萃取程序如LLE、SLM、ELM皆有處理時間冗長、萃取劑容易流失、操作程序繁瑣等問題，而CASX系統因為可產生大量油泡擁有極大的接觸表面積，使得處理時間縮短，且濃縮比例高，因此本研究選擇CASX系統作為萃取程序。
本萃取系統以Aliquat 336當萃取劑，以去除水中含鉻之重金屬廢水，Aliquat 336在水中並不受pH影響，影響其去率高低之因素取決於六價鉻在水中以何種形式存在（HCrO4-或CrO42-）。而當水中若同時有其他陰離子（Cl-或SO42-）存在則會與（HCrO4-或CrO42-）產生競爭萃取劑的現象，使得去除效率降低。
以陶瓷薄膜過濾含Aliquat 336萃取溶劑並不合適，雖然其他研究可以成功過濾含D2EHPA之萃取溶劑，但因Aliquat 336與D2EHPA其物理特性截然不同，使得薄膜內壓力容易累積升高，以及出流水COD偏高。
以NaCl與NaOH混合之脫附劑，在脫附六價鉻反應程序中，Cl-才是主要參與置換的物種，而NaOH只是在改變油相中六價鉻之化合物型態，因為與Aliquat 336結合之能力依序為HCrO4-＞Cl-＞CrO42-。

In this study, Aliquat 336 was used as extractant in CASX system for Cr(VI) removal. The speciation of Aliquat 336 is not affected by pH; however, Cr(VI) species (HCrO4- or CrO42-）are function of pH and have great impact on their removal efficiency. Meanwhile, other anions have slightly influence on Cr(VI) removal with increasing anionic concentration decreasing the removal efficiency of Cr(VI).
Although previous study has successfully shown the recovery of D2EHPA-containing solution by ceramic MF membrane, membrane filtration using ceramic membrane is not a suitable option for recovering Aliquat336 due to different physical characteristics of Aliquat 336 and D2EHPA. The relatively high viscosity and solubility of Aliquat336 caused severe membrane fouling and elevated COD in the permeate.
Mixtures of NaCl and NaOH were employed as regenerant during regeneration process. Chloride ions are the main species for stripping Cr(VI) from Aliquat336. However, alkaline condition (addition of NaOH) is needed to convert HCrO4- to CrO42- for achieving high regeneration efficiency. It is concluded that the affinity of these ions with Aliquat 336 follow the order of HCrO4-＞Cl-＞CrO42-

目錄.............................................................................................................I
圖目錄......................................................................................................IV
表目錄....................................................................................................VIII
第一章 前言...............................................................................................1
1-1研究起源......................................................................................1
1-2研究目的......................................................................................3
第二章 文獻回顧......................................................................................4
2-1鉻污染..........................................................................................4
2-2 金屬萃取與再生的程序.............................................................7
2-2-1 Bulk Liquid Membrane.....................................................8
2-2-2支撐式液態膜(Supported Liquid Membranes)................9
2-2-3乳化液態薄膜(Emulsion Liquid Membrane)................11
2-3溶劑與萃取劑............................................................................15
2-3-1溶劑(Solvent)..................................................................15
2-3-2萃取劑 (Extractant)- Aliquat 336..................................15
2-4萃取溶劑於CASX系統中之探討.............................................19
2-4-1 Aliquat 336與Cr(VI)的反應機制..................................19
2-4-2 pH的影響........................................................................19
II
2-4-3離子的影響.....................................................................20
2-5 六價鉻再生...............................................................................21
2-6 Extraction kinetics......................................................................22
第三章 實驗材料設備與方法................................................................25
3-1 實驗材料...................................................................................25
3-1-1廢水.................................................................................25
3-1-1-1人工廢水.....................................................................25
3-1-1-2實廠廢水.....................................................................26
3-1-2 Aliquat 336......................................................................26
3-1-3 Kerosene..........................................................................27
3-2實驗設備....................................................................................28
3-3實驗步驟與方法........................................................................33
3-3-1 批次式實驗流程............................................................33
3-3-2 連續式實驗流程............................................................34
3-3-3 六價鉻再生實驗流程....................................................38
3-4分析方法....................................................................................41
3-4-1六價鉻檢測方法.............................................................41
3-4-2 化學需氧量檢測方法....................................................42
第四章 結果與討論................................................................................44
4-1不同調配比例的萃取溶劑對去除率的影響............................44
4-2反應時間對去除率的影響........................................................46
III
4-3 pH對去除率的影響...................................................................50
4-4 Anion對去除率的影響..............................................................52
4-5壓縮氣體壓力的影響................................................................54
4-6以陶瓷薄膜回收含油廢水........................................................55
4-7六價鉻再生................................................................................64
第五章 結論.............................................................................................70
第六章 參考文獻....................................................................................72

圖目錄
圖 1、各濃度下不同pH變化之Cr6+主要物種圖。................5
圖 2、Cr6+於水中pH變化之物種濃度分佈圖，以MINEQL+繪製，鉻濃度設定為2 mM。..........................................6
圖 3、液態薄膜之離子交換示意圖........................................8
圖 4、BLM示意圖....................................................................9
圖 5、支撐式液態膜示意圖..................................................10
圖 6、中空纖維薄膜示意圖(14)............................................11
圖 7、一級胺,二級胺,三級胺結構示意圖............................18
圖 8、D2EHPA之結構圖(20).................................................20
圖 9、油泡構造示意圖..........................................................23
圖 10、CASX構造圖..............................................................28
圖 11、CASX混合槽構造及作用圖......................................29
圖 12、批次實驗流程............................................................34
圖 13、以”掃流”為清理薄膜之連續過濾流程圖.................35
圖 14、以”掃流”為清理薄膜之連續過濾設備配置圖.........36
圖 15、以”反沖洗”為清理薄膜之連續過濾流程圖.............37
圖 16、以”反沖洗”為清理薄膜之連續過濾設備配置圖....38
圖 17、Cr6+再生實驗流程圖..................................................39
圖 18、Cr6+檢量線偵測範圍0~1 ppm，分光光度計波長設定540 nm..............................................................................42
圖 19、不同比例萃取溶劑對去除率的影響，水樣500 ml（大興電鍍廠），pH 1.2~2.4，Cr6+ 644.7 mg/L反應時間180 sec.....................................................................................45
圖 20、Aliquat 336(3.6 g及2.54 g)在不同時間下去除率的變化，水樣500 ml（大興電鍍廠），pH 1.2~2.4，Cr6+644.7 mg/L，反應時間180 sec................................................47
圖 21、5 atm，Aliquat 336：kerosene＝1：1，噴出之油泡圖...........................................................................................47
圖 22、pH對去除率的影響 實驗以Cr6+ 100 mg/L 水樣500 ml 萃取溶劑1:10進行...................................................51
圖 23、陰離子對去除率的影響 實驗以Cr6+=100 mg/L pH 4之水樣500 ml萃取溶劑 1:10進行................................53
圖 24、陰離子對去除率的影響 實驗以Cr6+=100 mg/L pH 9之水樣500 ml萃取溶劑 1:10進行................................53
圖 25、施予不同的氣體壓力對去除率的影響，實驗以Cr6+=100 mg/L pH 4之水樣500 ml萃取溶劑 1:10進行...........................................................................................54
圖 26、（A）油水比0.4％之原水；（B）操作時間30分鐘之出流水..............................................................................55
圖 27、過濾0.4％及0.1％廢水之操作壓力圖，條件設定為進流30 LMH，每10 min掃流2 L/2 min，使用萃取溶劑比例為1：10。...............................................................56
圖 28、0.1％油水比之出流水COD值，操作條件為進流30 LMH，每10 min掃流2 L/2 min，使用萃取溶劑比例為1：10。............................................................................57
圖 29、過濾含D2EHPA廢水之操作壓力圖，D2EHPA：kerosene = 1：10，油/水=0.4，進流量30 LMH，掃流流量=1L/min，T=2 min......................................................58
圖 30、過濾含D2EHPA廢水之COD對操作時間關係圖，D2EHPA：kerosene = 1：10，油/水=0.4，進流量30 LMH，掃流流量=1L/min，T=2 min..........................................59
圖 31、分別過濾含D2EHPA及Aliquat 336之廢水系統壓力比較圖..................................................................................60
圖 32、萃取溶劑濃度分別為0.1％（Aliquat 336）及0.4％（D2EHPA）之出流水COD比較圖...............................60
圖 33、過濾時以”反沖洗”清理薄膜之操作壓力圖，油/水0.4％，，添加0.03 M NaCl，進流量15 LMH，反沖洗壓力1 atm............................................................................63
圖 34、過濾時以”反沖洗”清理薄膜之時間對出流水COD圖，條件設定油水比為0.4％，，添加0.03 M NaCl，進流量15 LMH，反沖洗壓力1 atm.................................63
圖 35、再生效率與加入Cl-量對pH變化關係圖...................65
圖 36、由油相回到水相中Cr6+濃度對pH關係圖，實驗以Cr6+=100 mg/L pH 4之水樣500 ml萃取溶劑1:10進行，噴入萃取劑量為6.35 g，添加0.071 M Cl-...................67
圖 37、由油相回到水相中Cr6+濃度對pH關係圖，實驗以Cr6+=100 mg/L pH 4之水樣500 ml萃取溶劑1:10進行，噴入萃取劑量為21.5 g，添加0.242 M Cl-...................68

表目錄
表 1、SLM、BLM、ELM優缺點整理表.............................14
表 2、Aliquat 336基本性質參照表......................................17
表 3、常見的萃取劑與溶劑..................................................18
表 4、對Aliquat 336常用之脫附劑及效率..........................21
表 5、液相薄膜研究比較表(26)............................................22
表 6、實驗藥材一覽表..........................................................25
表 7、大興電鍍廠水質特性..................................................26
表 8、Aliquat 336特性參照簡易表......................................26
表 9、批次實驗採用之濾紙規格..........................................30
表 10、經1.2 μm及0.45 μm濾紙過濾效率表。Aliquat 336：kerosene =1：10，注入3.88 g，Cr6+ =100 mg/L..........31
表 11、陶瓷薄膜規格及特性一覽表....................................32
表 12、推估CASX系統產生之油膜厚度、氣泡數量、總表面積、Flux.......................................................................48

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