200307060 玖、發明說明 【發明所屬之技術領域】 本發明係關於一種可使用單一之電解槽進行原料金屬 之熔解與採收之電解採收之高純度金屬之製造方法及裝置 〇 【先前技術】 一般，鎳、鈷、鐵、銦、銅等之高純度金屬，係要求 儘可能減少鹼金屬、放射性元素、過渡金屬元素、氣體成 分，其在VLSI之電極以及配線之形成、化合物半導體用或 磁性薄膜之形成方面，特別是作爲濺鍍靶材，使用範圍相 當廣泛。200307060 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a method and a device for manufacturing high-purity metals by electrolytic recovery, which can use a single electrolytic cell to melt and recover raw metal. [Previous technology] General High-purity metals such as nickel, cobalt, iron, indium, and copper are required to reduce alkali metals, radioactive elements, transition metal elements, and gas components as much as possible. The formation of electrodes and wiring in VLSI, compound semiconductors, or magnetic thin films In terms of formation, especially as a sputtering target, it is widely used.
Na、K等之鹼金屬在閘極絕緣膜中容易移動，會成爲 MOS-LSI界面特性惡化之原因。U，Th等之放射性元素，其 所釋放之α射線會成爲元件之軟性錯誤（soft error)的原因。 另一方面，鎳、鈷、銅等之材料做爲半導體之配線材 料使用時，依據所使用之場所，有時Fe等之過渡金屬元素 會成爲界面接合部之問題發生的原因。 再者，碳、氧等之氣體成分被認爲係灑鍍之際之粒子 產生之原因，故非所希望者。 通常，於製造5N等級之鎳、鈷、鐵、銦、銅等之高純 度金屬之時，一般係以離子交換或溶劑萃取等之來精製溶 液，將所得之物進一步以電解採收或電解精製來進行高純 度化，但事先進行溶劑萃取製程之方法，其製程繁雜且需 要特殊之溶劑，故非有效率的做法，此爲問題所在。 200307060 又，於製造5N等級之鎳、鈷、鐵、銦、銅等之高純度 金屬之時，使用含有該等金屬之溶液進行電解來製造被認 爲是較爲簡單的方法，但例如欲以電解來製造高純度鎳的 情況，由於電解液中含有多量之其他金屬元素（主要爲鐵）， 分離變得困難，不能說是有效率的做法。 【發明內容】 本發明之目的在於提供一種可從含有許多其他金屬元 素、碳、氧等之鎳、鈷、鐵、銦、銅等之金屬原料，使用 含有該金屬之溶液進行電解之簡便的方法；係提供一種可 從該原料有效地製造出純度5N(99.999重量％)以上之高純度 金屬之技術。 爲了解決上述問題，本發明者得到了以下見解：自含 有金屬之溶液的陽極電解液將其他金屬元素、其他雜質以 溶劑萃取來去除，將去除後之液體當作陰極電解液使用， 則可高效率地製造高純度金屬。 基於此見解，本發明係提供： 1. 一種高純度金屬之製造方法，其特徵在於：使用含有 高純度化用金屬之溶液做爲電解液進行電解之際，將陽極 與陰極以陰離子交換膜來分隔，將陽極電解液間歇或連續 地抽出而導入溶劑萃取槽，以該溶劑萃取槽將雜質去除， 再將此雜質去除後之高純度金屬電解液以間歇或連續的方 式導入陰極側。 2. 如上述1記載之高純度金屬之製造方法，其中，於單 一電解槽內同時進行金屬原料之熔解與金屬之採收，且以 200307060 離子交換膜來分離。 3. 如上述1或2記載之高純度金屬之製造方法，係將利 用溶劑萃取槽去除了雜質之高純度金屬電解液暫時儲存， 將高純度金屬電解液以間歇或連續方式導入陰極側。 4. 如上述1〜3中任一記載之高純度金屬之製造方法，係 使得陽極電解液以及陰極電解液做循環。 又，本發明係提供： 5. —種高純度金屬之製造裝置，係採用電解來製造高純 度金屬；其特徵在於，係由：裝入有金屬原料之陽極袋； 將陽極與陰極做分隔之陰離子交換膜；使得高純度金屬析 出之陰極；自金屬熔解液（陽極電解液）去除雜質之溶劑萃取 槽；將陽極電解液間歇或連續地抽出而導入溶劑萃取槽之 裝置；以及，將利用溶劑萃取所得之高純度金屬電解液以 間歇或連續方式導入陰極側之裝置；所構成。 6. 如上述5記載之高純度金屬之製造裝置，其中，金屬 原料之熔解以及金屬之採收係在單一電解槽內，且以離子 交換膜來分離。 7. 如上述5或6記載之高純度金屬之製造裝置，其中， 係具備一將利用溶劑萃取槽去除了雜質之高純度金屬電解 液暫時儲存之電解液儲槽。 8. 如上述5〜7中任一記載之高純度金屬之製造裝置，係 具備使得陽極電解液以及陰極電解液做循環之裝置。 【實施方式】 使用圖1所示之電解槽1，將4N等級之塊狀金屬原料 200307060 2放入陽極袋3當作陽極5，陰極4則使用與高純度化金屬 爲同種之金屬或其他之金屬材料來進行電解。於金屬原料 中係含有許多高純度金屬以外之金屬元素、碳、氧等之雜 質。 於電解之際，雖隨進行電解之金屬而不同，惟大致上 係以浴溫10〜70 °C、金屬濃度20〜120g/L、電流密度 0.1〜ΙΟΑ/dm2來實施。當電流密度低的情況，例如未滿 0.1 A/dm2時生產性差，又若電流密度過高的情況，例如超 過ΙΟΑ/dm2時，容易發生結球（nodule)。是以，通常電流密 度以0.1〜ΙΟΑ/dm2之範圍爲佳。 不過’如上所述般，隨進行電解之金屬種類，操作條 件會有所不同，所以未必要限制在上述範圍內。 前述陽極5與陰極4係以陰離子交換膜6來分隔，陽 極電解液7係一邊循環一邊做間歇或連續的抽出。陰極電 解液係隔著陰離子交換膜6而與外側之液體（陽極電解液）分 離。所抽出之陽極電解液7係導入溶劑萃取槽8。 於溶劑萃取槽8中，係將電解液中之其他金屬元素以 及其他雜質去除。藉此，電解液中之其他金屬元素濃度可 控制在約lmg/L以下。 溶劑萃取後之經高純度化之金屬電解液係以間歇或連 續的方式導入陰極側，當作陰極電解液9使用，進行電解 採收。 溶劑萃取後之經高純度化的金屬電解液可依必要性通 過活性碳等之過濾器（未圖示）。 200307060 攄器，具有將有機溶劑或離子交換膜所得 之有機物所產生之雜質去除之效果。 X ’ 將以溶劑萃取槽去除其他金屬元素等之雜 質之1¾純度金屬電解液暫時存放之電解液儲槽9，進行循環 ° 丨容劑萃取後之經高純度化之金屬電解液係暫時存 放於電解液儲槽9，而自該處以間歇或連續方式導入陰極側 ，當作陰極電解液9使用，進行電解採收。 電流效率係成爲80〜100%。藉此，可得到純度5N以上 之電析金屬（於陰極析出）。亦即，不計氣體成分爲4N以上 (99.99重量％)，依材料有可能達5N(99.999重量％)以上，且 雜質之〇：10〇wtppm以下（依材料有可能達〇 : 3〇wtppm以 下）、C，N，S，H分別爲i〇wtppm以下。 再者’可對藉由電解所得之電析金屬進行電子束熔解 等之真空熔解。藉由此真空熔解，可將Na、κ等之鹼金屬 以及其他揮發性雜質與氣體成分有效地去除。 (實施例與比較例） 以下，針對本發明之實施例做說明。又，本實施例充 其量不過爲一例，本發明並不受限於此例。亦即，在本發 明之技術思想之範圍內’亦包含實施例以外所有的態樣或 是變形。 (實施例1) 使用圖1所示之電解槽，以3N等級之塊狀鎳原料lkg 當作陽極，陰極則使用2N等級之鎳板，進行電解。原料之 雜質的含量係示於表1。於鎳原料中主要含有許多的鐵、碳 200307060 、氧等。 於浴溫50°C，使用硫酸系電解液，於pH2、電流密度 2A/dm2來實施。剛電解時，陽極側之Ni濃度爲20g/L。電 解後，以Ni濃度100g/L來抽出。 將所抽出之陽極電解液導入溶劑萃取槽。再者，將此 沉澱物等之雜質以活性碳過濾器來去除。藉此，電解液中 之鐵濃度可控制在lmg/L以下。 雜質去除後，將該液間歇地導入陰極側，當作陰極電 解液來使用進行電解採收。陰極側之Ni濃度爲100g/L，電 解後之Ni濃度則成爲20g/L。 得到電析鎳（於陰極析出）約lkg。純度達成5N。亦即， 不計氣體成分爲5N(99.999重量％)以上，雜質方面〇： 30wtppm以下，C，N,S分別爲lOwtppm以下。將以上的結果 與原料做對比，示於表1。 表1 wtppmAlkali metals such as Na and K easily move in the gate insulating film, which may cause deterioration of the MOS-LSI interface characteristics. The radioactive elements such as U and Th, the alpha rays released by them will cause the soft error of the element. On the other hand, when materials such as nickel, cobalt, and copper are used as wiring materials for semiconductors, depending on the place of use, transition metal elements such as Fe may cause problems at the interface junction. Furthermore, gas components such as carbon and oxygen are considered to be the cause of particles generated during plating, and are therefore not desirable. Generally, when manufacturing high-purity metals such as 5N grade nickel, cobalt, iron, indium, copper, etc., the solution is generally refined by ion exchange or solvent extraction, etc., and the obtained product is further electrolyzed or electrolytically refined. To achieve high purity, but the method of performing the solvent extraction process in advance, the process is complicated and requires a special solvent, so it is not an efficient method, which is the problem. 200307060 Also, when manufacturing high-purity metals such as 5N grade nickel, cobalt, iron, indium, and copper, it is considered to be a relatively simple method to use electrolysis to produce a solution containing these metals. In the case of electrolysis to produce high-purity nickel, since the electrolyte contains a large amount of other metal elements (mainly iron), separation becomes difficult and cannot be said to be an efficient method. [Summary of the Invention] The object of the present invention is to provide a simple method for electrolysis from a metal raw material containing nickel, cobalt, iron, indium, copper, etc. containing many other metal elements, carbon, oxygen, etc., using a solution containing the metal ; Provide a technology that can efficiently produce high-purity metals with a purity of 5N (99.999% by weight) or more from this raw material. In order to solve the above problems, the present inventors have obtained the following insights: extracting other metal elements and other impurities from the anolyte of a solution containing a metal by solvent extraction to remove the removed liquid as a catholyte can increase the Efficiently manufacture high-purity metals. Based on this knowledge, the present invention provides: 1. A method for manufacturing a high-purity metal, characterized in that, when a solution containing a high-purity metal is used as an electrolyte for electrolysis, the anode and the cathode are anion exchange membranes Separately, the anolyte is drawn out intermittently or continuously and introduced into a solvent extraction tank. Impurities are removed in the solvent extraction tank, and the high-purity metal electrolyte after the impurities are removed is introduced into the cathode side intermittently or continuously. 2. The method for manufacturing a high-purity metal as described in 1 above, wherein the melting of the metal raw materials and the recovery of the metals are performed simultaneously in a single electrolytic cell, and separated by a 200307060 ion exchange membrane. 3. The method for manufacturing a high-purity metal as described in 1 or 2 above, temporarily stores the high-purity metal electrolyte from which impurities have been removed by a solvent extraction tank, and introduces the high-purity metal electrolyte into the cathode side intermittently or continuously. 4. The method for manufacturing a high-purity metal according to any one of 1 to 3 above, is to circulate the anolyte and catholyte. In addition, the present invention provides: 5. A high-purity metal manufacturing device, which uses electrolysis to produce high-purity metal; and is characterized by: an anode bag filled with metal raw materials; and an anode and a cathode separated from each other. Anion exchange membrane; cathode for precipitation of high-purity metal; solvent extraction tank for removing impurities from metal melting solution (anolyte); device for extracting anolyte intermittently or continuously and introducing it into solvent extraction tank; and, using solvent The high-purity metal electrolyte obtained by the extraction is introduced into the cathode side device intermittently or continuously; 6. The high-purity metal manufacturing device according to the above 5, wherein the melting of the metal raw materials and the metal collection are in a single electrolytic cell and are separated by an ion exchange membrane. 7. The apparatus for manufacturing a high-purity metal as described in 5 or 6 above, further comprising an electrolytic solution storage tank for temporarily storing a high-purity metal electrolytic solution from which impurities have been removed by a solvent extraction tank. 8. The apparatus for manufacturing a high-purity metal as described in any of 5 to 7 above, is provided with a device that circulates the anolyte and the catholyte. [Embodiment] The electrolytic cell 1 shown in FIG. 1 is used, and a 4N-level bulk metal raw material 200307060 2 is put into an anode bag 3 as an anode 5, and the cathode 4 is a metal of the same kind as the high-purity metal or other Metal materials for electrolysis. The metal raw material contains impurities such as metal elements, carbon, and oxygen other than high-purity metals. At the time of electrolysis, although it varies depending on the metal to be electrolyzed, it is generally implemented at a bath temperature of 10 to 70 ° C, a metal concentration of 20 to 120 g / L, and a current density of 0.1 to 10A / dm2. When the current density is low, for example, the productivity is poor when it is less than 0.1 A / dm2, and when the current density is too high, for example, it is more than 10A / dm2, nodule is liable to occur. Therefore, the current density is usually in the range of 0.1 to 10 A / dm2. However, as described above, the operating conditions vary depending on the type of metal to be electrolyzed, so it is not necessary to be limited to the above range. The anode 5 and the cathode 4 are separated by an anion exchange membrane 6, and the anode electrolyte 7 is intermittently or continuously withdrawn while circulating. The catholyte is separated from the external liquid (anolyte) through the anion exchange membrane 6. The extracted anolyte 7 is introduced into the solvent extraction tank 8. In the solvent extraction tank 8, other metal elements and other impurities in the electrolytic solution are removed. Thereby, the concentration of other metal elements in the electrolytic solution can be controlled below about 1 mg / L. After the solvent extraction, the highly-purified metal electrolyte is introduced into the cathode side intermittently or continuously, and used as the catholyte 9 for electrolytic recovery. The highly purified metal electrolyte after solvent extraction can be passed through a filter (not shown) such as activated carbon, if necessary. 200307060 The device has the effect of removing impurities from organic solvents or organic substances obtained from ion exchange membranes. X 'The electrolyte storage tank 9 in which the 1¾ purity metal electrolyte is temporarily stored in the solvent extraction tank to remove impurities such as other metal elements is temporarily stored. 丨 The high-purity metal electrolyte after the solvent extraction is temporarily stored in The electrolyte storage tank 9 is introduced into the cathode side intermittently or continuously from there, and is used as the catholyte 9 for electrolytic recovery. The current efficiency is 80 to 100%. As a result, an electrodeposited metal (precipitated at the cathode) having a purity of 5N or more can be obtained. That is, excluding the gas component of 4N or more (99.99% by weight), it is possible to reach 5N (99.999% by weight) or more depending on the material, and the content of impurities is 0: 100wtppm or less (depending on the material, it may reach 0: 30wtppm or less) , C, N, S, H are respectively less than 10 wtppm. Furthermore, vacuum melting such as electron beam melting can be performed on the electrolyzed metal obtained by electrolysis. By this vacuum melting, alkali metals such as Na, κ, and other volatile impurities and gas components can be effectively removed. (Examples and Comparative Examples) Hereinafter, examples of the present invention will be described. In addition, this embodiment is merely an example at best, and the present invention is not limited to this example. That is, within the scope of the technical idea of the present invention ', it also includes all aspects or modifications other than the embodiments. (Example 1) An electrolytic cell shown in FIG. 1 was used, and 1 kg of a bulk nickel material of 3N grade was used as an anode, and a cathode of 2N grade nickel plate was used for electrolysis. The contents of impurities in the raw materials are shown in Table 1. The nickel raw material mainly contains a lot of iron, carbon 200307060, oxygen and the like. This was carried out at a bath temperature of 50 ° C using a sulfuric acid-based electrolyte at pH 2 and a current density of 2 A / dm2. At the time of electrolysis, the Ni concentration on the anode side was 20 g / L. After electrolysis, it was extracted at a Ni concentration of 100 g / L. The extracted anolyte is introduced into the solvent extraction tank. Further, impurities such as the precipitate are removed by an activated carbon filter. Thereby, the iron concentration in the electrolytic solution can be controlled to be less than 1 mg / L. After the impurities are removed, this liquid is intermittently introduced to the cathode side, and is used as a cathode electrolytic solution for electrolytic recovery. The Ni concentration on the cathode side was 100 g / L, and the Ni concentration after electrolysis was 20 g / L. About 1 kg of electrodeposited nickel (precipitated at the cathode) was obtained. The purity reached 5N. That is, excluding the gas component is 5N (99.999% by weight) or more, the impurity is 0: 30wtppm or less, and C, N, and S are 10wtppm or less, respectively. Table 1 compares the above results with the raw materials. Table 1 wtppm
Fe Co Na K 0 C Ν s Ni原料 50 20 20 1 200 50 10 10 實施例1 2 <1 <0.1 <0.1 <10 <10 <10 <1 比較例1 50 20 <0.1 <0.1 60 <10 <10 <1 (比較例1) 使用圖1所示之電解槽，但不使用陰離子交換膜，且 不實施溶劑萃取。 以3N等級之塊狀鎳原料lkg當作陽極，陰極則使用 11 200307060 2N等級之鎳板，進行電解。原料之雜質的含量係示於表1 〇 於浴溫50°C，使用硫酸系電解液，於Ni濃度60g/L、 電流密度2A/dm2來實施。 將液之pH調整爲2。此時，不抽出陽極電解液’直接 讓電解持續進行。之後，得到電析鎳(於陰極析出）約1kg ° 以上之結果同樣示於表1。 如表1所示般，在實施例1中，原料鐵從50wtppm降 爲2wtppm、氧從200wtppm降爲未滿lOwtppm、碳從 50wtppm降爲未滿lOwtppm、其他N爲未滿lOwtppm、S未 滿 lwtppm、Na、K 分別未滿 O.lwtppm。 相對於此，以比較例1而言，C、N分別未滿lOwtppm 、S未滿lwtppm、Na、K分別未滿O.lwtppm，但鐵 50wtppm、鈷20wtppm、氧60wtppm，相較於實施例1在精 製效果差，特別是難以去除鐵與鈷。 (實施例2) 與實施例1同樣，使用圖1所示之電解槽，以90重量 %等級之純度的鈷破片原料lkg當作陽極，陰極則使用2N 等級之鈷板，進行電解。原料之雜質的含量係示於表2。於 鈷原料中主要含有許多的鎢、鈦、鐵、碳、氧等。 於浴溫50°C，使用硫酸系電解液，於pH2、電流密度 2A/dm2來實施。剛電解時，陽極側之Co濃度爲20g/L。電 解後，以Co濃度100g/L來抽出。 將所抽出之陽極電解液導入溶劑萃取槽。再者，將此 12 200307060 沉澱物等之雜質以活性碳過濾器來去除。藉此，電解液中 之鐵、鎢等之金屬元素雜質濃度可分別控制在lmg/L以下 〇 雜質去除後’將該液間歇地導入陰極側，當作陰極電 解液來使用進行電解採收。陰極側之Co濃度爲100g/L，電 解後之Co濃度則成爲20g/L以下。 得到電析鈷（於陰極析出）約lkg。純度達成5N。亦即， 不計氣體成分爲5Ν(99·999重量％)以上，雜質方面〇： lOwtppm以下，C，N，S分別爲lOwtppm以下。將以上的結果 與原料做對比，示於表2。 表2 wtppm(%表不以外） 2/1 W sT A1 Ti Fe Ni Co原料 2% 0.5% 0.5% 1% 3% 10 實施例2 <0.1 <0.1 0.3 0.2 1.0 3.0 wtppm(%表不以外） 2/2 · Ο c Ν S Co原料 1% 1% 0.2% 0.01% 實施例2 <10 <10 <10 <10 (實施例3) 與實施例1同樣，使用圖1所示之電解槽，以2N等級 之塊狀鐵原料1 kg當作陽極，陰極則使用2N等級之鐵板， 進行電解。原料之雜質的含量係示於表3。於鐵原料中主要 13 200307060 含有許多的鋁、砷、硼、鈷、鉻、鎳、鋅、銅、碳、氧等 〇 於浴溫50°C，使用硫酸系電解液，於PH2、電流密度 2A/dm2來實施。剛電解時，陽極側之鐵濃度爲20g/L。電解 後，以鐵濃度100g/L來抽出。 將所抽出之陽極電解液導入溶劑萃取槽。再者，將此 沉澱物等之雜質以活性碳過濾器來去除。藉此，電解液中 之鎳、鈷等之金屬元素雜質濃度可分別控制在lmg/L以下 〇 雜質去除後，將該液間歇地導入陰極側，當作陰極電 解液來使用進行電解採收。陰極側之鐵濃度爲100g/L，電 解後之鐵濃度則成爲20g/L以下。 得到電析鐵（於陰極析出）約lkg。純度達成5N。亦即， 不計氣體成分爲5N(99.999重量％)以上，雜質方面〇： 20wtppm，C，N，S也分別在lOwtppm以下。將以上的結果與 原料做對比，示於表3。 表3 wtppm A1 As B Co Cr Ni Zn Cu 0 C N S H Fe原料 45 32 20 54 5 80 35 40 10 50 40 10 10 實施例3 <1 <1 <1 2 <1 <1 <1 <1 20 <10 <10 <10 <10 (實施例4)Fe Co Na K 0 C Ν s Ni raw material 50 20 20 1 200 50 10 10 Example 1 2 < 1 < 0.1 < 0.1 < 10 < 10 < 10 < 1 Comparative example 1 50 20 < 0.1 < 0.1 60 < 10 < 10 < 1 (Comparative Example 1) An electrolytic cell shown in Fig. 1 was used, but an anion exchange membrane was not used, and solvent extraction was not performed. 1 kg of 3N grade bulk nickel raw material is used as the anode, and the cathode uses 11 200307060 2N grade nickel plate for electrolysis. The content of impurities in the raw materials is shown in Table 10. The bath temperature was 50 ° C., and the sulfuric acid-based electrolyte was used at a Ni concentration of 60 g / L and a current density of 2 A / dm 2. The pH of the solution was adjusted to 2. At this time, the electrolysis was continued without extracting the anolyte '. Thereafter, the results of obtaining electrolytic nickel (precipitated at the cathode) of about 1 kg ° or more were also shown in Table 1. As shown in Table 1, in Example 1, the raw material iron was reduced from 50wtppm to 2wtppm, oxygen was reduced from 200wtppm to less than 10wtppm, carbon was reduced from 50wtppm to less than 10wtppm, other N was less than 10wtppm, and S was less than 1wtppm , Na, K are less than 0.1 wtppm. In contrast, in Comparative Example 1, C and N were less than 10 wtppm, S was less than 1 wtppm, Na and K were less than 0.1 wtppm, but 50 wtppm of iron, 20 wtppm of cobalt, and 60 wtppm of oxygen were compared to Example 1. Poor refining effect, especially difficult to remove iron and cobalt. (Example 2) In the same manner as in Example 1, an electrolytic cell shown in FIG. 1 was used, and 1 kg of cobalt fragment raw material with a purity of 90% by weight was used as an anode, and a cathode of 2N grade cobalt plate was used for electrolysis. The content of impurities in the raw materials is shown in Table 2. The cobalt raw material mainly contains a lot of tungsten, titanium, iron, carbon, and oxygen. This was carried out at a bath temperature of 50 ° C using a sulfuric acid-based electrolyte at pH 2 and a current density of 2 A / dm2. At the time of electrolysis, the Co concentration on the anode side was 20 g / L. After electrolysis, it was extracted at a Co concentration of 100 g / L. The extracted anolyte is introduced into the solvent extraction tank. In addition, impurities such as this 12 200307060 precipitate were removed with an activated carbon filter. Thereby, the concentration of impurities of metallic elements such as iron and tungsten in the electrolytic solution can be controlled to be less than 1 mg / L, respectively. After the impurities are removed, the liquid is intermittently introduced into the cathode side and used as a cathode electrolyte for electrolytic recovery. The Co concentration on the cathode side was 100 g / L, and the Co concentration after electrolysis was 20 g / L or less. About 1 kg of electrodeposited cobalt (precipitated at the cathode) was obtained. The purity reached 5N. That is, excluding the gas component is 5N (99.999% by weight) or more, and in terms of impurities 0: 10 wtppm or less, C, N, and S are 10 wtppm or less, respectively. The above results are compared with the raw materials and are shown in Table 2. Table 2 wtppm (% not shown) 2/1 W sT A1 Ti Fe Ni Co raw material 2% 0.5% 0.5% 1% 3% 10 Example 2 < 0.1 < 0.1 0.3 0.2 1.0 3.0 wtppm (% not shown) ) 2/2 · Ο c Ν S Co raw material 1% 1% 0.2% 0.01% Example 2 < 10 < 10 < 10 < 10 (Example 3) Same as Example 1, using FIG. 1 In the electrolytic cell, 1 kg of 2N-grade bulk iron material is used as the anode, and 2N-grade iron plates are used for the cathode for electrolysis. The content of impurities in the raw materials is shown in Table 3. Mainly in iron raw materials 13 200307060 Contains a lot of aluminum, arsenic, boron, cobalt, chromium, nickel, zinc, copper, carbon, oxygen, etc. 0 At a bath temperature of 50 ° C, using a sulfuric acid-based electrolyte at PH2 and a current density of 2A / dm2 to implement. Immediately after electrolysis, the iron concentration on the anode side was 20 g / L. After electrolysis, it was extracted at an iron concentration of 100 g / L. The extracted anolyte is introduced into the solvent extraction tank. Further, impurities such as the precipitate are removed by an activated carbon filter. Thereby, the concentration of impurities of metallic elements such as nickel and cobalt in the electrolytic solution can be controlled to be less than 1 mg / L, respectively. After the impurities are removed, the liquid is intermittently introduced to the cathode side and used as a cathode electrolyte for electrolytic recovery. The iron concentration on the cathode side was 100 g / L, and the iron concentration after electrolysis was 20 g / L or less. About 1 kg of electrolyzed iron (precipitated at the cathode) was obtained. The purity reached 5N. That is, excluding the gas component is 5N (99.999% by weight) or more, and in terms of impurities 0: 20wtppm, C, N, and S are also each 10wtppm or less. Table 3 shows the comparison between the above results and the raw materials. Table 3 wtppm A1 As B Co Cr Ni Zn Cu 0 CNSH Fe raw material 45 32 20 54 5 80 35 40 10 50 40 10 10 Example 3 < 1 < 1 < 1 2 < 1 < 1 < 1 < 1 20 < 10 < 10 < 10 < 10 (Example 4)
與實施例1同樣，使用圖1所示之電解槽，以90重量 %等級之純度之銦破片原料lkg當作陽極，陰極則使用2N 14 200307060 等級之銦板，進行電解。原料之雜質的含量係示於表4。於 銦原料中主要含有許多的鉍、銻、鉛、鐵、鋅、銀、銅、 銘、碳、氧等。 於浴溫50°C，使用鹽酸系電解液，於pH2、電流密度 2A/dm2來實施。剛電解時，陽極側之銦濃度爲2〇g/L。電解 後，以銦濃度l〇〇g/L來抽出。As in Example 1, the electrolytic cell shown in FIG. 1 was used, and 1 kg of indium fragment material with a purity of 90% by weight was used as the anode, and the cathode was electrolyzed using an indium plate of the 2N 14 200307060 grade. The content of impurities in the raw materials is shown in Table 4. The indium raw materials mainly contain many bismuth, antimony, lead, iron, zinc, silver, copper, metal, carbon, oxygen and so on. This was carried out at a bath temperature of 50 ° C using a hydrochloric acid-based electrolyte at pH 2 and a current density of 2 A / dm2. Immediately after electrolysis, the indium concentration on the anode side was 20 g / L. After electrolysis, it was extracted at an indium concentration of 100 g / L.
將所抽出之陽極電解液導入溶劑萃取槽。再者，將此 沉澱物等之雜質以活性碳過濾器來去除。藉此，電解液中 之金屬元素雜質濃度可分別控制在lmg/L以下。 雜質去除後，將該液間歇地導入陰極側，當作陰極電 解液來使用進行電解採收。陰極側之銦濃度爲l〇〇g/L，電 解後之銦濃度則成爲20g/L以下。The extracted anolyte is introduced into the solvent extraction tank. Further, impurities such as the precipitate are removed by an activated carbon filter. Thereby, the concentration of metal element impurities in the electrolytic solution can be controlled below 1 mg / L, respectively. After the impurities are removed, this liquid is intermittently introduced to the cathode side, and is used as a cathode electrolytic solution for electrolytic recovery. The indium concentration on the cathode side was 100 g / L, and the indium concentration after electrolysis became 20 g / L or less.
得到電析銦（於陰極析出）約lkg。純度達成4N。亦即， 不計氣體成分爲4Ν(99·99重量％)以上，雜質方面〇： 20wtppm，C，N，S也分別在lOwtppm以下。將以上的結果與 原料做對比，示於表4。 表4 wtppm(%表示以外） 4/1About 1 kg of electrolyzed indium (precipitated at the cathode) was obtained. The purity reached 4N. That is, excluding the gas component is 4N (99.99% by weight) or more, and in terms of impurities 0: 20wtppm, C, N, and S are each 10wtppm or less. Table 4 shows the results of the above comparison with the raw materials. Table 4 wtppm (except for%) 4/1
Bi Sb Pb Fe Cu Zn Mn Ag A1 In原料 500 600 80 5% 1% 40 8 5 2% 實施例4 5 2 3 <1 2 1 <1 <1 <1 wtppm(%表示以外) Ο c N s H In原料 1% 0.1% 100 0.1% <10 實施例4 20 <10 <10 <10 <10 15 200307060 (實施例5) 與實施例1同樣，使用圖1所示之電解槽，以4N等級 純度之銅原料lkg當作陽極，陰極則使用2N等級之銅板， 進行電解。原料之雜質的含量係示於表5。於銅原料中主要 含有許多的鐵、鉻、鎳、銀、鋁、銻、硒、矽、硫、氧等 〇 於浴溫50°C，使用硝酸系電解液，於PH2、電流密度 2A/dm2來實施。剛電解時，陽極側之銅濃度爲20g/L。電解 後，以銅濃度l〇〇g/L來抽出。 將所抽出之陽極電解液導入溶劑萃取槽。再者，將此 沉澱物等之雜質以活性碳過濾器來去除。藉此，電解液中 之金屬元素雜質濃度可分別控制在lmg/L以下。 雜質去除後，將該液間歇地導入陰極側，當作陰極電 解液來使用進行電解採收。陰極側之銅濃度爲l〇〇g/L，電 解後之銅濃度則成爲20g/L以下。 得到電析銅（於陰極析出）約lkg。純度達成6N。亦即， 不計氣體成分爲6N(99.9999重量％)以上，雜質方面〇，S : lwtppm以下，C，N，S也分別在lOwtppm以下。將以上的結 果與原料做對比，示於表5。 表5 wtppm 5/1Bi Sb Pb Fe Cu Zn Mn Ag A1 In raw material 500 600 80 5% 1% 40 8 5 2% Example 4 5 2 3 < 1 2 1 < 1 < 1 < 1 wtppm (except for%) 〇 c N s H In raw material 1% 0.1% 100 0.1% < 10 Example 4 20 < 10 < 10 < 10 < 10 15 200307060 (Example 5) Same as Example 1, using FIG. 1 In the electrolytic cell, 1 kg of copper raw material of 4N grade was used as the anode, and 2N grade copper plate was used for the cathode for electrolysis. The content of impurities in the raw materials is shown in Table 5. The copper raw material mainly contains a lot of iron, chromium, nickel, silver, aluminum, antimony, selenium, silicon, sulfur, oxygen, etc. 0 at a bath temperature of 50 ° C, using a nitric acid electrolyte, at PH2, current density 2A / dm2 To implement. At the time of electrolysis, the copper concentration on the anode side was 20 g / L. After electrolysis, it was extracted at a copper concentration of 100 g / L. The extracted anolyte is introduced into the solvent extraction tank. Further, impurities such as the precipitate are removed by an activated carbon filter. Thereby, the concentration of metal element impurities in the electrolytic solution can be controlled below 1 mg / L, respectively. After the impurities are removed, this liquid is intermittently introduced to the cathode side, and is used as a cathode electrolytic solution for electrolytic recovery. The copper concentration on the cathode side was 100 g / L, and the copper concentration after electrolysis was 20 g / L or less. About 1 kg of electrodeposited copper (precipitated at the cathode) was obtained. The purity reached 6N. That is, excluding gas components of 6N (99.9999% by weight) or more, in terms of impurities, 0, S: 1 wtppm or less, and C, N, S are also 10 wtppm or less. Table 5 compares the above results with the raw materials. Table 5 wtppm 5/1
Fe Cr Ni Ag A1 Sb As Se Si Cu原料 20 1 2 4 5 7 4 8 2 實施例5 <0.1 <0.1 <0.1 0.1 <0.1 <0.1 <0.1 0.4 <0.1 16 200307060 wtppm 5/2 0 C N S Η Cu原料 20 10 10 5 <10 一實施例5 <1 <10 1 <10 <1 <10 由以上可知，如本發明般將陽極與陰極以陰離子交換 膜來分隔，將陽極電解液以間歇或連續的方式抽出，對其 以有機溶劑來去除金屬元素等之雜質，進一步利用過濾器 來去除雜質，而將去除後之液體以間歇或連續的方式導入 陰極側做電解採收，可有效地去除金屬元素等之雜質，得 到高純度金屬，且屬簡便之方法，效果極佳。 發明效果 如以上所示，本發明可提供一種使用含有高純度化用 金屬之溶液做爲電解液，自含有許多其他金屬元素、非金 屬、碳、氧等之金屬原料，使用含有電解用金屬之溶液進 行電解採收之簡便的方法，藉由簡便之製程的改良’可從 前述原料有效率地製造出純度4Ν(99·99重量％)以上或是 5Ν(99.999重量％)以上之高純度金屬，此爲其顯著效果所在 【圖式簡單說明】 (一） 圖式部分 圖1所示係電解製程之示意圖。 (二） 元件代表符號 1 電解槽 金屬原料 17 2 200307060 3 4 5 6 7 8 9 陽極袋 陰極 陽極 陰離子交換膜 陽極電解液 溶劑萃取槽 陰極電解液Fe Cr Ni Ag A1 Sb As Se Si Cu raw material 20 1 2 4 5 7 4 8 2 Example 5 < 0.1 < 0.1 < 0.1 0.1 < 0.1 < 0.1 < 0.1 0.4 < 0.1 16 200307060 wtppm 5 / 2 0 CNS Η Cu raw material 20 10 10 5 < 10 Example 5 < 1 < 10 1 < 10 < 1 < 10 As can be seen from the above, the anode and cathode are anion exchange membranes as in the present invention. To separate, the anolyte is extracted intermittently or continuously, and the organic solvent is used to remove impurities such as metal elements. Further, the filter is used to remove impurities, and the removed liquid is introduced into the cathode intermittently or continuously. Electrolytic recovery on the side can effectively remove impurities such as metal elements and obtain high-purity metals. It is a simple method with excellent results. Effects of the Invention As shown above, the present invention can provide a solution containing a high-purity metal as an electrolyte, a metal raw material containing many other metal elements, nonmetals, carbon, oxygen, etc. A simple method for electrolytic recovery of a solution. Through the improvement of a simple process, high-purity metals with a purity of 4N (99.99% by weight) or 5N (99.999% by weight) can be efficiently produced from the aforementioned raw materials. This is where the significant effect lies. [Simplified description of the diagram] (1) The schematic diagram of the electrolytic process shown in Figure 1 in the diagram part. (II) Symbols for components 1 Electrolytic cell Metal materials 17 2 200307060 3 4 5 6 7 8 9 Anode bag Cathode Anode Anion exchange membrane Anode electrolyte Solvent extraction tank Catholyte
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