TWI760284B - Method for recycling vanadium electrolyte - Google Patents
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本發明係關於一種釩電解液的處理方法，尤其是一種釩電解液的回收再利用之方法。The present invention relates to a kind of treatment method of vanadium electrolyte, especially a kind of method of recovery and reuse of vanadium electrolyte.
釩液流電池（vanadium redox battery，VFB），又稱為全釩氧化還原液流電池（vanadium redox flow battery，VRFB），為利用不同氧化態的釩離子來儲存化學勢能（chemical potential energy）的可充電液流電池（rechargeable flow battery），釩液流電池由於具有極大的能量容量（energy capacity），非常適合用於大型電力存儲應用。Vanadium redox flow battery (VFB), also known as vanadium redox flow battery (VRFB), is a potential energy storage device that utilizes vanadium ions in different oxidation states to store chemical potential energy. Rechargeable flow batteries, vanadium flow batteries are well suited for large-scale power storage applications due to their enormous energy capacity.
釩液流電池係以釩電解液（vanadium electrolyte）作為電解液，該釩電解液包含三價釩離子（vanadium(III) ion，V 3+）及四價釩離子﹝vanadium(IV) ion，V 4+；以釩醯離子（vanadyl ion，VO 2+）的形式存在﹞，且三價釩離子與四價釩離子的莫耳數比約為1：1。 The vanadium redox flow battery uses a vanadium electrolyte as the electrolyte, and the vanadium electrolyte contains trivalent vanadium ions (vanadium(III) ion, V 3+ ) and tetravalent vanadium ions (vanadium(IV) ion, V 4+ ; exists in the form of vanadyl ion (VO 2+ ) ﹞, and the molar ratio of trivalent vanadium ion to tetravalent vanadium ion is about 1:1.
在充、放電的過程中，位於陽極端的釩電解液會依如下列式一所示之反應式進行反應，因而在放電的過程中，四價釩離子會氧化形成五價釩離子﹝vanadium(V) ion，V
5+；以過氧釩離子（pervanadyl ion，VO
2 +）的形式存在﹞，而在充電的過程中，五價釩離子則會還原形成四價釩離子。
而在充、放電的過程中，位於陰極端的釩電解液則會依如下列式二所示之反應式進行反應，因而在放電的過程中，三價釩離子會還原形成二價釩離子（vanadium(II) ion，V
2+），而在充電的過程中，二價釩離子則會氧化形成三價釩離子。
上述式一、式二所示之反應式為可逆反應，故釩液流電池可以不斷重複地充、放電，然而隨著充、放電的次數增加，使位於陽極端的釩電解液包含大量的五價釩離子，且位於陰極端的釩電解液包含大量的二價釩離子，嚴重影響釩液流電池的性能。The reaction formulas shown in the
前述回收釩電解液中包含大量的釩離子及硫酸，若直接廢棄則會對環境造成嚴重的破壞，因此如中國公開第106099223號、第106532079號等專利案，均揭示習知釩電解液的回收再利用之方法，係藉由加入氧化劑、還原劑，降低位於陽極端的釩電解液中的五價釩離子的含量，並降低位於陰極端的釩電解液中的二價釩離子的含量；然而前述習知方法中卻無法去除存在於釩電解液的雜質，有鑒於此，該習知釩電解液的回收再利用之方法確實仍有加以改善之必要。The aforementioned reclaimed vanadium electrolyte contains a large amount of vanadium ions and sulfuric acid. If it is directly discarded, it will cause serious damage to the environment. Therefore, as disclosed in Chinese patent cases such as No. 106099223 and No. 106532079, the recovery of conventional vanadium electrolytes is disclosed. The method of reuse is to reduce the content of pentavalent vanadium ions in the vanadium electrolyte at the anode end by adding an oxidant and a reducing agent, and reduce the content of divalent vanadium ions in the vanadium electrolyte at the cathode end; however, the aforementioned However, the conventional method cannot remove the impurities present in the vanadium electrolyte. In view of this, the conventional method for recycling and reusing the vanadium electrolyte still needs to be improved.
為解決上述問題，本發明的目的是提供一種釩電解液的回收再利用之方法，係可以去除釩電解液中的雜質者。In order to solve the above-mentioned problems, the object of the present invention is to provide a method for the recovery and reuse of a vanadium electrolyte, which can remove impurities in the vanadium electrolyte.
本發明的釩電解液的回收再利用之方法，可以包含：提供一回收釩電解液，包含價數不同的至少二釩離子；使該回收釩電解液中的至少二釩離子形成四價釩離子，以獲得一第一水相溶液，該第一水相溶液包含該四價釩離子；混合磷酸二辛酯及磺化煤油以形成一第一有機相溶液，並混合該第一有機相溶液及該第一水相溶液，待重新分層後，取得一第二有機相溶液，該第二有機相溶液包含該四價釩離子；以一硫酸水溶液作為一第二水相溶液，並混合該第二有機相溶液及該第二水相溶液，待重新分層後，取得一第三水相溶液，該第三水相溶液包含該四價釩離子；及提供一電解裝置，包含一陽極槽及一陰極槽，該陽極槽及該陰極槽中分別容置一陽極溶液及一陰極溶液，該陽極溶液為一硫酸水溶液，該陰極溶液為該第三水相溶液，並進行恆流電解，以於該陰極槽收取一再生成釩電解液。The method for recovering and reusing vanadium electrolyte of the present invention may include: providing a recovered vanadium electrolyte containing at least divanadium ions with different valences; making the at least divanadium ions in the recovered vanadium electrolyte form tetravalent vanadium ions , to obtain a first aqueous phase solution containing the tetravalent vanadium ion; mixing dioctyl phosphate and sulfonated kerosene to form a first organic phase solution, and mixing the first organic phase solution and After the first aqueous phase solution is re-stratified, a second organic phase solution is obtained, and the second organic phase solution contains the tetravalent vanadium ion; an aqueous sulfuric acid solution is used as a second aqueous phase solution, and the second organic phase solution is mixed. After the two organic phase solutions and the second aqueous phase solution are re-stratified, a third aqueous phase solution is obtained, and the third aqueous phase solution contains the tetravalent vanadium ion; and an electrolysis device is provided, which includes an anode tank and A cathode tank, an anode solution and a cathode solution are respectively accommodated in the anode tank and the cathode tank, the anode solution is an aqueous sulfuric acid solution, and the cathode solution is the third aqueous phase solution, and constant current electrolysis is performed to The cathode cell collects and regenerates the vanadium electrolyte.
依據上述，本發明的釩電解液的回收再利用之方法，藉由以磷酸二辛酯作為一萃取劑，使該四價釩離子以四價釩離子錯合物的形式，被萃取至該第二有機相溶液中，並藉由以該硫酸水溶液作為一反萃劑，使該四價釩離子錯合物以該四價釩離子的形式，被反萃取至該第三水相溶液中，再藉由該恆流電解反應，進而可以生成該再生成釩電解液，經由本發明的釩電解液的回收再利用之方法所獲得的再生成釩電解液含有的雜質較少，因而在用於釩液流電池時，有助於提升該釩液流電池的能量容量及壽命，為本發明之功效。According to the above, the method for recovering and reusing vanadium electrolyte of the present invention, by using dioctyl phosphate as an extractant, makes the tetravalent vanadium ions in the form of tetravalent vanadium ion complexes extracted to the first In the second organic phase solution, and by using the sulfuric acid aqueous solution as a stripping agent, the tetravalent vanadium ion complex in the form of the tetravalent vanadium ion is stripped back into the third aqueous phase solution, and then Through the constant current electrolysis reaction, the regenerated vanadium electrolyte can be generated, and the regenerated vanadium electrolyte obtained by the method for the recovery and reuse of the vanadium electrolyte of the present invention contains less impurities, so it is used for vanadium electrolytes. In the case of a flow battery, it helps to improve the energy capacity and life of the vanadium flow battery, which is the effect of the present invention.
本發明的釩電解液的回收再利用之方法，其中，該第一水相溶液的酸鹼值可以介於1～4之間，較佳可以介於2～3之間。如此，可以使該第一水相溶液中的四價釩離子較容易溶於由磷酸二辛酯及磺化煤油所形成的第一有機相溶液中，進而可以達成提升該第二有機相溶液中的釩離子含量之功效。In the method for recovering and reusing vanadium electrolyte of the present invention, wherein, the pH value of the first aqueous phase solution can be between 1 and 4, preferably between 2 and 3. In this way, the tetravalent vanadium ions in the first aqueous phase solution can be easily dissolved in the first organic phase solution formed by dioctyl phosphate and sulfonated kerosene, and then the second organic phase solution can be improved. The effect of vanadium ion content.
本發明的釩電解液的回收再利用之方法，其中，該第一有機相溶液可以包含以重量百分比計為10～50%的磷酸二辛酯及50～70%的磺化煤油，且亦可以另包含以重量百分比計為40%以下的磷酸三丁酯，較佳可以包含以重量百分比計為20～40%的磷酸二辛酯、10～30%的磷酸三丁酯及50%的磺化煤油。如此，可以使該第一水相溶液中的四價釩離子較容易溶於由磷酸二辛酯及磺化煤油所形成的第一有機相溶液中，進而可以達成提升該第二有機相溶液中的釩離子含量之功效。In the method for recovering and reusing vanadium electrolyte of the present invention, the first organic phase solution may contain 10-50% dioctyl phosphate and 50-70% sulfonated kerosene by weight percentage, and may also It also includes tributyl phosphate in an amount of 40% or less by weight, preferably 20-40% by weight of dioctyl phosphate, 10-30% of tributyl phosphate and 50% of sulfonated phosphate. kerosene. In this way, the tetravalent vanadium ions in the first aqueous phase solution can be easily dissolved in the first organic phase solution formed by dioctyl phosphate and sulfonated kerosene, and then the second organic phase solution can be improved. The effect of vanadium ion content.
本發明的釩電解液的回收再利用之方法，其中，能夠以1：1～1：3的體積比混合該第一有機相溶液及該第一水相溶液。如此，可以使該第一水相溶液中的四價釩離子較容易溶於由磷酸二辛酯及磺化煤油所形成的第一有機相溶液中，進而可以提升該第二有機相溶液中的釩離子含量之功效。In the method for recovering and reusing the vanadium electrolyte of the present invention, the first organic phase solution and the first aqueous phase solution can be mixed in a volume ratio of 1:1 to 1:3. In this way, the tetravalent vanadium ions in the first aqueous phase solution can be easily dissolved in the first organic phase solution formed by dioctyl phosphate and sulfonated kerosene, and then the tetravalent vanadium ions in the second organic phase solution can be improved. Effect of vanadium ion content.
本發明的釩電解液的回收再利用之方法，其中，該第二水相溶液可以為莫耳濃度為3～7 M的硫酸水溶液，較佳可以為莫耳濃度為5 M以上的硫酸水溶液。如此，可以使該第二有機相溶液中的四價釩離子較容易溶於由硫酸水溶液所形成的第二水相溶液中，進而可以達成提升該第三水相溶液中的釩離子含量之功效。In the method for the recovery and reuse of vanadium electrolyte of the present invention, the second aqueous phase solution can be an aqueous sulfuric acid solution with a molar concentration of 3 to 7 M, preferably an aqueous sulfuric acid solution with a molar concentration of 5 M or more. In this way, the tetravalent vanadium ions in the second organic phase solution can be easily dissolved in the second aqueous phase solution formed by the sulfuric acid aqueous solution, and then the effect of increasing the content of vanadium ions in the third aqueous phase solution can be achieved. .
本發明的釩電解液的回收再利用之方法，其中，能夠以1：5～1：8的體積比混合該第二有機相溶液及該第二水相溶液。如此，可以使該第二有機相溶液中的四價釩離子較容易溶於由硫酸水溶液所形成的第二水相溶液中，進而可以達成提升該第三水相溶液中的釩離子含量之功效。In the method for recovering and reusing the vanadium electrolyte of the present invention, the second organic phase solution and the second aqueous phase solution can be mixed in a volume ratio of 1:5 to 1:8. In this way, the tetravalent vanadium ions in the second organic phase solution can be easily dissolved in the second aqueous phase solution formed by the sulfuric acid aqueous solution, and then the effect of increasing the content of vanadium ions in the third aqueous phase solution can be achieved. .
本發明的釩電解液的回收再利用之方法，其中，該至少二釩離子可以包含二價釩離子及三價釩離子，且亦可以另包含四價釩離子，此時，能夠以一氧化劑使該二價釩離子及三價釩離子形成四價釩離子。舉例而言，該氧化劑可以為氯酸鈉、過氧化氫或高錳酸鉀。如此，可以達成使該回收釩電解液中的至少二釩離子中，至少有莫耳百分比90%以上形成該四價釩離子之功效。In the method for recovering and reusing vanadium electrolyte of the present invention, wherein, the at least divanadium ions can include divalent vanadium ions and trivalent vanadium ions, and can also include tetravalent vanadium ions. At this time, an oxidizing agent can be used to make The divalent vanadium ions and trivalent vanadium ions form tetravalent vanadium ions. For example, the oxidizing agent may be sodium chlorate, hydrogen peroxide or potassium permanganate. In this way, at least 90% of the divanadium ions in the recovered vanadium electrolyte can be formed into the tetravalent vanadium ions with a molar percentage of at least 90%.
本發明的釩電解液的回收再利用之方法，其中，該至少二釩離子可以包含五價釩離子及四價釩離子，此時，能夠以一還原劑使該五價釩離子形成四價釩離子。舉例而言，該還原劑可以為硫代硫酸鈉、草酸或次磷酸鈉。如此，可以達成使該回收釩電解液中的至少二釩離子中，至少有莫耳百分比90%以上形成該四價釩離子之功效。The method for recovering and reusing vanadium electrolyte of the present invention, wherein, the at least divanadium ions can include pentavalent vanadium ions and tetravalent vanadium ions, and at this time, the pentavalent vanadium ions can be formed into tetravalent vanadium by a reducing agent ion. For example, the reducing agent may be sodium thiosulfate, oxalic acid or sodium hypophosphite. In this way, at least 90% of the divanadium ions in the recovered vanadium electrolyte can be formed into the tetravalent vanadium ions with a molar percentage of at least 90%.
本發明的釩電解液的回收再利用之方法，其中，係以200～500 A的電流進行恆流電解20～30小時後，以於該陰極槽收取該再生成釩電解液。如此，藉由以該硫酸水溶液作為該陽極溶液，使該陽極溶液在該電解反應中不會涉及釩離子的氧化或還原，因此無須針對該陽極溶液進行替換或是額外的處理，即可以再次用於生成該再生成釩電解液，有助於減少製造該釩電解液的繁瑣程序，進而可以達成降低該釩電解液的製造成本之功效。In the method for recovering and reusing vanadium electrolyte of the present invention, the regenerated vanadium electrolyte is collected in the cathode cell after constant-current electrolysis with a current of 200-500 A for 20-30 hours. In this way, by using the sulfuric acid aqueous solution as the anode solution, the anode solution will not involve the oxidation or reduction of vanadium ions in the electrolysis reaction, so there is no need to replace or additionally treat the anode solution, that is, it can be used again. In generating the regenerated vanadium electrolyte, it is helpful to reduce the tedious procedures for manufacturing the vanadium electrolyte, thereby achieving the effect of reducing the manufacturing cost of the vanadium electrolyte.
為讓本發明之上述及其他目的、特徵及優點能更明顯易懂，下文特舉本發明之較佳實施例，並配合所附圖式，作詳細說明如下：In order to make the above-mentioned and other objects, features and advantages of the present invention more obvious and easy to understand, the preferred embodiments of the present invention are exemplified below, and are described in detail as follows in conjunction with the accompanying drawings:
請參照第1圖所示，本發明之一實施例的釩電解液的回收再利用之方法，可以包含：一前處理步驟S1、一萃取步驟S2、一反萃取步驟S3及一電解步驟S4，經由該四步驟之後，即能夠以回收自一釩液流電池的一釩電解液作為原料，重新再生成一釩電解液，為避免後續混淆，後續係將回收自該釩液流電池的釩電解液稱為〝回收釩電解液〞，且重新再生成的釩電解液稱為〝再生成釩電解液〞，該回收釩電解液及該再生成釩電解液中包含三價釩離子（vanadium(III) ion，V 3+）、四價釩離子﹝vanadium(IV) ion，V 4+；以釩醯離子（vanadyl ion，VO 2+）的形式存在﹞，且該釩離子與該釩醯離子的莫耳數比約為1：1（如莫耳百分比應介於45～60%：40～55%之間）。 Referring to FIG. 1, a method for recovering and reusing vanadium electrolyte according to an embodiment of the present invention may include: a pretreatment step S1, an extraction step S2, a back-extraction step S3, and an electrolysis step S4, After passing through the four steps, a vanadium electrolyte recovered from a vanadium redox flow battery can be used as a raw material to regenerate a vanadium electrolyte. In order to avoid subsequent confusion, the subsequent system will be recovered from the vanadium electrolyte of the vanadium redox flow battery. It is called "recovered vanadium electrolyte", and the regenerated vanadium electrolyte is called "regenerated vanadium electrolyte". The recovered vanadium electrolyte and the regenerated vanadium electrolyte contain trivalent vanadium ions (vanadium (III) ion, V 3+ ), tetravalent vanadium ion (vanadium(IV) ion, V 4+ ; exists in the form of vanadyl ion, VO 2+ ), and the vanadium ion and the vanadyl ion are incompatible with each other. The ear-to-number ratio is about 1:1 (for example, the molar percentage should be between 45-60%:40-55%).
詳而言之，於該前處理步驟S1中，係可以自該釩液流電池取得該回收釩電解液，該回收釩電解液係可以指經多次充、放電而包含五價釩離子的一陽極溶液，或指經多次充、放電而包含二價釩離子的一陰極溶液，亦可以為該陽極溶液及該陰極溶液的混合液，此為本發明所屬技術領域中具有通常知識者可以理解，於此不加以贅述。In detail, in the pretreatment step S1, the recovered vanadium electrolyte can be obtained from the vanadium redox flow battery, and the recovered vanadium electrolyte can refer to a compound containing pentavalent vanadium ions after repeated charging and discharging. Anode solution, or a cathode solution containing divalent vanadium ions after multiple charging and discharging, can also be a mixed solution of the anode solution and the cathode solution, which can be understood by those with ordinary knowledge in the technical field to which the present invention belongs , will not be repeated here.
該回收釩電解液可以包含價數不同的至少二釩離子，舉例而言，若該回收釩電解液為來自該釩液流電池的陽極溶液，則該回收釩電解液可以包含該五價釩離子及該四價釩離子；或者，若該回收釩電解液來自該釩液流電池的陰極溶液，則該回收釩電解液可以包含該二價釩離子及該三價釩離子；又或者，若該回收釩電解液為該陽極溶液及該陰極溶液的混合液，則該回收釩電解液亦可以同時包含該二價釩離子、該三價釩離子、該四價釩離子及該五價釩離子。惟需要注意的是，在將該回收釩電解液放置一段時間之後，該回收釩電解液中的該二價釩離子、該三價釩離子、該四價釩離子及該五價釩離子彼此會發生氧化還原反應，使該回收釩電解液中僅包含該二價釩離子及該三價釩離子、或僅包含該三價釩離子及該四價釩離子，或僅包含該四價釩離子及該五價釩離子。The recovered vanadium electrolyte may contain at least divanadium ions with different valences. For example, if the recovered vanadium electrolyte is an anode solution from the vanadium redox flow battery, the recovered vanadium electrolyte may contain the pentavalent vanadium ions And this tetravalent vanadium ion; Or, if this recovery vanadium electrolyte comes from the cathode solution of this vanadium redox flow battery, then this recovery vanadium electrolyte can comprise this divalent vanadium ion and this trivalent vanadium ion; Or, if this The recovered vanadium electrolyte is a mixture of the anode solution and the cathode solution, and the recovered vanadium electrolyte may also contain the divalent vanadium ion, the trivalent vanadium ion, the tetravalent vanadium ion and the pentavalent vanadium ion. It should be noted that, after the recovered vanadium electrolyte is placed for a period of time, the divalent vanadium ion, the trivalent vanadium ion, the tetravalent vanadium ion and the pentavalent vanadium ion in the recovered vanadium electrolyte will meet each other. Oxidation-reduction reaction occurs, so that the recovered vanadium electrolyte contains only the divalent vanadium ion and the trivalent vanadium ion, or only the trivalent vanadium ion and the tetravalent vanadium ion, or only the tetravalent vanadium ion and the pentavalent vanadium ion.
接著，工者可以依據該回收釩電解液中的釩離子的種類及比例，選擇以一氧化劑或一還原劑，使該回收釩電解液中的至少二釩離子形成該四價釩離子，以獲得包含該四價釩離子的一第一水相溶液。此時，該至少二釩離子中，至少有莫耳百分比90%以上為該四價釩離子，較佳至少有莫耳百分比99%以上為該四價釩離子。Then, the worker can select an oxidizing agent or a reducing agent according to the type and ratio of the vanadium ion in the recovered vanadium electrolyte to make at least divanadium ions in the recovered vanadium electrolyte form the tetravalent vanadium ion to obtain the tetravalent vanadium ion. A first aqueous solution containing the tetravalent vanadium ions. At this time, among the at least divanadium ions, at least 90% or more of the molar percentage is the tetravalent vanadium ion, and preferably at least 99% or more of the molar percentage is the tetravalent vanadium ion.
舉例而言，當該回收釩電解液包含該二價釩離子及該三價釩離子，工者可以於該回收釩電解液中加入該氧化劑，使該二價釩離子及該三價釩離子氧化形成該四價釩離子，且當該回收釩電解液中的四價釩離子佔釩離子總量（包含該二價釩離子、該三價釩離子及該四價釩離子）的莫耳百分比的90%以上時，即獲得該第一水相溶液；又或者，當該失效釩離子包含該四價釩離子及該五價釩離子時，則可以藉由於該回收釩電解液中加入該還原劑，使該五價釩離子還原形成該四價釩離子，且當該回收釩電解液中的四價釩離子佔釩離子總量（包含該五價釩離子及該四價釩離子）的莫耳百分比的90%以上時，即獲得該第一水相溶液。該氧化劑及該還原劑的種類不限，舉例而言，該氧化劑可以為氯酸鈉（sodium chlorate，NaClO 3）、過氧化氫（hydrogen peroxide，H 2O 2）或高錳酸鉀（potassium permanganate，KMnO 4）；且該還原劑可以為硫代硫酸鈉（sodium thiosulfate，Na 2S 2O 5）、草酸（oxalic acid，H 2C 2O 4）或次磷酸鈉（sodium hypophosphite，NaH 2PO 2）。 For example, when the recovered vanadium electrolyte contains the divalent vanadium ions and the trivalent vanadium ions, the worker can add the oxidant to the recovered vanadium electrolyte to oxidize the divalent vanadium ions and the trivalent vanadium ions This tetravalent vanadium ion is formed, and when the tetravalent vanadium ion in the recovered vanadium electrolyte accounts for the molar percentage of the total amount of vanadium ions (including the divalent vanadium ion, the trivalent vanadium ion and the tetravalent vanadium ion) When more than 90%, obtain this first aqueous phase solution; Or, when this invalid vanadium ion includes this tetravalent vanadium ion and this pentavalent vanadium ion, then can be by adding this reducing agent in this recovery vanadium electrolyte , reducing the pentavalent vanadium ion to form the tetravalent vanadium ion, and when the tetravalent vanadium ion in the recovered vanadium electrolyte accounts for mol of the total amount of vanadium ions (including the pentavalent vanadium ion and the tetravalent vanadium ion) When the percentage is more than 90%, the first aqueous phase solution is obtained. The types of the oxidizing agent and the reducing agent are not limited. For example, the oxidizing agent can be sodium chlorate (NaClO 3 ), hydrogen peroxide (H 2 O 2 ) or potassium permanganate (potassium permanganate). , KMnO 4 ); and the reducing agent can be sodium thiosulfate (sodium thiosulfate, Na 2 S 2 O 5 ), oxalic acid (oxalic acid, H 2 C 2 O 4 ) or sodium hypophosphite (sodium hypophosphite, NaH 2 PO ) 2 ).
又，為了確保該回收釩電解液中的至少二釩離子中，至少有莫耳百分比90%以上為該四價釩離子，工者可以藉由電位滴定法（potentiometric titration）來進行測定，舉例而言，在該回收釩電解液中僅包含該二價釩離子及該三價釩離子時，工者可以在緩慢加入該氧化劑的同時，測定該回收釩電解液的電位（potential），而當該回收釩電解液的電位大幅改變（即，發生〝突躍〞）時，即代表該氧化劑的加入量已達滴定終點（end point of titration），換言之，該回收釩電解液中的四價釩離子佔釩離子總量（包含該二價釩離子、該三價釩離子及該四價釩離子）的莫耳百分比的90%以上，此時即可以獲得該第一水相溶液。Also, in order to ensure that at least 90% of the molar percentage is the tetravalent vanadium ion in the at least divanadium ion in the recovered vanadium electrolyte, the worker can measure it by potentiometric titration. For example, In other words, when only comprising this divalent vanadium ion and this trivalent vanadium ion in this reclaimed vanadium electrolyte, the worker can measure the potential (potential) of this reclaimed vanadium electrolyte while slowly adding this oxidant, and when the When the potential of the recovered vanadium electrolyte changes greatly (that is, a "sudden jump" occurs), it means that the added amount of the oxidant has reached the end point of titration. In other words, the tetravalent vanadium ions in the recovered vanadium electrolyte The first aqueous phase solution can be obtained when the molar percentage of the total amount of vanadium ions (including the divalent vanadium ions, the trivalent vanadium ions and the tetravalent vanadium ions) is more than 90%.
於該萃取步驟S2中，工者係能夠以磷酸二辛酯（di(2-ethylhexyl)phosphate，又稱P204）作為一萃取劑，以自包含該四價釩離子的該第一水相溶液中分離出該四價釩離子，且為了提升該萃取劑的萃取能力，可以將該萃取劑溶於一磺化煤油（sulfonated kerosene；即，經硫酸磺化的煤油）中，使該萃取劑（磷酸二辛酯）與該磺化煤油共同形成一第一有機相溶液。接著，工者可以混合該第一有機相溶液及包含該四價釩離子的第一水相溶液，例如於室溫（15～35℃的溫度下），以1：1～1：3的體積比混合該第一有機相溶液及該第一水相溶液，此時，由於相較於該第一水相溶液，該第一有機相溶液中的磷酸二辛酯對該四價釩離子具有較大的親和力（affinity），且該磺化煤油的存在更有助於降低該四價釩離子的水溶解度，使該四價釩離子可以移動至該第一有機相溶液，並且與該第一有機相溶液中的磷酸二辛酯共同形成四價釩離子錯合物（coordination complex），因此在重新分層之後，工者即可以取得位於上層的一第二有機相溶液及位於下層的水相萃餘液，該第二有機相溶液包含該四價釩離子錯合物。In the extraction step S2, the worker can use dioctyl phosphate (di(2-ethylhexyl)phosphate, also known as P204) as an extractant to extract from the first aqueous solution containing the tetravalent vanadium ion. The tetravalent vanadium ion is separated, and in order to improve the extraction ability of the extractant, the extractant can be dissolved in a sulfonated kerosene (sulfonated kerosene; that is, sulfonated kerosene with sulfuric acid), so that the extractant (phosphoric acid) dioctyl ester) together with the sulfonated kerosene to form a first organic phase solution. Next, the worker can mix the first organic phase solution and the first aqueous phase solution containing the tetravalent vanadium ions, for example, at room temperature (at a temperature of 15-35° C.), in a volume of 1:1-1:3 The ratio of mixing the first organic phase solution and the first aqueous phase solution, at this time, because compared with the first aqueous phase solution, the dioctyl phosphate in the first organic phase solution has a relatively high tetravalent vanadium ion. Large affinity (affinity), and the presence of the sulfonated kerosene is more helpful to reduce the water solubility of the tetravalent vanadium ion, so that the tetravalent vanadium ion can move to the first organic phase solution, and with the first organic phase solution The dioctyl phosphate in the phase solution together forms a tetravalent vanadium ion complex (coordination complex), so after re-layering, the worker can obtain a second organic phase solution located in the upper layer and an aqueous phase extraction solution located in the lower layer. In the remaining liquid, the second organic phase solution contains the tetravalent vanadium ion complex.
值得注意的是，該第一有機相溶液可以包含以重量百分比計為10～50%的磷酸二辛酯及50～70%的磺化煤油，如此可以使足量的磺化煤油提供良好的萃取環境。此外，該第一有機相溶液還可以包含作為一協萃劑的磷酸三丁酯（tributyl phosphate，簡稱TBP），在該第一有機相溶液及該第一水相溶液均勻混合之後，磷酸三丁酯（TBP）的存在有助於該第二有機相溶液（油相溶液）與該水相萃餘液（水相溶液）的分層，因此可以使大部分的四價釩離子錯合物均可以溶解於該第二有機相溶液中。舉例而言，該第一有機相溶液可以另包含以重量百分比計為40%以下的磷酸三丁酯；較佳地，該第一有機相溶液可以包含以重量百分比計為20～40%的磷酸二辛酯、10～30%的磷酸三丁酯及50%的磺化煤油，如此可以提升所獲得的第二有機相溶液中的四價釩離子錯合物的含量。It is worth noting that the first organic phase solution may contain 10-50% by weight of dioctyl phosphate and 50-70% sulfonated kerosene, so that a sufficient amount of sulfonated kerosene can provide good extraction environment. In addition, the first organic phase solution may also include tributyl phosphate (TBP) as a co-extracting agent. After the first organic phase solution and the first aqueous phase solution are uniformly mixed, tributyl phosphate The presence of ester (TBP) facilitates the stratification of the second organic phase solution (oil phase solution) and the aqueous phase raffinate (aqueous phase solution), so that most of the tetravalent vanadium complex can be homogenized. Can be dissolved in the second organic phase solution. For example, the first organic phase solution may further include tributyl phosphate in an amount of less than 40% by weight; preferably, the first organic phase solution may further include phosphoric acid in an amount of 20-40% by weight Dioctyl ester, 10-30% tributyl phosphate and 50% sulfonated kerosene can increase the content of the tetravalent vanadium ion complex in the obtained second organic phase solution.
又，工者可以另調整該第一水相溶液的酸鹼值至介於1～4之間，較佳可以調整至介於2～3之間，如此由於磷酸二辛酯在此一酸鹼值下對該四價釩具有較大的親合力，可以使該第一水相溶液中的四價釩離子較容易溶於該第一有機相溶液中，進而提升所獲得的第二有機相溶液中的四價釩離子錯合物的含量。In addition, the worker can adjust the pH value of the first aqueous phase solution to be between 1 and 4, preferably between 2 and 3, so that because dioctyl phosphate is an acid-base value in this It has a greater affinity for the tetravalent vanadium under the value of The content of the tetravalent vanadium ion complex in the.
接著，在分離出該第二有機相溶液之後，於該反萃取步驟S3中，工者係以一硫酸水溶液作為一第二水相溶液，並混合該第二有機相溶液及該第二水相溶液，例如於室溫（15～35℃的溫度下），以1：5～1：8的體積比混合該第二有機相溶液及該第二水相溶液，該第二水相溶液可以使該四價釩離子錯合物重新分離為磷酸二辛酯及該四價釩離子，該四價釩離子可以再次回溶於水中，因此在重新分層之後，工者即可以取得位於下層的一第三水相溶液及位於上層的有機相萃餘液，該第三水相溶液包含該四價釩離子。Next, after separating the second organic phase solution, in the stripping step S3, the worker uses an aqueous sulfuric acid solution as a second aqueous phase solution, and mixes the second organic phase solution and the second aqueous phase For example, at room temperature (at a temperature of 15 to 35 ° C), the second organic phase solution and the second aqueous phase solution are mixed in a volume ratio of 1:5 to 1:8, and the second aqueous phase solution can be The tetravalent vanadium ion complex is re-separated into dioctyl phosphate and the tetravalent vanadium ion, and the tetravalent vanadium ion can be redissolved in water again, so after re-layering, the worker can obtain a The third aqueous phase solution and the organic phase raffinate located in the upper layer, the third aqueous phase solution contains the tetravalent vanadium ion.
舉例而言，該硫酸水溶液可以選擇為莫耳濃度為3～7 M的硫酸水溶液，較佳可以為莫耳濃度為5 M以上的硫酸水溶液，如此，可以使該第二有機相溶液中的四價釩離子較容易溶於由硫酸水溶液所形成的第二水相溶液中，進而提升所獲得的第三水相溶液中的四價釩離子的含量。For example, the sulfuric acid aqueous solution can be selected as a sulfuric acid aqueous solution with a molar concentration of 3 to 7 M, preferably a sulfuric acid aqueous solution with a molar concentration of more than 5 M, so that the tetramine in the second organic phase solution can be The valence vanadium ions are more easily dissolved in the second aqueous phase solution formed by the sulfuric acid aqueous solution, thereby increasing the content of the tetravalent vanadium ions in the obtained third aqueous phase solution.
於該電解步驟S4中，係設置如第2圖所示之電解裝置，該電解裝置可以包含一陽極槽1及一陰極槽2，該陽極槽1及該陰極槽2中分別容置一陽極溶液及一陰極溶液。又，該陽極槽1與該陰極槽2之間以一隔膜D相隔，使僅有離子能夠通過該隔膜D。In the electrolysis step S4, an electrolysis device as shown in FIG. 2 is provided. The electrolysis device may include an anode tank 1 and a
再請參照第2圖所示，一陽極電極11及一陰極電極21分別設置於該陽極溶液及該陰極溶液中，該陽極電極11連接一直流電源E的正極，且該陰極電極21連接該直流電極E的負極。舉例而言，該陽極電極11可以為一石墨電極、一鉛電極、一鋯電極、一鈦電極或一鉭電極，且該陰極電極21亦可以為一石墨電極、一鉛電極、一鋯電極、一鈦電極或一鉭電極。Please refer to FIG. 2 again, an
值得注意的是，容置於該陽極槽1中的陽極溶液可以為一硫酸水溶液。並且，容置於該陰極槽2中的陰極溶液則可以為包含該四價釩離子的第三水相溶液，其中，該四價釩離子係以釩醯離子的形式存在。It is worth noting that the anode solution contained in the anode tank 1 can be an aqueous sulfuric acid solution. In addition, the cathode solution accommodated in the
在該電解裝置設置完成後，工者即可以開啟該直流電源E，以200～500 A的電流進行恆流電解（constant current electrolysis），於20～30小時的電解時間後，即可以於該陰極槽2收取該釩電解液。After the electrolysis device is set up, the worker can turn on the DC power supply E to perform constant current electrolysis with a current of 200 to 500 A. After 20 to 30 hours of electrolysis, the cathode can be used for
此時，該電解反應於該陽極電極11處的半反應式（half equation）係如下列式三所示。
該電解反應於該陰極電極21處的半反應式係如下列式四所示。
該電解反應的全反應式（cell equation）如下列式五所示。
由於式二所示之半反應式並未涉及釩離子的氧化或還原，因此工者在自該陰極槽2中收取再生成的釩電解液之後，僅需重新於該陰極槽2中填充該陰極溶液即可以重新進行該電解反應以再次生成新的釩電解液，無須針對該陽極槽1中的陽極溶液進行替換或是額外的處理，有助於減少製造該釩電解液的繁瑣程序，進而可以降低該釩電解液的製造成本。Since the semi-reaction equation shown in
為證實依本實施例之釩電解液的回收再利用之方法確實可以再生成該釩電解液，遂進行以下試驗：In order to confirm that this vanadium electrolyte can be regenerated according to the method for the recovery and reuse of the vanadium electrolyte of the present embodiment, the following tests are then carried out:
（A）氧化劑的選用(A) Selection of oxidant
本試驗係取1,000公升的回收釩電解液，該回收釩電解液包含三價釩離子（V 3+）及四價釩離子（VO 2+），且三價釩離子（V 3+）與四價釩離子（VO 2+）的莫耳百分比為23%：77%。接著，分別以如第1表所示之氯酸鈉（溶於水，濃度為20%；第A1組）、過氧化氫（溶於水，濃度為20%；第A2組）及高錳酸鉀（溶於水，濃度為20%；第A3組）作為氧化劑，並且在緩慢加入前述氧化劑的同時，測定該回收釩電解液的電位，在達滴定終點之後，該產物進行氧化還原滴定檢測，以換算該產物中三價釩離子（V 3+）與四價釩離子（VO 2+）的莫耳百分比。 In this experiment, 1,000 liters of recovered vanadium electrolyte was taken. The recovered vanadium electrolyte contains trivalent vanadium ions (V 3+ ) and tetravalent vanadium ions (VO 2+ ), and trivalent vanadium ions (V 3+ ) and tetravalent vanadium ions The molar percentage of valence vanadium ions (VO 2+ ) was 23%: 77%. Next, sodium chlorate (dissolved in water, concentration of 20%; group A1), hydrogen peroxide (dissolved in water, concentration of 20%; group A2) and permanganic acid as shown in Table 1 were respectively added. Potassium (dissolved in water, the concentration is 20%; Group A3) is used as the oxidant, and while slowly adding the aforementioned oxidant, the potential of the recovered vanadium electrolyte is measured, and after reaching the end point of the titration, the product is detected by redox titration, To convert the molar percentage of trivalent vanadium ion (V 3+ ) to tetravalent vanadium ion (VO 2+ ) in the product.
第1表、本試驗各組所得的第一水相溶液中的三價釩離子與四價釩離子的莫耳百分比
請參照第1表所示，無論使用氯化鈉、過錳酸鉀或高錳酸鉀作為該氧化劑，均可以使該回收釩電解液中的三價釩離子（V 3+）被氧化形成四價釩離子（VO 2+），且該四價釩離子均佔釩離子總量（包含該三價釩離子及該四價釩離子）的莫耳百分比的99%以上，即均能夠獲得該第一水相溶液（第A1～A3組）。 Please refer to Table 1, no matter using sodium chloride, potassium permanganate or potassium permanganate as the oxidant, the trivalent vanadium ions (V 3+ ) in the recovered vanadium electrolyte can be oxidized to form tetravalent Valence vanadium ions (VO 2+ ), and the tetravalent vanadium ions all account for more than 99% of the molar percentage of the total amount of vanadium ions (including the trivalent vanadium ions and the tetravalent vanadium ions), that is, all can obtain the first Aqueous solution (groups A1-A3).
（B）還原劑的選用(B) Selection of reducing agent
本試驗係取1,000公升的回收釩電解液，該回收釩電解液包含四價釩離子（VO 2+）及五價釩離子（VO 2 +），且四價釩離子（VO 2+）與五價釩離子（VO 2 +）的莫耳百分比為89%：11%。接著，分別以如第2表所示之硫代硫酸鈉（溶於水，濃度為20%；第B1組）、草酸（溶於水，濃度為20%；第B2組）及次磷酸鈉（溶於水，濃度為20%；第B3組）作為還原劑，並且在緩慢加入前述還原劑的同時，測定該回收釩電解液的電位，在達滴定終點之後，該產物進行氧化還原滴定檢測，以換算該產物中四價釩離子（VO 2+）與五價釩離子（VO 2 +）的莫耳百分比。 In this experiment, 1,000 liters of recovered vanadium electrolyte was taken. The recovered vanadium electrolyte contains tetravalent vanadium ions (VO 2+ ) and pentavalent vanadium ions (VO 2 + ), and tetravalent vanadium ions (VO 2+ ) and pentavalent vanadium ions The molar percentage of valence vanadium ions (VO 2 + ) was 89%:11%. Then, as shown in Table 2, sodium thiosulfate (dissolved in water, concentration of 20%; group B1), oxalic acid (dissolved in water, concentration of 20%; group B2) and sodium hypophosphite ( Dissolved in water, the concentration is 20%; Group B3) as a reducing agent, and while slowly adding the aforementioned reducing agent, measure the potential of the recovered vanadium electrolyte, after reaching the titration end point, the product is subjected to redox titration detection, To convert the molar percentage of tetravalent vanadium ions (VO 2+ ) and pentavalent vanadium ions (VO 2 + ) in the product.
第2表、本試驗各組所得的第一水相溶液中的四價釩離子與五價釩離子的莫耳百分比
請參照第2表所示，無論使用硫代硫酸鈉、草酸或次磷酸鈉作為該還原劑，均可以使該回收釩電解液中的五價釩離子（VO 2 +）被還原形成四價釩離子（VO 2+），且該四價釩離子均佔釩離子總量（包含該五價釩離子及該四價釩離子）的莫耳百分比的99%以上，即均能夠獲得該第一水相溶液（第B1～B3組）。 Please refer to Table 2, no matter using sodium thiosulfate, oxalic acid or sodium hypophosphite as the reducing agent, the pentavalent vanadium ions (VO 2 + ) in the recovered vanadium electrolyte can be reduced to form tetravalent vanadium ions (VO 2+ ), and the tetravalent vanadium ions all account for more than 99% of the molar percentage of the total amount of vanadium ions (including the pentavalent vanadium ions and the tetravalent vanadium ions), that is, the first water can be obtained. Phase solution (groups B1-B3).
（C）第一水相溶液的酸鹼值的調整(C) Adjustment of the pH value of the first aqueous phase solution
本試驗係取1,000公升之第B1組所獲得的第一水相溶液，每公升的第一水相溶液包含86克的釩、2.7克的磷（phosphorus，P）、1克的鐵（iron，Fe）、0.9克的鋁（aluminum，Al），將該第一水相溶液的酸鹼值分別調整為如第3表所示之pH＝1（第C1組）、pH＝2（第C2組）、pH＝3（第C3組）、pH＝4（第C4組）後備用。This test is to take 1,000 liters of the first aqueous phase solution obtained in Group B1, and each liter of the first aqueous phase solution contains 86 grams of vanadium, 2.7 grams of phosphorus (phosphorus, P), 1 gram of iron (iron, Fe), 0.9 g of aluminum (aluminum, Al), adjust the pH value of the first aqueous solution to pH=1 (Group C1) and pH=2 (Group C2) as shown in Table 3, respectively. ), pH=3 (group C3), pH=4 (group C4), and use it for later use.
接著，取包含以重量百分比計為30%之磷酸二辛酯、20%的磷酸三丁酯及50%的磺化煤油的第一有機相溶液，以1：1的體積比混合該第一有機相溶液及該第一水相溶液，於室溫下混合約1分鐘之後，靜置待重新分層，並在取得位於上層的第二有機相溶液後，分析各組第二有機相溶液中的釩、磷、鐵及鋁等金屬元素的含量，進而換算前述各金屬元素的萃取率。Next, take the first organic phase solution containing 30% by weight of dioctyl phosphate, 20% of tributyl phosphate and 50% of sulfonated kerosene, and mix the first organic phase solution in a volume ratio of 1:1 The phase solution and the first aqueous phase solution were mixed at room temperature for about 1 minute, and then allowed to stand for re-stratification. The content of metal elements such as vanadium, phosphorus, iron, and aluminum, and then the extraction rate of the aforementioned metal elements is converted.
第3表、本試驗各組所得的第二有機相溶液中的各金屬元素的含量及換算出來的萃取率
請參照第3表所示，無論是將該第一水相溶液的酸鹼值為1、2、3或4，在與該第一有機相溶液混合後所得的第二有機相溶液中，幾乎均不含雜質（磷、鐵、鋁等金屬元素的萃取率均＜2%），且90%以上的釩均已以該四價釩離子錯合物的形式，被萃取至該第二有機相溶液中（第C1～C4組）；其中，當將該第一水相溶液的酸鹼值調整為介於2～3之間時，約有98%的釩能夠以該四價釩離子錯合物的形式，被萃取至該第二有機相溶液中（第C2、C3組）。Please refer to Table 3, whether the pH value of the first aqueous solution is 1, 2, 3 or 4, in the second organic solution obtained after mixing with the first organic solution, almost All contain no impurities (the extraction rate of metal elements such as phosphorus, iron, and aluminum is less than 2%), and more than 90% of vanadium has been extracted into the second organic phase in the form of the tetravalent vanadium ion complex In the solution (Groups C1 to C4); wherein, when the pH value of the first aqueous solution is adjusted to be between 2 and 3, about 98% of the vanadium can be complexed with the tetravalent vanadium ion in the form of substances extracted into this second organic phase solution (groups C2, C3).
（D）第一水相溶液的酸鹼值的調整(D) Adjustment of the pH value of the first aqueous solution
本試驗係取1,000公升之第B1組所獲得的第一水相溶液，每公升的第一水相溶液包含86克的釩、2.7克的磷（phosphorus，P）、1克的鐵（iron，Fe）、0.9克的鋁（aluminum，Al），將該第一水相溶液的酸鹼值調整為pH＝2後備用。This test is to take 1,000 liters of the first aqueous phase solution obtained in Group B1, and each liter of the first aqueous phase solution contains 86 grams of vanadium, 2.7 grams of phosphorus (phosphorus, P), 1 gram of iron (iron, Fe), 0.9 g of aluminum (aluminum, Al), the pH value of the first aqueous phase solution is adjusted to pH=2 and used for later use.
接著，取包含以重量百分比計為30%之磷酸二辛酯、20%的磷酸三丁酯及50%的磺化煤油的第一有機相溶液，以如第4表所示之體積比（第一有機相溶液：第一水相溶液）混合該第一有機相溶液及該第一水相溶液，於室溫下混合1分鐘之後，靜置待重新分層，並取得位於上層的第二有機相溶液後，分析各組第二有機相溶液中的釩、磷、鐵及鋁等金屬元素的含量，進而換算各金屬元素的萃取率。Next, take the first organic phase solution containing 30% by weight of dioctyl phosphate, 20% of tributyl phosphate and 50% of sulfonated kerosene, in the volume ratio shown in Table 4 (No. an organic phase solution: the first aqueous phase solution), mix the first organic phase solution and the first aqueous phase solution, and after mixing for 1 minute at room temperature, let stand for re-stratification, and obtain the second organic phase solution located in the upper layer. After the phase solution, the contents of metal elements such as vanadium, phosphorus, iron, and aluminum in each group of second organic phase solutions were analyzed, and then the extraction rate of each metal element was converted.
第4表、本試驗各組所得的第二有機相溶液中的各金屬元素的含量及換算出來的萃取率
請參照第4表所示，無論是以1：1或1：2或1：3之體積比混合該第一有機相溶液與第一水相溶液，在所得的第二有機相溶液中，幾乎均不含雜質（磷、鐵、鋁等金屬元素的萃取率均＜2%），且90%以上的釩均已以該四價釩離子錯合物的形式，被萃取至該第二有機相溶液中（第D1～D3組）。Please refer to Table 4, whether the first organic phase solution and the first aqueous phase solution are mixed in a volume ratio of 1:1, 1:2 or 1:3, in the obtained second organic phase solution, almost All contain no impurities (the extraction rate of metal elements such as phosphorus, iron, and aluminum is less than 2%), and more than 90% of vanadium has been extracted into the second organic phase in the form of the tetravalent vanadium ion complex. solution (groups D1-D3).
（E）第一水相溶液的酸鹼值的調整(E) Adjustment of pH value of the first aqueous solution
本試驗係取1,000公升之第B1組所獲得的第一水相溶液，每公升的第一水相溶液包含86克的釩、2.7克的磷（phosphorus，P）、1克的鐵（iron，Fe）、0.9克的鋁（aluminum，Al），將該第一水相溶液的酸鹼值調整為pH＝2後備用。This test is to take 1,000 liters of the first aqueous phase solution obtained in Group B1, and each liter of the first aqueous phase solution contains 86 grams of vanadium, 2.7 grams of phosphorus (phosphorus, P), 1 gram of iron (iron, Fe), 0.9 g of aluminum (aluminum, Al), the pH value of the first aqueous phase solution is adjusted to pH=2 and used for later use.
接著，以如第5表所示之重量百分比混合磷酸二辛酯（P204）、磷酸三丁酯（TBP）及磺化煤油，以形成該第一有機相溶液，再以1：1的體積比混合該第一有機相溶液及該第一水相溶液，於室溫下混合1分鐘之後，靜置待重新分層，並取得位於上層的第二有機相溶液後，分析各組第二有機相溶液中的釩、磷、鐵及鋁等金屬元素的含量，進而換算各金屬元素的萃取率。Next, dioctyl phosphate (P204), tributyl phosphate (TBP) and sulfonated kerosene were mixed in the weight percentages shown in Table 5 to form the first organic phase solution, and then in a volume ratio of 1:1 Mix the first organic phase solution and the first aqueous phase solution, and after mixing for 1 minute at room temperature, let stand for re-stratification, and after obtaining the second organic phase solution located in the upper layer, analyze each group of second organic phase The content of metal elements such as vanadium, phosphorus, iron, and aluminum in the solution is converted into the extraction rate of each metal element.
第5表、本試驗各組所得的第二有機相溶液中的各金屬元素的含量及換算出來的萃取率
請參照第5表所示，在磺化煤油的佔比為50%（重量百分比）的前提下，無論該第一有機相溶液是否包含磷酸三丁酯（TBP），所得的第二有機相溶液中，幾乎均不含雜質（磷、鐵、鋁等金屬元素的萃取率均＜2%），且90%以上的釩均已以該四價釩離子錯合物的形式，被萃取至該第二有機相溶液中（第E1～E5組）；其中，當磷酸二辛酯（P204）的佔比介於20～40%（重量百分比）時，至少有98%的釩能夠以該四價釩離子錯合物的形式，被萃取至該第二有機相溶液中（第E2～E4組）。Please refer to Table 5, under the premise that the proportion of sulfonated kerosene is 50% (weight percent), regardless of whether the first organic phase solution contains tributyl phosphate (TBP), the obtained second organic phase solution Almost all of them do not contain impurities (the extraction rate of metal elements such as phosphorus, iron, and aluminum is less than 2%), and more than 90% of the vanadium has been extracted to the tetravalent vanadium ion complex. In two organic phase solutions (groups E1 to E5); wherein, when the proportion of dioctyl phosphate (P204) is between 20 and 40% (weight percent), at least 98% of the vanadium can be used as the tetravalent vanadium. In the form of ionic complexes, extracted into this second organic phase solution (groups E2-E4).
（F）第二水相溶液的濃度的調整(F) Adjustment of the concentration of the second aqueous solution
本試驗係取1,000公升之第E3組所獲得的第二有機相溶液備用，該第二有機相溶液包含84.366克的釩。In this experiment, 1,000 liters of the second organic phase solution obtained in the E3 group was used, and the second organic phase solution contained 84.366 grams of vanadium.
接著，以如第6表所示之濃度的硫酸水溶液作為該第二水相溶液，再以3：1的體積比混合該第二有機相溶液及該第二水相溶液，於室溫下混合1分鐘之後，靜置待重新分層，並取得位於下層的第三水相溶液後，分析各組第三水相溶液中的釩金屬元素的含量，進而換算釩金屬元素的萃取率。Next, use the sulfuric acid aqueous solution with the concentration shown in Table 6 as the second aqueous phase solution, and then mix the second organic phase solution and the second aqueous phase solution in a volume ratio of 3:1, and mix at room temperature. After 1 minute, stand for re-stratification, and after obtaining the third aqueous phase solution in the lower layer, analyze the content of vanadium metal element in each group of third aqueous phase solutions, and then convert the extraction rate of vanadium metal element.
第6表、本試驗各組所得的第三水相溶液中的釩金屬元素的含量及換算出來的萃取率
請參照第6表所示，在該第二水相溶液的濃度為3～5 M之間時，90%以上的釩均已以該四價釩離子的形式，被反萃取至該第三水相溶液中（第F1～F3組）；其中，當該第二水相溶液的濃度為4 M以上時，至少有98%的釩能夠以該四價釩離子的形式，被反萃取至該第三水相溶液中（第F2、F3組）。Please refer to Table 6, when the concentration of the second aqueous solution is between 3 and 5 M, more than 90% of the vanadium has been back-extracted to the third water in the form of the tetravalent vanadium ion In the phase solution (groups F1 to F3); wherein, when the concentration of the second aqueous phase solution is above 4 M, at least 98% of the vanadium can be back-extracted to the first phase in the form of the tetravalent vanadium ion three-phase solution (groups F2 and F3).
（G）再生成釩電解液的獲得(G) Obtainment of regenerated vanadium electrolyte
本試驗係取1,000公升的硫酸水溶液（硫酸濃度為1.5 M）作為該陽極溶液，及取1,000公升的第F2組所獲得的第三水相溶液作為該陰極溶液，使該陽極溶液與該陰極溶液分別容置於該電解裝置的陽極槽1及陰極槽2中，以鉛電極及鋯電極分別作為該陽極11及陰極21，以電流為300 A的條件下進行該電解反應25小時，並於收集該陰極槽2中的再生成釩電解液後，對該再生成電解液進行氧化還原滴定檢測，以換算該再生成釩電解液中三價釩離子（V
3+）與四價釩離子（VO
2+）的莫耳百分比。
In this experiment, 1,000 liters of sulfuric acid aqueous solution (sulfuric acid concentration of 1.5 M) was used as the anode solution, and 1,000 liters of the third aqueous phase solution obtained in Group F2 was used as the cathode solution. Respectively accommodated in the anode tank 1 and the
結果顯示，該再生成釩電解液中的V 3+與VO 2+的莫耳百分比分別為50.1%及49.9%，符合釩液流電池之釩電解液的需求（釩離子與該釩醯離子的莫耳百分比介於45～60%：40～55%之間），故所生成之再生成釩電解液確實可以用於釩液流電池。 The results show that the molar percentages of V 3+ and VO 2+ in the regenerated vanadium electrolyte are 50.1% and 49.9%, respectively, which meet the requirements of vanadium electrolyte for vanadium redox flow batteries (the difference between vanadium ions and the vanadium amide ions). The molar percentage is between 45-60%: 40-55%), so the generated regenerated vanadium electrolyte can indeed be used in vanadium redox flow batteries.
綜上所述，本發明的釩電解液的回收再利用之方法，藉由以磷酸二辛酯作為一萃取劑，使該四價釩離子以四價釩離子錯合物的形式，被萃取至該第二有機相溶液中，並藉由以該硫酸水溶液作為一反萃劑，使該四價釩離子錯合物以該四價釩離子的形式，被反萃取至該第三水相溶液中，再藉由該恆流電解反應，進而可以生成該再生成釩電解液，經由本發明的釩電解液的回收再利用之方法所獲得的再生成釩電解液含有的雜質較少，因而在用於釩液流電池時，有助於提升該釩液流電池的能量容量及壽命，為本發明之功效。To sum up, the method for recovering and reusing vanadium electrolyte of the present invention uses dioctyl phosphate as an extractant, so that the tetravalent vanadium ion is extracted to the tetravalent vanadium ion complex in the form of In the second organic phase solution, and by using the sulfuric acid aqueous solution as a stripping agent, the tetravalent vanadium ion complex in the form of the tetravalent vanadium ion is stripped back into the third aqueous phase solution. , and then by the constant current electrolysis reaction, the regenerated vanadium electrolyte can be generated, and the regenerated vanadium electrolyte obtained by the method for the recovery and reuse of the vanadium electrolyte of the present invention contains less impurities, so it is When used in a vanadium redox flow battery, it helps to improve the energy capacity and life of the vanadium redox flow battery, which is the effect of the present invention.
雖然本發明已利用上述較佳實施例揭示，然其並非用以限定本發明，任何熟習此技藝者在不脫離本發明之精神和範圍之內，相對上述實施例進行各種更動與修改仍屬本發明所保護之技術範疇，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。Although the present invention has been disclosed by the above-mentioned preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make various changes and modifications relative to the above-mentioned embodiments without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the patent application attached hereto.
﹝本發明﹞ 1:陽極槽 11:陽極電極 2:陰極槽 21:陰極電極 D:隔膜 E:直流電源 S1:前處理步驟 S2:萃取步驟 S3:反萃取步驟 S4:電解步驟﹝this invention﹞ 1: Anode tank 11: Anode electrode 2: Cathode tank 21: Cathode electrode D: Diaphragm E: DC power supply S1: Pre-processing step S2: Extraction step S3: Back-extraction step S4: Electrolysis step
［第1圖］ 本發明之一實施例的釩電解液的回收再利用之方法之流程圖。 ［第2圖］ 用以實施本實施例之釩電解液的回收再利用之方法的電解裝置之示意圖。 [Fig. 1] A flow chart of a method for recovering and reusing vanadium electrolyte according to an embodiment of the present invention. [FIG. 2] A schematic diagram of an electrolysis device used to implement the method for recycling and reusing vanadium electrolyte in this embodiment.
S1:前處理步驟 S1: Pre-processing step
S2:萃取步驟 S2: Extraction step
S3:反萃取步驟 S3: Back-extraction step
S4:電解步驟 S4: Electrolysis step
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| CN106129442A (en) * | 2016-07-05 | 2016-11-16 | 河北钢铁股份有限公司承德分公司 | A kind of method utilizing resins exchange and chemical precipitation combination to prepare all-vanadium redox flow battery electrolyte |
| CN108707748A (en) * | 2018-05-25 | 2018-10-26 | 中国科学院过程工程研究所 | A method of purification bone coal pickle liquor simultaneously recycles aluminium, potassium and iron |
| CN109306404A (en) * | 2018-12-04 | 2019-02-05 | 攀钢集团攀枝花钢铁研究院有限公司 | Extraction vanadium extraction method containing vanadium solution |
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|---|---|---|---|---|
| CN106129442A (en) * | 2016-07-05 | 2016-11-16 | 河北钢铁股份有限公司承德分公司 | A kind of method utilizing resins exchange and chemical precipitation combination to prepare all-vanadium redox flow battery electrolyte |
| CN108707748A (en) * | 2018-05-25 | 2018-10-26 | 中国科学院过程工程研究所 | A method of purification bone coal pickle liquor simultaneously recycles aluminium, potassium and iron |
| CN109306404A (en) * | 2018-12-04 | 2019-02-05 | 攀钢集团攀枝花钢铁研究院有限公司 | Extraction vanadium extraction method containing vanadium solution |
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