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研究生：	張益國 Chang, Yi-Kuo
論文名稱：	黃酸鹽程序去除銅離子及其生成物之穩定性 Removal and Stabilization of Copper Ions by Xanthate Processes
指導教授：	張祖恩 Chang, Juu-En
學位類別：	博士 Doctor
系所名稱：	工學院 - 環境工程學系 Department of Environmental Engineering
論文出版年：	2003
畢業學年度：	91
語文別：	中文
論文頁數：	196
中文關鍵詞：	溶出性指標、水泥固化、穩定特性、黃酸鹽程序、銅離子去除、半動態溶出試驗
外文關鍵詞：	Xanthate process, Copper removal, Semi-dynamic leach test, Leaching index, Stability characteristics, Cementation
相關次數：	點閱：178 下載：2
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本研究利用黃酸鹽程序直接處理含銅離子廢水，並探討所生成銅錯合物之穩定性、反應機制及其取代傳統加鹼沉澱/水泥固化處理程序之可行性。研究內容除檢討乙基黃酸鹽(KEX)、正丁基黃酸鹽(KBX)去除銅離子可行性及生成乙基黃酸銅(Cu-EX)、正丁基黃酸銅(Cu-BX)之反應特性、影響因子，並建立最佳操作程序外，更以UV-vis光譜儀、化學電子分析光譜儀(XPS)、傅立葉轉換紅外光譜儀(FTIR)觀察Cu-BX於酸鹼環境下錯合物化學機制變化與穩定特性之關係，推估維持Cu-BX穩定性之關鍵機制。此外，進一步建立溶出性指標Lx（Lx≦5穩定性差；Lx = 5～10穩定性普通；Lx = 10～15穩定性良；Lx≧15，穩定性優）評比黃酸鹽穩定法生成物（Cu-BX）、水泥固化法生成物（Cu-BX/水泥固化物、Cu(OH)2/水泥固化物）於酸性環境下穩定特性差異，另以X光繞射儀(XRD)、電子顯微鏡(SEM/EDS)及FTIR分析結果探討其穩定機制，最後由研究結果總評黃酸鹽程序直接處理含重金屬離子廢水取代傳統加鹼沉澱/水泥固化處理程序之可行性。
實驗結果顯示，黃酸鹽程序中KBX優於KEX，KBX可直接應用於去除廢水中銅離子，化學計量黃酸鹽/銅莫爾比= 2、回分式操作情況下，KBX可將銅離子濃度50～1000 mg/L之溶液去除到殘存濃度N.D.～0.03 mg/L水準，符合銅放流水標準3 mg/L。黃酸鹽使用劑量、溶液pH值為主要影響黃酸鹽程序之因子，最佳操作條件為：(i) 黃酸鹽/銅反應莫爾比略超過化學計量；(ii) 含銅離子溶液pH值控制在4～9，可使銅去除率達99.9 %以上；而離子強度增加僅些微提高銅離子去除率。經檢討黃酸鹽/銅反應莫爾比添加條件對銅離子去除率影響與分析殘存溶液pH、ORP、TOC結果，證實黃酸鹽與銅離子間反應行為乃一化學計量反應。
經以每週更換萃取液（1N HAc、1N NaOH）一次，為期10週次之半動態溶出試驗結果證實Cu-BX錯合物不論酸鹼條件皆具優良長期穩定性。Cu-BX錯合物於酸性環境下（模擬掩埋50年）累積銅溶出百分比僅0.013 %（Lx = 16.66），穩定性判定為優，於鹼性環境下累積銅溶出百分比為0.103%（Lx = 14.86），穩定性判定為良。至於酸性條件下穩定性優於鹼性，則可由UV-vis光譜分析結果-鹼性較酸性環境易使Cu-BX分解得到佐證。另外由液相UV-vis光譜、固相XPS、FTIR、SEM/EDS、EA分析結果得知，Cu-BX於酸性環境中，CuII(BX)會逐漸還原成CuI(BX)型態，最後均以CuI(BX)型態維持穩定；鹼性環境雖減緩CuII(BX)還原為CuI(BX)速率，但過程中鹼會造成CuII(BX)分解，反而使銅溶出較多。惟不論酸鹼環境，XRD、XPS圖譜證實CuI(BX)為Cu-BX錯合物維持長期穩定性之穩定相。
再以半動態溶出試驗結果綜合比較Cu-BX、含銅水泥固化體及未經任何處理之氫氧化銅污泥於酸性環境之金屬穩定性，其穩定性優劣依序為Cu-BX錯合物（優, Lx = 16.66）＞Cu-BX/水泥固化物（良, Lx = 12.63～13.42）＞Cu(OH)2/水泥固化物（普通～良, Lx = 10.23～10.60）＞氫氧化銅污泥（差, Lx = 4.59），顯示黃酸鹽穩定法所產生生成物之穩定性優於水泥固化法。而Cu-BX於酸性環境中之穩定機制與水泥固化物明顯不同，黃酸銅生成物主要以Cu與黃酸鹽間強化學鍵結形式存在而穩定；Cu-BX/水泥固化物的穩定方式則同時存在有黃酸銅之低溶解度、強化學鍵結的穩定特性及水泥固化包封/匣限之特性；Cu(OH)2/水泥固化物的穩定方式則主要為水泥之包封/匣限功效。
由本研究結果可知，黃酸鹽程序可有效去除溶液中銅離子，去除率高達99.9 %以上，所生成的Cu-BX具良好穩定性，於模擬50年酸性掩埋環境下累積銅溶出百分比僅0.013 %（Lx = 16.66，屬-優等穩定性），毋須再行固化處理，可直接進行最終處置或暫存後利用資源化處理技術回收其中有價金屬。黃酸鹽直接穩定化處理銅離子之程序可綜合解決廢水中金屬離子去除及後續金屬污泥處置之問題，可取代傳統加鹼沉澱後再予以水泥固化之處理程序。

The xanthate process was applied to the removal of copper-containing wastewater, and stabilization behaviors of the formed copper-xanthate sludges, including the leaching toxicity, copper immobility, stability characteristics and leaching index (Lx) during leaching tests were investigated. Besides, stability evaluation of the resultants from traditional precipitation/cementation processes and xanthate processes were also discussed in this dissertation.

In copper removal treatments, the aqueous phase compositions, such as ionic strength, pH, soluble xanthate species (potassium ethyl xanthate (KEX) and potassium n-butyl xanthate (KBX)) and levels of different copper as well as xanthates present were employed to clarify which would influence the copper removal effectiveness by means of xanthate processes. Results from copper removal treatments showed that the KBX performed better than the KEX for treating copper-containing wastewater over a wide copper concentration range (50, 100 500, 1000 mg/L) to the level that meets the Taiwan EPA’s effluent regulations (3 mg/L). The results revealed that the ionic strength of the aqueous phase had little effect on the copper removal for both KEX and KEX. The removal of copper decreased with decrease in pH, it was due to the chemical decomposition rate of KEX and KBX became faster when been dissolved in lower pH (pH below 4) solutions. Also, the removal of copper decreased with decrease in the xanthate/copper molar ratio. The removal mechanism for copper appears to be stoichiometric reactions (the xanthate/copper molar ratio of 2). When the xanthate/copper molar ratio below 2, neither KBX nor KEX could effectively remove copper from solutions. Nevertheless, while the copper concentration below 1000 mg/L, the pH of the solution below 4 or the xanthate/copper molar ratio below 2, the KBX had better copper removal efficacy than the KEX. Thus, the optimum conditions for copper removal treatments by xanthate processes are (i) the xanthate/copper molar ratio slightly higher than 2, (ii) the pH of aqueous solutions is 4～9.

The formed copper-butyl xanthate (Cu-BX) complexes, which produced by the xanthate processes, must be handled in accordance with the Taiwan EPA’s waste disposal requirements. Thus, the toxicity characteristic leaching procedure (TCLP) was used as a pass/fail test to classify the leaching toxicity of the Cu-BX complexes. Additionally, the semi-dynamic leach tests (SDLTs) with 1 N HAc and 1 N NaOH solution as leachant was performed to investigate the longer-term copper released of upon complexes. The UV-vis, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and X-ray photoelectron spectroscopies (XPS) analyses were conducted to explicate a fundamental understanding of the complexs’ copper leaching potential, stability characteristics and chemical changes. Results from TCLP showed that the copper ions detected in the TCLP leachates of the Cu-BX complexes was N.D.～0.10 mg/L, and thus the Cu-BX complex could be treated as a non-hazardous material. The results of SDLTs indicated that the complexes exhibited better copper immobility in acidic leaching conditions (cumulative fraction of copper released was 0.013 %, Lx = 16.66 which be graded as “Excellent” metal stability) than in alkaline leaching conditions (cumulative fraction of copper released was 0.103 %, Lx = 14.86 which be graded as “Good” metal stability). Nevertheless, chemical structure of the Cu-BX complex varied during the acidic leaching conditions. XPS data suggested that the Cu-BX complex initially contained both cupric and cuprous xanthate, but the unstable cupric xanthate change to the cuprous form after acidic extraction, indicating the cuprous xanthate to be the final stabilizing structure. Despite that, the changes of chemical structure did not induce the rapid leaching of copper from the Cu-BX complex.

Moreover, the comparisons of the copper immobility and chemical changes of the resultants from xanthate processes and cement treatment processes (traditional precipitation/cementation processes) were also made by use of SDLT with 1 N HAc solution as leachant. The results indicated that the copper immobility of the resultants followed the sequence Cu-BX complexes (Lx = 16.66 which be graded as “Excellent” metal stability)＞Cu-BX/cement matrices (Lx = 12.63～13.42 which be graded as “Good” metal stability)＞Cu(OH)2/cement matrices (Lx = 10.23～10.60 which be graded as “Fair to Good” metal stability)＞Cu(OH)2 (Lx = 4.59 which be graded as “Bad” metal stability). Thus, differing from traditional precipitation/cementation treatment processes, the xanthate process offered a comprehensive strategy for solving both copper-containing wastewater problems and subsequent sludge disposal requirements, which could be a worthwhile alternative.

授權書………………………………………………………I
中文摘
要……………………………………………………………III
英文摘要……………………………………………………………VI
誌謝………………………………………………………………IX
目錄……………………………………………………………….X
表目錄…………………………………………………………XIV
圖目錄…………………………………………………………XVII

第一章 前言………………………………………………………1
1-1 研究動機與目的………………………………………….1
1-2 論文內容…………………………………………………..2

第二章 文獻回顧………………………………………………….6
2-1銅之宿命……………………………………………………6
2-1-1 銅之開採、生產與應用……………………………….6
2-1-2銅於環境之流佈………………………………………...9
2-2 銅廢污處理處置問題…………………………………..11
2-2-1 含銅廢水之來源及性質……………………………..11
2-2-2 含銅廢水處理概況…………………………………...11
2-2-3含銅污泥處理處置問題………………………………12
2-3 Xanthate的特性與應用……………………………………15
2-3-1 Xanthate的應用……………………………………..15
2-3-2 Alkyl xanthate 的有機特性………………………….21
2-3-3 Xanthate反應特性…………………………………….28
2-4 Metal-xanthate生成物特性……………………………33
2-4-1 Metal-Xanthate反應機制…………………………………33
2-4-2 Metal-xanthate生成物特性…………………………..37
2-5穩定性判斷方法………………………………………..42
2-6 小結……………………………………………………….45

第三章 可溶性黃酸鉀與銅離子反應行為研究………..……..…47
3-1 前言………………………………………………………47
3-2 實驗設備、材料及方法…………………………………49
3-2-1實驗設備………………………………………………..49
3-2-2實驗材料………………………………………………..55
3-2-3實驗步驟及方法……………………………………….56
3-3 結果與討論………………………………………………61
3-3-1 乙基、正丁基黃酸鉀特性鑑定……………………..61
3-3-2乙基黃酸鉀去除水中銅離子效能…………………...72
3-3-3正丁基黃酸鉀去除水中銅離子效能………………...81
3-4 小結………………………………………………………89

第四章 正丁基黃酸鉀與銅離子生成物之穩定特性與溶出行為…………………………………………………….90
4-1 前言………………………………………………………90
4-2實驗設備、材料及方法…………………………………92
4-2-1實驗設備………………………………………………..92
4-2-2實驗材料………………………………………………..93
4-2-3實驗步驟及方法………………………………………94
4-3 結果與討論……………………………………………99
4-3-1黃酸銅基本特性與溶出毒性………….…………….99
4-3-2黃酸銅在酸性環境下的穩定特性及溶出行為…….99
4-3-3黃酸銅在鹼性環境下的穩定特性及溶出行為……117
4-4 小結……………………………………………………..130

第五章 正丁基黃酸銅與含銅水泥固化物於酸性環境之穩定特性比較……………………………………………………………..132
5-1 前言……………………………………………………………132
5-2實驗設備、材料及方法……………………………………….134
5-2-1實驗設備……………………………………………………..134
5-2-2實驗材料……………………………………………………..135
5-2-3實驗步驟及方法……………………………………...136
5-3 結果與討論…………………………………………….139
5-3-1 正丁基黃酸銅/水泥固化物、氫氧化銅/水泥固化物之抗壓強度及毒性特性溶出濃度………………139
5-3-2 正丁基黃酸銅/水泥固化物於酸性環境之穩定特性…142
5-3-3 氫氧化銅/水泥固化物於酸性環境之穩定特性…….159
5-4  穩定法、水泥固化法處理含銅廢污生成物之穩定性綜合評估……………………………………………..172

第六章 總結與建議…………………………………………..178
6-1 總結……………………………………………………..178
6-2 建議……………………………………………………..181

參考文獻………………………………………………………..183

自述……………………………………………………………193
 
LIST OF TABLES

Table 2-1 Properties of some copper alloys………………………………8
Table 2-2 World production of new (mine) copper…………….……….10
Table 2-3 Original and derivative formula of thio-surfactants………….22
Table 2-4 Values of extinction coefficients for characteristic absorption 	bands that can be detected in xanthate solutions either before or after oxidation and decomposition reactions………………….24
Table 2-5 Infrared absorption band frequencies of xanthates and related compounds……………………………………………………27
Table 2-6 Solubility product of metal xanthate complexes……………..36
Table 2-7 Infrared absorption bands of functional groups in copper xanthate complexes…………………………………………...38
Table 3-1 Elemental analysis of potassium ethyl xanthate (KEX) and potassium n-butyl xanthate (KBX)………………………63
Table 3-2 Results of Cu removal experiments under the experimental conditions employed in various initial copper concentrations and ionic strength (KEX/Cu molar ratio of 2, reaction time = 30 mins, temperature = 25℃)……………………………………73
Table 3-3 Results of Cu removal experiments under the experimental conditions employed in various KEX/Cu molar ratio and ionic strength (Initial Cu concentration = 1000 mg/L, reaction time = 30 mins, temperature = 25℃)………………………………..74
Table 3-3 (continued) Results of Cu removal experiments under the experimental conditions employed in various KEX/Cu molar ratio and ionic strength (Initial Cu concentration = 1000 mg/L, reaction time = 30 mins, temperature = 25℃)……………….75
Table 3-4 Results of Cu removal experiments under the experimental conditions employed in various initial copper concentrations and ionic strength (KBX/Cu molar ratio of 2, reaction time = 30 mins, temperature = 25℃)……………………………………82
Table 3-5 Results of Cu removal experiments under the experimental conditions employed in various KBX/Cu molar ratio and ionic strength (Initial Cu concentration = 1000 mg/L, reaction time = 30 mins, temperature = 25℃)………………………………...83
Table 3-5 (continued)  Results of Cu removal experiments under the experimental conditions employed in various KBX/Cu molar ratio and ionic strength (Initial Cu concentration = 1000 mg/L, reaction time = 30 mins, temperature = 25℃)………………..84
Table 4-1 Summary of the elemental analysis of copper butyl xanthate complex before and after semi-dynamic leach test………….105
Table 5-1 The unconfined compressive strength of the copper butyl xanthate/ cement solidified matrices and the copper hydroxide/cement solidified matrices……………………….140
Table 5-2 The TCLP results of the copper butyl xanthate/cement solidified matrices and the copper hydroxide/cement solidified matrices……………………………………………………...140
Table 5-3 The pH, ORP and EC values of the 3-day curing Cu-BX/cement matrices’ leachate at various leaching cycle during semi-dynamic leach test……………………………..144
Table 5-4 The pH, ORP and EC values of the 7-day curing Cu-BX/cement matrices’ leachate at various leaching cycle during semi-dynamic leach test……………………………..146
Table 5-5 The pH, ORP and EC values of the 28-day curing Cu-BX/cement matrices’ leachate at various leaching cycle during semi-dynamic leach test……………………………..148
Table 5-6 The pH, ORP and EC values of the 3-day curing Cu(OH)2/cement matrices’ leachate at various leaching cycle during semi-dynamic leach test……………………………..161
Table 5-7 The pH, ORP and EC values of the 7-day curing Cu(OH)2/cement matrices’ leachate at various leaching cycle during semi-dynamic leach test……………………………..163
Table 5-8 The pH, ORP and EC values of the 28-day curing Cu(OH)2/cement matrices’ leachate at various leaching cycle during semi-dynamic leach test……………………………..165
 
LIST OF FIGURES

Figure 1-1 Schematic representation of research structure………………5
Figure 2-1 Solubility of Cu(OH)2 as a function of solution pH….……13
Figure 2-2 Frother-collector interaction complex………………...…….17
Figure 2-3 The possibility of six reactions govering the xanthate-dixanthogen system…………………………………26
Figure 2-4 Precipitation and complex formation regions for solutions of potassium ethyl xanthate (KEtX) and copper ion. Double-hatched region: coarse-size precipitate. Single-hatched region: very fine-size precipitate. Region of dots: invisible sol. Solid line: solubility line. Below the solid line: complexes formed. Line (1): theoretical limits of solubility, Ksp= (Cu2+)(EtX)2= 2*10-14. Line (2): (Cu+)2(EtX)2= 5.2*10-20……35
Figure 3-1 A flow diagram of the Cu removal experiments using xanthate process treatments…………………………………………….48
Figure 3-2 Procedure for synthesis of potassium ethyl xanthate (KEX)..58
Figure 3-3 Procedure for synthesis of potassium n-butyl xanthate (KBX)…………………………………………………………59
Figure 3-4 X-ray diffraction patterns of (a) commercial KEX, (b) synthetic KEX, (c) commercial KBX and (d) synthetic KBX………………………..…………………………………62
Figure 3-5 FTIR spectra of (a) commercial KEX, (b) synthetic KEX, (c) commercial KBX and (d) synthetic KBX……………………64
Figure 3-6 SEM photographs of potassium ethyl xanthate (a) commercial and (b) synthetic………………………………………………66
Figure 3-7 SEM photographs of potassium n-butyl xanthate (a) commercial and (b) synthetic……………………….………...67
Figure 3-8 UV-vis spectra of potassium ethyl xanthate (a) commercial and (b) synthetic and potassium n-butyl xanthate (c) commercial and (d) synthetic…………………………………68
Figure 3-9  UV-vis spectra of 1×10-4 mole KEX dispersed for 30 minutes in one liter (a) distilled water, final pH = 8.6; (b) 1 N HAc solution, final pH = 2.1 and (c) 1 N NaOH solution, final pH = 13.6………………………………………………….70
Figure 3-10  UV-vis spectra of 1×10-4 mole KBX dispersed for 30 minutes in one liter (a) distilled water, final pH = 8.8; (b) 1 N HAc solution, final pH = 2.1 and (c) 1 N NaOH solution, final pH = 13.7……………………………………………………71
Figure 3-11 X-ray diffraction patterns of Cu-EX complexes.  Initial Cu(II) concentration: (a) 50 mg/L, (b) 100 mg/L, (c) 500 mg/L and (d) 1000 mg/L…………………………………………….76
Figure 3-12 The effect of pH on Cu removal efficiency under the experimental conditions employed in initial Cu concentration = 1000 mg/L, KEX/Cu molar ratio of 2, reaction time = 30 mins, temperature = 25℃…………………………………………...80
Figure 3-13 The effect of pH on Cu removal efficiency under the experimental conditions employed in initial Cu concentration = 1000 mg/L, KBX/Cu molar ratio of 2, reaction time = 30 mins, temperature = 25℃………………………………...…………88
Figure 4-1 The content of the study for stability characteristics and leaching behaviors of the copper butyl xanthate complex……91
Figure 4-2 (a) Amount of copper released and (b) cumulative fraction of copper released from the copper butyl xanthate complex at various leaching cycles during the semi-dynamic leach test (1 N HAc solution as leachant)…………………………………100
Figure 4-3 (a) The pH values and (b) the ORP values of the leachates at various leaching cycles during semi-dynamic leach test (1 N HAc solution as leachant)…………………………………102
Figure 4-4 UV-vis absorbance of the leachate at various leaching cycles during the semi-dynamic leach test (1 N HAc solution as leachant)…………………………………………….………103
Figure 4-5 X-ray diffraction patterns of copper butyl xanthate complex (a) before and (b) after semi-dynamic leach test (1 N HAc solution as leachant)…………………………………………………106
Figure 4-6 SEM micrographs of copper butyl xanthate: (a) SEM, (b) mapping analysis of copper element and (c) mapping analysis of sulfur element……………………………………………….108
Figure 4-7 Microprobe EDS analysis of copper butyl xanthate in Figure 4-6(a)………………………………………………………...109
Figure 4-8 SEM micrographs of copper butyl xanthate after semi-dynamic leach test (1 N HAc solution as leachant): (a) SEM, (b) mapping analysis of copper element and (c) mapping analysis of sulfur element……………………………………110
Figure 4-9 Microprobe EDS analysis of copper butyl xanthate after semi-dynamic leach test in Figure 4-8(a)……………………111
Figure 4-10 FTIR spectra of the copper butyl xanthate complex (a) before and (b) after the semi-dynamic leach test (1 N HAc solution as leachant)……………………………………………………..112
Figure 4-11 X-ray photoelectron spectra of the copper butyl xanthate complex (a) before and (b) after the semi-dynamic leach test (1 N HAc solution as leachant)………………………………...114
Figure 4-12 (a) Amount of copper released and (b) cumulative fraction of copper released from the copper butyl xanthate complex at various leaching cycles during the semi-dynamic leach test (1N NaOH solution as leachant)…………………………………118
Figure 4-13 (a) The pH values and (b) the ORP values of the leachates at various leaching cycles during semi-dynamic leach test (1N NaOH solution as leachant)………………………………….119
Figure 4-14 UV-vis absorbance of the leachate at various leaching cycles during the semi-dynamic leach test (1N NaOH solution as leachant)……………………………………………………..121
Figure 4-15 X-ray diffraction patterns of copper butyl xanthate complex (a) before and (b) after semi-dynamic leach test（1N NaOH solution as leachant）……………………………………….123
Figure 4-16 SEM micrographs of copper butyl xanthate after semi-dynamic leach test (1 N NaOH solution as leachant): (a) SEM, (b) mapping analysis of copper element and (c) mapping analysis of sulfur element……………………………………125
Figure 4-17 Microprobe EDS analysis of copper butyl xanthate after semi-dynamic leach test in Figure 4-16(a)…………………..126
Figure 4-18 FTIR spectra of the copper butyl xanthate complex (a) before and (b) after the semi-dynamic leach test (1 N NaOH solution as leachant)……………………………………………………..127
Figure 4-19 X-ray photoelectron spectra of the copper butyl xanthate complex (a) before and (b) after the semi-dynamic leach test (1 N NaOH solution as leachant)……………………………….129
Figure 5-1 The content of the study for stability comparisons of the Cu-BX/cement matrices and the Cu(OH)2/cement matrices under acidic conditions……………………………………...133
Figure 5-2 (a) Copper ions released and (b) cumulative fraction of copper released from the 3-day curing Cu-BX/cement matrices at various leaching cycle during semi-dynamic leach test……..143
Figure 5-3 (a) Copper ions released and (b) cumulative fraction of copper released from the 7-day curing Cu-BX/cement matrices at various leaching cycle during semi-dynamic leach test……..145
Figure 5-4 (a) Copper ions released and (b) cumulative fraction of copper released from the 28-day curing Cu-BX/cement matrices at various leaching cycle during semi-dynamic leach test……..147
Figure 5-5 UV-vis absorbance of the 3-day curing Cu-BX/cement matrices’ leachate at (a) 1-week and (b) 10-week leaching cycle during semi-dynamic leach test……………………………..150
Figure 5-6 UV-vis absorbance of the 7-day curing Cu-BX/cement matrices’ leachate at (a) 1-week and (b) 10-week leaching cycle during semi-dynamic leach test……………………………..151
Figure 5-7 UV-vis absorbance of the 28-day curing Cu-BX/cement matrices’ leachate at (a) 1-week and (b) 10-week leaching cycle during semi-dynamic leach test……………………………..152
Figure 5-8 X-ray diffraction patterns of the 7-day curing Cu-BX/cement matrices (a) before and (b) after semi-dynamic leach test…..154
Figure 5-9 SEM micrographs of the 7-day curing Cu-BX/cement matrices (Cu-BX：cement＝1：1) before semi-dynamic leach test: (a) SEM, (b) mapping analysis of copper element and (c) mapping analysis of calcium element…………………………………155
Figure 5-10 SEM micrographs of the 7-day curing Cu-BX/cement matrices (Cu-BX：cement＝1：1) after semi-dynamic leach test: (a) SEM, (b) mapping analysis of copper element and (c) mapping analysis of calcium element……………………….156
Figure 5-11 FTIR spectra of the 7-day curing Cu-BX/cement matrices (a) before and (b) after semi-dynamic leach test (Cu-BX：cement＝1：1)………………………………………………………158
Figure 5-12 (a) Amount of Cu released and (b) cumulative fraction of copper released from the 3-day curing Cu(OH)2/cement matrices at various leaching cycle during semi-dynamic leach test…………………………………………………………...160
Figure 5-13 (a) Amount of Cu released and (b) cumulative fraction of copper released from the 7-day curing Cu(OH)2/cement matrices at various leaching cycle during semi-dynamic leach test…………………………………………………………...162
Figure 5-14 (a) Amount of Cu released and (b) cumulative fraction of copper released from the 28-day curing Cu(OH)2/cement matrices at various leaching cycle during semi-dynamic leach test…………………………………………………………..164
Figure 5-15 X-ray diffraction patterns of the 7-day curing Cu(OH)2/cement matrices (a) before and (b) after semi-dynamic leach test (Cu(OH)2：cement＝1：1).  Main crystalline compounds: c = CaCO3, JCPDS # 05-0586; h = Ca(OH)2, JCPDS # 44-1481; e = ettringite (3 CaO-Al2O3-3CaSO4-31H2O)……………………………….167
Figure 5-16 SEM micrographs of the 7-day curing Cu(OH)2/cement matrices (Cu(OH)2：cement＝1：1) (a) before and (b) after semi-dynamic leach test……………………………………..168
Figure 5-17 SEM micrographs of the 28-day curing Cu(OH)2/cement matrices (Cu(OH)2：cement＝1：1) (a) before and (b) after semi-dynamic leach test……………………………………..169
Figure 5-18 FTIR spectra of the 7-day curing Cu(OH)2/cement matrices (a) before and (b) after semi-dynamic leach test (Cu(OH)2：cement＝1：1)……………………………………………….171
Figure 5-19  (a) Amount of Cu released and (b) cumulative fraction of copper released from the Cu(OH)2 complex at various leaching cycle during semi-dynamic leach test……………………174
Figure 5-20 Cumulative fraction of copper released from the Cu-BX complexes, Cu-BX/cement matrices and Cu(OH)2/cement matrices after semi-dynamic leach test using 1 N HAc as leachant……………………………………………………...175
                                    

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