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研究生:陳氏芳瓊
研究生(外文):TRAN THI PHUONG QUYNH
論文名稱:氫氟酸廢水資源化︰高純度人造螢石製程開發
論文名稱(外文):Recovery of high purity fluorite from concentrated hydrogen fluoride wastewater
指導教授:林伯勳林伯勳引用關係
指導教授(外文):PO-HSUN LIN
口試委員:童心欣林伯勳陳錫金
口試委員(外文):HSIN-HSIN TUNGPO-HSUN LINHSI-JIEN CHEN
口試日期:2017-06-27
學位類別:碩士
校院名稱:明志科技大學
系所名稱:環境與安全衛生工程系環境工程碩士班
學門:工程學門
學類:環境工程學類
論文種類:學術論文
論文出版年:2017
畢業學年度:105
語文別:英文
論文頁數:86
外文關鍵詞:Fluoride recovery, calcium fluoride sludge, SWOT analysis, chemical precipitation, industrial wastewater treatment
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Chemical precipitation method utilizing calcium salt has been extensively used to treat concentrated hydrogen fluoride (HF) wastewater. Due to very fine precipitates of calcium fluoride (CaF2), coagulants/flocculants are used to facilitate better solid-liquid separation. As a result, a large amount of sludge is generated by CaF2 precipitation process. Therefore, we developed a new environment-friendly approach to treat concentrated HF industrial wastewater (117.2 g F/L) and recycled fluoride as high purity CaF2 to minimize the amount of waste for final disposal. This study attempts to move towards a circular economy that has both an environmental and economic rationale. The results indicated that CaCO3 dosages, the ratios of CaCO3 to DI water, types and dosages of polymers play an important role in the efficiency of the fluoride removal and the purity of fluorite. The product with the highest CaF2 purity of 88% was obtained at the following conditions: molar ratio: 0.625, the ratio of CaCO3 to DI water as reaction solution: [1:10], the selected polymer concentration: 17 ppm (>99.9% removal). After reaction, the residual fluoride concentration was 62.16 ppm. Moreover, a summary of SWOT analysis was conducted for assessment of the renewable potential of fluoride recovery from fluoride-containing industrial wastewater. Optimum operation parameters for synthesizing fluorite have been obtained and proposed for industrial applications
TABLE OF CONTENTS
RECOMMENDATION LETTER FROM THE THESIS ADVISOR i
THESIS ORAL DEFENSE COMMITTEE CERTIFICATION ii
ACKNOWLEDGEMENTS iii
ABSTRACT iv
TABLE OF CONTENTS v
LIST OF FIGURES viii
LIST OF TABLES xi
CHAPTER 1 1
INTRODUCTION 1
1.1. Background 1
1.2. Objectives 2
1.3. Scope of thesis 3
1.4. Layout of thesis 3
CHAPTER 2 4
LITERATURE REVIEW 4
2.1. Hydrogen fluoride wastewater 4
2.1.1. Sources of hydrogen fluoride wastewater 4
2.1.2. Impacts on human health 5
2.2. Technologies of defluoridation 10
2.2.1. Ion-exchange 10
2.2.2. Adsorption techniquies 13
2.2.3. Electrochemical treatments 15
2.2.4. Membrane filtration 15
2.2.5. Coagulation/precipitation 16
2.3. Calcium fluoride recovery from concentrated hydrogen fluoride wastewater 19
2.3.1. Introduction of Fluorite and Calcium fluoride (CaF2) 19
2.3.2. Applications 21
2.3.3. Calcium fluoride recovery from concentrated hydrogen fluoride wastewater 24
2.3.4. Factors affecting coagulation/flocculation operations 26
2.4. Resource recovery from wastewater for a circular economy 27
CHAPTER 3 31
EXPERIMENTAL MATERIALS AND METHODS 31
3.1. Characteristics of the concentrated hydrogen fluoride wastewater 31
3.2. Experimental procedure 32
3.3. Analytical methods 36
3.3.1. Evaluation of performance of fluoride removal 36
3.3.2. Evaluation of the purity of the product (Calcium fluoride) 36
3.4. SWOT analysis approach 46
CHAPTER 4 48
RESULTS AND DISCUSSIONS 48
4.1. Calculate the amount of CaCO3 required to the experiment 48
4.2. Estimate the residual fluoride concentration based on chart of the proportion of free fluoride ion in acid solutions 49
4.3. Effect of polymer type on the purity of product 53
4.4. Effect of ratio of CaCO3 to DI water on the purity of product 57
4.6. Effect of ratio on the purity of product 61
4.7. Assessment of the renewable potential of fluoride recovery from fluoride-containing industrial wastewater 65
CHAPTER 5 67
CONCLUSIONS 67
5.1. Summary of results 67
5.2. Future work 67
REFERENCES 68
LIST OF FIGURES
Figure 2.1. Photographs of dental fluorosis by Dr. Hardy Limeback and Dr. Iain Pretty, et al. 7
Figure 2.2. Photographs of skeletal fluorosisby India natural resource economics and management (INREM) foundation 8
Figure 2.3. The categories of HF burns 9
Figure 2.4. Fluoride pollution can be especially damaging to fish 10
Figure 2.5. Mechanism of fluoride removal by cation-exchanger resins 11
Figure 2.6. Functional group of the AMPA-resin after loading with aluminum-chloride 12
Figure 2.7. Reaction scheme of the selective fluoride removal by AMPA-resin 13
Figure 2.8. Fluorite crystal 20
Figure 2.9. Chemical structure of fluorite 21
Figure 2.10. Calcium fluoride 21
Figure 2.11. Fluidized bed reactor 25
Figure 3.1. Experimental procedure 33
Figure 3.2. Experimental flow chart 34
Figure 3.3. Coagulation and flocculation experiment in a hood 35
Figure 3.4. Adjust pH of the wet sample (solid phase) 35
Figure 3.5. Vacuum filter 35
Figure 3.6. Heat to remove water in the filtrated cake 35
Figure 3.7. Products 35
Figure 3.8. Calcium fluoride analysis procedure 38
Figure 3.9. Grind the sample with a pestle 39
Figure 3.10. Heat the beaker with a hot plate, cover with watchglass, mix with magnetic stir bar 39
Figure 3.11. Titrate with 0.1 M EDTA 39
Figure 3.12. Silica analysis procedure 42
Figure 3.13. The wipe paper and the filter paper with the residue in a 30 mL platinum crucible 43
Figure 3.14. Heat at 650oC until the paper is entirely burned off 43
Figure 3.15. The crucible after heated at 650oC for 5h 43
Figure 3.16. Gently heat the crucible over a hot plate in a hood until dry 43
Figure 3.17. Calcium carbonate analysis procedure 45
Figure 3.18. SWOT analysis diagram 46
Figure 4.1. Fraction of free fluoride as a function of solution pH, hydrogen is the only complexing species 50
Figure 4.2. Electrode response in alkaline solutions 51
Figure 4.3. Photographs of the solid-liquid separation by different types polymers. Experimental conditions: initial fluoride conc. = 117.2 g/L, CaCO3 dosage = 30g, polymer conc. = 17ppm 54
Figure 4.4. Effect of different types polymers on the solid-liquid separation 55
Figure 4.5. Comparison the purity of product when using P1 and P7 polymer. Experimental conditions: initial fluoride conc. = 117.2 g/L, CaCO3 dosage = 40g, polymer conc. = 17ppm 56
Figure 4.6. Comparison the fluoride removal efficiency when using P1 and P7 polymer. Experimental conditions: initial fluoride conc. = 117.2 g/L, CaCO3 dosage = 40g, polymer conc. = 17ppm 56
Figure 4.7. Effect of ratio of CaCO3 to DI water on the purity of product. Exper-imental conditions: initial fluoride conc. = 117.2 g/L, CaCO3 dosage = 40g, pol-ymer conc. = 17ppm 57
Figure 4.8. Effect of ratio of CaCO3 to DI water on the residual fluoride concen-tration. Experimental conditions: initial fluoride conc. = 117.2 g/L, CaCO3 dos-age = 40g, polymer conc. = 17ppm 58
Figure 4.9. Effect of ratio of CaCO3 to DI water on the removal of fluoride. Ex-perimental conditions: initial fluoride conc. = 117.2 g/L, CaCO3 dosage = 40g, polymer conc. = 17ppm 58
Figure 4.10. Effect of polymer dosage on the purity of product. Experimental conditions: initial fluoride conc. = 117.2 g/L, CaCO3 dosage = 40g, using P1 polymer 59
Figure 4.11. Effect of polymer dosage on the residual fluoride concentration. Experimental conditions: initial fluoride conc. = 117.2 g/L, CaCO3 dosage = 40g, using P1 polymer 60
Figure 4.12. Effect of polymer dosage on the fluoride removal efficiency. Experimental conditions: initial fluoride conc. = 117.2 g/L, CaCO3 dosage = 40g, using P1 polymer 60
Figure 4.13. Effect of the ratio of calcium to fluoride on the purity of product. Experimental conditions: initial fluoride conc. = 117.2 g/L, CaCO3 dosage = 40g, using 17 ppm P1 polymer, [CaCO3:DI water] ratio = [1:10] 61
Figure 4.14. Effect of the ratio of calcium to fluoride on the removal of fluoride. Experimental conditions: initial fluoride conc. = 117.2 g/L, CaCO3 dosage = 40g, using 17 ppm P1 polymer, [CaCO3:DI water] ratio = [1:10] 62
Figure 4.15. Effect of the ratio of calcium to fluoride on the fluoride removal efficiency. Experimental conditions: initial fluoride conc. = 117.2 g/L, CaCO3 dosage = 40g, using 17 ppm P1 polymer, [CaCO3:DI water] ratio = [1:10] 62
Figure 4.16. Effect of pH on the gel time of a colloidal silica-water system 64

LIST OF TABLES
Table 2.1. Concentrations of fluorides and biological effects 6
Table 2.2. Comparison of fluoride technologies 18
Table 2.3. The specific specification of commercial fluorite powder (Yantai Chengxing Minerals Co., Ltd.) 22
Table 2.4. Fluorite application 23
Table 3.1. Quality parameters of wastewater 31
Table 4.1. The amount of CaCO3 required to and neutralization and pre-cipitation 49
Table 4.2. The estimated values of residual fluoride concentration of the supernatants at pH = 5 52
Table 4.3. Comparison between commercial fluorite powder and calcium fluoride powder created from concentrated hydrogen fluoride wastewater 63
Table 4.4. Summary SWOT analysis for potential of fluoride recovery from fluoride-containing industrial wastewater 65


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