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研究生:駱明仁
研究生(外文):Ming-Jen Lo
論文名稱:尖晶石型態鋰錳氧吸附劑之製備、特性及其吸附-脫附行為之研究
論文名稱(外文):Preparations and Characteristics of Spinel Lithium Manganese Oxide Adsorbents and the Adsorption-Desorption of Lithium
指導教授:陳慧英陳慧英引用關係
指導教授(外文):Huey-Ing Chen
學位類別:碩士
校院名稱:國立成功大學
系所名稱:化學工程學系碩博士班
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
論文頁數:117
中文關鍵詞:尖晶石鋰吸附劑脫附固態燒結法溶液合成法
外文關鍵詞:spineldesorptionlithium adsorbentsolid-state sinteringsolution synthesislithium manganese oxide compounds
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本研究旨在以固態燒結法製備尖晶石型態鋰吸附劑,探討脫附程序中洗提劑種類、洗提劑濃度及溫度等變因之影響並對吸附-脫附循環操作中吸附劑之結構變化與鋰之嵌入、遷出機制作一探討。另外,以溶液合成法製備尖晶石型態鋰錳氧吸附劑,探討高分子種類、鋰錳比例及鍛燒條件等對鋰吸附劑之結構特性及其吸附容量之影響。
由脫附研究得知,以鹽酸及硝酸作洗提劑時之脫附速率較以過氧二硫酸銨為洗提劑時為快;而且脫附速率隨洗提劑濃度及溫度增高而增快。經由24 h洗提後,三種洗提劑之鋰回收率皆達98 %以上。以錳之溶出量而言,以鹽酸及硝酸作洗提劑時之溶出量較以過氧二硫酸銨為洗提劑時為大。
在循環操作中,以鹽酸作洗提劑時,發現鋰之吸附量會隨次數增加而降低,且伴隨錳離子溶出量亦增大。在脫附過程中,錳之溶出尤為顯著,使吸附劑之結構遭到破壞,而造成了吸附劑再使用性之降低。此現象可由SEM、XRD及EXAFS之分析,而得到相互印證。
在溶液合成法中,分別以PVP、PEG及PVA三種高分子包覆劑來製備鋰錳氧吸附劑。結果發現以PVA作為包覆劑,可在400 oC下鍛燒2 h即得到尖晶石型態之粉體。至於,PVA在微粉製備中之作用,由FT-IR及NMR分析結果顯示,PVA與鋰、錳應無明顯之鍵結存在。另外,分別改變鋰錳比例(Li/Mn= 1, 1/2)及鍛燒溫度(T= 400 oC, 800 oC)結果發現,當Li/Mn=1且鍛燒溫度為800oC所得之吸附劑對鋰之吸附容量最大,其飽和吸附量為44 mg/g;此值大於固態燒結法所得之吸附劑。由此顯示溶液合成法優於固態燒結法,可製備出具高吸附容量之尖晶石鋰錳氧吸附劑。
In this work, the spinel-type lithium adsorbent was firstly prepared by the solid-state sintering method. The effects of nature and the concentration of the eluents, and operating temperature on the lithium desorption were studied. The structural changes as well as the lithium insertion-extraction during multi-cycle operations were under investi- gation. Moreover, spinel adsorbents were prepared by solution synthesis. Three polymers, PVA、PEG and PVP, were used as dispersive agents. The calcination conditions on the characteristics and lithium adsorptivity of the adsorbents were also studied.
For desorption of lithium, the elution rate with the HCl and HNO3 was faster than that with (NH4)2S2O8. And, the rate was increased with increasing the concentration of the eluents and operating temperature. For the three kinds of eluents, the Li recoveries were all above 98 % after 24 h of elution. Nevertheless, much manganese was dissolved by using HCl and HNO3 as the eluent comparing with that eluted by (NH4)2S2O8.
In the multi-cycle operations with HCl as the eluent, the lithium adsorption amount was decreased with increasing the number of cycle. Furthermore, the Mn dissolution was increased and resulted in the collapse of the adsorbent structure. This result was in good consistency with those obtained from SEM, XRD and EXAFS analyses.
For the solution synthesis method, the spinel lithium manganese oxide adsorbent was prepared by using PVA, PVP and PEG as dispersive agents. It was found that the spinel phase could be obtained by using PVA and calcined at 400 oC for 2 hrs. From the FT-IR and NMR characterizations, there was no obvious chemical bonding between PVA and metal ions. Comparing various adsorbents prepared under different Li/Mn ratios and calcinations temperatures, the adsorbent obtained from Li/Mn=1 and calcined at 800 oC showed the largest adsorption capacity (i.e., 44 mg/g). Even, this adsorbent was superior to that obtained by solid-state sintering method.
總 目 錄
中文摘要
英文摘要
總目錄 Ⅰ
表目錄 Ⅳ
圖目錄 Ⅴ
第一章 1
1-1鋰錳氧化合物之簡介 1
1-2尖晶石鋰錳氧材料特性及其應用--------------------------------2
1-3鋰之提取 ------------------------------------------------------------4
1-4吸附劑之製備方法 -------------------------------------------------5
1-5研究目的及概要---------------------------------------------------- 7
第二章 鋰之吸附脫附機構 14
2-1鋰錳氧尖晶石結構 14
2-2 X-ray 吸收光譜之簡介與原理----------------------------------16
2-3 Rietveld 精算結構法 ---------------------------------------------19
第三章 實驗部分 --27
3-1藥品 27
3-2分析儀器及設備 28
3-3方法及實驗步驟 29
3-3-1 λ-MnO2吸附劑之製備 30
3-3-2 吸附實驗 31
3-3-3 脫附實驗--------------------------------------------------- 31
3-3-4 吸脫附循環實驗-------------------------------------------------31
3-3-5 X-ray吸收光譜實驗--------------------------------------32
3-3-6 FT-IR及NMR光譜實驗---------------------------------32
3-4 Rietveld結構精算------------------------------------------------ 33
3-5鋰錳氧化合物之化學式鑑定----------------------------------- 33
第四章 結果與討論 39
4-1脫附研究-------------------------------------------------------------39
4-1-1 吸附劑吸附容量---------------------------- -----------------39
4-1-2 鋰脫附行為之探討-------------------------------------- ----40
4-1-3 尖晶石吸附劑之鑑定分析 ---------------------------------42
4-1-4 Rietveld晶體結構解析 -------------------------------------45
4-2 循環實驗研究 ------------------------------------------------------45
4-2-1 洗提劑種類之影響 -----------------------------------------------46
4-2-2 鋰吸附量與錳溶出之影響 ---------------------------------46
4-2-3 吸附劑之特性 -----------------------------------------------46
4-3 溶液相合成尖晶石鋰吸附劑之初探 ----------------------------49
4-3-1 鋰錳氧吸附劑製備之探 討---------------------------------49
4-3-2溶液合成法中PVA之作用 ---------------------------------53
4-3-2-1 FT-IR光譜分析 ------------------------------------------53
4-3-2-2 NMR光譜解析 -------------------------------------------54
4-3-3鋰吸附能力之比較 ------------------------------------------55
第五章 結果及建議------------------------- ----------------------------109
5-1 固態燒結法所製備之鋰吸附劑 --------------------------------109
5-2 溶液合成法之鋰吸附劑-------------------------------- -------110
5-3 未來展望-----------------------------------------------------------110
參考文獻 -----111
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