沉澱去除光電廢水中磷酸鹽之研究｜國立臺灣科技大學博碩士論文系統

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研究生：	何俊明 Jiun-mimg He
論文名稱：	沉澱去除光電廢水中磷酸鹽之研究 Precipitation Removal of Phosphate from TFT-LCD Manufacturing Wastewater
指導教授：	劉志成 Jhy-chern Liu
口試委員:	黃志彬 Chih-pin Huang 李篤中 Duu-jong Lee 張維欽 Wei-chin Chang 顧洋 Young Ku
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：	2008
畢業學年度：	96
語文別：	英文
論文頁數：	99
中文關鍵詞：	光電廢水、化學處理、去除磷酸鹽、磷化鈣、磷化鎂、氫氧基磷灰石
外文關鍵詞：	Chemical precipitation
相關次數：	點閱：198 下載：16
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上一筆

本實驗主要目的在於利用沉澱法去除光電業蝕刻廢水中磷酸之可行性，利用鈣鹽及鎂鹽等四種化合物為沉澱劑。酸鹼值與濃度莫耳比為主要的參數，探討最適當之操作條件。同時利用電子掃描顯微鏡與X光繞射分析對單體顆粒表面進行微觀的定性分析。

結果顯示，酸鹼值與濃度莫耳比均為扮演重要的參數。以鈣鹽而言，過量的鈣鹽可獲得理想的移除效果。然而，酸鹼值必須控制在8.5至10.5之間。相形之下，鎂鹽在移除的整體表現上低於鈣鹽，但是鎂鹽較不受氟離子干擾，因此對磷酸鹽具較佳選擇性。

沉澱物定性分析結果顯示，磷酸鈣沉澱物形式主要隨著酸鹼值而變化。在酸性環境，主要以磷酸二鈣(dicalcium phosphate dihydrote, DCPD)為主要形成；在中性而言，結晶的氫氧基磷灰石(hydroxyapatite, HAP)以及非結晶HAP為主要優勢物種；鹼性中之沉澱物均為非結晶HAP的形式存在；但是高於酸鹼值11.5之環境氫氧化鈣將生成，導致移除效率降低。以鎂鹽而言，沉澱物均以磷酸三鎂(bobierrite)呈現，高於酸鹼值11.5，則氫氧化鎂將生成，導致移除效率的降低。

由本研究之結果可知，以沉澱法去除含磷酸鹽之廢水之效果非常好。除此之外，所生成之沉澱物具有很高的潛力回收再利用。因此非常適合應用在光電廢水中去除磷酸鹽之操作程序。

e etching wastewater from thin film transistor liquid crystal display (TFT-LCD) manufacturers contains high concentration of phosphate. The aim of this thesis was to investigate the feasibility of phosphate removal from TFT-LCD wastewater by precipitation with calcium and magnesium salts. Optimal operating conditions were determined. Besides , field-emission scanning electron microscope (FE-SEM) and X-ray diffraction (X-RD) were used in characterization of precipitates.
Both pH value and molar ratio of metal to phosphate play important roles in precipitation of phosphate. For calcium salts, excess dosage resulted in higher removal efficiency of phosphate. However, the pH value must be controlled between 8.5 and 10.5. Magnesium salts showed lower removal efficiency when compared to calcium salts. Yet, they were more selective in phosphate removal when in the presence of fluoride.
The results of precipitate characterization showed that the dominant phase of calcium phosphates precipitates depended on the pH value. When at pH value of 5.5, the dominant phase was found to be dicalcium phosphate dihydrate (DCPD), while hydroxyapitite (HAP) predominantly formed between a pH of 6.5 and 10.5. It was observed that bobierrite was predominantly formed between pH of 8.5 and 10.5 when magnesium salts were used.
Result from the study indicated that the removal efficiency of phosphate by precipitation was satisfactory. Besides, the precipitates were potentially reusable as fertilizers. The method is promising for application on phosphate removal from TFT-LCD wastewater.

Table of Content

中文摘要……………………………………………………………………………………I
Abstract……………………………………………………………………………………II
Acknowledgment……………………………………………………………………………lII
Table of Content…………………………………………………………………………lV
List of Figures……………………………………………………………………………Vl
List of Tables……………………………………………………………………………X
Chapter 1 Introduction1
1.1 Background       1
1.2 Objective        2
Chapter 2 Literature Review         3
2.1 TFT-LCD industry in Taiwan      3
2.2 Wastewater from TFT-LCD manufacturers	6
2.3 Phosphorus	7
2.4 Current techniques for phosphate removal	8
2.4.1 Biological treatment	8
2.4.2 Chemical treatment	9
2.4.3 Magnesium salt precipitation	21
2.4.2 Crystallization treatment	23
Chapter 3 Materials and Methods	24
3.1 Source of etching wastewater from TFT-LCD	24
3.2 Chemicals for experiment	24
3.3 Equipments and Instruments	25
3.4 Experimental methods and procedures	26
3.5 Analysis Procedures	28
3.5.1 Turbidity	28
3.5.2 pH Meter	28
3.5.3 Zeta Potential	29
3.5.4 Total Solid and Total Suspended Solid	29
3.5.5 Energy dispersion X-ray spectroscopy (EDS)	29
3.5.6 Ion chromatograph (IC)	30
3.5.7 X-Ray Diffraction	30
3.5.8 Fluoride selective electrode	30
3.5.9 PHREEQC Version 2	31
Chap 4 Results and Discussion	33
4.1 Characteristics of TFT- LCD wastewater	33
4.2 The effect of pH value and molar ratio on
phosphate removal	40
4.2.1 First wastewater	40
4.2.2 Second wastewater	44
4.2.3 Third wastewater	44
4.3 Particle size	54
4.4 The measurement of zeta potential	55
4.5 Residual concentration of fluoride	66
4.6 The property of precipitate	70
Chapter 5 Conclusions and Suggestions	89
References	91
Appendix	99

List of Figures

Figure 2-1 TFT-LCD manufacturing processes	4
Figure 2-2 TFT-LCD array manufacturing processes	5
Figure 2-3 Various species of phosphorous at different pH and 25℃	17
Figure 2-4 Ions necessary for the growth of HAP	19
Figure 2-4 Metastable zone for calcium phosphate crystallization according to
pH and phosphorus concentration	21
Figure 3-1 Block diagram of experiments	26
Figure 3-2 The process of chemical precipitation for experiments	27
Figure 4-1A EDS and SEM for raw wastewater No.2	35
Figure 4-1B EDS and SEM for raw wastewater No.2	36
Figure 4-1C EDS and SEM for raw wastewater No.2	37
Figure 4-1D EDS and SEM for raw wastewater No.2	38
Figure 4-2 Particle size distribution of TFT-LCD wastewater No.1 and No.2	..39
Figure 4-3 Residual PO43- as a function of the molar ratio for CaCl2 dosage and first wastewater	47
Figure 4-4 Residual PO43- as a function of the molar ratio for Ca(OH)2 dosage and first wastewater	47
Figure 4-5 Residual PO43- as a function of the molar ratio for MgCl2 dosage and first wastewater	49
Figure 4-6 Residual PO43- as a function of the molar ratio for MgO dosage and first wastewater	49
Figure 4-7 Residual PO43- as a function of the molar ratio for CaCl2 dosage and second wastewater	50
Figure 4-8 Residual PO43- as a function of the molar ratio for Ca(OH)2 dosage and second wastewater	50
Figure 4-9 Residual PO43- as a function of the molar ratio for MgCl2 dosage and second wastewater	51
Figure 4-10 Residual PO43- as a function of the molar ratio for MgO dosage and second wastewater	51
Figure 4-11 Residual PO43- as a function of the molar ratio for CaCl2 dosage and third wastewater at pH6.5	52
Figure 4-12 Residual PO43- as a function of the molar ratio for CaCl2 dosage and third wastewater at pH8.5	52
Figure 4-13 Residual PO43- as a function of the molar ratio for CaCl2 	53
Figure 4-14 Particle size distribution of wastewater No.2 for treated by CaCl2 and Ca(OH)2 dosage for wastewater No. 3	56
Figure 4-15 Particle size distribution of wastewater No.2 for treated by Ca(OH)2	56
Figure 4-16 Particle size distribution of wastewater No.2 for treated by MgCl2		57
Figure 4-17 Particle size distribution of wastewater No.2 for treated by MgO		57
Figure 4-18 Comparing particle size distribution of wastewater No.3 for treated by CaCl2 and Ca(OH)2 at molar ratio of 1.0	58
Figure 4-19 Comparing particle size distribution of wastewater No.3 for treated by CaCl2 and Ca(OH)2 at molar ratio of 2.5	59
Figure 4-20 Influence of molar ratio and pH on zeta potential using CaCl2 for wastewater No.1	60
Figure 4-21 Influence of molar ratio and pH on zeta potential using Ca(OH)2 for wastewater No.1	61
Figure 4-22 Zeta potential for untreated bobierrite Ca(OH)2	62
Figure 4-23 Influence of molar ratio and pH on zeta potential using MgCl2 for wastewater No.1	63
Figure 4-24 Influence of molar ratio and pH on zeta potential using MgO for wastewater No.1	64
Figure 4-25 Zeta potential for untreated bobierrite	65
Figure 4-26 Residual concentration of fluoride as a function of the molar ratio at pH 10.5 for wastewater No.1	67
Figure 4-27 Residual concentration of fluoride as a function of the molar ratio at pH 8.5 and 10.5 for second wastewater	68
Figure 4-28 Residual concentration of fluoride as a function of the molar ratio at pH 8.5 and 10.5 for second wastewater	69
Figure 4-29 XRD of a sludge obtained in the wastewater No.1 treated with CaCl2 at difference pH	72
Figure 4-30 XRD of a sludge obtained in the wastewater No.1 treated with Ca(OH)2 at difference pH	73
Figure 4-31 XRD of a sludge obtained in the wastewater No.3 treated with MgCl2 at difference pH	74
Figure 4-32 XRD of a sludge obtained in the wastewater No.3 treated with
CaCl2 at difference pH	75
Figure 4-33 Speciation of phosphate species predominant in solution for    Ca / PO4 molar ratio of 0.5	76
Figure 4-34 Speciation of phosphate species predominant in solution, for   Ca / PO4 molar ratio of 1.5	76
Figure 4-35 Speciation of phosphate species predominant in solution, for   Ca / PO4 molar ratio of 2.5	77
Figure 4-36 Speciation of phosphate species predominant in solution, for   Mg / PO4 molar ratio of 0.5	77
Figure 4-37 Speciation of phosphate species predominant in solution, for   Mg / PO4 molar ratio of 1.5	78
Figure 4-38 Speciation of phosphate species predominant in solution, for   Mg / PO4 molar ratio of 2.5	78
Figure 4-39 SEM and EDS of precipitate obtained in the wastewater No.1 treatment with CaCl2 at pH 6.5: 30K (A) and 100K(B)	81
Figure 4-40 SEM of precipitate obtained in the wastewater No.2 treated with Ca(OH)2 at pH 6.5	82
Figure 4-41 SEM of precipitate obtained in the wastewater No.1 treated with CaCl2: pH 6.5 (A), pH 8.5(B) and pH 10.5(C)	83
Figure 4-42 SEM and EDS of precipitate obtained in the wastewater No.1
treatment with MgCl2 pH 8.5: 4k (A) and 20k(B)	84
Figure 4-43 SEM of precipitate obtained in the wastewater No.1 treated with MgCl2: pH8.5 (A), pH9.5(B) and pH10.5(C)	85
Figure 4-44 SEM of precipitate obtained in the wastewater No.3 treated with CaCl2 at pH 8.5: CaF2 (A), FAP(B) and HAP(C)	86
Figure 4-45 EDS of precipitate obtained in the wastewater No.3 treated with CaCl2 at pH 8.5: CaF2 (A), FAP(B) and HAP(C)	87
Figure 4-46 Certain SEM images of crystal from reference were employed to comparing with this study	88

List of Tables

Table 2-1 Properties of the TFT-LCD inorganic wastewater	6
Table 2-2 The different forms of crystallized calcium phosphate are presented in	11
Table 2-3 Calcium phosphates and their molar ratios and solubilities
in TFT-LCD manufacturer	12
Table 4-1 Characteristics of TFT-LCD wastewater	34
Table 4-2 The concentration of fluoride at different date	44
Table 4-3 Phosphate removal by CaCl2, at different molar ratio	46
Table 4-4 Phosphate removal by Ca(OH)2, at different molar ratio	46
Table 4-5 Phosphate removal by MgCl2, at different molar ratio	48
Table 4-6 Phosphate removal by MgO, at different molar ratio	48
Table 4-7 The 2 θ angles of various species	71

                                

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