｒｐｍ、３００ｒｐｍおよび６００ｒｐｍで撹拌しながら４０℃の電解尾液に炭酸ストロンチウム粉末０．１ｇ／Ｌを１時間で２０回に分けて添加したところ、撹拌時間に対する電解尾液中のストロンチウムイオン濃度は図１に示すようになり、電解尾液に炭酸ストロンチウム粉末を添加した場合には最大１６ｍｇ／Ｌで過飽和になることがわかった。なお、４０℃の純水への炭酸ストロンチウムの溶解度は１０ｍｇ／Ｌ程度であり、通常の方法で炭酸ストロンチウム粉末を電解液に添加しても、電解液中のストロンチウムイオン濃度を１６ｍｇ／Ｌより高くすることができない。 On the other hand, an electrolytic tail solution obtained in the zinc smelting process was prepared as an electrolytic solution containing zinc sulfate, and 0.1 g / L of strontium carbonate powder was added to the electrolytic tail solution at 40 ° C. while stirring at 180 rpm, 300 rpm and 600 rpm, respectively. When it was added 20 times in 1 hour, the strontium ion concentration in the electrolytic tail solution with respect to the stirring time was as shown in FIG. 1, and when strontium carbonate powder was added to the electrolytic tail solution, the maximum was 16 mg / L. It turned out to be supersaturated. The solubility of strontium carbonate in pure water at 40 ° C. is about 10 mg / L. Even when strontium carbonate powder is added to the electrolyte by a usual method, the strontium ion concentration in the electrolyte is higher than 16 mg / L. Can not do it.
したがって、本実施の形態の亜鉛の電解採取方法では、作製したストロンチウムイオン濃度が２．６〜２．８ｇ／Ｌの高濃度のストロンチウム水溶液を１体積％より多く電解液に添加すれば、電解液中のストロンチウムイオン濃度を２６〜２８ｍｇ／Ｌより多くすることができ、２体積％以上電解液に添加すれば、電解液中のストロンチウムイオン濃度を５２〜５６ｍｇ／Ｌ以上にすることができ、炭酸ストロンチウム粉末を電解液に添加する場合（この場合のストロンチウムイオン濃度は最大１６ｍｇ／Ｌ）と比べて、電解液中のストロンチウムイオン濃度を極めて高くすることができる。また、本実施の形態の亜鉛の電解採取方法では、高濃度のストロンチウムイオンを含む水溶液を電解液に添加することにより、ストロンチウムイオンを電解液中に均一に分散させることができ、ストロンチウムによるＰｂ共沈効果を電解液全体にわたって発揮させて、カソード上の電着亜鉛中のＰｂ品位を数ｐｐｍまで低減させることができる。 Therefore, in the zinc electrowinning method of the present embodiment, if the strontium aqueous solution having a strontium ion concentration of 2.6 to 2.8 g / L is added in an amount of more than 1% by volume, the electrolyte solution The concentration of strontium ions in the electrolyte can be increased from 26 to 28 mg / L, and when added to the electrolyte by 2% by volume or more, the concentration of strontium ions in the electrolyte can be increased from 52 to 56 mg / L. Compared with the case where strontium powder is added to the electrolytic solution (the maximum strontium ion concentration in this case is 16 mg / L), the strontium ion concentration in the electrolytic solution can be made extremely high. In addition, in the zinc electrowinning method of the present embodiment, by adding an aqueous solution containing a high concentration of strontium ions to the electrolyte, the strontium ions can be uniformly dispersed in the electrolyte, and Pb co-generation with strontium is possible. The precipitation effect can be exerted over the entire electrolyte, and the Pb quality in the electrodeposited zinc on the cathode can be reduced to several ppm.
また、本実施の形態の亜鉛の電解採取方法では、電解採取後の電解液中の全ストロンチウム濃度が５０ｍｇ／Ｌ以上になるようにするのが好ましい。このような電解採取後の電解液中の全ストロンチウム濃度にするためには、例えば、ストロンチウムイオン濃度が２．６〜２．８ｇ／Ｌの水溶液を２体積％以上電解液に添加すればよい。 In the zinc electrowinning method of the present embodiment, it is preferable that the total strontium concentration in the electrolytic solution after electrowinning is 50 mg / L or more. In order to obtain such a total strontium concentration in the electrolytic solution after electrolytic collection, for example, an aqueous solution having a strontium ion concentration of 2.6 to 2.8 g / L may be added to the electrolytic solution in an amount of 2% by volume or more.
また、本実施の形態の亜鉛の電解採取方法では、純水に二酸化硫黄ガスを吹き込み且つ過剰の炭酸ストロンチウム粉末を添加することにより、炭酸ストロンチウムの一部を溶解させるとともに溶け残りを懸濁させた懸濁液として、ストロンチウムイオンを含む水溶液を作製してもよい。このようにすれば、ストロンチウムイオンを含む水溶液の電解液への添加量を少なくすることができる。この場合でも、高濃度のストロンチウムイオンを含む水溶液を電解液に添加することにより、カソード上の電着亜鉛中のＰｂ品位を数ｐｐｍまで低減させることができる。 Further, in the zinc electrowinning method of the present embodiment, sulfur dioxide gas was blown into pure water and excess strontium carbonate powder was added to dissolve part of the strontium carbonate and suspend the undissolved residue. An aqueous solution containing strontium ions may be prepared as a suspension. If it does in this way, the addition amount to the electrolyte solution of the aqueous solution containing strontium ion can be decreased. Even in this case, the quality of Pb in the electrodeposited zinc on the cathode can be reduced to several ppm by adding an aqueous solution containing a high concentration of strontium ions to the electrolyte.
また、本実施の形態の亜鉛の電解採取方法では、純水に硫化水素ガスを吹き込み且つ水酸化ストロンチウムを添加して、水酸化ストロンチウムを溶解させることによって、ストロンチウムイオンを含む水溶液を作製してもよい。このように純水に硫化水素ガスを吹き込み且つ水酸化ストロンチウムを添加して、水酸化ストロンチウムを溶解させることによって、ストロンチウムイオン濃度が３０ｇ／Ｌの極めて高濃度のストロンチウムイオンを含む水溶液を得ることができる。また、極めて高濃度のストロンチウムイオンを含む水溶液を得ることができるので、ストロンチウムイオンを含む水溶液の電解液への添加量を少なくすることができる。この場合でも、極めて高濃度のストロンチウムイオンを含む水溶液を電解液に添加することにより、カソード上の電着亜鉛中のＰｂ品位を数ｐｐｍまで低減させることができる。 In the zinc electrowinning method of the present embodiment, an aqueous solution containing strontium ions can be prepared by blowing hydrogen sulfide gas into pure water and adding strontium hydroxide to dissolve strontium hydroxide. Good. Thus, by blowing hydrogen sulfide gas into pure water and adding strontium hydroxide to dissolve strontium hydroxide, an aqueous solution containing a very high concentration of strontium ions having a strontium ion concentration of 30 g / L can be obtained. it can. In addition, since an aqueous solution containing a very high concentration of strontium ions can be obtained, the amount of the aqueous solution containing strontium ions added to the electrolyte can be reduced. Even in this case, the Pb quality in the electrodeposited zinc on the cathode can be reduced to several ppm by adding an aqueous solution containing a very high concentration of strontium ions to the electrolyte.
以下、本発明による亜鉛の電解採取方法の実施例について詳細に説明する。 Hereinafter, examples of the zinc electrowinning method according to the present invention will be described in detail.
［実施例１］
硫酸亜鉛を含む電解液として、亜鉛製錬工程で得られた電解尾液（Ｚｎ：６５ｇ／Ｌ、ＦＡ：１７０ｇ／Ｌ、全Ｐｂ：０．１ｍｇ／Ｌ）をろ過した電解液を用意した。また、純水に２００ｍＬ／分の流量でＳＯ２ガスを吹き込みながら、４０℃においてバッフル付きの二段タービンによって４００ｒｐｍで１０分間撹拌し、炭酸ストロンチウム５ｇ／Ｌを添加してさらに３０分間撹拌し、得られた水溶液を吸引ろ過して、ストロンチウムイオン濃度が２．５８ｇ／Ｌのストロンチウム含有水溶液を用意した。このストロンチウム含有水溶液２０ｍＬを電解液０．９８Ｌに添加して、電解採取用電解液１Ｌを得た。この電解液を使用し、アノードとしてＰｂ−Ａｇ板、カソードとしてＡｌ板を使用し、極間距離を２５ｍｍとし、４３℃において電流密度７００Ａ／ｍ２で２時間電解採取を行った。なお、この電解採取は、ストロンチウム含有水溶液を電解液に添加した直後（３分以内）に開始した。
[Example 1]
As an electrolytic solution containing zinc sulfate, an electrolytic solution obtained by filtering the electrolytic tail solution (Zn: 65 g / L, FA: 170 g / L, total Pb: 0.1 mg / L) obtained in the zinc smelting process was prepared. Further, while blowing pure water 200 mL / min flow rate with SO 2 gas, and stirred for 10 minutes at 400rpm by a two-stage turbine baffled at 40 ° C., and stirred for further 30 minutes with the addition of strontium carbonate 5 g / L, The obtained aqueous solution was subjected to suction filtration to prepare a strontium-containing aqueous solution having a strontium ion concentration of 2.58 g / L. 20 mL of this strontium-containing aqueous solution was added to 0.98 L of electrolytic solution to obtain 1 L of electrolytic solution for electrolytic collection. Using this electrolytic solution, a Pb—Ag plate was used as the anode, an Al plate was used as the cathode, the distance between the electrodes was 25 mm, and electrowinning was performed at 43 ° C. at a current density of 700 A / m 2 for 2 hours. This electrolytic collection was started immediately after the strontium-containing aqueous solution was added to the electrolytic solution (within 3 minutes).
電解後の電解液の一部を採取し、０．２μｍのフィルタでろ過した後、ポーラログラフィを用いた測定装置（Ｙａｎａｃｏ社製のＰＯＬＡＲＯＧＲＡＰＨＩＣ ＡＮＡＬＹＺＥＲ Ｐ−１１００）によりＰｂ２＋イオン濃度を測定し、ＩＣＰによりＳｒ２＋イオン濃度を測定した。その結果、電解後の電解液中のＰｂ２＋イオン濃度は検出限界以下（＜０．１ｍｇ／Ｌ）であり、Ｓｒ２＋イオン濃度は３６ｍｇ／Ｌであった。また、電解後の電解液の一部をろ過しないで測定した（電解液中に固体として存在するＰｂも含めた）全Ｐｂ濃度は０．６ｍｇ／Ｌであり、（電解液中に固体として存在するＳｒも含めた）全Ｓｒ濃度は５７．１ｍｇ／Ｌであった。また、得られた電着亜鉛中のＰｂ品位は４．０ｐｐｍであり、亜鉛の電着量は５．３４ｇであった。また、電流効率は８９．８％、平均槽電圧は３．２５Ｖ、電力原単位は２９６８（ｋｗｈ／ｔ−Ｚｎ）であった。 A part of the electrolytic solution after electrolysis was collected and filtered with a 0.2 μm filter, and then the Pb 2+ ion concentration was measured with a polarographic measurement device (POLAROGRAPHIC ANALYZER P-1100 manufactured by Yanaco), and ICP Was used to measure the Sr 2+ ion concentration. As a result, the Pb 2+ ion concentration in the electrolytic solution after electrolysis was below the detection limit (<0.1 mg / L), and the Sr 2+ ion concentration was 36 mg / L. Moreover, the total Pb concentration (including Pb present as a solid in the electrolytic solution) measured without filtering a part of the electrolytic solution after electrolysis was 0.6 mg / L, and existed as a solid in the electrolytic solution. The total Sr concentration (including Sr) was 57.1 mg / L. In addition, the Pb quality in the obtained electrodeposited zinc was 4.0 ppm, and the amount of zinc electrodeposited was 5.34 g. The current efficiency was 89.8%, the average cell voltage was 3.25 V, and the power consumption was 2968 (kwh / t-Zn).
［実施例２］
実施例１と同じ電解液０．９７Ｌに実施例１と同じストロンチウム含有水溶液３０ｍＬを添加して得られた電解採取用電解液１Ｌを使用した以外は、実施例１と同様の方法により電解採取を行った後、実施例１と同様の方法により電解液中のＰｂ２＋イオン濃度、Ｓｒ２＋イオン濃度、全Ｐｂ濃度、全Ｓｒ濃度を測定した。
[Example 2]
Electrolytic collection was carried out in the same manner as in Example 1 except that 1 L of electrolytic solution for electrowinning obtained by adding 30 mL of the same strontium-containing aqueous solution as in Example 1 to 0.97 L of the same electrolytic solution as in Example 1 was used. Then, the Pb 2+ ion concentration, Sr 2+ ion concentration, total Pb concentration, and total Sr concentration in the electrolytic solution were measured by the same method as in Example 1.
その結果、電解後の電解液中のＰｂ２＋イオン濃度は検出限界以下（＜０．１ｍｇ／Ｌ）、Ｓｒ２＋イオン濃度は３３．３ｍｇ／Ｌ、全Ｐｂ濃度は０．６ｍｇ／Ｌ、全Ｓｒ濃度は７４．６ｍｇ／Ｌであった。また、得られた電着亜鉛中のＰｂ品位は１．５ｐｐｍであり、亜鉛の電着量は５．５４ｇであった。また、電流効率は９３．１％、平均槽電圧は３．２５Ｖ、電力原単位は２８６３（ｋｗｈ／ｔ−Ｚｎ）であった。 As a result, the Pb 2+ ion concentration in the electrolytic solution after electrolysis is below the detection limit (<0.1 mg / L), the Sr 2+ ion concentration is 33.3 mg / L, the total Pb concentration is 0.6 mg / L, and the total Sr The concentration was 74.6 mg / L. Moreover, the Pb quality in the obtained electrodeposited zinc was 1.5 ppm, and the electrodeposition amount of zinc was 5.54 g. The current efficiency was 93.1%, the average cell voltage was 3.25 V, and the power consumption was 2863 (kwh / t-Zn).
［実施例３］
実施例１と同じ電解液０．９６Ｌに実施例１と同じストロンチウム含有水溶液４０ｍＬを添加して得られた電解採取用電解液１Ｌを使用した以外は、実施例１と同様の方法により電解採取を行った後、実施例１と同様の方法により電解液中のＰｂ２＋イオン濃度、Ｓｒ２＋イオン濃度、全Ｐｂ濃度、全Ｓｒ濃度を測定した。
[Example 3]
Electrolytic collection was performed in the same manner as in Example 1, except that 1L of electrolytic solution for electrolytic collection obtained by adding 40 mL of the same strontium-containing aqueous solution as in Example 1 to 0.96L of the same electrolytic solution as in Example 1 was used. Then, the Pb 2+ ion concentration, Sr 2+ ion concentration, total Pb concentration, and total Sr concentration in the electrolytic solution were measured by the same method as in Example 1.
その結果、電解後の電解液中のＰｂ２＋イオン濃度は０．１ｍｇ／Ｌ、Ｓｒ２＋イオン濃度は３０．１ｍｇ／Ｌ、全Ｐｂ濃度は０．７ｍｇ／Ｌ、全Ｓｒ濃度は９３．０ｍｇ／Ｌであった。また、得られた電着亜鉛中のＰｂ品位は１．９ｐｐｍであり、亜鉛の電着量は５．２５ｇであった。また、電流効率は８８．３％、平均槽電圧は３．２１Ｖ、電力原単位は２９８７（ｋｗｈ／ｔ−Ｚｎ）であった。 As a result, the Pb 2+ ion concentration in the electrolytic solution after electrolysis was 0.1 mg / L, the Sr 2+ ion concentration was 30.1 mg / L, the total Pb concentration was 0.7 mg / L, and the total Sr concentration was 93.0 mg / L. L. Moreover, Pb quality in the obtained electrodeposited zinc was 1.9 ppm, and the electrodeposition amount of zinc was 5.25 g. Moreover, the current efficiency was 88.3%, the average cell voltage was 3.21 V, and the electric power consumption was 2987 (kwh / t-Zn).
［実施例４］
実施例１と同じ電解液０．９５Ｌに実施例１と同じストロンチウム含有水溶液５０ｍＬを添加して得られた電解採取用電解液１Ｌを使用した以外は、実施例１と同様の方法により電解採取を行った後、実施例１と同様の方法により電解液中のＰｂ２＋イオン濃度、Ｓｒ２＋イオン濃度、全Ｐｂ濃度、全Ｓｒ濃度を測定した。
[Example 4]
Electrolytic collection was carried out in the same manner as in Example 1, except that 1 L of electrolytic solution for electrolytic collection obtained by adding 50 mL of the same strontium-containing aqueous solution as in Example 1 to 0.95 L of the same electrolytic solution as in Example 1 was used. Then, the Pb 2+ ion concentration, Sr 2+ ion concentration, total Pb concentration, and total Sr concentration in the electrolytic solution were measured by the same method as in Example 1.
その結果、電解後の電解液中のＰｂ２＋イオン濃度は検出限界以下（＜０．１ｍｇ／Ｌ）、Ｓｒ２＋イオン濃度は２４．６ｍｇ／Ｌ、全Ｐｂ濃度は０．６ｍｇ／Ｌ、全Ｓｒ濃度は１１６．７ｍｇ／Ｌであった。また、得られた電着亜鉛中のＰｂ品位は３ｐｐｍであり、亜鉛の電着量は５．２７ｇであった。また、電流効率は８８．６％、平均槽電圧は３．２３Ｖ、電力原単位は２９８８（ｋｗｈ／ｔ−Ｚｎ）であった。 As a result, the Pb 2+ ion concentration in the electrolytic solution after electrolysis is below the detection limit (<0.1 mg / L), the Sr 2+ ion concentration is 24.6 mg / L, the total Pb concentration is 0.6 mg / L, and the total Sr The concentration was 116.7 mg / L. Moreover, the Pb quality in the obtained electrodeposited zinc was 3 ppm, and the electrodeposition amount of zinc was 5.27 g. Moreover, the current efficiency was 88.6%, the average cell voltage was 3.23 V, and the electric power consumption was 2988 (kwh / t-Zn).
［比較例１］
実施例１と同じ電解液１Ｌにストロンチウム含有水溶液を添加しないで電解採取用電解液として使用した以外は、実施例１と同様の方法により電解採取を行った後、実施例１と同様の方法により電解液中のＰｂ２＋イオン濃度、Ｓｒ２＋イオン濃度、全Ｐｂ濃度を測定した。
[Comparative Example 1]
Except for using as an electrolytic solution for electrolytic collection without adding a strontium-containing aqueous solution to 1 L of the same electrolytic solution as in Example 1, after performing electrolytic collection by the same method as in Example 1, by the same method as in Example 1. Pb 2+ ion concentration, Sr 2+ ion concentration, and total Pb concentration in the electrolyte were measured.
その結果、電解後の電解液中のＰｂ２＋イオン濃度は０．２ｍｇ／Ｌ、Ｓｒ２＋イオン濃度は１２．４ｍｇ／Ｌ、全Ｐｂ濃度は１．１ｍｇ／Ｌであった。また、得られた電着亜鉛中のＰｂ品位は２９．０ｐｐｍであり、亜鉛の電着量は５．３９ｇであった。また、電流効率は９０．６％、平均槽電圧は３．２３Ｖ、電力原単位は２９２７（ｋｗｈ／ｔ−Ｚｎ）であった。 As a result, the Pb 2+ ion concentration in the electrolytic solution after electrolysis was 0.2 mg / L, the Sr 2+ ion concentration was 12.4 mg / L, and the total Pb concentration was 1.1 mg / L. Moreover, the Pb quality in the obtained electrodeposited zinc was 29.0 ppm, and the electrodeposition amount of zinc was 5.39 g. Moreover, the current efficiency was 90.6%, the average cell voltage was 3.23 V, and the electric power consumption was 2927 (kwh / t-Zn).
［比較例２］
実施例１と同じ電解液１Ｌに炭酸ストロンチウム０．０８５ｇを添加した後、４２℃においてスターラーで１０分間撹拌して、全ストロンチウム濃度が約６０ｍｇ／Ｌの電解採取用電解液１Ｌを得た。この電解液を使用して、実施例１と同様の方法により電解採取を行った後、実施例１と同様の方法により電解液中のＰｂ２＋イオン濃度、Ｓｒ２＋イオン濃度、全Ｐｂ濃度、全Ｓｒ濃度を測定した。
[Comparative Example 2]
After adding 0.085 g of strontium carbonate to 1 L of the same electrolyte as in Example 1, the mixture was stirred with a stirrer at 42 ° C. for 10 minutes to obtain 1 L of an electrowinning electrolyte having a total strontium concentration of about 60 mg / L. Using this electrolytic solution, the electrolytic collection was performed by the same method as in Example 1, and then the Pb 2+ ion concentration, Sr 2+ ion concentration, total Pb concentration, Sr concentration was measured.
その結果、電解後の電解液中のＰｂ２＋イオン濃度は０．１ｍｇ／Ｌ、Ｓｒ２＋イオン濃度は１４．２ｍｇ／Ｌ、全Ｐｂ濃度は０．８ｍｇ／Ｌ、全Ｓｒ濃度は４４．２ｍｇ／Ｌであった。また、得られた電着亜鉛中のＰｂ品位は１１．６ｐｐｍであり、亜鉛の電着量は５．５７ｇであった。また、電流効率は９３．６％、平均槽電圧は３．２１Ｖ、電力原単位は２８１４（ｋｗｈ／ｔ−Ｚｎ）であった。 As a result, the Pb 2+ ion concentration in the electrolytic solution after electrolysis was 0.1 mg / L, the Sr 2+ ion concentration was 14.2 mg / L, the total Pb concentration was 0.8 mg / L, and the total Sr concentration was 44.2 mg / L. L. Moreover, Pb quality in the obtained electrodeposited zinc was 11.6 ppm, and the electrodeposition amount of zinc was 5.57 g. Moreover, the current efficiency was 93.6%, the average cell voltage was 3.21 V, and the electric power consumption was 2814 (kwh / t-Zn).
［比較例３］
実施例１と同じ電解液０．９８ＬにＳＯ２溶液（純水に過剰の二酸化硫黄ガスを吹き込んで作製した溶液を１０ｍＬ分取して純水で１００ｍＬに希釈した溶液）２０ｍＬを添加して得られた電解採取用電解液１Ｌを使用した以外は、実施例１と同様の方法により電解採取を行った後、実施例１と同様の方法により電解液中のＰｂ２＋イオン濃度、Ｓｒ２＋イオン濃度、全Ｐｂ濃度を測定した。
[Comparative Example 3]
Obtained by adding 20 mL of SO 2 solution (solution prepared by blowing excess sulfur dioxide gas into pure water and diluting to 100 mL with pure water) to 0.98 L of the same electrolytic solution as in Example 1. Except for using the obtained electrolytic solution 1L for electrolytic collection, after performing electrolytic collection by the same method as in Example 1, Pb 2+ ion concentration and Sr 2+ ion concentration in the electrolytic solution by the same method as in Example 1 The total Pb concentration was measured.
その結果、電解後の電解液中のＰｂ２＋イオン濃度は０．５ｍｇ／Ｌ、Ｓｒ２＋イオン濃度は１３．２ｍｇ／Ｌ、全Ｐｂ濃度は１．３ｍｇ／Ｌであった。また、得られた電着亜鉛中のＰｂ品位は３０．１ｐｐｍであり、亜鉛の電着量は５．６７ｇであった。また、電流効率は９５．３％、平均槽電圧は３．１９Ｖ、電力原単位は２７４６（ｋｗｈ／ｔ−Ｚｎ）であった。 As a result, the Pb 2+ ion concentration in the electrolytic solution after electrolysis was 0.5 mg / L, the Sr 2+ ion concentration was 13.2 mg / L, and the total Pb concentration was 1.3 mg / L. Moreover, Pb quality in the obtained electrodeposited zinc was 30.1 ppm, and the electrodeposition amount of zinc was 5.67 g. The current efficiency was 95.3%, the average cell voltage was 3.19 V, and the power consumption was 2746 (kwh / t-Zn).
［比較例４］
実施例１と同じ電解液０．９８Ｌに（純水に炭酸ストロンチウム０．０８５ｇを添加した）炭酸ストロンチウムリパルプ液（Ｓｒ２＋イオン濃度１０ｍｇ／Ｌ）２０ｍＬを添加した後、４２℃においてスターラーで１０分間撹拌して、全Ｓｒ濃度が約６０ｍｇ／Ｌの電解採取用電解液１Ｌを得た。この電解液を使用して、実施例１と同様の方法により電解採取を行った後、実施例１と同様の方法により電解液中のＰｂ２＋イオン濃度、Ｓｒ２＋イオン濃度、全Ｐｂ濃度、全Ｓｒ濃度を測定した。
[Comparative Example 4]
After adding 20 mL of strontium carbonate repulp solution (Sr 2+ ion concentration 10 mg / L) (in which 0.085 g of strontium carbonate was added to pure water) to 0.98 L of the same electrolytic solution as in Example 1, 10 times with a stirrer at 42 ° C. The mixture was stirred for 1 minute to obtain 1 L of an electrolytic solution for electrowinning having a total Sr concentration of about 60 mg / L. Using this electrolytic solution, the electrolytic collection was performed by the same method as in Example 1, and then the Pb 2+ ion concentration, Sr 2+ ion concentration, total Pb concentration, Sr concentration was measured.
その結果、電解後の電解液中のＰｂ２＋イオン濃度は０．１ｍｇ／Ｌ、Ｓｒ２＋イオン濃度は１４．２ｍｇ／Ｌ、全Ｐｂ濃度は１．１ｍｇ／Ｌ、全Ｓｒ濃度は４５．４ｍｇ／Ｌであった。また、得られた電着亜鉛中のＰｂ品位は１６．９ｐｐｍであり、亜鉛の電着量は５．４５ｇであった。また、電流効率は９１．６％、平均槽電圧は３．１７Ｖ、電力原単位は２８３８（ｋｗｈ／ｔ−Ｚｎ）であった。 As a result, the Pb 2+ ion concentration in the electrolytic solution after electrolysis was 0.1 mg / L, the Sr 2+ ion concentration was 14.2 mg / L, the total Pb concentration was 1.1 mg / L, and the total Sr concentration was 45.4 mg / L. L. Moreover, Pb quality in the obtained electrodeposited zinc was 16.9 ppm, and the electrodeposition amount of zinc was 5.45 g. The current efficiency was 91.6%, the average cell voltage was 3.17 V, and the power consumption was 2838 (kwh / t-Zn).
［比較例５］
実施例１と同じ電解液０．９８ＬにＳＯ２溶液（純水に過剰の二酸化硫黄ガスを吹き込んで作製した溶液を１０ｍＬ分取して純水で１００ｍＬに希釈した溶液）２０ｍＬを添加するとともに炭酸ストロンチウム０．０８５ｇを添加して、全Ｓｒ濃度が約６０ｍｇ／Ｌの電解採取用電解液１Ｌを得た。この電解液を使用して、実施例１と同様の方法により電解採取を行った後、実施例１と同様の方法により電解液中のＰｂ２＋イオン濃度、Ｓｒ２＋イオン濃度、全Ｐｂ濃度、全Ｓｒ濃度を測定した。
[Comparative Example 5]
20 mL of an SO 2 solution (a solution prepared by blowing excess sulfur dioxide gas into pure water and taking 10 mL of the solution diluted to 100 mL with pure water) was added to 0.98 L of the same electrolytic solution as in Example 1 and carbonic acid was added. 0.085 g of strontium was added to obtain 1 L of an electrolytic solution for electrowinning having a total Sr concentration of about 60 mg / L. Using this electrolytic solution, the electrolytic collection was performed by the same method as in Example 1, and then the Pb 2+ ion concentration, Sr 2+ ion concentration, total Pb concentration, Sr concentration was measured.
その結果、電解後の電解液中のＰｂ２＋イオン濃度は０．１ｍｇ／Ｌ、Ｓｒ２＋イオン濃度は１３．７ｍｇ／Ｌ、全Ｐｂ濃度は０．８ｍｇ／Ｌ、全Ｓｒ濃度は４７．０ｍｇ／Ｌであった。また、得られた電着亜鉛中のＰｂ品位は１２．９ｐｐｍであり、亜鉛の電着量は５．３５ｇであった。また、電流効率は８９．９％、平均槽電圧は３．２０Ｖ、電力原単位は２９１４（ｋｗｈ／ｔ−Ｚｎ）であった。 As a result, the Pb 2+ ion concentration in the electrolytic solution after electrolysis was 0.1 mg / L, the Sr 2+ ion concentration was 13.7 mg / L, the total Pb concentration was 0.8 mg / L, and the total Sr concentration was 47.0 mg / L. L. Moreover, Pb quality in the obtained electrodeposited zinc was 12.9 ppm, and the electrodeposition amount of zinc was 5.35 g. Moreover, the current efficiency was 89.9%, the average cell voltage was 3.20 V, and the electric power consumption was 2914 (kwh / t-Zn).
実施例１〜４および比較例１〜５の結果を表１および表２に示し、実施例１〜４および比較例１〜２の電解後の電解液中の全Ｓｒ濃度とカソードの電着亜鉛中のＰｂ品位との関係を図２に示す。 The results of Examples 1 to 4 and Comparative Examples 1 to 5 are shown in Tables 1 and 2, and the total Sr concentration in the electrolytic solutions after electrolysis of Examples 1 to 4 and Comparative Examples 1 to 2 and the electrodeposited zinc of the cathode The relationship with the Pb quality in the middle is shown in FIG.
［実施例５］
硫酸亜鉛を含む電解液として、亜鉛製錬工程で得られた電解尾液（Ｚｎ：６５ｇ／Ｌ、ＦＡ：１７０ｇ／Ｌ、全Ｐｂ：０．１ｍｇ／Ｌ）をろ過した電解液を用意した。また、純水１Ｌに２００ｍＬ／分の流量でＳＯ２ガスを吹き込みながら、４０℃においてバッフル付きの二段タービンによって４００ｒｐｍで１０分間撹拌し、炭酸ストロンチウム５ｇ／Ｌを添加してさらに３０分間撹拌し、得られた炭酸ストロンチウムの懸濁液（溶解した炭酸ストロンチウムと溶け残りの炭酸ストロンチウムを含む懸濁液）を５Ｃのろ紙で吸引ろ過して、溶け残りの炭酸ストロンチウムを除去したストロンチウム含有水溶液を用意した。このストロンチウム含有水溶液を電解液に添加して、電解採取用電解液０．９５Ｌを得た。なお、ストロンチウム含有水溶液の添加量を変えて、種々のストロンチウム濃度の電解採取用電解液を得た。これらの電解液を使用し、アノードとして電極面積３５ｃｍ２のＰｂ−Ａｇ板、カソードとして電極面積３５ｃｍ２のＡｌ板を使用し、極間距離を２５ｍｍとし、４３℃において電流密度７００Ａ／ｍ２で２時間電解採取を行った。なお、この電解採取は、ストロンチウム含有水溶液を電解液に添加した直後（３分以内）に開始した。
[Example 5]
As an electrolytic solution containing zinc sulfate, an electrolytic solution obtained by filtering the electrolytic tail solution (Zn: 65 g / L, FA: 170 g / L, total Pb: 0.1 mg / L) obtained in the zinc smelting process was prepared. Further, while blowing SO 2 gas at a flow rate of 200 mL / min into 1 L of pure water, stirring was performed at 400 rpm for 10 minutes at 40 ° C. with a baffled two-stage turbine, 5 g / L of strontium carbonate was added, and stirring was further performed for 30 minutes. The obtained strontium carbonate suspension (suspension containing dissolved strontium carbonate and undissolved strontium carbonate) was suction filtered with 5C filter paper to prepare a strontium-containing aqueous solution from which undissolved strontium carbonate was removed. did. This strontium-containing aqueous solution was added to the electrolytic solution to obtain 0.95 L of an electrolytic solution for electrolytic collection. In addition, electrolytic solutions for electrowinning with various strontium concentrations were obtained by changing the addition amount of the strontium-containing aqueous solution. Using these electrolytes, a Pb-Ag plate with an electrode area of 35 cm 2 was used as the anode, an Al plate with an electrode area of 35 cm 2 was used as the cathode, the distance between the electrodes was 25 mm, and the current density was 700 A / m 2 at 43 ° C. Electrolytic collection was performed for 2 hours. This electrolytic collection was started immediately after the strontium-containing aqueous solution was added to the electrolytic solution (within 3 minutes).
［実施例６］
実施例５で得られた炭酸ストロンチウムの懸濁液を吸引ろ過しないで、溶け残りの炭酸ストロンチウムを含むストロンチウム含有水溶液を用意し、このストロンチウム含有水溶液を実施例５と同様の電解液に添加して、電解採取用電解液０．９５Ｌを得た。なお、ストロンチウム含有水溶液のパルプ濃度および添加量を変えて、種々のストロンチウム濃度の電解採取用電解液を得た。これらの電解液を使用して、実施例５と同様の方法により電解採取を行った。
[Example 6]
A strontium-containing aqueous solution containing undissolved strontium carbonate was prepared without suction filtration of the strontium carbonate suspension obtained in Example 5, and this strontium-containing aqueous solution was added to the same electrolyte as in Example 5. As a result, 0.95 L of an electrolytic solution for electrolytic collection was obtained. In addition, the electrolytic solution for electrowinning of various strontium concentrations was obtained by changing the pulp concentration and the amount of strontium-containing aqueous solution. Using these electrolytic solutions, electrolytic collection was performed in the same manner as in Example 5.
ストロンチウム含有水溶液の添加量を５ｍＬとした場合の電解後の電解液中の（Ｓｒ２＋イオンと固体として存在するＳｒを含む）全Ｓｒ濃度は５１．８ｍｇ／Ｌであり、得られた電着亜鉛中のＰｂ品位は７．７ｐｐｍ、電力原単位は２８６４（ｋｗｈ／ｔ−Ｚｎ）であった。また、ストロンチウム含有水溶液の添加量を１０ｍＬとした場合の電解後の電解液中の（Ｓｒ２＋イオンと固体として存在するＳｒを含む）全Ｓｒ濃度は５４．１０ｍｇ／Ｌであり、得られた電着亜鉛中のＰｂ品位は８．９ｐｐｍ、電力原単位は２８６４（ｋｗｈ／ｔ−Ｚｎ）であった。 When the addition amount of the strontium-containing aqueous solution is 5 mL, the total Sr concentration (including Sr 2+ ions and Sr present as a solid) in the electrolytic solution after electrolysis is 51.8 mg / L, and the obtained electrodeposited zinc Among them, the Pb quality was 7.7 ppm, and the electric power consumption was 2864 (kwh / t-Zn). In addition, the total Sr concentration (including Sr 2+ ions and Sr present as a solid) in the electrolytic solution after electrolysis when the addition amount of the strontium-containing aqueous solution was 10 mL was 54.10 mg / L. The Pb quality in the zinc deposit was 8.9 ppm, and the power consumption was 2864 (kwh / t-Zn).
［実施例７］
硫酸亜鉛を含む電解液として、亜鉛製錬工程で得られた電解尾液（Ｚｎ：６５ｇ／Ｌ、ＦＡ：１７０ｇ／Ｌ、全Ｐｂ：０．１ｍｇ／Ｌ）をろ過した電解液を用意した。また、純水３００ｍＬに水酸化ストロンチウム３０ｇを添加してリパルプした後、２００ｍＬ／分の流量でＨ２Ｓガスを吹き込みながら、４０℃においてバッフル付きの二段タービンによって４００ｒｐｍで３０分間撹拌した後、得られた水溶液を５Ｃのろ紙で吸引ろ過して、ストロンチウム含有水溶液を用意した。なお、吸引ろ過による残渣は殆どなく、ストロンチウム含有水溶液中の全Ｓｒ濃度は３０．３ｇ／Ｌであった。このストロンチウム含有水溶液を電解液に添加して、電解採取用電解液０．９５Ｌを得た。ストロンチウム含有水溶液を電解液に添加すると局部的に白色の析出物が生じ、撹拌すると液の赤色がなくなって白濁した。ＸＲＤ測定の結果、析出物はＳｒＳＯ４であり、それ以外のピークは見当たらなかった。なお、ストロンチウム含有水溶液の添加量を変えて、種々のストロンチウム濃度の電解採取用電解液を得た。これらの電解液を使用して、実施例５と同様の方法により電解採取を行った。
[Example 7]
As an electrolytic solution containing zinc sulfate, an electrolytic solution obtained by filtering the electrolytic tail solution (Zn: 65 g / L, FA: 170 g / L, total Pb: 0.1 mg / L) obtained in the zinc smelting process was prepared. Moreover, after adding 30 g of strontium hydroxide to 300 mL of pure water and repulping, the mixture was stirred at 400 rpm for 30 minutes by a two-stage turbine with a baffle at 40 ° C. while blowing H 2 S gas at a flow rate of 200 mL / min. The obtained aqueous solution was suction filtered with 5C filter paper to prepare a strontium-containing aqueous solution. In addition, there was almost no residue by suction filtration and the total Sr density | concentration in strontium containing aqueous solution was 30.3 g / L. This strontium-containing aqueous solution was added to the electrolytic solution to obtain 0.95 L of an electrolytic solution for electrolytic collection. When a strontium-containing aqueous solution was added to the electrolytic solution, a white precipitate was locally generated, and when stirred, the liquid became red and clouded. As a result of XRD measurement, the precipitate was SrSO 4 , and no other peak was found. In addition, electrolytic solutions for electrowinning with various strontium concentrations were obtained by changing the addition amount of the strontium-containing aqueous solution. Using these electrolytic solutions, electrolytic collection was performed in the same manner as in Example 5.
ストロンチウム含有水溶液の添加量を２ｍＬとした場合の電解後の電解液中の（Ｓｒ２＋イオンと固体として存在するＳｒを含む）全Ｓｒ濃度は５３．９ｍｇ／Ｌであり、得られた電着亜鉛中のＰｂ品位は５．１ｐｐｍ、電流効率は８１．９％、電力原単位は３２５９（ｋｗｈ／ｔ−Ｚｎ）であった。また、ストロンチウム含有水溶液の添加量を３ｍＬとした場合の電解後の電解液中の（Ｓｒ２＋イオンと固体として存在するＳｒを含む）全Ｓｒ濃度は９０．１２ｍｇ／Ｌであり、得られた電着亜鉛中のＰｂ品位は３．０ｐｐｍ、電流効率は８４．６％、電力原単位は３１６３（ｋｗｈ／ｔ−Ｚｎ）であった。 When the addition amount of the strontium-containing aqueous solution is 2 mL, the total Sr concentration (including Sr 2+ ions and Sr present as a solid) in the electrolytic solution after electrolysis is 53.9 mg / L, and the obtained electrodeposited zinc Among them, the Pb quality was 5.1 ppm, the current efficiency was 81.9%, and the power consumption was 3259 (kwh / t-Zn). The total Sr concentration (including Sr 2+ ions and Sr present as a solid) in the electrolytic solution after electrolysis when the addition amount of the strontium-containing aqueous solution was 3 mL was 90.12 mg / L. The Pb quality in the zinc deposit was 3.0 ppm, the current efficiency was 84.6%, and the power consumption was 3163 (kwh / t-Zn).
実施例５〜７の電解後の電解液中の全Ｓｒ濃度と電力原単位との関係を図３に示し、全Ｓｒ濃度とカソードの電着亜鉛中のＰｂ品位との関係を図４に示す。 FIG. 3 shows the relationship between the total Sr concentration in the electrolytic solution after electrolysis of Examples 5 to 7 and the electric power consumption, and FIG. 4 shows the relationship between the total Sr concentration and the Pb quality in the electrodeposited zinc of the cathode. .
図３に示すように、ＳＯ２ガスを吹き込みながら炭酸ストロンチウムを溶解させ且つ溶け残りの炭酸ストロンチウムを含むストロンチウム含有水溶液（炭酸ストロンチウムの懸濁液）を電解尾液に添加した電解液を使用して電解採取した場合（実施例６）では、炭酸ストロンチウムの懸濁液の添加量によらず電力原単位が殆ど等しく、また、ＳＯ２ガスを吹き込みながら炭酸ストロンチウムを溶解させ且つ溶け残りの炭酸ストロンチウムを除去したストロンチウム含有水溶液を電解尾液に添加した電解液を使用して電解採取した場合（実施例５）と比べて、電力原単位が１００ｋｗｈ／ｔ−Ｚｎ程度向上した。 As shown in FIG. 3, by using an electrolytic solution in which strontium carbonate is dissolved while blowing SO 2 gas and a strontium-containing aqueous solution (suspension of strontium carbonate) containing undissolved strontium carbonate is added to the electrolytic tail solution. In the case of electrolytic collection (Example 6), the power unit is almost equal regardless of the amount of strontium carbonate suspension added, and strontium carbonate is dissolved while blowing SO 2 gas, and the remaining strontium carbonate is dissolved. Compared with the case where the electrolytic solution obtained by adding the removed strontium-containing aqueous solution to the electrolytic tail solution was used for electrowinning (Example 5), the power unit was improved by about 100 kwh / t-Zn.
図４に示すように、実施例５、実施例６および実施例７（Ｈ２Ｓガスを吹き込みながら水酸化ストロンチウムを溶解させ且つ溶け残りの水酸化ストロンチウムを除去したストロンチウム含有水溶液を電解尾液に添加した電解液を使用して電解採取した場合）のいずれも、電解後の電解液中の全Ｓｒ濃度の増加とともにカソードの電着亜鉛中のＰｂ品位が減少する傾向があった。また、懸濁の有無によるＰｂ品位の違いはほとんど見られなかった。 As shown in FIG. 4, Example 5, Example 6 and Example 7 (the strontium-containing aqueous solution in which strontium hydroxide was dissolved while H 2 S gas was blown and the remaining strontium hydroxide was removed was used as the electrolytic tail solution. In all cases where the electrolysis was performed using the added electrolyte, the Pb quality in the electrodeposited zinc of the cathode tended to decrease as the total Sr concentration in the electrolyte after electrolysis increased. Moreover, the difference of Pb quality by the presence or absence of suspension was hardly seen.
Claims (7)
The electrolytic solution for electrolytic collection of zinc according to claim 6, wherein the total strontium concentration is 50 mg / L or more.
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