588122 經濟部中夬標準局員工消費合作社印装 A7 _____B7_ 五、發明説明（1 ) 發明領域 本發明係有關一種從滷水/海水生産碳酸鋰的方法，尤 其有關一種結合使用吸附法及電透析法兩種提濃技術，從 滷水生産鋰濃縮液及碳酸鋰的方法。 發明背景 近年來由於筆記型電腦、行動電話與電動汽機車之發 展，使得鋰離子電池之需求量大增。此外，鋰之化學品種 類繁多，應用在工業上的範圍亦廣，例如使用在陶瓷、.玻 璃、鋁電解熔融與合成橡膠業等。而使用量最大的鋰化學 品爲碳酸鋰，且大部分之鋰Jfk學品皆由碳酸鋰所延伸製. 得，因此碳酸鋰爲最重要之鋰化學品之一。 目前工業界上製造碳酸鋰，主要的原料爲礦石與滷水 兩者，臺灣本身並沒有蘊藏鋰的礦石，因此需把海水當成 獲取鋰資源的主要來源。臺灣目前擁有的海水資源有兩 個，一種是未經濃縮的海水，另一種是經濃縮的滷水。一 般海水中之鋰濃度約在0.1〜0.5 ppm左右，濃度極低，而 經製鹽或海水淡化處理後所産生之濃縮廢滷水，其中所含 的鋰濃度約在10 ppm;兩者相對於生産碳酸鋰所需要的最 低鋰濃度15000 ppm，仍有一段極大的差距。 申請人於2001年12月19日申請的我國第90131574號專 利申請案揭示一種以吸附劑由含鋰水溶液吸附其中鋰離子 的方法，包含將一含鋰的錳氧化物的吸附劑與一含有鋰離 子的水溶液接觸，於是該水溶液中的鋰離子被吸附於該吸 本紙浪尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ! Bill tm mm «—>1-— «Βϋϋ am— 11ϋ» :1 .ms* —i n (請先閲讀背面之注意事項寫本買)588122 Printed by the Consumers' Cooperative of the China Standards Bureau of the Ministry of Economic Affairs A7 _____B7_ V. Description of the Invention (1) Field of the Invention The present invention relates to a method for producing lithium carbonate from brine / seawater, and particularly relates to a combination of adsorption and electrodialysis. A concentration technology, a method for producing lithium concentrate and lithium carbonate from brine. BACKGROUND OF THE INVENTION In recent years, due to the development of notebook computers, mobile phones, and electric vehicles, the demand for lithium-ion batteries has increased greatly. In addition, lithium has a wide range of chemical varieties and is widely used in industry, such as ceramics, glass, aluminum electrolytic melting and synthetic rubber. The most widely used lithium chemical is lithium carbonate, and most of the lithium Jfk grades are derived from lithium carbonate. Therefore, lithium carbonate is one of the most important lithium chemicals. At present, lithium carbonate is produced in the industrial world. The main raw materials are both ore and brine. Taiwan itself does not contain lithium ore. Therefore, seawater should be used as the main source of lithium resources. Taiwan currently has two marine water resources, one is unconcentrated seawater and the other is concentrated brine. Generally, the concentration of lithium in seawater is about 0.1 ~ 0.5 ppm, the concentration is extremely low, and the concentrated waste brine produced after salt making or seawater desalination treatment contains lithium concentration of about 10 ppm; both are relative to production The minimum lithium concentration required for lithium carbonate is 15,000 ppm, and there is still a large gap. Chinese Patent Application No. 90131574, filed by the applicant on December 19, 2001, discloses a method for adsorbing lithium ions in a lithium-containing aqueous solution with an adsorbent, comprising a lithium-containing manganese oxide adsorbent and a lithium-containing The aqueous solution of ions came into contact, so the lithium ions in the aqueous solution were adsorbed on the absorbent paper. The standard of China National Standard (CNS) A4 (210X297 mm) was applied! Bill tm mm «— > 1-—« Βϋϋ am— 11ϋ »: 1 .ms * —in (please read the notes on the back first to buy)
、1T 588122 Λ7 _B7__ 五、發明説明（2 ) 附劑上，其特徵在於該含有鋰離子的水溶液具有一不小於 10的pH値。較佳的，該含鋰的錳氧化物的吸附劑包含 LiMn204或Li2Mn03。該案的內容藉由參考方式被並入本案 說明書。此前案方法由滷水所産生的鋰濃縮液的鋰濃度有 一定的限制，約在1 500ppm左右。因此如何將鋰濃度由1500 ppm進一步提升到可以生産碳酸鋰的1 50()() ppm左右乃爲一 重要的課題。 美國專利US4636295揭示使用多階段電透析從滷水製 備鎂與鋰之重量比爲5 : 1或更低的鋰增濃水溶液。該 US4636295使用附加化合物使鎂離子沈澱及過濾之步驟，使 鋰增濃水溶液之鎂離子降低/再以電透析進一步增濃其中 的鋰濃度至15. 5 g/L，約1. 5%。 本發明的一主要目的在提出一種從滷水生産鋰濃縮液 的方法，其具有高鋰離子回收率及不産生固體廢棄物的優 點。 發明槪述 經濟部中夬標準局員工消资合作杜印¾ 本發明的一種從滷水生産鋰濃縮液的方法，包含下列 步驟： a) 將滷水導入一吸附劑床而使得滷水中的鋰離子相較於. 鈉、鉀、鈣及鎂離子被較強的吸附於該吸附劑床中的吸 附劑； b) 將水導入該吸附劑床使得被吸附的鈉、鉀、鈣及鎂離子 從該吸附劑被脫附； 本紙浪尺度適用中國國家標準（CNS ) A4規格（2 Η) X m公釐） 588122 經濟部中夬標準局員工消費合作社印51 A7 B7 五、發明説明（3 ) C)將一酸水溶液導入該吸附劑床以脫附被吸附於該吸附 劑上的鋰離子，於是獲得一鋰離子濃度爲1200-1500 ppm 的水溶液； d) 以電透析法將來自步驟c)的鋰離子濃度1200-1500 ppm 的水溶液的鋰離子濃度增濃（enriching)至8000-10000 PPM ； e) 以電透析法將來自步驟d)的鋰離子濃度8000-10000 ppm的水溶液的鋰離子濃度增濃至14000-18000 ppm。 較佳的，步驟e)産生一鋰離子濃度爲1200-1500 ppm 的鋰脫除（lithium depleted)水溶液，該方法進一步包含將 此鋰離子濃度爲1200-1500 ppm的鋰脫除水溶液再循環至 步驟d)作爲進料。 較佳的，步驟d)産生一鋰離子濃度爲250-400 ppm的 鋰脫除水溶液，該方法進一步包含以電透析法將此鋰離子 濃度爲250-400 ppm的鋰脫除水溶液的鋰離子濃度增濃至 1200-1500 ppm，及將此鋰離子濃度增濃至1200-1500 ppm 的水溶液再循環至步驟d)作爲進料。更佳的，於以電透析 法將鋰離子濃度由25 0-400 ppm增濃至1200-15 00 ppm的 同時，一鋰離子濃度爲10-100 ppm的鋰脫除水溶液被産 生，該方法進一步包含將此鋰離子濃度爲10-100 ppm的鋰 脫除水溶液再循環至步驟a)作爲該吸附劑床的進料。 發明之詳細說明 本發明結合使用吸附法及電透析法兩種提濃技術，將 本紙浪尺度適用中國國家標準（CNS ) A4現格（210X297公釐） (請先閲讀背面之注意事項寫本頁) 、νά 588122 經濟部中夬橾準局員工消費合作杜印«. Λ7 B7_ 五、發明説明（4 ) 製鹽滷水中之鋰濃度由數ppm提升至製造碳酸鋰所需之 1.5%左右。首先以吸附法將數ppm的鋰水溶液提升至1 200 -1 500 ppm;再以二階段接續進行的電透析處理，將鋰濃度 增濃至1. 5%左右。 本發明方法，較佳的，在將滷水導入一塡充有鋰離子 吸附劑的吸附劑床進行吸附前，先將一鹼例如氫氧化鈉加 入滷水而提高其pH値至10-11，於是提升該吸附劑的飽和吸 附量。 較佳的，該吸附劑爲含鋰的錳氧化物的粒狀吸附劑， 其包含鋰的錳氧化物粉末及作爲黏結劑的聚合物。適合作 爲黏結劑的聚合物包括（但不限於）聚氯乙烯。 適用於本發明的該含鋰的錳氧化物的吸附劑包含（但 不限於）LiMn204或 Li2Mn03。 該含鋰的錳氧化物粉末的一適合製備方法例如美國專 利第4665049號所揭示者，其細節在此藉由參考方式被合倂 於本案。 該粒狀含鋰的錳氧化物的吸附劑的一適合製備方法例 如曰本特開平3-8439號專利案所揭示者，其細節在此藉由 參考方式被合倂於本案。 本發明方法利用精鹽廠生産食鹽製程所産生的廢滷水 或直接使用海水，將其流通過一塡充有鋰離子吸附劑之管 柱，於吸附劑達到吸附飽和後，採用二段式脫附方式擷取 高濃度脫附液。第一階段先以清水流過管柱，藉由水洗去 除吸附劑上吸附力較差的鈉、鉀、鈣及鎂等主要雜質，於 本紙張尺度適用中國國家標準（CNS ) A4規格（2l〇X：Z97公釐） (請先閱讀背面之注意事項^本頁) 裝----- 訂 588122 A7 B7 五、發明説明（5 ) 這些雜質離子降低至1〇 ppm以下時才停止水洗步驟。第二 階段再導入一脫附液（例如稀鹽酸）來脫附吸附較強的鋰離 子，並以光學檢知器對排出流作同步偵測鋰離子濃度，藉 由排出流鋰離子濃度與偵測光穿透率之相關性，於鋰離子 含量達到預定濃度之特定區段擷取排出流，不僅可獲得鋰 濃度較大之濃縮液，同時可減低其他雜質含量。 從該吸附劑管柱獲得的鋰濃度1 200-1 500 ppm的排出 流；再以二階段接續進行的電透析處理，將鋰濃度增濃至 1.5%左右。第二階段的電透析處理所産生的鋰脫除水溶液 具有1 200-1 50 0 ppm的鋰濃度，其被再循環至第一階段的電 透析處理作爲進料。第一階段的電透析處理所産生的鋰脫 除水溶液可被進一步施以附加的電透析處理，而産生一鋰 濃度爲1 200-1 500 ppm的鋰增濃水溶液，其同樣被再循環至 第一階段的電透析處理作爲進料。該附加的電透析處理所 産生的鋰脫除水溶液則作爲該吸附劑床的進料，於是充分 的擷取了滷水中之鋰離子。 經濟部中夬橾隼局員工消费合作社印χ - I I t ϋ^ι— n n^— f : 11 ijl » _ - - 1 1--(請先閲讀背面之注事項寫本\貝) 一適合使用於本發明方法的電透析設備己爲業界所熟 知，例如美國專利US3063924所揭示者。此前案之內容，藉 由參考方式被並入本案。 本發明方法的一較佳實施例將參考圖1被說明如下。將 精鹽場結晶罐蒸發製取氯化鈉及氯化鉀後之滷水1通過塡 充含鋰的錳氧化物吸附劑之吸附塔2進行吸附。滷水空間流 速控制在18〜40 L/hr之間，流速太小使得吸附速率太慢， 流速太大則降低了滷水之鋰回收率。分析滷水吸附前後鋰 本紙张尺度適用中國國家標隼（CNS ) A4規格（210X 297公釐） 588122 經濟部中夬標準局員工消費合作.杜印¾ Λ7 _ B7五、發明説明（6 ) 濃度，待其濃度相近，即表示吸附劑達到吸附飽和。吸附 飽和後之管柱先以清水清洗吸附劑，此時吸附劑上大量之 鈉、鉀、鈣、鎂等主要雜質離子會被脫附出來，而鋰離子 只有少量會自吸附劑洗出，此階段之排出流不予以收集。 接著以0.5〜1.0NHC1進行脫附，將鋰離子自吸附劑中脫附 出來，排出流之鋰離子濃度以光學檢知計3作同步式偵測， 以760 nm波長之光源照射，測得之排出流光穿透率値會隨 著排出流中鋰濃度增加而降低，如圖2所示。於穿透率曲線 出現轉折之處開始擺取排出流，此時光穿透率値會降低至 2%以下，而排出流中鋰離子濃度大於800 ppm。當鋰離子 大量被脫附出來時，排出流#鋰離子濃度會逐漸降低，偵測 所得之排出流光穿透率値也會隨著升高至2%以上，此時則 停止收集。未收集之其他排出流4則回流至原滷水中，可再 進行吸附。光穿透率値於2%以下所收集到之鋰排出流中， 鈉、鉀、鈣、鎂離子的濃度已明顯的低於鋰離子。排出流 停止收集後，可繼續酸洗，將吸附劑上離子幾近完全脫附 出來，使得吸附劑再進行下次吸附時能維持幾近原有之吸 附量。在停止擷取排出流後繼續酸脫附時，排出流之鋰離 子濃度會越來越低，相對之光穿透率値會越來越高，當光 穿透率値大於96%時，鋰離子濃度小於2 ppm，此時即可停 止酸洗程式。選擇性地，鋰離子濃度高的排出流被停止收 集後，可停止對吸附劑酸洗而直接導入進料進行吸附。 將鋰濃度1200〜1500 ppm之脫附液由一第一儲槽5送 入一第一階段電透析設備6中，以定電壓15〜20V操作，而 -9- 本紙浪尺度適用中國國家標準（CNS ) A4規格（210x297公慶） (請先閱讀背面之注意事項 本\貝) ，裝！ ,ιτ 588122 經濟部中夬標隼局員工消资合作社印¾ Λ7 B7 五、發明説明（7 ) 得到含鋰濃度8000〜10000 ppm之鋰增濃液，並被收集於一 第二儲槽7。由第二儲槽7將鋰濃度8000〜10000 ppm之鋰增 濃液送入一第二階段電透析設備8中，以定電壓爲15〜20V 操作，而得到含鋰濃度14000〜1 8000 ppm之鋰增濃液並被 收集於一第三儲槽9中。於該第三儲槽9的下游鋰濃度14000 〜1 8000 ppm的鋰增濃液被加入碳酸鈉10,而沈澱出碳酸鋰 結晶11。 另外於第二階段電透析設備8進行增濃時，其同時會産 生一含鋰濃度1500〜2000 ppm之鋰脫除液，其被送入第一 儲槽5作爲第一階段電透析設備6的進料。而於第一階段電 透析設備6進行增濃時，其同時會産生一含鋰濃度3 00〜400 ppm之殘液，其被送入一殘液電透析設備12中進行增濃， .以定電壓爲20〜25V操作，得到與第一儲槽5者近似濃度之 增濃液，其被送入第一儲槽5作爲第一階段電透析設備6的 進料，達到殘液回收之目的。而殘液電透析設備12所産生 的鋰脫除液（鋰濃度約50〜100 ppm)被送回與滷水合倂作 爲該吸附塔2的進料。 在電透析濃縮過程中，若進料與鋰增濃液的槽離子濃 度相差太大，會有逆滲透現象之發生，進而導致增濃效率 降低，造成電能之浪費。本發明技巧的將電透析增濃分階 段進行，使每一階段之操作不會産生逆滲透之現象，以達 到較佳的增濃效率，且每一階段電透析增濃所産生的鋰脫 除液可方便的被再循環利用於本發明方法本身。因此，本 發明方法幾無污染物質生成，爲一清淨製程。 -10- 本紙浪尺度適用中國國家標準（CNS ) A4说格（210X 297公釐） (請先閱讀背面之注意事項\^^寫本頁) -裝. 訂 588122 經濟部中夬標準局員工消资合作杜印¾ A7 B7五、發明説明（8 ) 本發明可藉由以下實施例被進一步瞭解，該實施例僅 作爲說明之用，而非用於限制本發明範圍。 準備例1 取聚氯乙烯（聚合度620±20)約73克溶解於980 ml的N-甲基-2-萝咯院酮（N-methyl-2-pyrrolidone;NMP)溶劑中，再 將300克的尖晶石相（spinel phase) Li133Ma16704粉體加入 於所獲得的PVC溶液中，並充分捏揉（kneading)所獲得的混 合物。捏揉後的混合物由一細管（管徑3 mm)被滴入1200 ml 的水與甲醇（1:1體積比）的混合液體中，於是形成粒徑3.5-4.3 mm的顆粒。過濾分離該混合液體與顆粒，再藉由降壓 揮發而移除其中的液體，於是獲得的乾燥的吸附劑顆粒， 其比重爲0.41 g/cm3。 實施例1 準備例1所造的吸附劑顆粒40克在被以去離子水浸泡 濕潤後分別被充塡於一管柱內形成一吸附劑床，以去離子 水清洗該吸附劑床，再以0.5N鹽酸水溶液1300 ml酸洗，接 著以去離子水清洗即可進行吸附。對該管柱連續通以精鹽 廠精鹽過程産生之滷水，空間流速控制在35 L/hr，經過14 天吸附後，吸附劑即可達飽和狀態。吸附飽和之管柱，先 通以去離子水脫附吸附劑，其空間流速控制在3 L/hr，流 通120毫升之後，再以1.0N鹽酸脫附吸附劑。 以光學檢知器偵測脫附液光穿透率，通以光波長760 -11- 本紙浪^1適用中國國家標準（。呢）人4见格（210父297公釐） (請先閱讀背面之注意事項 忒頁) 裝----- ，tr 588122 經濟部中夬標準局員工消费合作杜印¾ A7 五、發明説明（9 ) nm條件下，偵測脫附流光穿透率値。擷取光穿透率値小於 2%之部份脫附流，此部份脫附流鋰離子濃度大於800 ppm，混合之脫附流的離子含量如表一所示。 表一滷水進料成分及脫附流之金屬離子含量 離子濃度（ppm) 鋰 鈉 鉀 鈣 鉄 滷水 9〜12 29100 37000 17700 35300 脫附液 1484 109 144 154 246 使用日本ANSANICS Co.，Ltd.公司，型號DS-0的電透 析設備進行以下的電透析增-濃。 第一階段電透析：將脫鹽槽注滿鋰離子濃度爲1484 ppm之脫附液，濃縮槽則注入5L之相同脫附液，並配置 10L 0.5N之硫酸鈉溶液作爲電極液放入電極槽中。以7.6 L/min的流速持續將脫附液由脫鹽槽導入該電透析設備的 脫鹽室的入口，並由該電透析設備的脫鹽室的出口流出至 該脫鹽槽。以7.2 L/min的流速持續將脫附液由濃縮槽導 入該電透析設備的濃縮室的入口，並由該電透析設備的濃 縮室的出口流出至該濃縮槽。以6.8 L/min的流速持續將 電極液由電極槽導入該電透析設備的電極室的入口，並由 該電透析設備的電極室的出口流出至該電極槽。上述脫鹽 槽室、濃縮槽室及電極槽室之內循環流速均爲與設備規格 相關之操作參數。此外，以一進料流速150ml/min持續對 脫鹽槽持續進料鋰離子濃度爲1484 ppm之脫附液。於定電 -12- 本紙張適用中國國家標準（CNS ) A4規格（210X297公釐） · ^ . 裝 (請先閲讀背面之注意事項寫本一貝) 、tr 588122 經濟部中夬橾隼局員工消費合作社印¾ Λ7 B7 五、發明説明（10 ) 壓23伏特之狀況下操作300 min，脫鹽槽中溶液將因持續 進料而溢流出料。濃縮槽不進料亦不出料，鋰離子將由濃 縮槽透過透析薄膜進入濃縮槽。300 min時脫鹽率可達80% 以上，此時完成脫鹽後由脫鹽槽溢流出之脫鹽液中鋰離子 濃度約爲290 ppm，此部份將成爲下游的一殘液回收電透 析之進料。濃縮槽內的鋰增濃液的鋰離子濃度達9450 ppm，被作爲第二階段之濃縮。 第二階段電透析：將此階段脫鹽槽注滿第一階段電透 析所獲得鋰離子濃度爲9450 ppm之鋰增濃液10 L ;濃縮 槽注入10 L之相同鋰增濃液；及配置10 L 0.5N之硫酸鈉 溶液作爲電極液放入電極槽中。以7.6 L/min的流速持續 將脫附液由脫鹽槽導入該電透析設備的脫鹽室的入口，並 由該電透析設備的脫鹽室的出口流出至該脫鹽槽。以7.2 L/min的流速持續將脫附液由濃縮槽導入該電透析設備的 濃縮室的入口，並由該電透析設備的濃縮室的出口流出至 該濃縮槽。以6.8 L/min的流速持續將電極液由電極槽導 入該電透析設備的電極室的入口，並由該電透析設備的電 極室的出口流出至該電極槽。上述脫鹽槽室、濃縮槽室及 電極槽室之內循環流速均爲與設備規格相關之操作參數。 此階段脫鹽槽不另外對脫鹽槽連續進料。於定電壓2〇伏特 之狀況下操作，鋰離子將由濃縮槽透過透析薄膜進入濃縮 槽。270 min時脫鹽率達85%，此時完成脫鹽後脫鹽槽中 鋰離子濃度約爲1320 ppm，此部份將成爲第一階段電透析 之進料；而濃縮槽側中鋰離子濃度達17250 ppm。 -13- 本紙浪Λ度適用中國國家標準（CNS ) A4洗格（210X 297公釐） •二·-·. I : - - - -1 II m mu I ti 1 I 11- ·1 i (請先閱讀背面之注意事項寫本一貝) 訂 588122 經濟部中夬標準局員工消资合作社印¾. A7 __B7五、發明説明（11 ) 殘液回收電透析：將殘液回收電透析設備中的脫鹽槽 注滿第一階段脫鹽槽脫鹽後鋰離子濃度爲290 ppm之殘 液；而濃縮槽則注入5 L之相同殘液，並配置10L 0.5N之 硫酸鈉溶液作爲電極液放入電極槽中。以7.6 L/min的流 速持續將脫附液由脫鹽槽導入該電透析設備的脫鹽室的入 口，並由該電透析設備的脫鹽室的出口流出至該脫鹽槽。 以7.2 L/min的流速持續將脫附液由濃縮槽導入該電透析 設備的濃縮室的入口，並由該電透析設備的濃縮室的出口 流出至該濃縮槽。以6.8L/min的流速持續將電極液由電極 槽導入該電透析設備的電極室的入口，並由該電透析設備 的電極室的出口流出至該電極槽。上述脫鹽槽室、濃縮槽 室及電極槽室之內循環流速均爲與設備規格相關之操作參 數。此外，以一進料流速200 ml/min持續對脫鹽槽持續進 料鋰離子濃度爲290 ppm之殘液。於定電壓30伏特之狀況 下操作，脫鹽槽中溶液將因持續進料而溢流出料，濃縮槽 不進料亦不出料，鋰離子將由濃縮槽透過透析薄膜進入濃 縮槽。60 min時脫鹽率可達85%以上，此時完成脫鹽後由 脫鹽槽溢流出之脫鹽液中鋰離子濃度約爲37 ppm，此部份 可與滷水合倂作爲吸附劑管柱之進料。濃縮槽內的鋰增濃 液的鋰離子濃度達1270 ppm，可成爲第一階段電透析之進 料。 表二爲以上各階段濃縮所獲得的位於濃縮槽內的鋰增 濃液的金屬離子濃度。 -14- 本紙浪尺度適用中國國家標準（CNS ) A4規格（210 X 297公慶） (請先閱讀背*之注意事項 本頁) 裝I!1T 588122 Λ7 _B7__ 5. Description of the invention (2) The appendix is characterized in that the aqueous solution containing lithium ions has a pH of not less than 10. Preferably, the adsorbent containing lithium manganese oxide comprises LiMn204 or Li2Mn03. The contents of the case are incorporated into the description of the case by reference. The lithium concentration of the lithium concentrate produced by the brine in the previous method has a certain limit, about 1,500 ppm. Therefore, how to further increase the lithium concentration from 1500 ppm to about 50 () () ppm which can produce lithium carbonate is an important issue. U.S. Patent No. 4,636,295 discloses the use of multi-stage electrodialysis to prepare a lithium-enriched aqueous solution with a magnesium to lithium weight ratio of 5: 1 or less from brine. The US4636295 uses additional compounds to precipitate and filter magnesium ions, so that the magnesium ions in the lithium-enriched aqueous solution are reduced / re-enriched by electrodialysis to a lithium concentration of 15.5 g / L, about 1.5%. A main object of the present invention is to propose a method for producing a lithium concentrated solution from brine, which has the advantages of high lithium ion recovery and no solid waste. The invention is described by Du Yin, an employee of the China Standards Bureau of the Ministry of Economic Affairs. The method for producing lithium concentrate from brine includes the following steps: a) The brine is introduced into an adsorbent bed to make the lithium ion phase in the brine. Compared with. Sodium, potassium, calcium and magnesium ions are strongly adsorbed in the adsorbent bed; b) water is introduced into the adsorbent bed so that the adsorbed sodium, potassium, calcium and magnesium ions are adsorbed from the adsorbent The agent is desorbed; the paper scale is applicable to the Chinese National Standard (CNS) A4 specification (2mm) X mmm) 588122 Printed by the Consumer Cooperatives of the China Standards Bureau of the Ministry of Economic Affairs 51 A7 B7 V. Description of the invention (3) C) will An aqueous acid solution is introduced into the adsorbent bed to desorb the lithium ions adsorbed on the adsorbent, thereby obtaining an aqueous solution having a lithium ion concentration of 1200-1500 ppm; d) electrolyzing the lithium ions from step c) The lithium ion concentration of the aqueous solution having a concentration of 1200-1500 ppm is enriched to 8000-10000 PPM; e) the lithium ion concentration of the aqueous solution having a lithium ion concentration of 8000-10000 ppm from step d) is increased by electrodialysis to 14000-18000 ppm. Preferably, step e) generates a lithium depleted aqueous solution having a lithium ion concentration of 1200-1500 ppm, and the method further includes recycling the lithium depleted aqueous solution having a lithium ion concentration of 1200-1500 ppm to the step. d) as feed. Preferably, step d) generates a lithium removal aqueous solution having a lithium ion concentration of 250-400 ppm, and the method further includes electrolyzing the lithium ion concentration of the lithium removal aqueous solution having a lithium ion concentration of 250-400 ppm. The aqueous solution was concentrated to 1200-1500 ppm, and this aqueous solution having the lithium ion concentration concentrated to 1200-1500 ppm was recycled to step d) as a feed. More preferably, while the lithium ion concentration is increased from 25 0-400 ppm to 1200-15 00 ppm by electrodialysis, a lithium removal aqueous solution with a lithium ion concentration of 10-100 ppm is generated. This method further It comprises recycling this lithium removal aqueous solution having a lithium ion concentration of 10-100 ppm to step a) as a feed to the adsorbent bed. Detailed description of the invention The present invention combines the two concentration techniques of adsorption method and electrodialysis method to apply the paper scale to Chinese National Standard (CNS) A4 (210X297 mm) (please read the precautions on the back to write this page) ), Νά 588122 Du Yin, a consumer cooperation agreement with the staff of the China Prospective Bureau of the Ministry of Economic Affairs «7 Λ7 B7_ V. Description of the invention (4) The lithium concentration in the brine for salt production was raised from a few ppm to about 1.5% required for the manufacture of lithium carbonate. 5%。 First, the adsorption method to raise the lithium aqueous solution of several ppm to 1 200 -1 500 ppm; and then in a two-stage sequential electrodialysis treatment, the lithium concentration was increased to about 1.5%. In the method of the present invention, preferably, before the brine is introduced into an adsorbent bed filled with a lithium ion adsorbent for adsorption, a base such as sodium hydroxide is first added to the brine to raise its pH to 10-11, so that it is raised. The saturated adsorption capacity of the adsorbent. Preferably, the adsorbent is a granular adsorbent containing lithium manganese oxide, which contains lithium manganese oxide powder and a polymer as a binder. Polymers suitable as binders include, but are not limited to, polyvinyl chloride. The lithium-containing manganese oxide adsorbent suitable for use in the present invention includes, but is not limited to, LiMn204 or Li2Mn03. A suitable method for preparing the lithium-containing manganese oxide powder is disclosed in, for example, U.S. Patent No. 4,665,049, the details of which are incorporated herein by reference. A suitable preparation method of the particulate lithium-containing manganese oxide adsorbent is disclosed in, for example, Japanese Patent Application Laid-Open No. 3-8439, the details of which are incorporated herein by reference. The method of the present invention uses waste brine produced by the salt production process of a salt refinery or directly uses seawater, and passes it through a stack of lithium ion adsorbents filled with a column. After the adsorbent reaches adsorption saturation, a two-stage desorption method is adopted. Capture high concentration desorption solution. In the first stage, clean water is passed through the column, and the main impurities such as sodium, potassium, calcium, and magnesium, which have poor adsorption power, are removed by washing with water. The Chinese national standard (CNS) A4 specification (2l0X) : Z97mm) (Please read the precautions on the back ^ this page first) Installation ----- Order 588122 A7 B7 V. Description of the invention (5) Stop the water washing step when these impurity ions are reduced to less than 10ppm. In the second stage, a desorption solution (such as dilute hydrochloric acid) is introduced to desorb the strongly adsorbed lithium ions, and the optical detector is used to detect the lithium ion concentration synchronously with the lithium ion concentration. Correlation of photometric transmittance, extracting the exhaust stream in a specific section where the lithium ion content reaches a predetermined concentration, can not only obtain a concentrated solution with a large lithium concentration, but also reduce the content of other impurities. The effluent with a lithium concentration of 1 200-1 500 ppm obtained from the sorbent column; and the subsequent electrodialysis in two stages to increase the lithium concentration to about 1.5%. The lithium removal aqueous solution produced by the second-stage electrodialysis treatment has a lithium concentration of 1 200-1 500 ppm, which is recycled to the first-stage electrodialysis treatment as a feed. The lithium removal aqueous solution produced in the first stage of electrodialysis treatment can be further subjected to additional electrodialysis treatment to produce a lithium concentrated aqueous solution having a lithium concentration of 1 200-1 500 ppm, which is also recycled to the first One stage of electrodialysis treatment was used as feed. The lithium removal aqueous solution produced by the additional electrodialysis treatment is used as the feed for the adsorbent bed, and lithium ions in the brine are sufficiently captured. Printed by the Consumer Affairs Cooperative of the China Economic and Trade Bureau of the Ministry of Economic Affairs χ-II t ϋ ^ ι— nn ^ — f: 11 ijl »_--1 1-(Please read the notes on the back first \ Shell)-Suitable for use in The electrodialysis device of the method of the present invention is well known in the industry, for example, as disclosed in US Pat. No. 3063924. The content of the previous case was incorporated into the case by reference. A preferred embodiment of the method of the present invention will be explained with reference to FIG. 1 as follows. The brine 1 obtained by evaporating the crystallizing tank of the fine salt field to obtain sodium chloride and potassium chloride is adsorbed by an adsorption tower 2 filled with a lithium manganese oxide adsorbent. The brine flow rate is controlled between 18 ~ 40 L / hr. The flow rate is too small to make the adsorption rate too slow. Too large a flow rate reduces the lithium recovery rate of the brine. Analyze the lithium before and after the brine adsorption. The paper size applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm). 588122 Employees' cooperation with the China Standards Bureau of the Ministry of Economic Affairs. Du Yin ¾ Λ7 _ B7 V. Description of the invention (6) Concentration, When the concentrations are similar, it means that the adsorbent has reached adsorption saturation. After the adsorption is saturated, the column is first washed with water. At this time, a large amount of sodium, potassium, calcium, magnesium and other major impurity ions on the adsorbent will be desorbed, and only a small amount of lithium ions will be washed out from the adsorbent. The phase effluent is not collected. Then use 0.5 ~ 1.0NHC1 for desorption to desorb the lithium ions from the adsorbent. The lithium ion concentration in the exhaust stream is detected synchronously by the optical detector 3 and irradiated with a light source with a wavelength of 760 nm. The exhaust stream light transmittance 値 will decrease as the lithium concentration in the exhaust stream increases, as shown in Figure 2. At the turning point of the transmittance curve, the exhaust stream starts to be drawn. At this time, the light transmittance 値 will decrease to less than 2%, and the lithium ion concentration in the exhaust stream will be greater than 800 ppm. When a large amount of lithium ions are desorbed, the concentration of lithium ion in the exhaust stream # gradually decreases, and the detected transmittance light transmittance 値 will also increase to more than 2%. At this time, the collection is stopped. The other effluent stream 4 not collected is returned to the original brine, and can be adsorbed again. In the lithium effluent collected with a light transmittance below 2%, the concentrations of sodium, potassium, calcium, and magnesium ions are significantly lower than those of lithium ions. After the exhaust stream stops collecting, you can continue acid pickling to almost completely desorb the ions from the adsorbent, so that the adsorbent can maintain the original adsorption amount when it is next adsorbed. When the acid desorption is continued after the extraction of the exhaust stream is stopped, the lithium ion concentration in the exhaust stream will become lower and lower, and the light transmittance 値 will become higher and higher. When the light transmittance 値 is greater than 96%, the lithium The ion concentration is less than 2 ppm, and the pickling program can be stopped at this time. Optionally, after the exhaust stream with a high lithium ion concentration is stopped, the pickling of the adsorbent can be stopped and the feed can be directly introduced into the feed for adsorption. The desorption solution with a lithium concentration of 1200 to 1500 ppm is sent from a first storage tank 5 to a first-stage electrodialysis equipment 6 to operate at a constant voltage of 15 to 20V, and the -9-paper scale is applicable to Chinese national standards ( CNS) A4 size (210x297 public holiday) (please read the notes on the back first), install! ιτ 588122 Printed by the Consumers' Cooperative of the Ministry of Economic Affairs, China Standards Bureau ¾ Λ7 B7 V. Description of the invention (7) A lithium enrichment solution containing a lithium concentration of 8000 to 10000 ppm was obtained and collected in a second storage tank 7. A lithium storage solution with a lithium concentration of 8000 to 10,000 ppm is sent from a second storage tank 7 to a second-stage electrodialysis equipment 8 and operated at a constant voltage of 15 to 20 V to obtain a lithium-containing concentration of 14000 to 1 8000 ppm. The lithium enrichment solution is collected in a third storage tank 9. A lithium enrichment solution having a lithium concentration of 14000 to 18000 ppm downstream of the third storage tank 9 is added with sodium carbonate 10, and lithium carbonate crystals 11 are precipitated. In addition, when the second-stage electrodialysis equipment 8 is enriched, it will also produce a lithium removal solution with a lithium concentration of 1500 to 2000 ppm, which will be sent to the first storage tank 5 as the first-stage electrodialysis equipment 6 Feed. When the electrodialysis equipment 6 is enriched in the first stage, it will also generate a residual liquid with a lithium concentration of 300 to 400 ppm, which will be sent to a residual electrodialysis equipment 12 for enrichment. The operation is performed at a voltage of 20 ~ 25V, and a concentrated solution having a concentration similar to that of the first storage tank 5 is obtained, which is sent to the first storage tank 5 as a feed for the first-stage electrodialysis equipment 6 to achieve the purpose of recovering the residual liquid. The lithium removal solution (a lithium concentration of about 50 to 100 ppm) produced by the residual liquid electrodialysis equipment 12 is returned to the hydration solution with brine as the feed for the adsorption tower 2. During the electrodialysis concentration process, if the difference between the ion concentration of the feed tank and the lithium concentration solution is too large, reverse osmosis will occur, which will lead to a decrease in the concentration efficiency and waste of electrical energy. The technique of the invention performs the electrodialysis enrichment in stages, so that the operation of each stage does not cause reverse osmosis to achieve better enrichment efficiency, and the lithium produced by the electrodialysis enrichment at each stage is removed. The liquid can be easily recycled for use in the method of the invention. Therefore, the method of the present invention generates almost no pollutants and is a clean process. -10- This paper wave scale is applicable to the Chinese National Standard (CNS) A4 scale (210X 297 mm) (Please read the notes on the back first \ ^^ Write this page)-Pack. Order 588122 Cooperative cooperation Du Yin ¾ A7 B7 V. Description of the invention (8) The present invention can be further understood through the following examples, which are only for illustration purposes and not for limiting the scope of the present invention. Preparation Example 1 Take approximately 73 grams of polyvinyl chloride (degree of polymerization 620 ± 20) and dissolve in 980 ml of N-methyl-2-pyrrolidone (NMP) solvent, and then dissolve 300 A gram of spinel phase Li133Ma16704 powder was added to the obtained PVC solution, and the obtained mixture was kneaded sufficiently. The kneaded mixture was dropped into a 1200 ml mixed liquid of water and methanol (1: 1 volume ratio) through a thin tube (diameter 3 mm), and particles with a diameter of 3.5-4.3 mm were formed. The mixed liquid and particles were separated by filtration, and the liquid was removed by depressurization and volatilization, and the dry adsorbent particles thus obtained had a specific gravity of 0.41 g / cm3. Example 1 40 g of the adsorbent particles prepared in Preparation Example 1 were soaked and moistened with deionized water, and then filled with a column to form an adsorbent bed. The adsorbent bed was washed with deionized water, and then 1300 ml of 0.5N aqueous hydrochloric acid solution was pickled, followed by washing with deionized water to perform adsorption. The column was continuously fed with brine produced in the salt refinery process of the salt refinery plant. The space flow rate was controlled at 35 L / hr. After 14 days of adsorption, the adsorbent could reach a saturated state. For the adsorption saturated column, firstly desorb the adsorbent with deionized water, and control the space flow rate at 3 L / hr. After passing 120 ml, desorb the adsorbent with 1.0N hydrochloric acid. Detect the light transmittance of the desorption liquid with an optical detector. The wavelength of the light is 760 -11. This paper wave ^ 1 applies the Chinese national standard (...) People 4 see the case (210 father 297 mm) (Please read first Note on the back cover page) Installation -----, tr 588122 China National Standards Bureau, Ministry of Economic Affairs, Consumer Co-operation, Du Yin ¾ A7 V. Description of the invention (9) Detect streamer transmittance under nm conditions. Capture a part of the desorbed stream with a light transmission rate 値 less than 2%. The lithium ion concentration in this part of the desorbed stream is greater than 800 ppm. The ion content of the mixed desorbed stream is shown in Table 1. Table 1 Feed composition of brine and metal ion content in the desorption stream. Ion concentration (ppm) Lithium sodium potassium calcium 鉄 brine 9 ~ 12 29100 37000 17700 35300 Desorption solution 1484 109 144 154 246 Use Japan ANSANICS Co., Ltd., Model DS-0 electrodialysis equipment performs the following electrodialysis enrichment. The first stage of electrodialysis: the desalting tank is filled with a desorption solution with a lithium ion concentration of 1484 ppm, and the concentration tank is filled with 5L of the same desorption solution, and 10L of 0.5N sodium sulfate solution is placed in the electrode tank into the electrode tank . At a flow rate of 7.6 L / min, the desorption liquid was continuously introduced from the desalination tank to the inlet of the desalination chamber of the electrodialysis equipment, and flowed out from the outlet of the desalination chamber of the electrodialysis equipment to the desalination tank. The desorption solution was continuously introduced from the concentration tank to the inlet of the concentration chamber of the electrodialysis apparatus at a flow rate of 7.2 L / min, and flowed out of the concentration chamber of the electrodialysis apparatus to the concentration tank. The electrode liquid was continuously introduced from the electrode tank to the inlet of the electrode chamber of the electrodialysis apparatus at a flow rate of 6.8 L / min, and flowed out of the electrode chamber of the electrodialysis apparatus to the electrode tank. The internal circulation flow rates of the desalination tank chamber, concentration tank chamber and electrode tank chamber are all operating parameters related to the equipment specifications. In addition, the desalination tank was continuously fed with a desorption solution having a lithium ion concentration of 1484 ppm at a feed flow rate of 150 ml / min. Yu Dingdian-12- This paper conforms to the Chinese National Standard (CNS) A4 specification (210X297 mm) · ^. Packing (please read the notes on the back to write a copy), tr 588122 Employees of the China Railway Bureau of the Ministry of Economic Affairs Cooperative cooperative seal ¾ Λ7 B7 V. Description of the invention (10) Operating at a pressure of 23 volts for 300 min, the solution in the desalination tank will overflow due to continuous feeding. The enrichment tank does not feed or discharge, and lithium ions will enter the concentration tank through the dialysis membrane from the concentration tank. At 300 minutes, the desalination rate can reach more than 80%. At this time, after the desalination is completed, the lithium ion concentration in the desalination solution overflowing from the desalination tank is about 290 ppm. This part will become the feed for electrodialysis of a residual liquid downstream. The lithium ion concentration in the concentration tank reached 9450 ppm, and was used as the second-stage concentration. Second stage electrodialysis: Fill the desalination tank of this stage with 10 L of lithium enriched solution with a lithium ion concentration of 9450 ppm obtained in the first stage of electrodialysis; inject 10 L of the same lithium enriched solution into the concentration tank; and configure 10 L A 0.5N sodium sulfate solution was placed in the electrode tank as the electrode solution. At a flow rate of 7.6 L / min, the desorption solution was continuously introduced from the desalination tank to the inlet of the desalination chamber of the electrodialysis equipment, and flowed out from the outlet of the desalination chamber of the electrodialysis equipment to the desalination tank. The desorption solution was continuously introduced from the concentration tank to the inlet of the concentration chamber of the electrodialysis apparatus at a flow rate of 7.2 L / min, and flowed out of the concentration chamber of the electrodialysis apparatus to the concentration tank. The electrode liquid was continuously introduced from the electrode tank to the inlet of the electrode chamber of the electrodialysis apparatus at a flow rate of 6.8 L / min, and flowed out of the electrode chamber of the electrodialysis apparatus to the electrode tank. The internal circulation flow rate of the above desalination tank chamber, concentration tank chamber and electrode tank chamber are all operating parameters related to the equipment specifications. In this stage, the desalination tank does not separately feed the desalination tank continuously. Operating at a constant voltage of 20 volts, lithium ions will enter the concentration tank from the concentration tank through the dialysis membrane. The desalination rate reached 85% at 270 minutes. At this time, the lithium ion concentration in the desalination tank was about 1320 ppm after desalination was completed. This part will become the feed for the first stage of electrodialysis; and the lithium ion concentration in the concentration tank side reached 17250 ppm. . -13- The paper Λ degree applies to the Chinese National Standard (CNS) A4 wash case (210X 297 mm) • Two ···. I:----1 II m mu I ti 1 I 11- · 1 i (Please First read the notes on the back of the book) Order 588122 Printed by the Consumers' Cooperative of the China Standards Bureau of the Ministry of Economic Affairs ¾. A7 __B7 V. Description of the Invention (11) Residual liquid recovery electrodialysis: Residual liquid recovery electrodialysis equipment The tank was filled with the residual liquid with a lithium ion concentration of 290 ppm after desalination in the first stage of the desalination tank; while the concentration tank was filled with 5 L of the same residual liquid, and 10 L of 0.5N sodium sulfate solution was placed in the electrode tank. At a flow rate of 7.6 L / min, the desorption liquid was continuously introduced from the desalination tank to the inlet of the desalination chamber of the electrodialysis equipment, and flowed out from the outlet of the desalination chamber of the electrodialysis equipment to the desalination tank. The desorption solution was continuously introduced from the concentration tank to the inlet of the concentration chamber of the electrodialysis apparatus at a flow rate of 7.2 L / min, and flowed out of the concentration chamber of the electrodialysis apparatus to the concentration tank. The electrode solution was continuously introduced into the electrode chamber of the electrodialysis apparatus from the electrode tank at the flow rate of 6.8 L / min, and flowed out of the electrode chamber of the electrodialysis apparatus to the electrode tank. The internal circulation flow rates of the desalination tank chamber, concentration tank chamber and electrode tank chamber are all operating parameters related to the equipment specifications. In addition, the desalination tank was continuously fed with a residual liquid having a lithium ion concentration of 290 ppm at a feed flow rate of 200 ml / min. Operate at a constant voltage of 30 volts. The solution in the desalination tank will overflow due to continuous feeding. The concentration tank will not feed or discharge. Lithium ions will enter the concentration tank from the concentration tank through the dialysis membrane. The desalination rate can reach more than 85% at 60 minutes. At this time, the lithium ion concentration in the desalination solution overflowing from the desalination tank after desalination is about 37 ppm. This part can be combined with brine to be used as the feed for the adsorbent column. The lithium ion concentration in the concentration tank reaches 1270 ppm, which can be used as the feed for the first stage of electrodialysis. Table 2 shows the concentration of metal ions in the lithium enrichment solution in the concentration tank obtained in the above-mentioned stages of concentration. -14- This paper wave scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 public holidays) (Please read the notes on the back * first page) Install I!
、1T 588122 Λ7 B7 五、發明説明（12 ) 表二 各階段濃縮後其濃縮液中各離子之濃度 濃縮階段^\ Li Na K Ca Mg 第一階段濃縮 9450 2333 882 959 1561 第二階段濃縮 17250 3820 2049 2114 2776 殘液濃縮 1270 788 343 515 528 圖式之簡單說明 圖1爲本發明方法的一較佳實施例的流程方塊圖。 圖2顯示圖1中的吸附塔被脫附時，在不同脫附液量之 脫附流的鋰離子濃度與脫附i光穿透率的關係。 符號說明 2..吸附塔 3..光學檢知計 5,7,9..儲槽 6,8，12..電透析設備 (請先閲讀背面之注意事項寫本頁) .裝I! 經濟部中夬標準局員工消費合作社印製 -15- 本紙伕尺度適用中國國家標準（CNS ) Μ規格（2丨0X297公釐）1T 588122 Λ7 B7 V. Explanation of the invention (12) Table 2 Concentration of each ion in the concentrated solution after each stage of concentration ^ \ Li Na K Ca Mg First stage of concentration 9450 2333 882 959 1561 Second stage of concentration 17250 3820 2049 2114 2776 Residual liquid concentration 1270 788 343 515 528 Simple illustration of the diagram FIG. 1 is a flow block diagram of a preferred embodiment of the method of the present invention. Fig. 2 shows the relationship between the lithium ion concentration of the desorption flow and the light transmittance of the desorption i when the adsorption tower in Fig. 1 is desorbed at different amounts of the desorption liquid. Explanation of symbols 2. Adsorption tower 3. Optical detector 5,7,9. Storage tanks 6,8,12 .. Electrodialysis equipment (Please read the precautions on the back first to write this page). Installation I! Economy Printed by the Ministry of Economic Affairs and Standards Bureau Consumer Cooperatives -15- The standard of this paper is applicable to Chinese National Standards (CNS) M specifications (2 丨 0X297 mm)