嵌入不同團聯共聚物之黏土複合材料其吸持特性研究

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研究生：	吳御穎 Yu-Ying Wu
論文名稱：	嵌入不同團聯共聚物之黏土複合材料其吸持特性研究 Absorption Characteristics of Clay Composites Modified by Different Block Copolymers
指導教授：	李俊福
口試委員:
學位類別：	碩士 Master
系所名稱：	工學院 - 環境工程研究所 Graduate Institute of Environmental Engineering
論文出版年：	2019
畢業學年度：	107
語文別：	中文
論文頁數：	133
中文關鍵詞：	團聯共聚物、改質土壤、無機污染物、BTEX
外文關鍵詞：	Block copolymer, Modified clay, Cu2+ Pb2+ Cr2O72-, BTEX
相關次數：	點閱：9 下載：0
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天然土壤由於表面帶有負電荷，對陽離子重金屬具有親和力，而對於有機污染物，通常因有機質含量過少，導致吸持效果不佳，無法同時對有機與無機污染物兼具吸持性。近年來，團聯共聚物之相關研究蓬勃發展，被廣泛應用於奈米材料產業，因此本研究將三種團聯共聚物嵌入高嶺石、伊萊石、鈣蒙特石進行改質，製備出黏土奈米複合材料，探討改質效果及對非離子、陰離子、陽離子污染物的吸持能力。
由土壤的特性鑑定發現，三種土壤改質後的有機碳含量皆高於改質前的土壤，透過FTIR的分析圖譜確認，改質土壤表面含有團聯共聚物上具備的特殊官能基，而從X光繞射分析得知每種改質土壤層隙間距皆有所提高，最後由ASAP分析得知土壤改質後其比表面積減少、孔洞大小增加，證實團聯共聚物已成功嵌入土壤中。
改質土壤於BTEX的吸持結果，可發現雖然有土壤機質含量提高，但因改質劑結構性質的影響，而使吸持效果有所差異，也可看出分佈常數（Kd）與有機碳含量確實有相關性，且經校正後得log Kom值皆大於文獻值。對無機污染物吸附的結果，可看出帶有羧基的改質土壤，在鹼性條件下對Cu2+及Pb2+有最高的吸附量；帶有胺基的改質土壤，在酸性條件下對Cr2O72-有最高的吸附量；同時帶有羧基及胺基的改質土壤對陰、陽離子的吸附量皆居中，而每種改質土壤對無機污染物的吸附量皆高於文獻中的天然土壤。綜合有機分佈與無機吸附實驗的結果，證實本研究之團聯共聚物改質土壤，可同時對非離子（BTEX）、陽離子（Cu2+、Pb2+）、陰離子（Cr2O72-）污染物兼具親和力。

The natural soil possesses negatively charged and has high affinity for metal cations. But for the nonionic organic contaminats, due to lack of organic matters content, the capacity of partitioning is not effectively. Thus, the natural soil is not effective for the simultaneous removal of both organic and inorganic contaminats. In recent years, the researches of block copolymer are developed and have been widely applied on nanomaterial. Therefore, in this study, we use kaolinite, illite and Ca-montmorillonite which are intercalated diblock copolymer and tribiock copolymer separately to prepare clay-composite materials. Exploring the adsortion capacity of these clay-composite materials for noionic, cation and anion contaminats.
From the characterization analysis of the clay-composite materials, we found that the organic carbon content of these three soils was higher than that before been modified. The FTIR analysis, the spectrum showed that the modified clay suface contained the specific functional group of the block copolymer. As for the X-ray diffraction (XRD) technique was applied to reveal intercalated materials in the layer, which provides informations on layered structure and the basal spacing. The results showed that the basal spacing of the modified clays all increased and the increased degree was mainly dependent on the molecular weight and intercalated amount of the block copolymer. Finally, the ASAP analysis showed that the specific surface area decreased and the pore size increased after soil modification. These analytical data comfirmed that the block copolymer has been intercalated into the inter-layer of soil successfully.

The BTEX experimental results showed that although the modified clay organic matter content is increased, due to the structural properties of the modifier, the partitioning effect was defferent. Simultaneously, it can been observed that the partition coefficient (Kd) was indeed related to the organic matter content. Comparing to the literatures, the modified clay of this study possesses better distribution ability and higher log Kom values. The adsorption experiment of inorganic contaminats (Cu2+, Pb2+, Cr2O72-) showed that the modified clay with carboxyl group has the highest adsorption capacity for Cu2+ and Pb2+ under alkaline conditions. The modified clay with amine group has the highest adsorption capacity for Cr2O72- under acidic conditions. The modified clay with both carboxyl and amine group have the middle adsorption capacity for cation and anion contaminats. The adsorption capacity of inorganic contaminats adsorbed by each modified soil is higher than natural soil of the literature. Eventually, the results of comprehensive organic partitioning and inorganic adsorption experiments confirmed that the modified clay with block copolymer of this study provide the affinity of nonionic (BTEX), cation (Cu2+, Pb2+), anion (Cr2O72-) contaminats.

目錄    …………………………………………………………………I
圖目錄    …………………………………………………………………IV
表目錄    …………………………………………………………………XI
第一章    研究緣起與目的……………………………………………1
1-1    研究緣起…………………………………………………………1
1-2    研究目的與內容……………………………………………3
第二章    文獻回顧…………………………………………………………4
2-1    土壤特性…………………………………………………………4
2-1-1    土壤基本性質…………………………………………………4
2-1-2    土壤無機相………………………………………………………4
2-1-3    土壤有機質………………………………………………………5
2-1-4    土壤陽離子交換容量……………………………………7
2-1-5    層狀矽酸鹽材料……………………………………………7
2-2    土壤對污染物之吸持作用……………………………9
2-2-1    土壤無機相吸附………………………………………………9
2-2-2    土壤有機質之兩相分佈作用…………………………9
2-2-3    土壤之分佈常數…………………………………………………12
2-3    吸附理論………………………………………………………………13
2-3-1    等溫吸附曲線………………………………………………………13
2-3-2    等溫吸附模式………………………………………………………15
2-4    團聯共聚物……………………………………………………………18
2-4-1    團聯共聚物基本性質…………………………………………18
2-4-2    pH值對團聯共聚物的微胞化影響…………………21
2-4-3    團聯共聚物之合成………………………………………………24
2-5    團聯共聚物於高分子材料之反應機制…………29
2-5-1    層狀黏土之分散型態…………………………………………28
2-5-2    團聯共聚物於黏土間隙之作用機制………………30
2-5-3    團聯共聚物於層狀黏土間隙之嵌入方法………31
第三章    研究方法……………………………………………………………………34
3-1    研究內容與流程………………………………………………………34
3-2    實驗設備與儀器………………………………………………………36
3-2-1    實驗設備……………………………………………………………………36
3-2-2    實驗儀器……………………………………………………………………37
3-3    實驗材料……………………………………………………………………41
3-3-1    不含有機質土壤………………………………………………………41
3-3-2    團聯共聚物………………………………………………………………41
3-3-3    非離子性有機污染物……………………………………………43
3-3-4    重金屬標準品…………………………………………………………43
3-3-5    溶劑……………………………………………………………………………44
3-4    實驗方法……………………………………………………………………46
3-4-1    改質土壤之製備……………………………………………………45
3-4-2    團聯共聚物合成實驗……………………………………………45
3-4-3    改質土壤對污染物之吸持實驗…………………………48
第四章    結果與討論………………………………………………………………50
4-1    團聯共聚物之特性分析………………………………………50
4-1-1    團聯共聚物之基本性質………………………………………50
4-1-2    自行合成之三團聯共聚物GPC分子量分析……51
4-2    黏土材料之特性分析……………………………………………53
4-2-1    有機碳含量測定（TOC）……………………………………54
4-2-2    穿透式電子顯微鏡（TEM）………………………………56
4-2-3    傅立葉轉換紅外線光譜分析（FTIR）…………60
4-2-4    X光繞射分析（XRD）……………………………………………64
4-2-5    比表面積、平均孔徑與孔徑分佈（ASAP）……67
4-3    改質黏土對有機污染物（BTEX）之吸持作用…72
4-3-1    BTEX之吸持行為…………………………………………………………72
4-3-2    不同改質劑對BTEX之吸持影響………………………………78
4-3-3    改質劑特性對BTEX分佈常數之影響……………………83
4-4    改質黏土對無機污染物之吸附作用………………………88
4-4-1    不同改質黏土對重金屬之吸附影響………………………88
4-4-2    不同土壤基材對重金屬之吸附差異………………………97
4-4-3    不同改質黏土對無機陰離子之吸附影響……………101
4-4-4    不同土壤基材對無機陰離子之吸附差異……………106
第五章    結論與建議……………………………………………………………………109
5-1    結論…………………………………………………………………………………109
5-2    建議…………………………………………………………………………………110
參考文獻    ……………………………………………………………………………………………111


                                

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