JP2008050229A - Method for producing copper sulfate solution - Google Patents
Method for producing copper sulfate solution Download PDFInfo
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- JP2008050229A JP2008050229A JP2006230102A JP2006230102A JP2008050229A JP 2008050229 A JP2008050229 A JP 2008050229A JP 2006230102 A JP2006230102 A JP 2006230102A JP 2006230102 A JP2006230102 A JP 2006230102A JP 2008050229 A JP2008050229 A JP 2008050229A
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- 229910000365 copper sulfate Inorganic materials 0.000 title claims abstract description 59
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 102
- 229910052802 copper Inorganic materials 0.000 claims abstract description 94
- 239000010949 copper Substances 0.000 claims abstract description 94
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000000243 solution Substances 0.000 claims abstract description 45
- 239000007864 aqueous solution Substances 0.000 claims abstract description 35
- 239000012535 impurity Substances 0.000 claims abstract description 35
- 239000000126 substance Substances 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000011135 tin Substances 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052785 arsenic Inorganic materials 0.000 claims description 6
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000011133 lead Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000003570 air Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 10
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Abstract
Description
本発明は、硫酸銅溶液の製造方法に関し、特に、硫酸銅を原料とする薬品などの製造や銅電解製錬などに使用する高純度の硫酸銅溶液を製造する方法に関する。 The present invention relates to a method for producing a copper sulfate solution, and more particularly, to a method for producing a high-purity copper sulfate solution used for production of chemicals using copper sulfate as a raw material, copper electrolytic smelting and the like.
硫酸銅は、電解液、肥料、医薬などの原料として使用されている。特に、硫酸銅を水溶液にして電解採取や電解精製によって高純度の銅を製造する場合には、原料となる硫酸銅の純度が高いことが望まれている。 Copper sulfate is used as a raw material for electrolytes, fertilizers, medicines and the like. In particular, when high-purity copper is produced by electrolytic collection or electrolytic purification using copper sulfate as an aqueous solution, it is desired that the purity of copper sulfate as a raw material is high.
従来、高純度硫酸銅の製造方法として、硫酸銅結晶を純水に溶解した後、蒸発濃縮を行い、初期に析出する結晶を除去した後、さらに蒸発濃縮することにより結晶化させ、これを濾過して高純度硫酸銅とする方法が提案されている（例えば、特許文献１参照）。また、他の硫酸銅の製造方法として、電解液から電析させて回収した電解銅粉などのように不純物としてニッケルを含む銅粉を原料とし、この銅粉を酸溶液中に浸漬することにより銅粉中に含まれるニッケルを溶解除去し、濾過後に銅粉を硫酸に溶解させ、結晶化させることによって、ニッケル品位が１０ｐｐｍ以下の硫酸銅を得る方法が提案されている（例えば、特許文献２参照）。さらに、有機溶媒を用いた溶媒抽出法や、イオン交換樹脂やキレート樹脂を用いた方法によって、銅含有物質を溶解した液から不純物を取り除いて電解液とする方法も知られている。 Conventionally, as a method for producing high-purity copper sulfate, after dissolving copper sulfate crystals in pure water, evaporation and concentration are performed, and after initial removal of crystals, the crystals are crystallized by further evaporation and filtered. Thus, a method for producing high-purity copper sulfate has been proposed (see, for example, Patent Document 1). As another method for producing copper sulfate, copper powder containing nickel as an impurity is used as a raw material, such as electrolytic copper powder collected by electrolytic deposition from an electrolytic solution, and the copper powder is immersed in an acid solution. A method has been proposed in which nickel contained in copper powder is dissolved and removed, and after filtration, copper powder is dissolved in sulfuric acid and crystallized to obtain copper sulfate having a nickel quality of 10 ppm or less (for example, Patent Document 2). reference). Furthermore, a method of removing impurities from a solution in which a copper-containing substance is dissolved to obtain an electrolytic solution by a solvent extraction method using an organic solvent or a method using an ion exchange resin or a chelate resin is also known.
しかし、特許文献１の方法では、出発原料が市販硫酸銅であり、また、蒸発濃縮を行うと、エネルギーコストが高くなり、蒸気の処理も必要になるので、製造コストや設備費が高くなる。また、特許文献２の方法では、原料として純度の高い銅粉が必要になり、原料の銅粉の品位を管理する必要がある。さらに、有機溶媒を用いた溶媒抽出法や、イオン交換樹脂やキレート樹脂を用いた方法では、有機溶媒を水に溶解したり、あるいはその逆に水を有機溶媒に溶解して、第３相を生成するため、また、溶媒や樹脂の寿命などによって、環境的に排水処理に多大な負荷がかかり、製造コストや設備費が高くなるという問題がある。このように、従来の硫酸銅の製造方法では、製造コストや設備費が高くなったり、原材料の選定や管理が必要になるという問題がある。 However, in the method of Patent Document 1, the starting material is commercially available copper sulfate, and when evaporating and concentrating, the energy cost becomes high and the treatment of steam becomes necessary, so that the manufacturing cost and equipment cost become high. Moreover, in the method of patent document 2, copper powder with high purity is required as a raw material, and it is necessary to manage the quality of the raw material copper powder. Furthermore, in a solvent extraction method using an organic solvent or a method using an ion exchange resin or a chelate resin, the organic solvent is dissolved in water, or vice versa. In addition, there is a problem that the wastewater treatment is environmentally burdened due to the generation of the solvent and the life of the resin, and the manufacturing cost and the equipment cost increase. As described above, the conventional method for producing copper sulfate has problems that the production cost and the equipment cost are increased, and selection and management of raw materials are required.
したがって、本発明は、このような従来の問題点に鑑み、安価に且つ簡便に高純度の硫酸銅を製造する方法を提供することを目的とする。 Therefore, in view of such conventional problems, an object of the present invention is to provide a method for producing high-purity copper sulfate inexpensively and easily.
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、不純物を含み且つ銅と遊離硫酸を含む水溶液中に銅含有物質と酸化剤を添加して加熱し、銅含有物質を溶解させた後に硫酸銅を晶析させ、その後、固液分離により回収した固形分に水を加え、さらに固液分離を行って硫酸銅溶液を回収することにより、安価に且つ簡便に高純度の硫酸銅を製造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 earnest research to solve the above problems, the present inventors have added a copper-containing substance and an oxidizing agent to an aqueous solution containing impurities and containing copper and free sulfuric acid, and heated to dissolve the copper-containing substance. After that, copper sulfate is crystallized, and then water is added to the solid content recovered by solid-liquid separation, and further, solid-liquid separation is performed to recover the copper sulfate solution. Has been found to be able to be produced, and the present invention has been completed.
すなわち、本発明による硫酸銅溶液の製造方法は、不純物を含み且つ銅と遊離硫酸を含む水溶液中に銅含有物質と酸化剤を添加して加熱し、銅含有物質を溶解させた後に硫酸銅を晶析させ、その後、固液分離により回収した固形分に水を加え、さらに固液分離を行って硫酸銅溶液を回収することを特徴とする。この硫酸銅溶液の製造方法において、不純物を含み且つ銅と遊離硫酸を含む水溶液が１００〜１６０ｇ／Ｌの銅を含むのが好ましい。また、不純物を含み且つ銅と遊離硫酸を含む水溶液が、砒素、アンチモン、ビスマス、錫、ニッケル及び亜鉛からなる群から選ばれる少なくとも一種の元素を不純物として含んでもよく、銅含有物質が、砒素、アンチモン、ビスマス、スズ、ニッケル、亜鉛、鉄および鉛から選ばれる少なくとも一種の元素を不純物として含んでもよい。さらに、酸化剤として酸素、空気または過酸化水素を使用してもよい。 That is, in the method for producing a copper sulfate solution according to the present invention, a copper-containing substance and an oxidant are added and heated in an aqueous solution containing impurities and containing copper and free sulfuric acid. Crystallization is performed, and then water is added to the solid content recovered by solid-liquid separation, and solid-liquid separation is further performed to recover a copper sulfate solution. In this method for producing a copper sulfate solution, the aqueous solution containing impurities and containing copper and free sulfuric acid preferably contains 100 to 160 g / L of copper. Further, the aqueous solution containing impurities and containing copper and free sulfuric acid may contain at least one element selected from the group consisting of arsenic, antimony, bismuth, tin, nickel and zinc as impurities, and the copper-containing substance may contain arsenic, At least one element selected from antimony, bismuth, tin, nickel, zinc, iron and lead may be contained as an impurity. Further, oxygen, air or hydrogen peroxide may be used as the oxidant.
本発明によれば、不純物を含み且つ銅と遊離硫酸を含む水溶液から安価に且つ簡便に高純度の硫酸銅を製造することができる。 According to the present invention, high-purity copper sulfate can be produced inexpensively and simply from an aqueous solution containing impurities and containing copper and free sulfuric acid.
図１に示すように、本発明による硫酸銅溶液の製造方法の実施の形態では、原料として、不純物を含む銅・遊離硫酸含有水溶液（銅と遊離硫酸を含む水溶液）と銅含有物質を用意し、銅・遊離硫酸含有水溶液中に銅含有物質と酸化剤を添加して加熱し、銅含有物質を溶解させた後に硫酸銅を晶析させ、その後、固液分離により回収した固形分（硫酸銅結晶と溶解残渣）に水を加え、さらに固液分離を行って不純物濃度が低い硫酸銅溶液を回収する。 As shown in FIG. 1, in the embodiment of the method for producing a copper sulfate solution according to the present invention, a copper / free sulfuric acid-containing aqueous solution containing impurities (an aqueous solution containing copper and free sulfuric acid) and a copper-containing substance are prepared as raw materials. Then, a copper-containing substance and an oxidizing agent are added to a copper / free sulfuric acid-containing aqueous solution and heated. After the copper-containing substance is dissolved, copper sulfate is crystallized, and then solids recovered by solid-liquid separation (copper sulfate Water is added to the crystals and dissolved residue), and solid-liquid separation is further performed to recover a copper sulfate solution having a low impurity concentration.
銅・遊離硫酸含有水溶液としては、硫酸銅溶液のように、水中に銅がイオンとして存在し、遊離硫酸を含む水溶液であればよい。銅・遊離硫酸含有水溶液中の銅と遊離硫酸の濃度は、銅と遊離硫酸を含む水溶液として存在することができれば適宜設定することができるが、銅・遊離硫酸含有水溶液中に遊離硫酸の他に１００〜１６０ｇ／Ｌ程度の銅が含まれるのが好ましい。銅・遊離硫酸含有水溶液中の銅の濃度がこの範囲より低い場合には、銅・遊離硫酸含有水溶液中に溶解させる銅含有物質の量を多くして適宜調整すればよい。なお、銅・遊離硫酸含有水溶液に含まれる不純物としては、砒素（Ａｓ）、アンチモン（Ｓｂ）、ビスマス（Ｂｉ）、錫（Ｓｎ）、ニッケル（Ｎｉ）、亜鉛（Ｚｎ）などが挙げられる。また、銅・遊離硫酸含有水溶液として、電解排液を使用することができ、また、電解排液を混合した水溶液を使用してもよい。最終的に得られる不純物濃度が低い硫酸銅溶液を電解液として使用する場合には、電解に必要な給液中の銅と遊離硫酸の濃度になるように、銅・遊離硫酸含有水溶液中の銅と遊離硫酸の濃度を適宜調整すればよい。 The aqueous solution containing copper / free sulfuric acid may be an aqueous solution containing copper as ions and containing free sulfuric acid, such as a copper sulfate solution. The concentration of copper and free sulfuric acid in the aqueous solution containing copper and free sulfuric acid can be appropriately set as long as it can be present as an aqueous solution containing copper and free sulfuric acid. It is preferable that about 100 to 160 g / L of copper is contained. When the copper concentration in the copper / free sulfuric acid-containing aqueous solution is lower than this range, the amount of the copper-containing substance dissolved in the copper / free sulfuric acid-containing aqueous solution may be increased and adjusted as appropriate. Examples of impurities contained in the copper / free sulfuric acid-containing aqueous solution include arsenic (As), antimony (Sb), bismuth (Bi), tin (Sn), nickel (Ni), and zinc (Zn). Further, as the copper / free sulfuric acid-containing aqueous solution, an electrolytic effluent can be used, or an aqueous solution in which the electrolytic effluent is mixed may be used. When using a copper sulfate solution with a low impurity concentration finally obtained as the electrolyte, the copper in the aqueous solution containing copper and free sulfuric acid is adjusted so that the concentration of copper and free sulfuric acid in the feed solution required for electrolysis is reached. And the concentration of free sulfuric acid may be appropriately adjusted.
銅含有物質は、銅源として銅を含有する物質であればよく、金属銅のように銅が単体でイオン化できる状態にあるのが望ましい。銅含有物質として金属銅を使用する場合には、製錬中間物である銅品位が９９．９％以下の粗銅を使用してもよく、銅品位がさらに低くてもよい。また、銅含有物質として、銅スクラップや、銅を含む残渣、銅粉、銅粒などを使用してもよい。さらに、銅含有物質として、金属銅でなくても、硫酸銅やその他の銅塩などの水溶液中で銅イオンになる物質を使用してもよい。また、銅含有物質中に、砒素（Ａｓ）、アンチモン（Ｓｂ）、ビスマス（Ｂｉ）、錫（Ｓｎ）、ニッケル（Ｎｉ）、亜鉛（Ｚｎ）、鉄（Ｆｅ）、鉛（Ｐｂ）などが含まれてもよい。 The copper-containing material may be any material that contains copper as a copper source, and it is desirable that the copper-containing material can be ionized alone, such as metallic copper. When metal copper is used as the copper-containing substance, crude copper having a copper grade of 99.9% or less as a smelting intermediate may be used, or the copper grade may be further lowered. Moreover, you may use a copper scrap, the residue containing copper, copper powder, a copper grain, etc. as a copper containing material. Furthermore, as the copper-containing material, a material that becomes copper ions in an aqueous solution such as copper sulfate or other copper salts may be used instead of metallic copper. Also, copper-containing materials include arsenic (As), antimony (Sb), bismuth (Bi), tin (Sn), nickel (Ni), zinc (Zn), iron (Fe), lead (Pb), etc. May be.
酸化剤としては、酸素や空気などの酸素を含むガスを使用することができ、過酸化水素を使用することもできるが、ランニングコストの面から空気を使用するのが好ましい。 As the oxidant, a gas containing oxygen such as oxygen or air can be used, and hydrogen peroxide can be used. However, it is preferable to use air from the viewpoint of running cost.
銅・遊離硫酸含有水溶液中に銅含有物質と酸化剤を添加して加熱する温度は、できるだけ多量の銅ができるだけ早く溶解するような温度にした方が晶析の際に有利であり、６０℃以上であるのが好ましい。 The temperature at which the copper-containing substance and the oxidizing agent are added to the copper / free sulfuric acid-containing aqueous solution and heated is such that as much copper as possible dissolves as soon as possible. The above is preferable.
本発明による硫酸銅溶液の製造方法の実施の形態では、不純物を含む銅・遊離硫酸含有水溶液（銅と遊離硫酸を含む水溶液）中に銅含有物質と酸化剤を添加して加熱することにより、銅を酸化するとともに、銅・遊離硫酸含有水溶液に銅含有物質を溶解させる。この水溶液は、銅・遊離硫酸含有水溶液にさらに銅含有物質を添加して溶解させた水溶液であり、所定時間放置すると、硫酸銅が晶析して硫酸銅結晶になって液中または液面に浮遊し、溶解液中に浮遊する硫酸銅結晶と溶解残渣を含むスラリーが得られる。このスラリーを濾過などで固液分離すれば、溶解液から固形分（硫酸銅結晶と溶解残渣）を分離して回収することができる。なお、溶解液は、銅・遊離硫酸含有水溶液として銅含有物質の溶解に使用することができる。 In the embodiment of the method for producing a copper sulfate solution according to the present invention, a copper-containing substance and an oxidizing agent are added to a copper-free sulfuric acid-containing aqueous solution containing impurities (an aqueous solution containing copper and free sulfuric acid) and heated. While oxidizing copper, a copper-containing substance is dissolved in an aqueous solution containing copper and free sulfuric acid. This aqueous solution is an aqueous solution in which a copper-containing substance is further added and dissolved in an aqueous solution containing copper / free sulfuric acid, and when left for a predetermined time, copper sulfate crystallizes to form copper sulfate crystals in the liquid or on the liquid surface. A slurry containing copper sulfate crystals and dissolution residues floating and floating in the solution is obtained. If this slurry is subjected to solid-liquid separation by filtration or the like, solid components (copper sulfate crystals and dissolution residues) can be separated and recovered from the solution. In addition, a solution can be used for melt | dissolution of a copper containing material as copper and a free sulfuric acid containing aqueous solution.
その後、回収した固形分に水を加えて再溶解させた後、固液分離により不純物濃度が低い硫酸銅溶液を回収することができる。なお、この再溶解後の固液分離により得られた溶解残渣は、有価金属が含まれているので製錬原料として使用することもできる。 Then, after adding water to the collected solid and re-dissolving it, a copper sulfate solution having a low impurity concentration can be collected by solid-liquid separation. In addition, since the melt | dissolution residue obtained by solid-liquid separation after this re-dissolution contains valuable metals, it can also be used as a smelting raw material.
このようにして回収された硫酸銅溶液を電解用の母液として使用すれば、銅電解により４Ｎ（９９．９９質量％）〜５Ｎ（９９．９９９質量％）の純度の高い銅金属を得ることができる。また、電解採取後の電解液は、銅濃度は低減しているが、銅・遊離硫酸含有水溶液として使用することができる。 If the copper sulfate solution thus recovered is used as a mother liquor for electrolysis, a copper metal having a high purity of 4N (99.99 mass%) to 5N (99.999 mass%) can be obtained by copper electrolysis. it can. Moreover, although the copper concentration is reducing the electrolytic solution after electrowinning, it can be used as an aqueous solution containing copper / free sulfuric acid.
以下、本発明による硫酸銅溶液の製造方法の実施例について詳細に説明する。 Hereinafter, the Example of the manufacturing method of the copper sulfate solution by this invention is described in detail.
表１に示す組成の不純物を含む硫酸銅溶液（１５７ｇ／Ｌの銅と１９２ｇ／Ｌの遊離硫酸を含む硫酸銅溶液）と、表２に示す組成の銅含有物質を用意した。 A copper sulfate solution containing an impurity having the composition shown in Table 1 (a copper sulfate solution containing 157 g / L of copper and 192 g / L of free sulfuric acid) and a copper-containing material having a composition shown in Table 2 were prepared.
上記の硫酸銅溶液０．４６Ｌと銅含有物質１９ｇを容器内に投入し、この溶液の液温を７５℃として溶液中に３Ｌ／分の流量で空気を吹き込んで１時間攪拌した後、容器中のスラリーを吸引濾過で濾別し、硫酸銅結晶と溶解残渣を回収した。濾別後の濾液（硫酸銅溶液）の量は０．４２Ｌになっていた。この濾液の組成を表３に示す。表３から、濾別後の溶液では、銅と不純物の濃度が高くなっており、銅が溶解していることがわかる。また、遊離硫酸の濃度が減少して、銅の溶解に消費されていることがわかる。 0.46 L of the above copper sulfate solution and 19 g of a copper-containing substance were put into a container, the temperature of this solution was 75 ° C., air was blown into the solution at a flow rate of 3 L / min, and the mixture was stirred for 1 hour. The slurry was separated by suction filtration, and copper sulfate crystals and dissolved residues were recovered. The amount of filtrate (copper sulfate solution) after filtration was 0.42 L. The composition of this filtrate is shown in Table 3. From Table 3, it can be seen that in the solution after separation, the concentrations of copper and impurities are high and copper is dissolved. Moreover, it turns out that the density | concentration of a free sulfuric acid reduces and it is consumed for melt | dissolution of copper.
次に、ロート内の濾紙上に硫酸銅結晶と溶解残渣を残したまま、ロート内に純水１Ｌを入れて、再び吸引濾過したところ、濾過瓶に青色の溶液１．０２Ｌが出てきた。なお、溶解残渣の量は２．８９ｇであった。 Next, 1 L of pure water was put into the funnel while leaving the copper sulfate crystals and dissolution residue on the filter paper in the funnel, and suction filtration was performed again. As a result, 1.02 L of a blue solution appeared in the filter bottle. The amount of dissolution residue was 2.89 g.
この濾別後の溶液の組成を表４に示す。表４から、この濾別後の溶液では、不純物の濃度が低くなり、銅の濃度だけが高くなって、硫酸銅が溶解していることがわかる。また、得られた溶液を電解液として使用して電解を行ったところ、不純物の少ない電解銅が得られた。 The composition of the solution after filtration is shown in Table 4. From Table 4, it can be seen that in this solution after filtration, the concentration of impurities is low, only the concentration of copper is high, and copper sulfate is dissolved. Moreover, when it electrolyzed using the obtained solution as electrolyte solution, electrolytic copper with few impurities was obtained.
これらの結果から、実施例では、表１に示すような不純物を含む硫酸銅溶液に表２に示すような数％程度の不純物を含む銅含有物質を溶解して、表４に示すように不純物の割合が銅含有物質に含まれる不純物の割合の１／１００以下の硫酸銅溶液を得ることができ、この硫酸銅溶液を電解液として電解を行って不純物の少ない電解銅を得ることができるのがわかる。 From these results, in the example, a copper-containing material containing about several percent of impurities as shown in Table 2 was dissolved in a copper sulfate solution containing impurities as shown in Table 1, and impurities as shown in Table 4 were obtained. Copper sulfate solution with a ratio of 1/100 or less of the ratio of impurities contained in the copper-containing material can be obtained, and electrolytic copper with less impurities can be obtained by performing electrolysis using this copper sulfate solution as an electrolytic solution. I understand.
また、比較例として、実施例で使用した表１に示す組成の不純物を含む硫酸銅溶液の代わりに、表５に示す組成の不純物を含む硫酸溶液に銅を溶解して作成した硫酸銅溶液を使用した以外は、実施例と同様に溶解晶析および濾別を行った。その結果、表６に示すように、濾別後の濾液に多くの不純物が硫酸溶液に溶解していた。なお、溶解残渣の量は６．１８ｇであった。また、この比較例で得られた溶液を電解液として使用して電解を行ったところ、電解銅に多くの不純物が含まれていた。 As a comparative example, instead of the copper sulfate solution containing the impurities shown in Table 1 used in the examples, a copper sulfate solution prepared by dissolving copper in a sulfuric acid solution containing the impurities shown in Table 5 was used. Except for the use, dissolution crystallization and filtration were carried out in the same manner as in the Examples. As a result, as shown in Table 6, many impurities were dissolved in the sulfuric acid solution in the filtrate after filtration. The amount of dissolution residue was 6.18 g. Moreover, when electrolysis was performed using the solution obtained in this comparative example as an electrolytic solution, many impurities were contained in the electrolytic copper.
Claims (5)
The method for producing copper sulfate according to any one of claims 1 to 4, wherein the oxidizing agent is oxygen, air, or hydrogen peroxide.
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| CN103977584A (en) * | 2014-05-12 | 2014-08-13 | 江西众合装备技术有限公司 | Automatic feeding and discharging control method of copper sulfate vacuum evaporator |
| CN113683116A (en) * | 2021-08-18 | 2021-11-23 | 西北矿冶研究院 | Method for preparing high-purity copper sulfate from waste electrolyte |
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| JPS54155196A (en) * | 1978-03-09 | 1979-12-06 | Norddeutsche Affinerie | Manufacture of copper sulfate solution |
| JPS6183625A (en) * | 1984-09-27 | 1986-04-28 | Sumitomo Metal Mining Co Ltd | Method for producing aqueous solution of cupric sulfate having low antimony and bismuth content from decopperization slime |
| JP2006291352A (en) * | 2005-03-04 | 2006-10-26 | Phibro-Tech Inc | Regeneration of cupric etchants and recovery of copper sulfate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS54155196A (en) * | 1978-03-09 | 1979-12-06 | Norddeutsche Affinerie | Manufacture of copper sulfate solution |
| JPS6183625A (en) * | 1984-09-27 | 1986-04-28 | Sumitomo Metal Mining Co Ltd | Method for producing aqueous solution of cupric sulfate having low antimony and bismuth content from decopperization slime |
| JP2006291352A (en) * | 2005-03-04 | 2006-10-26 | Phibro-Tech Inc | Regeneration of cupric etchants and recovery of copper sulfate |
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| CN103977584A (en) * | 2014-05-12 | 2014-08-13 | 江西众合装备技术有限公司 | Automatic feeding and discharging control method of copper sulfate vacuum evaporator |
| CN113683116A (en) * | 2021-08-18 | 2021-11-23 | 西北矿冶研究院 | Method for preparing high-purity copper sulfate from waste electrolyte |
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