Removal of Boron from Polarizer Manufacturing Wastewater by Using Mg-Al (NO3) Layered Double Hydroxides

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研究生：	柯莉莉 Liana - Kentjono
論文名稱：	Removal of Boron from Polarizer Manufacturing Wastewater by Using Mg-Al (NO3) Layered Double Hydroxides Removal of Boron from Polarizer Manufacturing Wastewater by Using Mg-Al (NO3) Layered Double Hydroxides
指導教授：	劉志成 Jhy-Chern Liu
口試委員:	張維欽 Wei-qin Chang 顧洋 Young Ku 黃志彬 Chih-Pin Huang 李篤中 Duu-Jong Lee
學位類別：	碩士 Master
系所名稱：	工程學院 - 化學工程系 Department of Chemical Engineering
論文出版年：	2009
畢業學年度：	97
語文別：	英文
論文頁數：	112
中文關鍵詞：	吸附，硼，碘，離子交換，鎂鋁硝酸雙層金屬氫氧化物，光電，偏光板，廢水
外文關鍵詞：	ion exchange; LDHs, optoelectronic, polarizer
相關次數：	點閱：257 下載：6
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偏光板製造業產生含有高濃度硼、碘和化學需氧量的廢水。在此研究中，我們合成鎂鋁硝酸雙層金屬氫氧化物(Mg-Al(NO3) - layered double hydroxides, LDHs)，用為移除合成廢水與偏光板製造業廢水中的硼。去除硼程序中的反應機制將是被探討的重點。
鎂鋁硝酸雙層金屬氫氧化物可以移除廢水中98%以上的硼，而最適合硼移除的酸鹼值為9.0。實驗數據也與蘭謨爾吸附等溫線(Langmuir isotherm)相符合。對於合成廢水，硼的單層吸收負載能力(Qo)和蘭謨爾吸附常數(b)分別為26.1 mg/g與 0.36 L/mg；而在室溫下，酸鹼值為9.0的工廠廢水，硼的單層吸收負載能力(Qo)和蘭謨爾吸附常數(b)分別為37.9 mg/g 與0.0806 L/mg。由熱力學的分析顯示，硼的移除過程是自發性、放熱並且亂度是增加的。然而，移除硼的過程中，與溫度較無較大的關係。由酸鹼值效應的實驗結果與反應熱(ΔHo)值等於3.22 kcal/mol看起來，硼的移除是離子交換與物理吸附機制的結合。利用偽一階(Pseudo first order)及二階(Pseudo second order)動力學模式所產生的數據相當符合添加鎂鋁硝酸雙層金屬氫氧化物時所得到的實驗數據。由偽一階(Pseudo first order)及二階(Pseudo second order)動力學模式所計算出的反應活化能分別為3.25 kJ/mol與7.14 kJ/mol。在計算化學劑量時，硝酸根離子的釋放量高於被鎂鋁硝酸雙層金屬氫氧化物所吸附的總離子量。大量的硝酸根離子被釋出可能是因為與碳酸根離子產生交換。廢水中的碘離子雖然也被移除，並不能與硼離子來競爭鎂鋁硝酸雙層金屬氫氧化物表面的活性位置，這是因鎂鋁硝酸雙層金屬氫氧化物對於碘離子的選擇性較低的緣故。

The polarizer manufacturing industries generate wastewater that contains high concentration of boron, iodide, and chemical oxygen demand (COD). In this study Mg-Al (NO3) layered double hydroxides (LDHs) were used to remove boron from synthetic wastewater and polarizer manufacturing wastewater. The mechanism in boron removal process was investigated.
LDHs showed high efficiency (up to 98%) in removing boron from wastewater. The optimum pH for boron removal process was 9.0. The boron uptake capacity (Qo) value and Langmuir constant (b) value for synthetic wastewater were 26.1 mg/g and 0.36 L/mg, respectively. At room temperature and pH~9.0, the boron uptake capacity (Qo) value and Langmuir constant (b) value for industrial wastewater were 37.9 mg/g and 0.0806 L/mg, respectively. The boron removal process was spontaneous, exothermic and exhibited randomness behavior as indicated by thermodynamic parameters. However, the boron removal process was independent on temperature. The ΔHo value of 3.22 kcal/mol suggested there was a combination of ion exchange and physical adsorption mechanisms. Pseudo first order and pseudo second order kinetic models perfectly represented the experimental data of boron removal by using LDHs. The activation energy obtained from the pseudo first order and pseudo second order kinetic models were 3.25 kJ/mol and 7.14 kJ/mol, respectively. In the stoichiometry calculation the nitrate anions released was higher than total anions taken up by LDHs. The excessive nitrate anions released may be due to the exchange with carbonate anions. Iodide anions present in wastewater can not compete with borate anions for LDHs surface sites because of low selectivity of LDHs toward iodide anions.

ABSTRACT (ENGLISH)   …………………………………………………………………i
ABSTRACT (CHINESE)   …………………………………………………………………ii
ACKNOWLEDGEMENTS       ………………………………………………………………iii
TABLE OF CONTENT     …………………………………………………………………iv
LIST OF FIGURES  ………………………………………………………………………vi
LIST OF TABLES	 ………………………………………………………………………viii
CHAPTER I. INTRODUCTION    …………………………………………………………1
1.	Background ……………………………………………………………………1
2.	Objectives ……………………………………………………………………2
CHAPTER II. LITERATURE REVIEW    …………………………………………………3
1. Polarizer structure and manufacturing process …………………………3
2. Theory of Boron and Removal of Boron …………………………………….4
2.1. Source of Boron 	 …………………………………………………………..4
2.2. Boron Deficiency and Toxicity …………………………………………..4
2.3. Regulation for Boron level ……………………………………………….5
2.4. Removal of boron …………………………………………...............6
2.5. Removal of boron by adsorption processes  ……………………………6
3. Theory in Layered Double Hydroxides (LDHs)	……………………………12
3.1. LDHs definition and application	………………………………………12
3.2. The Structure of LDHs	…………………………………………………12
3.3. Synthesis of LDHs	…………………………………………………14
4. Adsorption of boron on LDHs	………………………………………16
5. Adsorption and Ion Exchange…………………………………………………20
5.1. Adsorption     ………………………………………………………………20
5.2. Ion Exchange	……………………………………………………………21
6. Equilibrium Isotherm………………………………………………………….21
7. Kinetic Study ………………………………………………………………….22
CHAPTER III. MATERIALS AND METHODS     ……………………………………….24
1. Source of Wastewater …………………………………………………………24
2. Chemicals	……………………………………………………………………..24
3. Equipments and Instruments	…………………………………………………25
4. Experimental Method  …………………………………………………………27
4.1. Synthesis of LDHs    ………………………………………………………27
4.2. Removal of boron experiment  …………………………………………..28
4.3. Sample analytical methods  ……………………………………………..29
CHAPTER IV. RESULTS AND DISCUSSION    ………………………………………..31
1. Characterization of LDHs…………………………………………………….31
2. Removal of boron experiment by using LDHs …………………………….41
2.1. Synthetic wastewater   ……………………………………………………41
2.1.1. Equilibrium time determination	    …………………………………41
2.1.2. Effect of equilibrium pH     ………………………………………..43
2.1.3. Effect of LDHs dose      …………………………………………....46
2.1.4. Equilibrium isotherm	    ……………………………………………48
2.1.5. Stoichiometry calculation   …………………………………….....50
2.2. Industrial wastewater  ……………………………………………………51
2.2.1. Characteristics of industrial wastewater………………………...51
2.2.2. Effect of equilibrium pH    ………………………………………...52
2.2.3. Effect of LDHs dose	    ……………………………………………56
2.2.4. Effect of temperature	    ……………………………………………58
2.2.5. Effect of other ions	  ………………………………………………63
2.2.6. Kinetic study	      ……………………………………………………67
2.2.7. Stoichiometry calculation     ……………………………………….70
3. Analysis of loaded LDHs …………………………………………………….72
4. Removal of COD by using LDHs  …………………………………………….77
5. Mechanism of boron removal	…………………………………………………77
CHAPTER V. CONCLUSIONS AND SUGESTIONS      ………………………………...79
1. Conclusions  ……………………………………………………………………79
2. Suggestions  ……………………………………………………………………80
REFERENCES  …………………………………………………………………………..81
APPENDIX  …………………………………………………………………………….A-1

                                

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