臺灣博碩士論文加值系統

牡蠣殼、蛋殼、粉筆灰皆為明確之廢棄物，每年使用量高故廢棄產量也大，進而形成廢棄處理及環境問題。因牡蠣殼等廢棄物其主要化學成分皆為碳酸鈣且含量頗高，利用此成分特性加以應用期以解決廢棄物之問題為本研究之主要目的。氫氧基磷灰石(HA)為一種非常重要之生醫材料，其主要成分為鈣及磷Ca/P =1.67條件下可得此材料，本研究利用牡蠣殼等廢棄物做為鈣源，磷酸作為磷源，利用水熱法加入氫氧化鈉(NaOH)，改變製程中各項參數使其合成氫氧基磷灰石達最佳化，加以燒結穩定獲得合成之氫氧基磷灰石。將合成之氫氧基磷灰石進行對溶液中含Cu2+之吸附研究。
實驗結果顯示於水熱溫度150℃、水熱時間2小時、800℃鍛燒參數條件下，XRD分析繞射結果最為符合HA晶相。水熱溫度若控制於100℃時各項m-HA仍有β-TAP晶相存在而隨水熱溫度提高β-TAP晶相減少顯示HA趨向更穩定。 FTIR官能基分析所製備之m-HA主要為PO43-ν、C-O及CO32-、H-O等官能基，而經過鍛燒後之影響主要為H-O變化。熱重分析顯示所製備之HA於溫度1000℃鍛燒溫度下重量損失僅5%，與市售HA相比差距不大，顯示晶相結構非常穩定。表面特性分析；BET比表面積分析結果為9.6〜11.8m2/g且為type II乙型等溫吸附線，鍛燒前後結果比較為比表面積降低孔洞體積亦降低，顯示HA鍛燒後顆粒愈為緻密。SEM外觀測定發現所製備之HA主要為圓球或圓柱形，粒徑約為〈 250nm，表面平滑孔洞較少，呼應比表面積分析結果。牡蠣殼等不同物種所製備HA於特性分析並無明顯差異，顯示牡蠣殼等物種可順利水熱合成HA。
吸附應用實驗發現所製備之m-HA對Cu2+於起始濃度於100ppm以上條件下吸附去除率可達80%以上，吸附容量可達16.9〜18 mg/g。主要為表面官能基與銅離子作用所致。等溫吸附模式Langmuir model R2皆於0.90以上，較符合本吸附研究。Freundlich model中n值大於1，顯見為有利於吸附條件。Kf吸附常數值為P-HA 3.159 〉 Oy.-HA 3.06 〉 Egg-HA 〉 Ch.-HA 0.931。動力吸附實驗擬二階方程式R2皆於0.99以上且推估吸附量與實驗吸附量非常相近，顯示此吸附實驗屬化學吸附。

The annual production and consumption of oyster shell, eggshell, and chalk dust are huge, thus resulting waste disposal and environmental problems. The main composition of these waste is high content calcium carbonate. How to utilize the calcium carbonate to solve waste problem is the major objectives of this study. Hydroxyapatite (HA) is a very important biomaterials, which could be obtained under the condition when calcium/ phosphorous ratio equals to 1.67. This study used oyster shell and other waste as calcium source, and phosphoric acid as phosphorous source for HA production. HA was produced by hydrothermal method, while sodium hydroxide was added during the production process. Different factors were adjusted to optimize the HA production process to obtain the stable sintered synthesized HA, which were further applied in the study of copper adsorption from solutions.
The experimental result shows that under 150 ℃ hydrothermal temperature, 2-hour duration, and 800 ℃ calcination, XRD diffraction analysis results corresponded mostly with HA crystalline structure. When hydrothermal temperature is 100 ℃, m-HA still has some β-TAP crystalline structures, which will decrease with hydrothermal temperature rising, forming more stable HA. The functional groups of m-HA prepared for FTIR analysis are primarily PO43-ν, C-O, CO32-, H-O, etc., and calcination mostly influences on the change of H-O. The thermal gravity analysis shows the weight loss of the prepared HA is only 5% under 1000℃. The result is similar with commercially available HA, indicating the crystalline structure is very stable. BET specific surface is 9.6-11.8 m2/g, and corresponds to type II isothermal adsorption curve. The specific surface area and pore volume are decreased after calcination, generating the finer HA particles. SEM shows that the appearance of HA are primarily spherical and cylindrical. The particle size is less than 250 nm with smooth surface and less pores, which is in accordance with specific surface analysis results. The characteristics of HA prepared by different materials have no obvious differences. Oyster shell, eggshell and chalk dust can hydrothermally synthesized into HA successfully.
The prepared m-HA is used in adsorption experiment. When initial concentration of copper is 100 ppm, the removal is above 80%, and adsorption volume is 16.9-18 mg/g. The adsorption is mainly due to the functional groups on the surface and copper ion. The R2 value of the isothermal adsorption model, Langmuir model, is greater than 0.90, corresponding with the experimental result. The n value of Freundlich model is greater than 1, indicating the adsorption favorable condition. The adsorption constants Kf are P-HA 3.159 〉 Oy.-HA 3.06 〉 Egg-HA 〉 Ch.-HA 0.931. The R2 values of second-order kinetic adsorption experiments are all greater than 0.99. The presumed adsorption volumes are very similar to experimental result, indicating the experiment is chemical adsorption.

中文摘要………………………………….………………………………….II
英文摘要………………………………………………………………….....IV
致謝………………………………………………………………………….VI
目錄………………………………………………………………………..VIII
表目錄……………………………………………………………………...XII
圖目錄…………………………………….……………………………….XIV
符號對照表………………………………………………………………XVII
第一章 緒論………………………..………….…………………….……….1
§1-1研究動機…………………………………….…………………….….1
§1-2研究目的………………………………………...…………….……...2
第二章 文獻回顧………………………………….…………………………3
§2-1本研究含鈣物料相關資料….………………………………………..3
2-1-1蛋殼之構造、成份…………………………………………..……..3
2-1-2蛋殼之相關研究…………………………………………………..3
2-1-3牡蠣殼產量及成分………………………………………..………6
2-1-4牡蠣殼之相關研究……………………………………………..…6
2-1-5三種合成物料之成分比較……………………………………….7
§2-2氫氧基磷灰石(HA)之背景說明……………………...………….….11
2-2-1氫氧基磷灰石組成………………………………………………11
2-2-2氫氧基磷灰石應用………………………………………...…….14
§2-3氫氧基磷灰石之研究…………………….………………………....17
2-3-1國內HA相關學術研究…………….……….………………….. 17
2-3-2國內以HA為題目相關研究專利……………………………….17
2-3-3國際期刊相關HA研究……………………………...…………..20
§2-4氫氧機磷灰石行為特性……..……………………………….……31
2-4-1氫氧基磷灰石離子交換型態…………...……………………….31
2-4-2氫氧基磷灰石(HA)吸附研究……………..…………………….32
2-4-3合成氫氧基磷灰石粉末影響因素………………………………35
2-4-4磷酸鈣鹽類形成..………………………………………………..37
2-4-5磷酸鈣鹽類的高溫特性…………………………………………37
§2-5實驗相關文獻………………………......………………………….43
2-5-1吸附導論……………………………..……………………..........43
2-5-2等溫吸附模式……………………………………………............45
2-5-3等溫吸附曲線……………………………………………............50
2-5-4孔洞大小分佈測定………………………………………………53
2-5-5孔洞型態分類……………………………………………………54
§2-6界達電位(Zeta-potential)….………………………...………..........56
2-6-1界達電位分析原理………………………………………………56
2-6-2零電荷點..…………………………………………………..........57
§2-7主要實驗方法(水熱法)介紹..………………………………...........59
2-7-1(水熱法)概述及原理……………………………………………..59
2-7-2水熱法製備粉體的優點…………………………………………62
第三章 實驗方法…………………………………………………………...64
§3-1實驗方法簡介…..……………………………………….…............64
§3-2原料藥品來源及合成儀器...…………………………….………...66
3-2-1合成材料分析(相關圖示如圖3-2)...…………………...........66
§3-3實驗步驟………………………………..………………………….67
§3-4合成實驗系統…………………………...………………...……….69
第四章 結果與討論……………………………………………………….75
§4-1含鈣廢棄物之處理及合成….…...………...………………............75
4-1-1前處理CO2產量……………..………….………………...........75
4-1-2前處理含鈣量分析…………..…………………………………76
§4-2合成氫氧機磷灰石特性分析…..………………………………….78
4-2-1XRD晶像分析………………..………………………………..78
4-2-1-1三種含鈣物質800℃鍛燒反應..………………………......78
4-2-1-2不同水熱溫度條件……………..………………………….81
4-2-1-3不同pH環境影響………………..………………………...87
4-2-1-4不同水熱控制時間影響…………..……………………….91
4-2-2官能基測定(FTIR)……………………………………………...93
4-2-2-1不同水熱溫度條件FTIR分析……..……………………...93
4-2-2-2不同pH環境影響FTIR分析………..…………………….94
4-2-2-3不同水熱控制時間影響……………..…………………….97
4-2-3熱重分析(TGA/DTG/DSC)…..……………………………...100
4-2-4界達電位測定(Zeta patential).………………………………105
4-2-5表面特性定……..……………………………………………109
4-2-5-1比表面積、孔洞體積…………………………………….109
4-2-5-2孔洞體積與孔徑關係....………………………………...109
4-2-5-3孔洞型態……………..…….……………………………110
4-2-5-4氮氣等溫吸脫附曲線…..…..…………………………...110
4-2-6外觀特性測定(SEM).……..……..…………………………116
4-2-7小結…………………………………………………………122
§4-3吸附應用研究....………………………………………………..123
4-3-1平衡吸附研究…….…………………………………………...124
4-3-1-1不同pH條件下吸附比較..……………………………….124
4-3-1-2不同吸附劑量比較………..……………………………...127
4-3-1-3不同反應時間比較………..……………………………...127
4-3-2 等溫吸附研究………………………………………………133
4-3-3 吸附動力研究…………………..……………………………141
4-3-4小結…………………………………………………………..146
第五章結論………………………………………………………………...147
第六章 建議…………………………………………………….…………149
第七章參考文獻……………………………………………………...........150

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