1241211 玫、發明說明： 【發明所屬之技術領域】 本發明係關於一種支撐式液態膜分離系統，係可用於回收含 有價金屬之溶液。 【先前技術】 重金屬分離是資源化重金屬首要之課題，其分離方式包含化 學沉降法、蒸發法、離子交換法、溶劑萃取法、電解法及液態膜 分離法等。液態膜分離法為近年來開發之較新技術，具有溶劑使 用量少、反應體積小及能量消耗量小等優點。利用液態膜分離技 術可從低濃度廢液中將金屬離子富集分離，回收其中有價物質， 達到無害化環境保護及資源回收的目的。 依不同反應機制，液態膜主要可分為乳化式液態膜（emulsion liquid membrane，ELM)及支樓式液態膜（supported liquid membrane，SLM)兩種。乳化式液態膜具有高質傳通量，惟薄膜穩 定性、水份的吸收、二次乳化的形成及控制變因的複雜性，使得 乳化式液態膜的應用受到限制。最常見的支撐式液態膜的型態是 將適當的有機溶劑填充於多孔性的高分子基材中，此多孔性高分 子基材的主要功用為提供液態膜的支撐基材（supporting matrix)。液態膜對離子的選擇性主要是由進料相與液膜間的分佈 係數所決定，而分佈係數為金屬物質在兩相間溶解度與擴散係數 的函數。為了增加液態膜對於金屬離子的選擇性，必須添加萃取 劑於液膜中，使得膜對於特定金屬離子有較高的分配係數。 在支撐式液態膜中，因進料相界面之有機金屬錯合物濃度較 高而具擴散至反萃相界面之驅動力，而載體則在反萃相界面有較 高濃度而擴散至進料相界面。整個分離過程就在置換反應及濃度 梯度造成之擴散作用下持續不斷進行。在適當的操作條件下，金 屬之回收率可達99%以上。 1241211 支撐式液態膜分離方法結合了萃取、反萃取和擴散程序於一體， 進料相主要進行金屬離子擴散與載體和金屬離子萃取行為，而液 態膜中則為有機金屬錯合物之擴散作用，最後在反萃相中進行反 萃取動作。影響液態膜分離之參數主要有pH值、濃度、離子強 度、攪拌速度、反萃相種類及液態膜組成、厚度等。一般而言液 態膜之成效可以滲透率（Permeability)、分離選擇率（Membrane separation factor)及金屬回收率表示。 應用支撐式液態膜於分離重金屬目前相關文獻皆屬於研究 室規模，如第一圖所示係為傳統平板支撐式液態膜裝置，主要是 以較為簡易之液態膜1隔開之一個進料相區2及一反萃相區3， 且無pH值控制之功能，其進料處理量小於1公升。一般平板式 支撐液態膜優點為質傳模式簡單，容易預測分離程序之成效。但 傳統平板式支撐液態膜之缺點在於有效反應面積小，另一方面， 由於pH值影響分離速率及金屬離子之狀態，因此，截至目前為 止，放大系統並商業化仍為支撐式液態膜系統的最大挑戰。本發 明最主要係提供有效反應面積極大，且具有控制進料相pH值功 能之新型平板支撐液態膜分離系統。 【發明内容】 有鑑於習知支撐式液態膜分離裝置之缺點，本發明即設計 一可處理大量進料之支撐液態膜系統，以利其應用於工業上。 本發明係關於一種支撐式液態膜分，系統，包含： 一分離反應槽，係以兩個支撐液態膜區隔三個區域， 左右兩區域為進料相區’中間為反卒相區’其中二個區域各自 設有排氣管及排液管； 一進料相桶，係貯存進料相溶液； 一進料相緩衝桶，係貯存溢流之進料相溶液； 一反萃相桶，係貯存反萃液； 1241211 一反萃相緩衝桶係貯存溢流之反萃液； 一 pH值控制系統，係可偵測並控制前述分離反應槽 之pH值； 一複數個排液管，係用以連通各進料相或連通各反萃 相； 一複數個排氣管，係用以排除液態膜兩側之壓差；及 一複數個泵浦，係提供動力使系統中的溶液循環流 動。 前述系統中進料相桶、分離反應槽之進料相區及進料相緩 衝桶係以排液管相連通，並以泵浦幫助進料相溶液循環於其中。 前述系統中反萃相桶、分離反應槽之反萃相區及反萃相緩 衝桶係以排液管相連通，並以泵浦幫助反萃液循環於其中。 前述系統中分離反應槽係可視實際處理液體之量，以串連 方式增加，彈性增加系統中支撐液態膜之面積，該串聯式支撐 式液態膜分離系統中各分離反應槽中之進料相區之各排液管相 > 連通，反萃相區之各排液管相連通，進料相區之各排氣管相連 通，及反萃相區之各排氣管相連通；前述串聯式支撐式液態膜 分離系統中各分離反應槽之進料相區並以排液管與進料相缓衝 桶相連通，反萃相區以排液管與反萃相緩衝通相連通。 前述之pH值控制系統係包含pH調整液桶、pH測定控制 儀及pH調整幫浦，係用於控制系統運作過程中pH值之變化， 使其維持於適當之pH反應條件，避免金屬沉澱現象。 前述分離反應槽之支撐式液態膜係為含萃取劑之多孔性 薄膜，其中前述之多孔性薄膜係包含聚四氟乙烯(PTFE)、聚氟 化亞乙烯（PVDF)、聚丙烯、聚苯乙烯之多孔性薄膜或其他類似 之多孔性薄膜。 前述之萃取劑包含酸性萃取劑或鹼性萃取劑，其中酸性萃 1241211 取劑包含羧酸、磺酸或酸性含磷萃取劑，其中鹼性萃取劑包含 一級、二級、三級或四級胺鹽。 前述之支撐式液態膜係可進一步為包含稀釋劑和萃取劑 之多孔性薄膜，其中稀釋劑係用於改變萃取劑濃度或金屬錯合 物在有機相之溶解度，以提昇萃取劑之萃取能力，使萃取劑發 揮最大效用。 前述之反萃液係為無機酸，包含鹽酸(HC1)、硫酸(H2S04)、 硝酸（HN〇3)、氟化銨(NH4F)或硫代硫酸鈉（Na2S203)。 前述之反應槽材質係為抗酸鹼及有機溶劑之材料，包含聚 氣乙烯（PVC)、特弗龍或聚四氟乙烯（PTFE)。 前述進料相桶之進料相溶液與反卒相桶之反卒液係以重 力流方式充滿反應槽之進料相與反卒相’並溢流至進料相緩衝 桶與反萃相緩衝桶中。 金屬分離程序必須具有低處理成本、高效能、及低二次污 染之分離技術。本發明主要特點在於串聯分離反應槽以增加液 態膜之有效分離反應面積，並以pH控制系統固定進料相之pH 值，以維持反應速率及解決進料相金屬因pH改變而產生沉澱 之現象，並以重力流配合泵浦循環系統溶液以解決因壓差而產 生液態膜之漏失現象，提供一嶄新之支撐液態膜分離系統，有 效分離回收有價金屬。 【實施方式】 第二圖係為本發明之支撐式液態膜分離系統100之一實施 例，包含：一分離反應槽10，係以兩個支撐液態膜80區隔三 個區域，左右兩區域為進料相區11及12,中間為反萃相區13， 其中三個區域各自設有排氣管及排液管；一進料相桶20,係貯 存進料相溶液；一進料相緩衝桶30，係貯存溢流之進料相溶 液；一反萃相桶40，係貯存反萃液；一反萃相緩衝桶50係貯 1241211 流之反萃液；一 pH值控制系統，包含pH調整液桶6i、 周整泵浦62及PH測定儀63，係可偵測並控制前述分離反 1〇之pH值；一複數個排液管（實線部分），係肖以連通各 _相或連通各反萃相卜複數個排氣管（虛線部分），係用以 非除=膜兩側之壓差；及一複數個泵浦，包含進料相泵浦71 反:相泵浦72，係可提供動力使系統中的溶液循環流動。 前述分離反應槽，U)之支撐式液態膜8〇係為含萃取劑之多 ▼ ^薄膜’其中前述之多孔性薄膜係包含聚四氟乙稀(PTFE)、 :鼠化亞乙烯(PVDF)、聚丙烯或聚苯乙烯之多孔性薄膜。支撐 心膜80中所含的萃取劑係依據所欲分離之金屬而選擇，並 配合適當之稀釋劑使萃取劑能發揮最佳效用；例如，鈷金屬可 用+二乙基己基）磷酸酯（D2EHPA)配合煤油（ker〇sene)稀釋劑 别述之反萃液一般為無機酸，包含鹽酸（Ηα)、硫酸 =〇4)、硝酸⑽〇3)、敦化銨_4f)或硫代硫酸納（Na2S2〇3)。 二述之反應槽材質係為抗酸鹼及有機溶劑之材料，包含聚氣乙 婦（PVc)、特弗龍或聚四氟乙烯（PTFE)。1241211 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a support type liquid membrane separation system, which can be used for recovering solutions containing valuable metals. [Previous technology] Separation of heavy metals is the most important issue for the recycling of heavy metals. The separation methods include chemical sedimentation, evaporation, ion exchange, solvent extraction, electrolysis, and liquid membrane separation. The liquid membrane separation method is a relatively new technology developed in recent years, and has the advantages of a small amount of solvent, a small reaction volume, and a small energy consumption. Liquid membrane separation technology can be used to enrich and separate metal ions from low-concentration waste liquids, recover valuable substances, and achieve the purpose of harmless environmental protection and resource recovery. According to different reaction mechanisms, liquid membranes can be mainly divided into two types: emulsion liquid membrane (ELM) and supported liquid membrane (SLM). Emulsified liquid membranes have high mass flux, but the stability of the membrane, the absorption of water, the formation of secondary emulsification, and the complexity of controlling the variables make the application of emulsified liquid membranes limited. The most common type of supporting liquid film is to fill a porous polymer substrate with an appropriate organic solvent. The main function of this porous polymer substrate is to provide a supporting matrix for the liquid film. The selectivity of a liquid film to ions is mainly determined by the distribution coefficient between the feed phase and the liquid film, and the distribution coefficient is a function of the solubility and diffusion coefficient of the metal substance between the two phases. In order to increase the selectivity of the liquid membrane for metal ions, an extractant must be added to the liquid membrane so that the membrane has a higher partition coefficient for specific metal ions. In the supporting liquid film, the driving force for diffusion to the stripped phase interface is driven by the higher concentration of the organometallic complex at the phase interface of the feed, and the carrier diffuses to the feed at a higher concentration at the stripped phase interface. Phase interface. The entire separation process continues under the effect of displacement reaction and diffusion caused by concentration gradient. Under proper operating conditions, the metal recovery rate can reach over 99%. 1241211 Supported liquid membrane separation method combines extraction, back extraction and diffusion procedures. The feed phase mainly conducts metal ion diffusion and carrier and metal ion extraction behavior, while the liquid film is the diffusion effect of organic metal complexes. Finally, a back extraction operation is performed in the back extraction phase. The parameters affecting liquid membrane separation mainly include pH, concentration, ionic strength, stirring speed, type of back extraction phase, composition and thickness of liquid membrane, etc. In general, the effectiveness of liquid membranes can be expressed in terms of Permeability, Membrane separation factor, and metal recovery. The application of supporting liquid membranes for separating heavy metals is currently related to the research laboratory scale. As shown in the first figure, it is a traditional flat-supported liquid membrane device, which is mainly a feed phase zone separated by a relatively simple liquid membrane 1. 2 and a reverse extraction phase zone 3, without the function of pH control, the feed processing capacity is less than 1 liter. The advantages of the general flat-type support liquid membrane are that the mass transfer mode is simple and it is easy to predict the effectiveness of the separation process. However, the disadvantage of the traditional flat support liquid membrane is that the effective reaction area is small. On the other hand, because the pH value affects the separation rate and the state of the metal ions, so far, the system has been scaled up and commercialized as a support liquid membrane system. The biggest challenge. The present invention mainly provides a new flat-supported liquid membrane separation system with a large effective reaction area and a function of controlling the pH value of the feed phase. [Summary of the Invention] In view of the shortcomings of the conventional support type liquid membrane separation device, the present invention is to design a support liquid membrane system that can handle a large amount of feed in order to facilitate its application in industry. The invention relates to a supported liquid membrane separation system comprising: a separation reaction tank, which is divided into three regions by two supporting liquid membranes, and the left and right regions are the feed phase region and the middle is the anti-depression phase region. The two areas are provided with exhaust pipes and liquid discharge pipes respectively; a feed phase bucket is used to store the feed phase solution; a feed phase buffer bucket is used to store the overflowed feed phase solution; a back extraction phase bucket, It is used to store back-extracted liquid. 1241211 A back-extracted phase buffer tank is used to store overflowed back-extracted liquid. A pH control system can detect and control the pH value of the aforementioned separation reaction tank. It is used to connect the feed phases or back extraction phases; a plurality of exhaust pipes are used to eliminate the pressure difference between the two sides of the liquid membrane; and a plurality of pumps are used to provide power to circulate the solution in the system . In the foregoing system, the feed phase barrel, the feed phase area of the separation reaction tank, and the feed phase buffer barrel are connected by a drain pipe, and a pump is used to help the feed phase solution circulate therein. In the foregoing system, the back-extraction phase barrel, the back-extraction phase area of the separation reaction tank, and the back-extraction phase buffer barrel are connected by a drain pipe, and a pump is used to help the back-extraction liquid circulate therein. The separation reaction tank in the foregoing system can be increased in series according to the actual amount of liquid processed, and the area of the supporting liquid membrane in the system can be increased elastically. The feed phase zone in each separation reaction tank in the tandem-supported liquid membrane separation system The drainage pipe phases are connected, the drainage pipes in the reverse extraction phase zone are in communication, the exhaust pipes in the feed phase zone are in communication, and the exhaust pipes in the reverse extraction phase zone are in communication; In the supported liquid membrane separation system, the feed phase area of each separation reaction tank is communicated with the feed phase buffer barrel through a drain pipe, and the back extraction phase area is communicated with the back extract phase buffer through a drain pipe. The aforementioned pH value control system includes a pH adjusting liquid bucket, a pH measuring controller and a pH adjusting pump, and is used to control the change of the pH value during the operation of the system, so as to maintain the appropriate pH reaction conditions and avoid metal precipitation. . The supporting liquid membrane of the aforementioned separation reaction tank is a porous film containing an extractant, wherein the aforementioned porous film system includes polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polypropylene, polystyrene Porous film or other similar porous film. The aforementioned extraction agent includes an acidic extraction agent or an alkaline extraction agent, wherein the acidic extraction 1241211 extractant includes a carboxylic acid, a sulfonic acid, or an acidic phosphorus-containing extraction agent, wherein the alkaline extraction agent includes a primary, secondary, tertiary, or quaternary amine. salt. The aforementioned supporting liquid film system may further be a porous thin film containing a diluent and an extractant, wherein the diluent is used to change the concentration of the extractant or the solubility of the metal complex in the organic phase, so as to improve the extractive ability of the extractant. Maximize the effectiveness of the extractant. The aforementioned back-extraction liquid is an inorganic acid, including hydrochloric acid (HC1), sulfuric acid (H2S04), nitric acid (HN03), ammonium fluoride (NH4F), or sodium thiosulfate (Na2S203). The material of the aforementioned reaction tank is a material resistant to acids and alkalis and organic solvents, and includes polyvinyl chloride (PVC), Teflon or polytetrafluoroethylene (PTFE). The feed phase solution of the aforementioned feed phase bucket and the anti-depleted liquid of the anti-depleted phase bucket are filled with the feed phase and anti-depleted phase of the reaction tank by gravity flow, and overflow to the feed-phase buffer bucket and back-extracted phase buffer. In the bucket. Metal separation procedures must have separation technologies with low treatment costs, high performance, and low secondary pollution. The main feature of the invention is that the reaction tank is separated in series to increase the effective separation reaction area of the liquid membrane, and the pH value of the feed phase is fixed by a pH control system to maintain the reaction rate and solve the phenomenon of precipitation of the metal in the feed phase due to pH change. In addition, the gravity flow is used to cooperate with the pump circulation system solution to solve the phenomenon of liquid film leakage due to pressure difference, and provides a new supporting liquid film separation system to effectively separate and recover valuable metals. [Embodiment] The second figure is an embodiment of the supported liquid membrane separation system 100 of the present invention, including: a separation reaction tank 10, which is divided into three regions by two supporting liquid membranes 80, and the left and right regions are Feed phase zones 11 and 12, with a reverse extraction phase zone 13 in the middle, three of which are equipped with exhaust pipes and liquid discharge pipes; a feed phase barrel 20 is used to store the feed phase solution; a feed phase buffer Bucket 30 is used to store the feed phase solution that overflows; a back-extracted phase bucket 40 is used to store the back-extracted liquid; a back-extracted phase buffer bucket 50 is used to store the back-extracted liquid of 1241211 flow; a pH control system containing pH Adjust the liquid tank 6i, the whole-cycle pump 62 and the pH meter 63, which can detect and control the pH value of the aforementioned separation inverse 10; a plurality of liquid discharge pipes (solid line parts), which are connected to each phase Or connect each back extraction phase with a plurality of exhaust pipes (the dotted line), which are used to divide the pressure difference between the two sides of the membrane; and a plurality of pumps, including the feed phase pump 71 reverse: phase pump 72 The system can provide power to circulate the solution in the system. The supporting liquid membrane 80 of the aforementioned separation reaction tank, U, is as much as containing the extractant ▼ ^ thin film 'wherein the aforementioned porous thin film includes polytetrafluoroethylene (PTFE), ratified vinylidene oxide (PVDF) , Polypropylene or polystyrene porous film. The extracting agent contained in the supporting pericardium 80 is selected according to the metal to be separated, and the appropriate diluent is used to make the extracting agent perform the best effect; for example, cobalt metal can be used + diethylhexyl) phosphate (D2EHPA ) In combination with kerosene (kerosene) diluent, the back-extracting liquid is generally an inorganic acid, including hydrochloric acid (Ηα), sulfuric acid = 〇4), nitric acid 敦 〇3), ammonium _4f) or sodium thiosulfate ( Na2S203). The material of the second reaction tank is a material resistant to acids and alkalis and organic solvents, including PVC, Teflon or polytetrafluoroethylene (PTFE).
人亡1吏用本發明之第二圖所示之支撐液態膜分離系統10015 二^屬之溶液之操作方式如下：首先將欲回收之含有十 所右八二人進料相桶2G’另配製反萃液倒人反萃相桶40, ^ 值H广f應槽10各區域之排氣閥90 ’打開進料相桶20、 干^Ϊ 及反萃相桶*與分離反應槽1G之閥門（圖乂 應样ίο)方絲補相雜歧萃相歸充滿所有分黃 衝#相區U、12與反萃相區13,並溢流至進料才 相泵哺7?反萃相緩衝桶4” ’之後開啟進料相泵浦71 1 3a W 2 PH值調整I浦62，使進料相溶液由進料相緩ί 丁入進料相桶20中進行循環，而同樣地反萃相溶液以 10 1241211 相緩衝桶50打入反萃相桶40中進行循環，同時pH值調整泵 浦62依據所設定之pH值將pH值調整液打入進料相桶20中， 以固定進料相之pH值。 本發明之支撐式液態膜分離系統中的分離反應槽1〇係可 視需要串聯方式增加，參考第三、四、五、六圖，例如將十一 個之分離反應槽10串聯，同時將各進料相區11、12之各排液 管相連通，反萃相區13之各排液管相連通，進料相區11、12 之各排氣管相連通，及反萃相區13之各排氣管相連通，藉此增 加有效分應面積。第三圖係顯示進料液在串聯式支撐式液態膜 分離系統中的路徑示意圖，系統中的進料相桶20、分離反應槽 10之進料相區11、12及進料相緩衝桶30係以排液管相連通， 進料相桶20之進料相溶液藉由重力流入分離反應槽10之進料 相區11、12，並依序通過以排液管串聯之分離反應槽10之進 料相區11、12，然後溢流至進料相緩衝桶30，其中各分離反應 槽10之進料相區11、12除了有一排液管與其他反應槽10之進 料相區11、12串聯外，並同時有一取樣用之排液管可直接將過 多之進料相液導入進料相緩衝桶30中（參考第五圖），之後藉由 進料相泵浦71幫助進料相溶液輸送至進料相桶20，使進料相 溶液循環於系統中持續進行分離。 第四圖係顯示反萃液在串聯式支撐式液態膜系統中的路徑 示意圖，系統中的反萃相桶40、分離反應槽10之反萃相區13 及反萃相緩衝桶50也同樣排液管相連通，與進料相區原理相 同，反萃相桶40之反萃相溶液藉由重力流入分離反應槽10之 反萃相區13，依序通過以排液管串聯之分離反應槽10之反萃 相區13，然後溢流至反萃相緩衝桶50，各單獨分離反應槽10 之反萃相區13也同樣有一取樣用之排液管可直接將過多之反 萃液溢流至反萃相緩衝桶中50中（參考第五圖），並以反萃相泵 1241211 浦72幫助反萃液循環於其中。第六圖為串聯式支撐液態膜分離 系統中排氣管分布#意圖，系統中各個分離反應# 1()之進料相 區11、12之排氣管係連通至一總進料相排氣管，反萃相區13 之排氣管亦連通至一反萃相總排氣管。 下歹J貫知例係用於了解本發明，並非用於限制本發明，任 何熟習本技術領域之人士皆可基與本發明之特色，在不脫離本 發明精神與目的下，對本發明做不同的更動與修飾，使其適用 於不同的情況與對象，因此，其他實施態樣也包含在本發明之 申請專利範圍内。 實施例The operation of a person using the supporting liquid membrane separation system 10015 shown in the second figure of the present invention is as follows: First, prepare the right-handed feed tank 2G 'containing ten right-handed people and prepare it separately. The reverse extraction liquid is poured into the reverse extraction phase barrel 40, and the exhaust valve 90 in each area of the reaction tank 10 is opened. 'Open the feed phase barrel 20, dry Ϊ and reverse extraction phase barrel * and the valve of the separation reaction tank 1G. (Picture should be like ο) The square wire complement phase heterogeneous extraction phase is filled with all sub-diluted red #phase zone U, 12 and reverse extraction phase zone 13 and overflow to the feed before pumping 7? Reverse extraction phase buffer Bucket 4 ”', then turn on the feed phase pump 71 1 3a W 2 PH value adjustment I pump 62, so that the feed phase solution is slowly fed from the feed phase into the feed phase barrel 20 for circulation, and the same back extraction The phase solution is circulated in 10 1241211 phase buffer barrel 50 into reverse extraction phase barrel 40 for circulation. At the same time, the pH adjustment pump 62 pumps the pH adjustment liquid into the feed phase barrel 20 according to the set pH value to fix the phase solution. The pH value of the material phase. The separation reaction tank 10 in the supported liquid membrane separation system of the present invention can be increased in series according to need. Refer to the third, fourth, fifth, and sixth figures, for example, One separation reaction tank 10 is connected in series, and at the same time, the liquid discharge pipes of the feed phase zones 11 and 12 are connected, the liquid discharge pipes of the reverse extraction phase zone 13 are connected, and the exhaust gases of the feed phase zones 11 and 12 are connected. The tubes are connected to each other and the exhaust pipes of the stripping phase zone 13 are connected to increase the effective separation area. The third diagram is a schematic diagram showing the path of the feed liquid in the tandem supported liquid membrane separation system. The feed phase buckets 20, 11 and 12 of the separation reaction tank 10 and the feed phase buffer buckets 30 are connected by drain pipes. The feed phase solution of the feed phase bucket 20 flows into the separation reaction by gravity. The feed phase zones 11 and 12 of the tank 10 are sequentially passed through the feed phase zones 11 and 12 of the separation reaction tank 10 connected in series by a drain pipe, and then overflow to the feed phase buffer tank 30, where each of the separation reaction tanks In addition to the feed phase zones 11 and 12 of 10, in addition to a series of liquid pipes connected to the feed phase zones 11 and 12 of other reaction tanks 10, there is also a liquid discharge pipe for sampling that can directly introduce excess feed phase liquid into the The material phase buffer tank 30 (refer to the fifth figure), and then the feed phase solution is conveyed to the inlet by the feed phase pump 71. Phase barrel 20, which allows the feed phase solution to circulate in the system for continuous separation. The fourth diagram is a schematic diagram showing the path of the back-extracted liquid in the tandem support liquid membrane system. The back-extracted phase barrel 40 and the separation reaction tank in the system The reverse extraction phase zone 13 of 10 and the reverse extraction phase buffer tank 50 are also connected to the drain pipe. The principle is the same as that of the feed phase zone. The reverse extraction phase solution of the reverse extraction phase bucket 40 flows into the separation reaction tank 10 by gravity. The extraction phase zone 13 passes through the reverse extraction phase zone 13 of the separation reaction tank 10 connected in series by a drain pipe, and then overflows to the reverse extraction phase buffer tank 50. The reverse extraction phase zone 13 of each separate reaction tank 10 is also the same. A drain pipe for sampling can directly overflow too much back-extracted liquid into the back-extracted phase buffer tank 50 (refer to the fifth figure), and a back-extracted phase pump 1241211, pump 72 helps the back-extracted liquid circulate in it. The sixth figure shows the exhaust pipe distribution in the tandem-supported liquid membrane separation system. # Intent, the exhaust pipes in the feed phase zones 11 and 12 of each separation reaction # 1 () in the system are connected to a total feed phase exhaust. The exhaust pipe of the reverse extraction phase zone 13 is also connected to a reverse extraction general exhaust pipe. The following examples are used to understand the present invention, and are not intended to limit the present invention. Any person skilled in the art can base on the features of the present invention, and make changes to the present invention without departing from the spirit and purpose of the present invention. The changes and modifications of s are suitable for different situations and objects. Therefore, other implementation aspects are also included in the scope of the patent application of the present invention. Examples
本實施例所使用之分離回收有價金屬之支撐液態膜分離系 統係如第三、四、i、六圖所示，該系統中包含一個容積為 公升PW材質進料相桶，—個容積為％公升pvc材質進料相 緩衝桶’-個容積為30公升pvc材質反萃相桶，一個容積為 30公升PVC材質反萃相緩衝桶，一個容積為％公升pvC材質 PH值調整液桶，一個進料相栗浦’一個反萃相栗浦，-個pH =整：：樂系浦’十—個pvc分離反應槽，其中分離反應槽 中刀為左右兩個進料相區及中間-個反萃相區，三個區域由 ，開，其中左右兩個進料相區容積各為0.9公升， 為“公升，三個區域各有-個排氣管及 :=L相各排氣管相連通、反萃相各排氣管相 連通’、進枓相各排液管相連通、反萃相各排液管相連通。 、本心月之支撑式液㉟膜分離系統進行坤化鎵之分離實 驗，以PC88A為萃取劑，〇 2μπι pTFE薄膜為支樓構體，進料 相pH值曲維持在1.8 ’反萃相為2M HC卜分離時間及反萃相中 砷及鎵濃度如表-所示’進料原液含鎵12()()mg/卜神糊^， 經72小時分離後’反萃相中含錄删mg/1、石申】㈣八，嫁回 12 1241211 . 收率為91%，鎵/砷比由3 : 1提高為800 : 1。此一結果顯示本 發明之支撐式液態膜分離系統能依據所選擇之萃取液，自進料 相溶液中有效萃取出有價金屬。The supporting liquid membrane separation system for separating and recovering valuable metals used in this embodiment is shown in Figs. 3, 4, i, and 6. The system includes a feed phase barrel of PW material with a volume of one liter, and a volume of%. 1 litre pvc material feed phase buffer barrel '-a 30 litre pvc material back extraction phase buffer barrel, a 30 litre pvc material back extraction phase buffer barrel, a volume of% litre pvC material pH adjustment liquid barrel, one inlet Material phase Lipu 'a reverse extraction phase Lipu,-one pH = whole ::: Lexipu' ten-PVC separation reaction tanks, where the knife in the separation reaction tank is the left and right two feed phase regions and the middle-one reaction Extraction phase zone, three zones are opened, and the left and right feed phase zones each have a volume of 0.9 liters, which is "liters. Each of the three zones has one exhaust pipe and: = L phase exhaust pipes connected. The back extraction phase is connected with the exhaust pipes', the inlet phase is connected with the drainage pipes, and the back extraction phase is connected with the drainage pipes. In the experiment, PC88A was used as the extraction agent, 〇2μm pTFE film was used as the supporting structure, and the pH of the feed phase was The curve was maintained at 1.8 'The back extraction phase was 2M HC. The separation time and the arsenic and gallium concentrations in the back extraction phase are shown in Table-'. Post-reverse extraction phase contains mg / 1, Shi Shen】 ㈣ 八, marry 12 1241211. The yield was 91%, and the gallium / arsenic ratio increased from 3: 1 to 800: 1. This result shows that the present invention The supported liquid membrane separation system can effectively extract valuable metals from the feed phase solution according to the selected extraction liquid.
表一、反萃相中砷及鎵濃度變化 0H 24 Η 48 H 72 H Ga (mg/1) (mg/l) Ga (mg/1) (mg/1) Ga (mg/1) (mg/1) Ga (mg/1) (mg/1) 0 0 565 0.4 876 0.8 1090 1.3 13 1241211 【圖式簡單說明】 第一圖係為傳統支撐式液態膜系統之示意圖。 第二圖係為本發明之支撐式液態膜分離系統之示意圖。 第三圖係為進料液在本發明之串聯式支撐式液態膜分離系統中 的路徑示意圖。 第四圖係為反'萃液在本發明之串聯式支撐式液態膜分離系統中 的路徑示意圖。 第五圖係為本發明之串聯式支撐式液態膜分離系統中各分離反 應槽與料相緩衝桶及反萃相反衝桶之排液管串聯方式示意圖。 第六圖係為本發明之串聯式支撐液態膜分離系統中各分離反應 槽之排氣管分布示意圖。 【主要元件符號對照說明】 1— 支樓式液怨膜 2— 進料相區 3— 反卒相區 10…分離反應槽 11、12—進料相區 13—反卒相區 20—進料相桶 30—進料相緩衝桶 40…反萃相桶 50…反萃相緩衝桶 1241211 61…pH調整液桶 62…pH調整泵浦 63…pH測定儀 71 —進料相果滤 72—反卒相果 '浦 80…支撐式液態膜 90…排氣閥 100--支撐式液態膜分離系統Table 1. Variations in Arsenic and Gallium Concentrations in Back Extraction Phase 0H 24 Η 48 H 72 H Ga (mg / 1) (mg / l) Ga (mg / 1) (mg / 1) Ga (mg / 1) (mg / 1) Ga (mg / 1) (mg / 1) 0 0 565 0.4 876 0.8 1090 1.3 13 1241211 [Brief description of the diagram] The first diagram is a schematic diagram of a traditional supporting liquid membrane system. The second figure is a schematic diagram of the supported liquid membrane separation system of the present invention. The third figure is a schematic diagram of the path of the feed liquid in the tandem support type liquid membrane separation system of the present invention. The fourth diagram is a schematic diagram of the path of the reverse extraction liquid in the tandem support type liquid membrane separation system of the present invention. The fifth figure is a schematic view showing the series connection of the liquid discharge pipes of each separation reaction tank, the material buffer tank and the reverse extraction tank in the tandem support type liquid membrane separation system of the present invention. The sixth figure is a schematic diagram of the exhaust pipe distribution of each separation reaction tank in the tandem support liquid membrane separation system of the present invention. [Comparison of main component symbols] 1—Branch type liquid grieving film 2—Feeding phase area 3—Anti-depression phase area 10… Separation reaction tank 11, 12—Feeding phase area 13—Anti-depression phase area 20—Feeding Phase barrel 30—feed phase buffer barrel 40… reverse phase extraction barrel 50… reverse phase extraction buffer barrel 1241211 61… pH adjustment liquid barrel 62… pH adjustment pump 63… pH analyzer 71—feed phase fruit filter 72—reverse phase Dead phase 'Pu 80 ... supported liquid membrane 90 ... exhaust valve 100--supported liquid membrane separation system