TWI687550B - Cell for metal electrowinning - Google Patents
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- TWI687550B TWI687550B TW104123961A TW104123961A TWI687550B TW I687550 B TWI687550 B TW I687550B TW 104123961 A TW104123961 A TW 104123961A TW 104123961 A TW104123961 A TW 104123961A TW I687550 B TWI687550 B TW I687550B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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- 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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- 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
- C25C7/02—Electrodes; Connections thereof
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- 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
- C25C7/06—Operating or servicing
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Abstract
Description
本發明係關於一種電解槽，包括複數單位電池，適於金屬電煉，尤其是從離子溶液起，電解生產銅和其他非鐵金屬，以及進行此種電煉之電化廠。 The invention relates to an electrolytic cell, which includes a plurality of unit cells, and is suitable for metal electrorefining, especially from ionic solution, electrolytic production of copper and other non-ferrous metals, and an electrochemical plant for such electrorefining.
電解澱積非鐵金屬用之電化廠，例如電解萃取和精煉廠，亦分別稱為電煉廠和電精煉廠，通常使用至少一個電解槽，包括複數單位電池，各由陽極和陰極組成。 Electrochemical plants for electrolytic deposition of non-ferrous metals, such as electrolytic extraction and refining plants, also known as electric refineries and electric refineries, respectively, usually use at least one electrolytic cell, including a plurality of unit cells, each composed of an anode and a cathode.
旨在為上述工廠使用之電解槽中，陽極和陰極一般置放電解浴內，呈交替位置且彼此平行。各電極以機械方式和電氣方式連接至吊桿，並令其吊桿與匯流排接觸以饋電。在電解槽中，同一匯流排在同樣極性的電極間共享，彼此並聯。 In the electrolytic cell intended for use in the above-mentioned plant, the anode and cathode are generally placed in a discharge solution bath at alternating positions and parallel to each other. Each electrode is mechanically and electrically connected to the boom, and the boom is brought into contact with the bus bar to feed power. In the electrolytic cell, the same bus bar is shared between electrodes of the same polarity and connected in parallel with each other.
以生產銅、鈷、鋅或鎳等非鐵金屬之工廠為例，電化反應生成之金屬，是在電流通過時，澱積在各單位電池之陰極，並以定期間隔(通常是幾天)收成，藉從個別電解槽萃取陰極為之。金屬澱積於陰極會以非均勻方式發生，引起局部化澱積，亦稱為樹枝晶體或樹枝晶體形成，在電流通過的效應下，朝面向陽極以遞增速度發展，造成電氣短路。在此情況下，陽極溫度上升，相當於樹枝晶體形成造成損害，也會發生樹枝晶體形成會局部熔接於陽極表面，妨礙金屬收成操作。 Take a factory that produces non-ferrous metals such as copper, cobalt, zinc, or nickel as an example. The metal produced by the electrochemical reaction is deposited on the cathode of each unit cell when current passes, and harvested at regular intervals (usually several days) , By extracting the cathode from individual electrolytic cells. Metal deposition on the cathode occurs in a non-uniform manner, causing localized deposition, also known as dendrite or dendrite formation. Under the effect of current flow, it progresses toward the anode at an increasing rate, causing an electrical short circuit. In this case, the temperature of the anode rises, which is equivalent to damage caused by dendrite formation, and it may also occur that the dendrite formation will locally weld to the surface of the anode, hindering the metal harvesting operation.
關於樹枝晶體形成之上述通常問題，特別關係到現代觀念之陽極，由鈦網或網狀片材製成，設有催化材料塗料，比習知鉛陽極更有效，因為短路情況會造成昂貴且無法修復的損壞。此等問題亦可由專利申請案WO2013060786所載更進一步陽極型確認，其中塗催化材料之鈦網，***透過性材料，諸如多孔性聚合物隔離材料或離子交換隔膜，所組成外層內 側。陽極損壞暗示一直較高之工廠保養成本，較低量之金屬製品，可能進一步受損，關聯到工廠可能被逼停工。 The above-mentioned common problems with the formation of dendrites, especially related to the modern concept of anodes, are made of titanium mesh or mesh sheets and are provided with catalytic material coatings, which are more effective than conventional lead anodes because short-circuit conditions can be expensive and impossible Repair the damage. These problems can also be confirmed by the further anode type contained in the patent application WO2013060786, in which a titanium mesh coated with a catalytic material is inserted into a permeable material, such as a porous polymer isolation material or an ion exchange membrane, which is formed in the outer layer side. The anode damage implies that the factory maintenance cost is always higher, and the lower amount of metal products may be further damaged, and the factory may be forced to stop work.
所以，在樹枝晶體形成成長時，亟需提供保護電解槽的單位電池陽極之形式，亦需即刻識別和報告個別陽極或個別電解槽陽極，其中一個或多個樹枝晶體形成之成長，構成潛在威脅。由於上述工廠為有礙健康之環境，因為在電解槽附近，高溫且可能存在酸霧之故，檢測且特別是發訊受到樹枝晶體形成影響之個別陽極，另有目的，在於容許工廠保養人員快速介入，以減少在電解槽室內停留時間。 Therefore, when dendrites are formed, it is urgent to provide a form of unit cell anode that protects the electrolytic cell. It is also necessary to immediately identify and report individual anodes or individual electrolytic cell anodes. The growth of one or more dendrites constitutes a potential threat . Because the above-mentioned factory is a health-prohibiting environment, because of the high temperature and the possibility of acid mist near the electrolytic cell, the detection and especially the sending of individual anodes affected by the formation of dendrites are also aimed at allowing the factory maintenance personnel to quickly Intervene to reduce the residence time in the cell.
本發明諸要旨規範於附帶申請專利範圍。 The gist of the present invention is regulated in the scope of accompanying patent application.
本發明一要旨，係關於金屬電煉電解槽，包括複數單位電池，各電池包括陽極和陰極，陽極設有朝向釋氧反應之催化表面，陰極適於從電解浴澱積金屬，和多孔網，介置於陽極和陰極之間。電池又包括導電性陽極吊桿，以電氣方式和機械方式連接於陽極，和導電性陰極吊桿，以電氣方式和機械方式連接於陰極。各單位電池亦包括裝置，適於直接或間接檢測電流流過相對應陽極吊桿。電解槽亦裝設陽極匯流排，以電氣方式連接到各電池之陽極吊桿，和陰極匯流排，以電氣方式連接到各電池之陰極吊桿。電解槽亦包括陰極平衡桿，平行設置，並在陽極匯流排附近。 A gist of the present invention relates to a metal electrolysis cell including a plurality of unit cells. Each cell includes an anode and a cathode. The anode is provided with a catalytic surface facing the oxygen releasing reaction. The cathode is suitable for depositing metal from an electrolytic bath, and a porous mesh. Interposed between anode and cathode. The battery further includes a conductive anode boom, which is electrically and mechanically connected to the anode, and a conductive cathode boom, which is electrically and mechanically connected to the cathode. Each unit battery also includes a device suitable for directly or indirectly detecting the current flowing through the corresponding anode boom. The electrolytic cell is also equipped with an anode bus bar, which is electrically connected to the anode boom of each battery, and a cathode bus bar, which is electrically connected to the cathode boom of each battery. The electrolytic cell also includes cathode balance bars, which are arranged in parallel and near the anode bus bar.
多孔網(可視情形具導電性)介置於單位電池的陽極和陰極之間，其結構可呈不同之緊密程度，並製成容許電解溶液通過，不會干擾陽極和陰極間離子傳導。 The porous mesh (which is electrically conductive depending on the situation) is interposed between the anode and cathode of the unit cell. Its structure can be of different degrees of tightness and is made to allow the electrolytic solution to pass without interfering with the ion conduction between the anode and cathode.
以前述電解槽設計進行電解，在單位電池一個或多個陰極可能形成之樹枝晶體，在到達陽極表面背後之前，即接觸到面向多孔網，故即停止其成長，或在任何情況下減緩。茲觀察到，在樹枝晶體形成碰觸到多孔網之情況時，即使呈現極小導電係數，電池內生成之部份金屬，會直接澱積於網上，加以塗佈。在此情況時，陰極、樹枝晶體和多孔網組成之總成，因為在此等元件間存在電氣連接，另外遂行置於位在比原有組態更靠近陽極的單位電池新陰極之功能。在此情形時，與新陰極和陽極間減少間隙關聯的電解質內較低電阻降，造成流過相對應陽極吊桿之電流增加。已知此電流增加程度，可用來指示樹枝晶體成長。 With the aforementioned electrolysis cell design for electrolysis, the dendrites that may form in one or more cathodes of the unit cell are exposed to the porous network before reaching the anode surface, so their growth is stopped or slowed down in any case. It is observed that, when the dendrite formation contacts the porous mesh, even if it exhibits a very small conductivity, some of the metal generated in the battery will be directly deposited on the mesh and coated. In this case, the assembly of the cathode, dendrite and porous mesh, because there is electrical connection between these elements, in addition to the function of placing the new cathode of the unit cell closer to the anode than the original configuration. In this case, the lower resistance drop in the electrolyte associated with the reduced gap between the new cathode and the anode causes an increase in the current flowing through the corresponding anode boom. This increase in current is known to indicate dendrite growth.
在一具體例中，直接或間接檢測流入各陽極吊桿之電流，可在吊桿本身，或於與其電氣連接之元件為之，利用已檢測裝置，能夠測量電壓或溫度之變異。 In a specific example, the current flowing directly into each anode boom can be directly or indirectly detected on the boom itself, or on a component electrically connected to it, and the detected device can be used to measure the variation in voltage or temperature.
在一具體例中，電壓變異之測量，一方面藉檢測裝置連接於相關陽極匯流排，另方面利用導電性和視情形撓性壓力觸點連接於陰極吊桿為之。此組態之優點是，避免固定電氣連接於陽極吊桿，終於使電池之保養操作更容易。 In a specific example, the measurement of the voltage variation is connected to the relevant anode bus bar on the one hand by means of a detection device, and on the other hand by using conductive and optionally flexible pressure contacts to be connected to the cathode boom. The advantage of this configuration is that it avoids the fixed electrical connection to the anode boom, which finally makes the battery maintenance operation easier.
在又一具體例中，電壓變異之測量，是把檢測裝置透過位於沿其主軸一定距離之二點，連接於相對應陽極吊桿為之。 In yet another specific example, the measurement of the voltage variation is to connect the detection device to the corresponding anode boom through two points located at a certain distance along its main axis.
在一具體例中，溫度變異測量，可利用熱敏性裝置為之，例如熱電偶。此項測量可例如以熱敏性裝置安裝在各陽極吊桿，最好在末端部，或另外在陽極匯流排上相當於與陽極吊桿各觸點為之。熱敏性裝置可裝設抗化學性襯材，適於保護和/或提高隔熱，免受週圍環境影響。 In a specific example, the temperature variation measurement may use a thermosensitive device, such as a thermocouple. This measurement can be installed on each anode boom, for example, with a heat-sensitive device, preferably at the end, or otherwise on the anode busbar, corresponding to each contact with the anode boom. The heat-sensitive device can be equipped with chemical-resistant lining materials, suitable for protecting and/or improving thermal insulation from the surrounding environment.
在另一具體例中，溫度變異之測量，可藉用溫度變色漆為之，在溫度超過預定臨限值時會變色。此漆可施加於陽極吊桿，或相當於與陽極吊桿觸點之陽極匯流排。此具體例之優點是，由樹枝晶體形成成長確定之潛在臨界狀況，可使電化廠內之工作人員立刻看到，並且很快識別發生此狀況的電解槽，以及電解槽內之陽極或陰極。 In another specific example, temperature variability can be measured using temperature-changing paint, which changes color when the temperature exceeds a predetermined threshold. This paint can be applied to the anode boom, or equivalent to the anode busbar in contact with the anode boom. The advantage of this specific example is that the potential critical condition determined by the growth of dendrites can be seen immediately by the staff in the electrochemical plant and quickly identify the electrolytic cell where this condition occurs, as well as the anode or cathode in the electrolytic cell.
在一具體例中，各檢測裝置可連接至其本身微處理器，構成比較裝置所得測量與預定參考範圍；若測量不在參考範圍內，微處理器可作動發訊系統，或是依序或同時作動之更多發訊系統。微處理器和/或發訊系統，可在陰極摘取操作中關閉。微處理器可與發訊系統和/或檢測裝置整合於單一單位內。 In a specific example, each detection device can be connected to its own microprocessor to form the measurement obtained by the comparison device and the predetermined reference range; if the measurement is not within the reference range, the microprocessor can activate the signaling system, either sequentially or simultaneously Act on more messaging systems. The microprocessor and/or signaling system can be turned off during the cathode extraction operation. The microprocessor can be integrated with the signaling system and/or the detection device in a single unit.
在一具體例中，微處理器是由製程電壓供電，避免使用需定期更換操作之電池組。尤其是微處理器可直接連接到陽極匯流排，和陰極平衡桿，若電解槽有裝設的話。若電解槽不含陰極平衡桿，而想要避免固定接線以免干擾工廠操作，則針對監視某一陽極吊桿之微處理器，係經由最好是可撓性壓力觸點，連接至陽極匯流排和相鄰陰極之吊桿。 In a specific example, the microprocessor is powered by the process voltage to avoid the use of battery packs that require regular replacement operations. In particular, the microprocessor can be directly connected to the anode bus bar, and the cathode balance bar, if the electrolytic cell is installed. If the electrolytic cell does not contain a cathode balance bar and you want to avoid fixed wiring so as not to interfere with factory operations, the microprocessor for monitoring an anode boom is connected to the anode bus bar via a preferably flexible pressure contact And the boom of the adjacent cathode.
在一具體例中，微處理器作動至少一發訊系統，包含發光二極體，可與光纖耦合，不論是直接或透過光耦合裝置。光纖可視情形襯以 聚合物料，容許傳送光訊號至各陽極吊桿末端，或更好是到電解槽外側，以方便工廠操作人員識別，得以快速辨認電解槽，和電解槽陽極，或呈現直接或間接電流數值在預定數值範圍以外之陽極。 In a specific example, the microprocessor operates at least one signaling system, including a light-emitting diode, which can be coupled with an optical fiber, either directly or through an optical coupling device. The optical fiber is lined with the situation The polymer material allows optical signals to be transmitted to the end of each anode hanger, or preferably to the outside of the electrolytic cell, to facilitate factory operator identification, to quickly identify the electrolytic cell, and the anode of the electrolytic cell, or to show the direct or indirect current value at the predetermined Anodes outside the numerical range.
在一具體例中，多孔網可由適當厚度之碳織物製成。在另一具體例中，防腐蝕金屬，例如鈦，製成的多孔網可由篩網或打孔片材組成，具有對釋氧反應催化惰性的塗料。在一具體例中，催化惰性塗料可基於錫、鉭、鈮或鈦，例如氧化物之形式。在一具體例中，陽極是由鈦篩網或伸張片材，塗佈催化材料所形成。在又一具體例中，塗佈觸媒之鈦篩網，***透過性隔板組成之外層內側，例如聚合物多孔性片材或陰離子隔膜，固定於機架，覆以除濕器。 In a specific example, the porous mesh may be made of carbon fabric of appropriate thickness. In another specific example, a porous mesh made of a corrosion-resistant metal, such as titanium, can be composed of a mesh or perforated sheet material, and has a coating that is catalytically inert to the oxygen release reaction. In a specific example, the catalytically inert coating may be based on tin, tantalum, niobium or titanium, for example in the form of oxides. In a specific example, the anode is formed by a titanium mesh or stretched sheet coated with a catalytic material. In yet another specific example, a catalyst-coated titanium mesh is inserted into the outer layer composed of a permeable separator, such as a polymer porous sheet or an anion membrane, fixed to the frame and covered with a dehumidifier.
最佳多孔網對陽極表面之間隙，視製程特徵和工廠整體規模而定。在用來證明本發明之工廠內，可得最佳效益，是電池採用陽極和陰極隔開25-100mm，而多孔性篩網離面向陽極之距離為1-20mm。 The gap between the best porous mesh and the anode surface depends on the process characteristics and the overall scale of the plant. In the factory used to prove the invention, the best benefit can be obtained by using the anode and the cathode separated by 25-100mm, and the distance between the porous screen and the anode facing the anode is 1-20mm.
本發明另一要旨係關於金屬電煉用電解槽單位電池之陽極元件，包括具有對釋氧反應的催化表面之陽極，多孔網，以機械方式和電氣方式連接於陽極之陽極吊桿，以及適於直接或間接檢測流過陽極吊桿的電流之裝置。適於直接或間接檢測電流之裝置，可按上述製造，並可視需要連接至處理器，適於將檢測值與預定數值範圍比較，在檢測值未包括於預設定範圍時，作動一個或多個警報訊號。警報訊號可為音響、視覺、電磁波，或任何其他性質，並可由複數訊號組合所組成。 Another gist of the present invention relates to an anode element of a unit cell of an electrolysis cell for metal electrorefining, including an anode having a catalytic surface for oxygen release reaction, a porous mesh, an anode boom connected mechanically and electrically to the anode, and suitable A device for directly or indirectly detecting the current flowing through the anode boom. The device suitable for direct or indirect current detection can be manufactured as described above, and can be connected to the processor as required. It is suitable for comparing the detection value with a predetermined value range. When the detection value is not included in the preset range, one or more Alarm signal. The alarm signal can be acoustic, visual, electromagnetic, or any other nature, and can be composed of a combination of plural signals.
本發明另一要旨係關於金屬電煉電解槽之單位電池，包括：˙陽極，具有對釋氧反應之催化表面；˙陰極，與該陽極並列配置，適於從電解浴澱積金屬；˙多孔網，介置於該陽極和該陰極之間；˙導電性陽極吊桿，與陽極形成一體，並以電氣方式相連接；˙裝置，適於直接或間接檢測流經陽極吊桿之電流；˙陽極匯流排，具導電性，且以電氣方式連接至陽極吊桿。 Another gist of the present invention relates to a unit cell of a metal electrolysis cell including: an anode with a catalytic surface for oxygen release reaction; a cathode arranged in parallel with the anode, suitable for depositing metal from an electrolytic bath; a porous Net, interposed between the anode and the cathode; ˙ conductive anode boom, integrated with the anode, and electrically connected; ˙ device, suitable for direct or indirect detection of current flowing through the anode boom; ˙ The anode bus bar is electrically conductive and electrically connected to the anode boom.
本發明另一要旨係關於從含亞銅和/或銅離子之溶液，獲取銅之製法，包括在上述電解槽內對溶液進行電解。 Another gist of the present invention relates to a method for obtaining copper from a solution containing cuprous copper and/or copper ions, which includes electrolyzing the solution in the above electrolytic cell.
100‧‧‧陽極 100‧‧‧Anode
200‧‧‧陰極 200‧‧‧Cathode
300‧‧‧多孔網 300‧‧‧porous mesh
400‧‧‧陽極吊桿 400‧‧‧Anode boom
450‧‧‧陰極吊桿 450‧‧‧Cathode boom
500‧‧‧裝置 500‧‧‧device
600‧‧‧導電性陽極匯流排 600‧‧‧ Conductive anode busbar
700‧‧‧微處理器 700‧‧‧Microprocessor
800‧‧‧發訊系統 800‧‧‧Sending system
801‧‧‧發光二極體 801‧‧‧ LED
802‧‧‧光耦合系統 802‧‧‧Optical coupling system
803‧‧‧光纖 803‧‧‧ Fiber
900‧‧‧職員 900‧‧‧ Staff
第1圖簡略表示本發明具體例金屬電煉電解槽之單位電池；第2圖簡略表示本發明具體例金屬電煉電解槽之單位電池內樹枝晶體形成成長可用發訊系統。 Fig. 1 schematically shows a specific example of the unit cell of the metal electrolysis electrolyzer according to the present invention; Fig. 2 schematically shows the usable transmission system for the formation of dendrites in the unit cell of the metal electrolysis electrolyzer according to the specific example of the invention.
茲參照附圖說明本發明具體化之若干實施方式，附圖之唯一目的在於繪示本發明該特別實施方式不同元件彼此相對配置，特別是附圖不一定照比例繪出。 The embodiments of the present invention are described with reference to the accompanying drawings. The sole purpose of the drawings is to illustrate that the different elements of this particular embodiment of the present invention are arranged relative to each other. In particular, the drawings are not necessarily drawn to scale.
第1圖簡略表示金屬電煉電解槽之單位電池，包括陽極100，與陽極並列配置之陰極200，適於從電解浴澱積金屬；多孔網300，介置於陽極和陰極之間；陽極吊桿400，與陽極成為一體，並以電氣方式相連接；陰極吊桿450；裝置500，適於直接或間接檢測流經陽極吊桿400之電流；導電性陽極匯流排600，與陽極吊桿400呈電氣連接。適於直接或間接檢測電流之裝置500，可連接至微處理器700，構成就裝置500檢測量與預定值範圍進行比較。微處理器700連接於發訊系統800，於檢測提供數值超出參考範圍外時，即被作動。
Figure 1 schematically shows the unit cell of a metal electrolysis cell, including an
第2圖表示裝置500，適於直接或間接檢測電流，連接至微處理器700，供該檢測與預定數值範圍比較。微處理器700構成是在檢測提供數值超出參考範圍時，作動發訊系統800。發訊系統800可由發光二極體801組成，在被微處理器700作動時，發出光訊號。二極體801訊號由光纖803傳送，光纖可視情形經由光耦合系統802，與二極體801耦合。
Figure 2 shows a
光纖在輸出光訊號803的極端，放在預定位置，讓在工廠操作的職員900容易識別。
The optical fiber is placed at a predetermined position at the extreme of the output optical signal 803, so that the
前述無意限制本發明，可按照不同具體例使用，不違其範圍，而其程度純以附帶申請專利範圍為準。 The foregoing is not intended to limit the present invention and can be used in accordance with different specific examples, without violating its scope, and its extent is purely based on the scope of the accompanying patent application.
在本案說明書和申請專利範圍裡，「包括」一辭及其變化語句，無意排除其他元件、組件或另外製法步驟存在。 In the description and patent application scope of this case, the word "including" and its variations are not intended to exclude the existence of other elements, components or other manufacturing steps.
本說明書內提到的文件、規章、材料、裝置、論文等，純為提供本發明文脈之目的，並未建議或代表此等事物之任何部份或全部，形成先前技術基礎之部份，且為本案各申請專利範圍優先權日之前，本發明 相關領域之一般常識。 The documents, regulations, materials, devices, papers, etc. mentioned in this specification are purely for the purpose of providing the context of the present invention, and do not suggest or represent any part or all of these things, forming part of the previous technical basis, and Before the priority date of each patent application for this case, the invention General knowledge in related fields.
100‧‧‧陽極 100‧‧‧Anode
200‧‧‧陰極 200‧‧‧Cathode
300‧‧‧多孔網 300‧‧‧porous mesh
400‧‧‧陽極吊桿 400‧‧‧Anode boom
450‧‧‧陰極吊桿 450‧‧‧Cathode boom
500‧‧‧裝置 500‧‧‧device
600‧‧‧導電性陽極匯流排 600‧‧‧ Conductive anode busbar
700‧‧‧微處理器 700‧‧‧Microprocessor
800‧‧‧發訊系統 800‧‧‧Sending system
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| ITMI20141416 | 2014-08-01 | ||
| ITMI2014A001416 | 2014-08-01 |
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| WO2017147388A1 (en) | 2016-02-25 | 2017-08-31 | Calera Corporation | On-line monitoring of process/system |
| WO2018156480A1 (en) * | 2017-02-24 | 2018-08-30 | Calera Corporation | Monitoring condition of electrochemical cells |
| KR102017567B1 (en) * | 2018-11-27 | 2019-09-03 | 주식회사 웨스코일렉트로드 | An anode for electrolysis |
| CN109879376A (en) * | 2019-03-04 | 2019-06-14 | 苏州博创环保科技有限公司 | A kind of Closed electrochemical reaction unit |
| EP4389940A1 (en) | 2022-12-21 | 2024-06-26 | John Cockerill SA | Device for electrodeposition against dendritic substances |
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| BR112017002063A2 (en) | 2018-01-30 |
| WO2016016406A1 (en) | 2016-02-04 |
| PH12016502567B1 (en) | 2017-04-17 |
| US20170211195A1 (en) | 2017-07-27 |
| EA201790300A1 (en) | 2017-06-30 |
| CA2953274A1 (en) | 2016-02-04 |
| EA032134B1 (en) | 2019-04-30 |
| CL2017000259A1 (en) | 2017-07-21 |
| TW201606139A (en) | 2016-02-16 |
| MX2017001467A (en) | 2017-05-10 |
| AU2015295324A1 (en) | 2017-01-12 |
| EP3175020B1 (en) | 2018-07-18 |
| PH12016502567A1 (en) | 2017-04-17 |
| AR101935A1 (en) | 2017-01-25 |
| AU2015295324B2 (en) | 2019-11-28 |
| JP6660387B2 (en) | 2020-03-11 |
| ZA201700176B (en) | 2018-08-29 |
| KR20170038880A (en) | 2017-04-07 |
| EP3175020A1 (en) | 2017-06-07 |
| AP2017009682A0 (en) | 2017-01-31 |
| CN106574385B (en) | 2020-06-05 |
| PE20170233A1 (en) | 2017-04-19 |
| ES2687602T3 (en) | 2018-10-26 |
| JP2017524074A (en) | 2017-08-24 |
| CN106574385A (en) | 2017-04-19 |
| PL3175020T3 (en) | 2018-12-31 |
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