TWI252875B - Method and device for producing high-purity metal - Google Patents

Abstract

A method of producing a high-purity metal is characterized by comprising the step of, when metal-containing solution is used as an electrolyte in electrolyzing, partitioning an anode from a cathode by a negative ion exchange membrane, intermittently or continuously extracting an anolyte for introduction into a solvent extraction tank, and intermittently or continuously introducing toward the cathode a high-purity metal electrolyte having impurities such as iron removed in the solvent extraction tank. A simple method of effecting electrolysis from a metal material containing large amounts of iron, carbon and oxygen by using a metal-containing solution is provided, which is capable of efficiently producing a high-purity metal having a purity of at least 4N (99.99 wt.%) or at least 5N (99.999 wt.%).

Description

1252875 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g 【先前技術】 一般，鎳、站、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。1252875 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明High-purity metals such as nickel, station, iron, indium, and copper are required to reduce alkali metal, radioactive elements, transition metal elements, and gas components as much as possible, in the formation of electrodes and wirings in VLSI, in compound semiconductors or in magnetic films. In terms of formation, particularly as a sputtering target, the scope of use is quite wide.

Na、K等之鹼金屬在閘極絕緣膜中容易移動，會成爲 M〇S_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濺鍍之際之粒子 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。 1252875 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 1252875 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 1252875 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 Ο.ΙΑ/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）。 1252875 活性碳之過濾器，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。 又，設置可將以溶劑萃取槽去除其他金屬元素等之雜 質之高純度金屬電解液暫時存放之電解液儲槽9，進行循環 。此時，溶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：lOOwtppm以下（依材料有可能達〇：30wtppm以 下）、C,N，S，H分別爲lOwtppm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、K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 1252875 、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Νι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Νι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 wtppmThe alkali metal such as Na or K easily moves in the gate insulating film, which may cause deterioration of the interface characteristics of M〇S_LSI. The radioactive elements of U, Th, etc., which are emitted by the alpha ray, may be the cause of the soft error of the component. On the other hand, when a material such as nickel, cobalt or copper is used as a wiring material for a semiconductor, depending on the place to be used, a transition metal element such as Fe may cause a problem of the interface joint portion. Further, since the gas component such as carbon or oxygen is considered to be a cause of particles generated during sputtering, it is not desirable. Usually, when a high-purity metal such as nickel, cobalt, iron, indium or copper of 5N grade is produced, the solution is generally purified by ion exchange or solvent extraction, and the obtained product is further subjected to electrolytic recovery or electrolytic refining. For the purpose of high purity, but the solvent extraction process is carried out in advance, the process is complicated and requires a special solvent, so it is not efficient, and this is the problem. 1252875 Further, when a high-purity metal such as nickel, cobalt, iron, indium or copper of 5N grade is produced, it is considered to be a relatively simple method of electrolysis using a solution containing the metals, but for example, 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 it cannot be said that it is efficient. SUMMARY OF THE INVENTION An object of the present invention is to provide a simple method for electrolysis from a metal material containing nickel, cobalt, iron, indium, copper, or the like containing many other metal elements, carbon, oxygen, or the like, using a solution containing the metal. A technique for efficiently producing a high purity metal having a purity of 5 N (99.999 wt%) or more from the raw material is provided. In order to solve the above problems, the present inventors have obtained the following findings: an anolyte from a metal-containing solution removes other metal elements and other impurities by solvent extraction, and the removed liquid is used as a catholyte, which can be high. Efficiently manufacture high purity metals. Based on this finding, the present invention provides: 1. A method for producing a high-purity metal, characterized in that an anode and a cathode are anion exchange membranes when electrolysis is carried out using a solution containing a metal for high purity as an electrolyte. Separation, the anolyte is intermittently or continuously withdrawn and introduced into a solvent extraction tank, and the impurities are removed by the solvent extraction tank, and the high-purity metal electrolyte after the impurities are removed is introduced into the cathode side in a batch or continuous manner. 2. The method for producing a high-purity metal according to the above 1, wherein the melting of the metal raw material and the recovery of the metal are simultaneously performed in a single electrolytic cell, and separated by an ion exchange membrane of 1,252,875. 3. The method for producing a high-purity metal according to the above 1 or 2, wherein the high-purity metal electrolyte having the impurities removed by the solvent extraction tank is temporarily stored, and the high-purity metal electrolyte is introduced into the cathode side intermittently or continuously. 4. The method for producing a high-purity metal according to any one of the above 1 to 3, wherein the anolyte and the catholyte are circulated. Further, the present invention provides: 5. A high-purity metal manufacturing apparatus for producing high-purity metal by electrolysis; characterized by: an anode bag filled with a metal material; and an anode and a cathode are separated Anion exchange membrane; a cathode for precipitating high-purity metal; a solvent extraction tank for removing impurities from a metal melt solution (anolyte); a device for introducing the anolyte intermittently or continuously into a solvent extraction tank; and, using a solvent The high-purity metal electrolyte obtained by the extraction is introduced into the device on the cathode side in a batch or continuous manner; 6. The apparatus for producing a high-purity metal according to the above 5, wherein the melting of the metal raw material and the recovery of the metal are carried out in a single electrolytic cell and separated by an ion exchange membrane. 7. The apparatus for producing a high-purity metal according to the above 5 or 6, which further comprises an electrolyte storage tank for temporarily storing a high-purity metal electrolytic solution in which impurities are removed by a solvent extraction tank. 8. The apparatus for producing a high-purity metal according to any one of the above 5 to 7, which is characterized in that the anolyte and the catholyte are circulated. [Embodiment] Using the electrolytic cell 1 shown in Fig. 1, a 4N grade bulk metal material 1252875 2 is placed in the anode bag 3 as the anode 5, and the cathode 4 is made of the same metal as the high purity metal or the like. Metal materials are used for electrolysis. The metal raw material contains impurities such as metal elements other than high-purity metals, carbon, oxygen, and the like. In the case of electrolysis, it differs depending on the metal to be electrolyzed, but is substantially carried out 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 ΙΟΑ/dm 2 . When the current density is low, for example, when the temperature is less than ΙΑ.ΙΑ/dm2, the productivity is poor, and if the current density is too high, for example, when the temperature exceeds ΙΟΑ/dm2, nodule is likely to occur. Therefore, the current density is usually in the range of 0.1 to ΙΟΑ/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 extracted while circulating. The cathode electrolyte is separated from the liquid (anolyte) on the outside by 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 in the electrolyte and other impurities are removed. Thereby, the concentration of other metal elements in the electrolyte can be controlled to be less than about 1 mg/L. The highly purified metal electrolyte after solvent extraction 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 may pass through a filter (not shown) such as activated carbon as necessary. 1252875 A filter for activated carbon having the effect of removing impurities generated by an organic solvent or an organic material obtained by an ion exchange membrane. Further, an electrolyte storage tank 9 for temporarily storing a high-purity metal electrolyte which removes impurities such as other metal elements in a solvent extraction tank is provided and circulated. At this time, the highly purified metal electrolyte after solvent extraction is temporarily stored in the electrolytic solution storage tank 9, and is introduced into the cathode side intermittently or continuously from there, and used as the catholyte 9 to perform electrolytic recovery. The current efficiency is 80 to 100%. Thereby, an electrodeposited metal having a purity of 5 N or more (precipitated at the cathode) can be obtained. That is, regardless of the gas composition of 4N or more (99.99% by weight), depending on the material, it may be 5N (99.999% by weight) or more, and the impurity 〇: lOOwtppm or less (depending on the material may reach 30: 30wtppm or less), C, N , S, H are respectively below 10 wtppm. Further, vacuum melting of electron beam melting or the like by electrolysis of the metal obtained by electrolysis can be performed. By this vacuum melting, alkali metals such as Na, K, and the like, and other volatile impurities and gas components can be effectively removed. (Embodiment and Comparative Example) Hereinafter, an embodiment of the present invention will be described. Further, the present embodiment is merely an example, and the present invention is not limited to this example. That is, all aspects or variations other than the embodiments are also included in the scope of the technical idea of the present invention. (Example 1) Using the electrolytic cell shown in Fig. 1, a bulk nickel raw material lkg of 3N grade was used as an anode, and a cathode of 2N grade nickel plate was used for electrolysis. The contents of the impurities of the raw materials are shown in Table 1. The nickel raw material mainly contains a lot of iron, carbon 1252875, oxygen and the like. This was carried out at a bath temperature of 50 ° C using a sulfuric acid-based electrolytic solution at pH 2 and a current density of 2 A/dm 2 . At the time of electrolysis, the Ni concentration on the anode side was 20 g/L. After electrolysis, it was extracted at a concentration of 100 g/L. The extracted anolyte is introduced into a solvent extraction tank. Further, impurities such as the precipitate are removed by an activated carbon filter. Thereby, the concentration of iron in the electrolyte can be controlled to be 1 mg/L or less. After the impurities were removed, the liquid was intermittently introduced into the cathode side, and used as a cathode electrolyte to carry out electrolytic recovery. The concentration of Ni on the cathode side was 100 g/L, and the concentration of ITO after electrolysis was 20 g/L. Electrodeposited nickel (precipitated at the cathode) was obtained in about lkg. The purity reached 5N. That is, the gas component is 5 N (99.999 wt%) or more, the impurity is 30 wtppm or less, and C, N, and S are 10 wtppm or less, respectively. The above results are compared with the raw materials and are shown in Table 1. 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 1252875 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5(TC，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lkg。 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 1 wtppm、Na、K 分別未滿 0.1 wtppm。 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、姑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 1252875 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 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5N(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(%表示以外） 2/1 W Si 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(%表示以外） 2/2 Ο c N S Co原料 1% 1% 0.2% 0.01% 實施例2 <10 <10 <10 <10Fe 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 < 10 < 1 Comparative Example 1 50 20 < 0.1 < 0.1 60 < 10 < 10 < 1 (Comparative Example 1) The electrolytic cell shown in Fig. 1 was used, but an anion exchange membrane was not used, and solvent extraction was not carried out. The bulk nickel raw material lkg of 3N grade is used as the anode, and the cathode is electrolyzed by using the nickel plate of 11 1252875 2N grade. The content of the impurities of the raw materials is shown in Table 1. The bath temperature was 5 (TC, using a sulfuric acid-based electrolyte, and the Ni concentration was 60 g/L, and the current density was 2 A/dm2. The pH of the liquid was adjusted to 2. The electrolysis was continued without withdrawing the anolyte, and then nickel was electrolyzed (precipitated at the cathode) to about lkg. The above results are also shown in Table 1. As shown in Table 1, in Example 1, the raw material iron was used. From 50 wtppm to 2 wtppm, oxygen from 200 wtppm to less than 10 wtppm, carbon from 50 wtppm to less than 10 wtppm, other N to less than 10 wtppm, S less than 1 wtppm, and Na, K less than 0.1 wtppm, respectively. In Comparative Example 1, C and N are less than 10 wtppm, S is less than 1 wtppm, and Na and K are less than 0.1 wt%, respectively, but iron is 50 wtppm, 20 wtppm, and oxygen is 60 wtppm, which is inferior to the first embodiment. In particular, it is difficult to remove iron and cobalt. (Example 2) As in Example 1, using the electrolytic cell shown in Fig. 1, a cobalt fragment raw material lkg of a purity of 90% by weight was used as an anode, and a cathode of 2N was used. The cobalt plate was subjected to electrolysis. The content of impurities in the raw materials is shown in Table 2. The material mainly contains a large amount of tungsten, titanium, iron, carbon, oxygen, etc. It is 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/dm 2 . It is 20 g/L. After electrolysis, it is extracted at a Co concentration of 100 g/L. The extracted anolyte is introduced into a solvent extraction tank. Further, impurities such as 12 1252875 precipitate are removed by an activated carbon filter. Therefore, the impurity concentration of the metal element such as iron or tungsten in the electrolytic solution can be controlled to be less than 1 mg/L, and the liquid is intermittently introduced into the cathode side, and used as a catholyte for electrolytic recovery. The Co concentration is 100 g/L, and the Co concentration after electrolysis is 20 g/L or less. The electrodeposited cobalt (precipitated at the cathode) is about lkg, and the purity is 5 N. That is, the gas component is 5 N (99.999 wt%) or more. In terms of impurities, l: lOwtppm or less, C, N, and S are respectively below 10 wtppm. The above results are compared with raw materials and are shown in Table 2. Table 2 wtppm (except for %) 2/1 W Si 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 (except for %) 2/2 Ο c N S Co raw material 1% 1% 0.2% 0.01% Example 2 <10 <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lkg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 1252875 含有S午多的錦、神、砸、銘、絡、錬、鉢、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)(Example 3) In the same manner as in Example 1, the electrolytic cell shown in Fig. 1 was used, and a block-shaped iron raw material lkg of 2N grade was used as an anode, and a cathode of 2N grade was used for electrolysis. The content of the impurities of the raw materials is shown in Table 3. In the iron raw material, the main 13 1252875 contains S, 砸, 砸, Ming, 錬, 錬, 钵, copper, carbon, oxygen, etc. at a bath temperature of 50 ° C, using a sulfuric acid electrolyte, at pH 2, current The density is 2A/dm2 to implement. At the time of electrolysis, the iron concentration on the anode side was 20 g/L. After electrolysis, it was extracted with an iron concentration of 100 g/L. The extracted anolyte is introduced into a solvent extraction tank. Further, impurities such as the precipitate are removed by an activated carbon filter. Thereby, the concentration of the metal element impurities such as nickel or cobalt in the electrolytic solution can be controlled to be 1 mg/L or less. 〇 After the impurities are removed, the liquid is intermittently introduced into the cathode side, and used as a cathode electrolyte to carry out 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. Electrodeposited iron (precipitated at the cathode) was obtained in about lkg. The purity reached 5N. That is, the gas component is 5 N (99.999 wt%) or more, and the impurity is 20 wtppm, and C, N, and S are also 10 wtppm or less. The above results are compared with the raw materials and are shown in Table 3. Table 3 wtppm A1 As B Co Cr Ni Zn Cu 0 c NSH 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 <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 1252875 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、 錦、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20g/L。電解 後，以銦濃度l〇〇g/L來抽出。In the same manner as in Example 1, using an electrolytic cell shown in Fig. 1, an indium fragment raw material lkg of a purity of 90% by weight was used as an anode. A cathode was used for electrolysis using a 2N 14 1252875 grade indium plate. The content of the impurities of the raw materials is shown in Table 4. Indium raw materials mainly contain many kinds of antimony, bismuth, lead, iron, zinc, silver, copper, bromine, carbon, oxygen and the like. This was carried out at a bath temperature of 50 ° C using a hydrochloric acid-based electrolytic solution at pH 2 and a current density of 2 A/dm 2 . At the time of electrolysis, the indium concentration on the anode side was 20 g/L. After electrolysis, it was extracted with an indium concentration of l〇〇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 a solvent extraction tank. Further, impurities such as the precipitate are removed by an activated carbon filter. Thereby, the metal element impurity concentration in the electrolytic solution can be controlled to be 1 mg/L or less, respectively. After the impurities were removed, the liquid was intermittently introduced into the cathode side, and used as a cathode electrolyte to carry out electrolytic recovery. The indium concentration on the cathode side is l〇〇g/L, and the indium concentration after electrolysis is 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4N(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） 4/1An indium (precipitated at the cathode) of about lkg is obtained. The purity reached 4N. That is, the gas component is 4 N (99.99 wt%) or more, and the impurity is 20 wtppm, and C, N, and S are also 10 wtppm or less. The above results are compared with the raw materials and are shown in Table 4. Table 4 wtppm (% other than) 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） 4/2 Ο C Ν s Η In原料 1% 0.1% 100 0.1% <10 實施例4 20 <10 <10 <10 <10 15 1252875 (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100g/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 (% other than) 4 /2 Ο C Ν s Η In raw material 1% 0.1% 100 0.1% <10 Example 4 20 <10 <10 <10 <10 <10 15 1252875 (Example 5) As in Example 1, the use chart The electrolytic cell shown in Fig. 1 uses a copper raw material lkg of 4N grade purity as an anode, and a cathode uses a 2N grade copper plate for electrolysis. The content of the impurities of the raw materials is shown in Table 5. The copper raw material mainly contains a lot of iron, chromium, nickel, silver, aluminum, antimony, selenium, antimony, sulfur, oxygen, etc. at a bath temperature of 50 ° C, using a nitric acid electrolyte ' at pH 2, current density 2 A / dm 2 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 a solvent extraction tank. Further, impurities such as the precipitate are removed by an activated carbon filter. Thereby, the metal element impurity concentration in the electrolytic solution can be controlled to be 1 mg/L or less, respectively. After the impurities were removed, the liquid was intermittently introduced into the cathode side, and used as a cathode electrolyte to carry out 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. An electrolytic copper (precipitated at the cathode) was obtained in about lkg. The purity reached 6N. That is, the gas component is 6 N (99.9999 wt%) or more, the impurity is 〇, S: lwtppm or less, and C, N, and S are also 10 wtppm or less. The above results are compared with the raw materials and are shown in Table 5. 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 1252875 wtppm 5/2 0 C N S Η Cu原料 20 10 10 5 <10 實施例5 <1 <10 <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4N(99.99重量％)以上或是 5N(99.999重量％)以上之高純度金屬，此爲其顯著效果所在 〇 【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 2 金屬原料 1252875 3 陽極袋 4 陰極 5 陽極 6 陰離子交換膜 7 陽極電解液 8 溶劑萃取槽 9 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 1252875 wtppm 5 /2 0 CNS Η Cu raw material 20 10 10 5 < 10 Example 5 < 1 < 10 < 10 < 10 < 1 < 10 From the above, the anode and the cathode are separated by an anion exchange membrane as in the present invention The anolyte is extracted in a batch or continuous manner, and an organic solvent is used to remove impurities such as metal elements, and a filter is further used to remove impurities, and the removed liquid is introduced into the cathode side in a batch or continuous manner. Electrolytic recovery can effectively remove impurities such as metal elements and obtain high-purity metals, and is a simple method with excellent effect. Advantageous Effects of Invention As described above, the present invention can provide a solution using a metal containing a high purity metal as an electrolytic solution, and a metal material containing many other metal elements, nonmetals, carbon, oxygen, etc., using a metal containing electrolysis. A simple method for electrolytically recovering a solution, and a high-purity metal having a purity of 4N (99.99% by weight) or more or 5N (99.999% by weight) or more can be efficiently produced from the above-mentioned raw materials by a simple process improvement. For its significant effect 〇 [Simple description of the schema] (1) Schematic diagram of the electrolysis process shown in Figure 1. (2) Component symbol 1 Cell 2 Metal material 1252875 3 Anode bag 4 Cathode 5 Anode 6 Anion exchange membrane 7 Anode electrolyte 8 Solvent extraction tank 9 Catholyte

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Claims (1)

1252875 拾、申請專利範圍 … έ ' . ’ …丨 1. 一種高純度金屬之製造方法，其薇SiT:便用含有 高純度化用金屬之溶液做爲電解液進行電解之際，電解係 以浴溫10〜70 °C、金屬濃度20〜120g/L、電流密度 0.1〜ΙΟΑ/dm2來實施，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，使得陽極電解 液以及陰極電解液做循環。 2. 如申請專利範圍第1項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，且以離子交換膜來分離。 3. 如申請專利範圍第1或2項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. 一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： 陽極袋3裝有金屬原料2之陽極5; 使得高純度金屬析出之陰極4 ; 將陽極5與陰極4做分隔之陰離子交換膜6 ; 自陽極5側之金屬熔解液（陽極電解液）去除雜質之溶劑 萃取槽8 ; 將陽極電解液間歇或連續地抽出而導入溶劑萃取槽8 19 1252875 之裝置；以及 將利用溶劑萃取槽8之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4側之裝置 所構成。 5. 如申請專利範圍第4項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。 6. 如申請專利範圍第4或5項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。 7. 如申請專利範圍第4或5項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 〇 8. 如申請專利範圍第6項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。 拾壹、圖式 如次頁1252875 Picking up, applying for a patent range... έ ' . ' ... 丨 1. A method for producing a high-purity metal, which is a bath of electrolysis with a solution containing a metal of high purity for electrolysis. The temperature is 10 to 70 ° C, the metal concentration is 20 to 120 g/L, and the current density is 0.1 to ΙΟΑ/dm2. The anode and the cathode are separated by an anion exchange membrane, and the anolyte is intermittently or continuously withdrawn and introduced into the solvent extraction tank. The impurities are removed by the solvent extraction tank, and the high-purity metal electrolyte after the impurities are removed is introduced into the cathode side in a batch or continuous manner, so that the anolyte and the catholyte are circulated. 2. The method for producing a high-purity metal according to the first aspect of the patent application, wherein the melting of the metal raw material and the metal are simultaneously carried out in a single electrolytic cell, and are separated by an ion exchange membrane. 3. The method for producing a high-purity metal according to the first or second patent application is to temporarily store a high-purity metal electrolyte having impurities removed by a solvent extraction tank, and introduce the high-purity metal electrolyte into the cathode in a batch or continuous manner. side. 4. A high-purity metal manufacturing apparatus for producing high-purity metal by electrolysis; characterized by: an anode bag 3 containing an anode 5 of a metal material 2; a cathode 4 for precipitating high-purity metal; and an anode 5 Anion exchange membrane 6 separated from cathode 4; solvent extraction tank 8 for removing impurities from metal melt (anolyte) on the anode 5 side; intermittent or continuous extraction of anolyte into solvent extraction tank 8 19 1252875 And a device for introducing a high-purity metal electrolyte obtained by solvent extraction of the solvent extraction tank 8 into the cathode 4 side in a batch or continuous manner. 5. The apparatus for manufacturing a high-purity metal according to item 4 of the patent application, wherein the melting of the metal raw material and the recovery of the metal are carried out in a single electrolytic cell and separated by an ion exchange membrane. 6. The manufacturing apparatus of the high-purity metal according to the fourth or fifth aspect of the patent application, wherein the electrolyte storage tank for temporarily storing the high-purity metal electrolyte having the impurities removed by the solvent extraction tank is provided. 7. A manufacturing apparatus for a high-purity metal according to claim 4 or 5, which is provided with a device for circulating an anolyte and a catholyte. 8. A manufacturing apparatus for high-purity metal according to claim 6 A device for circulating an anolyte and a catholyte. Pick up, pattern, such as the next page