TW200839035A - Method for recovering and refining platinum group metal using molten salt electrolytic process - Google Patents
Method for recovering and refining platinum group metal using molten salt electrolytic process Download PDFInfo
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- TW200839035A TW200839035A TW97105132A TW97105132A TW200839035A TW 200839035 A TW200839035 A TW 200839035A TW 97105132 A TW97105132 A TW 97105132A TW 97105132 A TW97105132 A TW 97105132A TW 200839035 A TW200839035 A TW 200839035A
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- 238000000034 method Methods 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 title claims description 24
- 239000002184 metal Substances 0.000 title claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims description 16
- 238000007670 refining Methods 0.000 title claims description 6
- 150000003839 salts Chemical class 0.000 title abstract 5
- 238000004090 dissolution Methods 0.000 claims abstract description 25
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000460 chlorine Substances 0.000 claims abstract description 13
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 7
- 239000010439 graphite Substances 0.000 claims abstract description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 3
- 239000010935 stainless steel Substances 0.000 claims abstract description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 27
- 230000008018 melting Effects 0.000 claims description 17
- 238000002844 melting Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 13
- 238000007664 blowing Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- 229910052742 iron Inorganic materials 0.000 claims 1
- 238000005215 recombination Methods 0.000 claims 1
- 230000006798 recombination Effects 0.000 claims 1
- 239000010970 precious metal Substances 0.000 abstract description 20
- 238000011084 recovery Methods 0.000 abstract description 11
- 239000007789 gas Substances 0.000 abstract description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052786 argon Inorganic materials 0.000 abstract description 2
- 230000000149 penetrating effect Effects 0.000 abstract 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 20
- 229910052707 ruthenium Inorganic materials 0.000 description 20
- 229910000510 noble metal Inorganic materials 0.000 description 16
- 239000002699 waste material Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000239226 Scorpiones Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- -1 nails Chemical compound 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
200839035 九、發明說明： 【發明所屬之技術領域】 本發明係有關於藉由熔融塩電解法，從含有釕、銥* 的白金族金屬的廢棄物回收白金族金屬的方法。銥等 【先前技術】 釕、銥等的白金族金屬（以下亦有稱之為「貴金屬 的情況）’除了因為具有高耐熱性、高耐#性而成為用^ 熔解各種無機材料的坩堝等的構造材料之外，其亦因具有 優異的電性而用於電子部件的電極材料等等。另—方八， 由於這些貴金屬為稀少且高價的金屬，有必要作不浪=而 有效的利用•消費，而有發展回收技術的需求。 本案申請人擁有貴金屬的回收•精製技術中的藉由 溶融运的處理技術’例如如以下已公開的方法。 【專利文獻1】 特開第2004-99975號公報 本案申請人所揭露的從廢棄物的白金族金屬回收 法，是含有將含有銥等的貴金屬的廢棄物溶解於含有铯塩 的氯化物熔融塩中，使廢棄物中的貴金屬成為鉋的氯化銥 酸塩等，將反應後的熔融塩與水混合而將鉋的氯化銥酸塩 等分離回收的步驟。此一使用熔融塩的技術，可以使用較 少的步驟來回收白金族金屬。 另外’除了上述將氯化物溶融垣中的貴金屬以化合物 的形態回收的技術之外，本案發明人亦揭露了將氯化物熔 田虫运電解而使貝金屬析出的方法。 2169-9417-PF 6 200839035 【專利文獻2】 特開第2001-089890號公報 【專利文獻3】 特開第2001-1 52381號公報 在上述藉由熔融塩電解法的貴金屬回收中，將作為處 理標的物的廢棄物作為陽極，將碳等不溶性的電極作為陰 極’將上述物體浸潰於氣化物熔融塩（較好為使用氯化200839035 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a method for recovering a platinum group metal from waste of a platinum group metal containing ruthenium and osmium* by a melt enthalpy electrolysis method.先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 先前 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白 白In addition to the structural materials, it is also used as an electrode material for electronic components due to its excellent electrical properties, etc. In addition, since these precious metals are rare and expensive metals, it is necessary to use them effectively. In the case of consumption, there is a demand for the development of recycling technology. The applicant of the present invention has a treatment technique of melting and transportation in the recovery and refining technology of precious metals, for example, as disclosed in the following. [Patent Document 1] Japanese Patent Laid-Open No. 2004-99975 The method for recovering the platinum group metal from waste disclosed in the present application is a method of dissolving waste containing a noble metal such as ruthenium in a ruthenium chloride-containing ruthenium to make the precious metal in the waste a planer. A ruthenium ruthenate or the like, a step of mixing and separating the molten ruthenium after the reaction with water to separate and recover the ruthenium ruthenate or the like. This technique using molten ruthenium can be used. There are few steps to recover the platinum group metal. In addition to the above-mentioned technique of recovering the precious metal in the chloride melted ruthenium in the form of a compound, the inventors of the present invention have also disclosed that the chloride fused field is electrolyzed to precipitate the shell metal. [Patent Document 2] JP-A-2001-089890 [Patent Document 3] JP-A-2001-1 52381, in the above-mentioned precious metal recovery by the melt enthalpy electrolysis method, The waste as the treatment target is used as an anode, and an insoluble electrode such as carbon is used as a cathode. The object is immersed in a vaporized ruthenium (preferably, chlorination is used).
鈉、氯化鉀、氯化鉋等的鹼金族的氯化物的單一塩類或混 合塩類）中，將兩極通電。藉此，將陽極中的貴金屬溶出 至熔融塩中，而同時使其析出於陰極表面而得以回收。上 述熔融塩電解法，其優點在於可直接回收貴金屬，且回收 純度亦高。 【發明内容】 【發明所欲解決的問題】 _然而，使用熔融塩的責金屬的回收效率是因溶解於熔 融堪的貴金屬的含量、即從含有貴金屬的處理標的物的溶 解至熔融塩的溶解量而有變化。 然而，處理標的物中的貴金屬溶解速度，雖然可藉由 溶融塩的溫度等可作某種程度的調整，但其範圍受/ 外，即使可調整溶解速度但有其限度，而需要在同— 下更有效率進行溶解的方法。 本發明疋在上述背景之下所完成，其目的在於提供一 種使用炼融塩來回收眚今屬& ’、 貝屬的方法與裝置，其可以提升Φ 处理標的物的貴金屬的溶解 . 鮮連度，而可有效率地進行責In a single hydrazine or a mixed hydrazine of an alkali metal chloride such as sodium, potassium chloride or chlorinated planer, the two poles are energized. Thereby, the noble metal in the anode is eluted into the molten crucible while being deposited on the surface of the cathode to be recovered. The above melt enthalpy electrolysis method has the advantage that the precious metal can be directly recovered and the recovery purity is also high. SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] _However, the recovery efficiency of the responsible metal using the molten ruthenium is due to the dissolution of the molten metal, that is, the dissolution from the treatment target containing the noble metal to the dissolution of the molten ruthenium. There is a change in quantity. However, the rate of dissolution of the precious metal in the target can be adjusted to some extent by the temperature of the molten crucible, etc., but its range is affected. Even if the dissolution rate can be adjusted, there is a limit, and it is necessary to The method of dissolving more efficiently is carried out. The present invention has been accomplished under the above background, and an object thereof is to provide a method and apparatus for recovering a genus of the genus & genus using a smelting crucible, which can improve the dissolution of the precious metal of the Φ treatment target. Degree, but can be efficiently blamed
2169-9417-PF 7 .200839035 金屬的回收。 【用以解決問題的手段】 為了解決上述問題，本發明係提供一種藉由熔融塩電 解法以回收•精製白金族金屬之方法，包含：—溶解步 驟’將含有白金族金屬的一處理標的物浸潰於—氯化物炼 融塩中，而使上述白金族金屬溶解於上述氯化物熔融塩； 其中上述溶解步驟是將氯吹人上述氯化㈣㈣、並對上 述氯化物熔融塩進行電解。 在熔融塩中的貴金屬的溶解，是基於貴金屬的離子 化以及將所產生的貴金屬離子與氯反應而形成氯化物。 由於上述的反應有反應平衡的關係，#了促進貴金屬的溶 解，需要增加貴金屬離子與氯離子的濃度。在本發明中， 藉由熔融塩的電解貴金屬離子及氯離子上升、且藉由氣氣 的人，而、加氯離子的來源’藉此將上述反應平衡關係： 生成氣化物的一側推移。 【實施方式】 以下，針對本發明進行詳細說明。在本發明中，含責 金屬的處理標的物是作為陽極，而貴金屬的含量並無特別 限疋。關於處理標的物的形狀，只要可以通電亦無特別限 定。另外，亦可使用已經一度的熔解、鑄造的含貴金屬^ 廢料。另外，陰極較好為使用不溶性電極，較好為使用碳 製電極。而本發明的回收對象是屬於白金族元素者，可^ 進行白金、釘、銀、鍺、餓的回收、精製。 作為電解質的氯化物熔融塩的組成較好為鹼金族金 2169-9417-PF 8 200839035 屬氯化物的熔融塩，從取用性熔融塩的觀點來看特別較好 者為含有氯化鈉、氯化鉀、氯化鏠的至少其中之一者 外，亦可使用上述的混合垣，可藉由混合比 '的調整而調= 熔融混合垣的熔點。使用三種的混合盘的情況較好的組成 為：氣化納：氯化鉀：氯化鉋备35 fflol%:2〇〜3。 mol%:40〜50 mol%。熔融塩的溫度較好為49〇〜5初它。2169-9417-PF 7 .200839035 Recovery of metals. [Means for Solving the Problem] In order to solve the above problems, the present invention provides a method for recovering and refining a platinum group metal by a melt enthalpy electrolysis method, comprising: a dissolution step of a treatment target containing a platinum group metal The platinum group metal is dissolved in the chloride smelting crucible, and the platinum group metal is dissolved in the chloride melting enthalpy; wherein the dissolving step is to chlorinate the chlorination (4) (4) and electrolyze the lanthanum chloride. The dissolution of the noble metal in the molten crucible is based on the ionization of the noble metal and the reaction of the generated noble metal ions with chlorine to form a chloride. Since the above reaction has a reaction equilibrium relationship, it is necessary to increase the concentration of noble metal ions and chloride ions in order to promote the dissolution of the noble metal. In the present invention, the above-mentioned reaction equilibrium relationship is caused by the melting of the electrolytic noble metal ions and the chloride ions of the ruthenium, and the source of the chlorinated ions by the person of the gas gas: the side on which the vaporization is formed is shifted. [Embodiment] Hereinafter, the present invention will be described in detail. In the present invention, the subject matter of the metal-containing treatment is used as an anode, and the content of the noble metal is not particularly limited. Regarding the shape of the object to be treated, there is no particular limitation as long as it can be energized. In addition, it is also possible to use a precious metal-containing scrap which has been melted and cast once. Further, it is preferred to use an insoluble electrode for the cathode, and it is preferred to use a carbon electrode. However, the object of the present invention is a member of the Platinum group, and can be used for the recovery and refining of platinum, nails, silver, enamel, and starving. The composition of the chloride melting ruthenium as the electrolyte is preferably a molten ruthenium of the alkali metal gold 2169-9417-PF 8 200839035 chlorinated metal, and particularly preferably contains sodium chloride from the viewpoint of reductive melting enthalpy. In addition to at least one of potassium chloride and cesium chloride, the above mixed mash may be used, and the melting point of the enthalpy may be adjusted by adjusting the mixing ratio. The preferred composition for the use of three types of mixing discs is: gasification nano: potassium chloride: chlorinated planing 35 fflol%: 2 〇 ~3. Mol%: 40 to 50 mol%. The temperature of the molten crucible is preferably 49 〇 5 5 early.
接下來是關於貴金屬溶解步驟中的條件。首先關於電 解條件，陰極電流密度較好為5〜4GniA/Gin2、更好為2㈣ 浙’另外’吹人熔融㈣氯氣，純度較好為使用約職 者。關於氯氣的吹入量’是隨著電極面積及陰極電流密度 而變化’較好為吹入相當於依據上述關係所換算的電化學 t量的1倍量以上、2倍量以下的氯氣。若是吹入的氣氣 置超出電化學當量的2倍，反應容器中的氣分壓會上升礼 :會=速反應容器的腐钱的進行之虞。另外，雖然就算 口人入未達電化學當量的氯氣，溶解還是會進行，作是 :會便慢。此時，即使使陰極電流密度上升而伴隨著貴金 =陰極侧的析出’無法期待溶解速度的上升。因此 好為吹入電化學當量以上的氯氣。 另外’在溶解步驟中’關於以上述條件來進行 入及電解的時間的標準，較好為8〜24小時。另外，若; 慮其f的貴金屬的回收效率，溶融步驟較好為進行至相對 於熔融塩的熔融塩中的貴金屬濃度到達〇·卜0.4m〇l%。 在本發明中，腺主 吹入，而從炫融二解於_之後’停止氯的 化口收貝金屬。關於此一回收步驟，雖然This is followed by the conditions in the precious metal dissolution step. First, regarding the electrolysis conditions, the cathode current density is preferably 5 to 4 GniA/Gin2, more preferably 2 (four), and the other is a person who blows (4) chlorine gas, and the purity is preferably used. The amount of the chlorine gas to be injected is changed by the electrode area and the cathode current density. It is preferable that the amount of chlorine gas equivalent to one or more times the amount of the electrochemical amount converted according to the above relationship is equal to or less than two times the amount. If the blown gas is more than twice the electrochemical equivalent, the partial pressure of the gas in the reaction vessel will rise: Will = the progress of the decay of the reaction vessel. In addition, even if the mouth does not reach the electrochemical equivalent of chlorine, the dissolution will proceed, as follows: it will be slow. At this time, even if the cathode current density is increased, it is impossible to expect an increase in the dissolution rate due to the deposition of precious gold = cathode side. Therefore, it is preferable to blow chlorine gas equal to or higher than the electrochemical equivalent. Further, in the "dissolution step", the standard of the time for carrying in and electrolyzing under the above conditions is preferably from 8 to 24 hours. Further, in consideration of the recovery efficiency of the noble metal of f, the melting step is preferably carried out until the concentration of the noble metal in the molten crucible relative to the molten crucible reaches 0.4 m%. In the present invention, the gland is mainly blown in, and the metal is stopped after the smelting of the smear. Regarding this recycling step, though
2169-9417-PF 9 .200839035 可以進行溶解步驟後的熔融塩的溶解處理而以貴金 合物的形態回收；但是較好為進行溶解步驟後 ^ 電解’而使貴金屬析出。可μ接使發解步驟 = 的電解裝置’其原因為可加速從溶解步驟轉移至回收： :二：麗藉由實行電解析出’其原因在於可以回收高二 度的貝金屬，並可以與回收同時進行精製。2169-9417-PF 9 .200839035 The molten ruthenium after the dissolution step can be dissolved and recovered in the form of a noble metal; however, it is preferred to carry out the electrolysis after the dissolution step to precipitate the noble metal. The electrolysis device that can be connected to the solution step = the reason is that the transfer from the dissolution step to the recovery can be accelerated: : 2: Li is electrolyzed by electrolysis] because the high-grade bead metal can be recovered and can be recycled Refined at the same time.
此一藉由電解析出的回收步驟的電解條件較好為 10, I0A/W、更好為3〇〜5“A/cm、上述範圍高於貴金 屬溶解時的電流密度的原因是：此階段的目的是促進 析出。 籍由電解析出而回收的貴金屬，是析出於溶解步驟時 的陰極上。將析出的金屬從陰極剝除後，再經由洗淨等步 驟而回收。亦可依需求進行溶解處理等步驟。另外，藉^ 熔融塩電解法所析出的貴金屬具有高純度，藉由洗淨、成 幵y加工了直接成為製品（例如賤鑛用的乾材）。 【發明的效果】 藉由以上說明所述的本發明，可使含釕、銥等的貴金 屬的廢棄物等的處理標的物中的貴金屬，高速溶解於溶融 塩藉此，可達成高效率的貴金屬的回收·精製。 另外’藉由上述而對溶解有貴金屬的熔融塩進行電 解’可以有效率地回收高純度的貴金屬。藉由上述溶解步 驟與電解析出的組合，可以較少的步驟從廢棄物製造出製 W。藉由本發明，可達成資源的有效利用，亦一併達成使 用貴金屬的製品的成本的降低。The electrolysis condition of the recovery step by electrolysis is preferably 10, I0A/W, more preferably 3〇~5"A/cm, and the above range is higher than the current density when the precious metal is dissolved: this stage The purpose of the precipitation is to promote precipitation. The precious metal recovered by electrolysis is deposited on the cathode during the dissolution step. The precipitated metal is removed from the cathode and then recovered by washing or the like. In addition, the noble metal precipitated by the melt enthalpy electrolysis method has a high purity, and is directly processed into a product (for example, a dry material for bismuth ore) by washing and mashing y. [Effect of the invention] According to the present invention described above, the precious metal in the treatment target such as the waste material of the noble metal such as ruthenium or osmium can be dissolved in the molten slag at a high speed, thereby achieving high-efficiency recovery and purification of the precious metal. 'Electrolysis of molten ruthenium dissolved in precious metal by the above' can efficiently recover high-purity precious metals. By combining the above-mentioned dissolution step with electrolysis, fewer steps can be taken from waste. The waste material is manufactured to produce W. By the present invention, efficient use of resources can be achieved, and the cost of using a precious metal product can be reduced.
2169-9417-PF 10 ,200839035 以下係顯示本發明的較佳實施例。在本實施例 b 使用既定的熔融複電解裝置，而疋 為虛理亵沾弘 方貝鱼屬的廢棄物作 ^處里W物，㈣料㈣與析出步驟而進行貴金屬回 第1圖是顯示本實施例中所使用的溶 構成。熔融塩電解曰目“ 电鮮裝置的 电解衮置I疋具有容納熔融盘 的内容器20、容纟内内交哭、9n M 的石墨製 、、内内谷态20的石墨製的容器3〇、以 納容器30的不銹鋼製的外 ^ 乃辦表的外合為4〇。内容器2〇是祜 的遮蔽板21所密蘭，s< 墨裏 所在閉，另外設置貫通外容 的氯導入管50與排氣管5卜me ”遮蔽板21 、讲巩s bl。而在内容器20 設有陽極60，陰極目,丨；、主 氐P貝J疋舖 π極61則次 >貝於陰極61的對向。 另外’在外容器40中，為了使外容器内充 而設置鈍性氣體導入管52。由 、軋’ 顧虐到本發明中是使用氯，而會 中關於無法避免與氣接觸 刃谷肩熔融埴的内容器2 ❿ 板U將内容器❹閉^ 墨所構成，—併以遮蔽 於有強声〜， 納所有裝置的外容器4〇,由 =強度•動性的要求，而以不錢鋼所構成， 軋體充滿外容器内而抑制 开鈍性 極間距的調整，較好二Μ。而關於陰極61，為了電 時的析出物的厚度均―，陰極 關於氯化物熔融塩，是 …、 另外，是& 下組成的混合熔融塩。 另外疋以用過的釕靶材作為陽極。 氯化納 氯化鉀 3U〇g (53-7mol> 325〇g (43.6mol)2169-9417-PF 10, 200839035 The following shows a preferred embodiment of the invention. In the present embodiment b, a predetermined molten double electrolysis device is used, and the waste material of the genus 虚 弘 弘 弘 弘 弘 弘 弘 作 作 作 作 , , , , , , , , , , , , , , , 弘 弘 弘 弘 弘 弘 弘 贵 贵 贵 贵 贵 贵 贵 贵The composition of the solution used in this example. The enthalpy of the enthalpy of electrolysis is "the electrolysis device of the electro-mechanical device", which has a container 20 for accommodating a molten disk, a container made of graphite, which is made of graphite, 9n M, and a container of graphite. The outer surface of the stainless steel container of the nano container 30 is 4 〇. The inner container 2 is the slab of the scorpion shielding plate 21, s < the ink is closed, and the chlorine is introduced through the external volume. The tube 50 and the exhaust pipe 5 are "me" shielding plates 21, and sb bl. On the other hand, the inner container 20 is provided with an anode 60, a cathode, and a crucible; a main crucible, a π pole 61, and a counter opposite to the cathode 61. Further, in the outer container 40, a passive gas introduction pipe 52 is provided in order to fill the outer container. By using, rolling, the use of chlorine in the present invention, and the inner container 2 ❿ U U 无法 无法 无法 内容 内容 内容 内容 内容 内容 内容 内容 内容 内容 内容 内容 内容 内容 内容 内容 内容 内容 内容 内容 内容 内容 内容 内容 内容 内容 内容 内容 内容 内容There is a strong sound ~, the outer container of all the devices 4 〇, consisting of = strength and dynamic requirements, but not composed of steel, the rolling body is filled in the outer container to suppress the adjustment of the blunt pole spacing, preferably two Hey. On the other hand, in the cathode 61, the thickness of the precipitate in the case of electricity is "the cathode is melted by the chloride", and is a mixed melting crucible of the composition of & In addition, a used ruthenium target is used as the anode. Chlorinated sodium chloride 3U〇g (53-7mol> 325〇g (43.6mol)
2169-9417-PF 200839035 氯化鉋 溫度2169-9417-PF 200839035 Chlorination planer temperature
13690g (81.3mol) 520〇C 在本只轭例中的溶解步驟中，首先將⑽的氯氣以 〇.2L/min的速率吹人未進行電解的溶融迄。在此過程中， 以5L/m_in的速率向外容器内注人氬氣。在此過程中，以 既疋間隔測定溶融盘中的釕漠度。13690 g (81.3 mol) 520 〇C In the dissolution step of the present yoke example, the chlorine gas of (10) was first blown at a rate of 〇.2 L/min until the electrolysis was not performed. During this process, argon gas was injected into the container at a rate of 5 L/m_in. In this process, the degree of awkwardness in the molten disk is measured at intervals.
a而在氯人入里達2〇 〇l的時間點，仍維持原狀繼續氯 的人入2 進行溶融塩的電解。電解條#是電極面積為 1〇〇〇Cm2、陰極電流密度為 20mA/Cm2 (20A)。 弟2圖係顯示上述溶解步驟中所測定的炼融垣中的釘 濃度的變化。從第2圖可以瞭解，只進行氯的吹入的溶融 塩中的：濃度為緩慢上升，而此時進行電解則可看到釕濃 度的^著上升。其原因在於氯的吹人與電解雙方的作用之 下，而加速了舒的溶解。 接下來，對經過溶解步驟的熔融塩停止氯的吹入，而 進行電解使釘析出。此時電解條件是電流密度為 3〇raA/cni2、析出時間為24〇小時。電解析出後，以鹽酸對 陰極上的析出物進行酸洗，再將析出物從石墨電極剝離。 此結果是得到9028g的釕，其純度經過測定為99 99%以 上。 【圖式簡單說明】 第1圖是顯示本實施例中所使用的熔融塩電解裝置的 概略。 第2圖是顯示溶解步驟時的熔融塩中的釕濃度變化的 2169-9417-PF 12 200839035 示意圖。 【主要元件符號說明】 1〜熔融塩電解裝置 20〜内容器 30〜容器 50〜氯導入管 52〜鈍性氣體導入管 61〜陰極 10〜熔融垣 21〜遮蔽板 40〜外容器 51〜排氣管 6 0〜陽極a. At the time when the chlorine intruder reaches 2〇 〇l, the person who continues to maintain the chlorine in the original state enters 2 to carry out the electrolysis of the molten helium. Electrolytic strip # is an electrode area of 1 〇〇〇 Cm 2 and a cathode current density of 20 mA / Cm 2 (20 A). The second diagram shows the change in the nail concentration in the smelting crucible measured in the above dissolution step. As can be seen from Fig. 2, in the molten crucible in which only chlorine is blown, the concentration is gradually increased, and at this time, electrolysis can be observed to increase the concentration of rhodium. The reason is that the action of both chlorine blowing and electrolysis accelerates the dissolution of Shu. Next, the molten enthalpy which has passed through the dissolution step is stopped by blowing chlorine, and electrolysis is performed to precipitate the nail. The electrolysis conditions at this time were a current density of 3〇raA/cni2 and a precipitation time of 24 hours. After electrolysis, the precipitate on the cathode was pickled with hydrochloric acid, and the precipitate was peeled off from the graphite electrode. As a result, 9028 g of hydrazine was obtained, and its purity was determined to be 99 99% or more. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing the outline of a molten tantalum electrolysis apparatus used in the present embodiment. Fig. 2 is a schematic view showing the change of the concentration of ruthenium in the molten ruthenium in the dissolution step, 2169-9417-PF 12 200839035. [Description of main component symbols] 1 to the melting enthalpy electrolysis device 20 to the inner container 30 to the container 50 to the chlorine introduction tube 52 to the passive gas introduction tube 61 to the cathode 10 to the melting enthalpy 21 to the shielding plate 40 to the outer container 51 to the exhaust Tube 6 0~ anode
2169-9417-PF 132169-9417-PF 13
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| WO2013022020A1 (en) | 2011-08-10 | 2013-02-14 | 住友電気工業株式会社 | Method for recovering element and apparatus for recovering element |
| JP2013117063A (en) * | 2011-11-04 | 2013-06-13 | Sumitomo Electric Ind Ltd | Method of producing metal by molten salt electrolysis |
| JP2013147731A (en) * | 2011-12-22 | 2013-08-01 | Sumitomo Electric Ind Ltd | Molten salt electrolysis metal fabrication method |
| KR101405619B1 (en) | 2012-08-27 | 2014-06-10 | 한국수력원자력 주식회사 | Integrated anode-liquid cathode structure for electrowinning process |
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|---|---|---|---|---|
| US4089770A (en) * | 1977-07-11 | 1978-05-16 | E. I. Du Pont De Nemours And Company | Electrolytic cell |
| JPS63183189A (en) * | 1987-01-23 | 1988-07-28 | Komatsu Denshi Kinzoku Kk | Molten-salt electrolysis method |
| GB8707782D0 (en) * | 1987-04-01 | 1987-05-07 | Shell Int Research | Electrolytic production of metals |
| JP4162809B2 (en) * | 1999-09-24 | 2008-10-08 | 田中貴金属工業株式会社 | Molten salt electrolysis equipment |
| JP2002194581A (en) * | 2000-12-27 | 2002-07-10 | Furuya Kinzoku:Kk | Method for recovering platinum group metals from metal electrodes |
| JP4087196B2 (en) * | 2002-09-10 | 2008-05-21 | 田中貴金属工業株式会社 | Method for recovering ruthenium and / or iridium |
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2008
- 2008-02-07 WO PCT/JP2008/052013 patent/WO2008099748A1/en not_active Ceased
- 2008-02-14 TW TW97105132A patent/TW200839035A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI418660B (en) * | 2010-07-02 | 2013-12-11 | Univ Chang Gung | Preparation of Transparent Conductive Multicomponent Metal Oxide Powders by Modified Electrolysis |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008202064A (en) | 2008-09-04 |
| WO2008099748A1 (en) | 2008-08-21 |
| JP4783310B2 (en) | 2011-09-28 |
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