本研究旨在初步評估從地熱發電後之低濃度含鋰地熱滷水中回收與濃縮鋰的可行性，並採行了 D2EHPA 溶劑萃取與化學沉澱相結合之策略。在溶劑萃取部分，確定25℃為最佳操作條件，其參數為 D2EHPA/煤油重量比1.12 g/g、有機相/水相（O/A）比0.08及總D2EHPA量0.0029 莫耳。鋰萃取效率穩定維持在85-86% 之間。然而，在較高溫度下，D2EHPA對鈉之選擇性（α_Na^Li）略有增強，其值從1.8降至1.75。總有機碳（TOC）分析證實，水相中之TOC主要源自 D2EHPA 之溶出，而煤油溶出所導致之 TOC 僅為1.6-5 mg/L。反萃取研究顯示，在初始有機相含鋰0.0032 M 及鈉0.049 M 的條件下，即使使用3 M HCl ，鋰之反萃取效率僅12.29%，遠低於預期；而鈉之反萃取效率則顯著較高（高達 55%），濃縮倍率達133.85倍。
在化學沉澱部分，本研究利用水化學模擬預測沉澱效率，比較了氟化鋰（LiF）、碳酸鋰（Li2CO3）及磷酸鋰Li3PO4之沉澱行為。模擬結果預測，碳酸鋰需 5 M 之鋰濃度方能達到40%的沉澱效率，相較於氟化鋰和磷酸鋰並無優勢；因此，本研究主要採用氟化鋰及磷酸鋰之程序。氟化鋰與磷酸鋰之沉澱特性，在初始鋰濃度800 mg/L、反應時間 5 小時，以及飽和指數（SI）和鈉/鋰莫耳比變化下進行了探討。氟化鋰沉澱在SI約1時即可達到80-90%之效率。然而，60℃下之沉澱效率僅略低於30℃，顯示較高溫度對氟化鋰沉澱並無顯著影響。相反地，磷酸鋰之沉澱效率與溫度呈正相關；例如在60℃時可達97%之效率，且在較高溫度下，鈉/鋰莫耳比（如3.56）對其影響較小。在較低初始鋰濃度（例如400 mg/L）下，高鈉/鋰莫耳比（例如1.14至2.54）會導致磷酸鋰沉澱效率顯著下降（從77.42%降至66.85%)，甚至可能降至0%，這或許存在鈉離子間之競爭效應。

This study aimed to conduct a preliminary feasibility assessment for the recovery and concentration of lithium from low-concentration geothermal brines, employing a combined strategy of D2EHPA solvent extraction and chemical precipitation.
In the solvent extraction section, optimal operating conditions were established at
25◦C: a D2EHPA/kerosene concentration of 1.12 g/g, an organic-to-aqueous (O/A) ratio of 0.08, and a total D2EHPA amount of 0.0029 moles. Lithium extraction efficiency consistently remained within 85-86%. However, the selectivity of D2EHPA for sodium (α_Na^Li) slightly increased at elevated temperatures, decreasing from 1.8 to 1.75. Total Organic Carbon (TOC) analysis confirmed that the aqueous phase TOC primarily originated from D2EHPA dissolution, with kerosene dissolution contributing only 1.6 − 5mg/L of TOC. Back-extraction studies revealed that under initial organic phase conditions of 0.0032 M lithium and 0.049 M sodium, the lithium back-extraction efficiency was merely 12.29% even with 3 M HCl , significantly lower than anticipated. Conversely, the sodium back-extraction efficiency was remarkably high (up to 55%), achieving a concentration factor of 133.85.
In the chemical precipitation section, the study compared the precipitation efficiencies of lithium fluoride (LiF), lithium carbonate (Li2CO3), and lithium phosphate (Li3PO4) using water chemistry simulations. Predictions indicated that lithium carbonate required a 5 M lithium concentration to achieve only 40% precipitation efficiency, offering no advantage compared to lithium fluoride and lithium phosphate. Consequently, this study adopted lithium fluoride and lithium phosphate procedures. The precipitation characteristics of LiF and Li3PO4 were investigated under an initial lithium concentration of 800mg/L, a reaction time of 5 hours, and varying saturation index (SI) and Na/Li molar ratios. LiF precipitation achieved an 80-90% efficiency at an SI of approximately 1. However, the efficiency at 60◦C was only marginally lower than at 30◦C, indicating no significant effect of higher temperatures on LiF precipitation. In contrast, lithium phosphate precipitation efficiency demonstrated a positive correlation with increasing temperature; for instance, at 60◦C, an efficiency of 97% was achieved, with the effect of the Na/Li molar ratio (e.g., 3.56 ) being less pronounced at higher temperatures. At lower initial lithium concentrations (e.g., 400mg/L ), high Na/Li molar ratios (e.g., 1.14 to 2.54 ) led to a significant decrease in lithium phosphate precipitation efficiency (from 77.42% to 66.85% ), or even 0%, potentially due to competitive effects from sodium.

CONTENTS

Acknowledgements  i
中文摘要  ii
Abstract  iv
Contents  vi
List of Tables  viii
List of Figures  ix
1 Introduction  1
1.1 Background  1
1.2 Objectives  4
2 Literature reviews  6
2.1 Lithium  6
2.1.1 Importance of lithium in Electric Vehicles (EVs)  7
2.1.2 Lithium Supply for the Electric Vehicle Industry  10
2.2 Lithium extraction technologies  15
2.2.1 Lithium extraction from ore  16
2.2.2 Evaporative precipitation method  17
2.2.3 Adsorption  19
2.2.4 Precipitation  22
2.2.5 Solvent Extraction  24
2.2.6 Membrane Technology  25
2.3 Feasibility assessment of lithium extraction technologies  26
2.3.1 The extraction and stripping behavior of metals using D2EHPA  27
2.3.2 Lithium precipitation reactions  31
3 Materials and methods  33
3.1 Research Framework and Experimental Design  33
3.2 Experimental Materials  34
3.3 Analysis Methods  35
3.4 Lithium ion extraction experiment  37
3.5 Lithium ion stripping experiment  42
3.6 Lithium Chemical Precipitation  45
4 Results and discuss  48
4.1 lithium extraction efficiency  48
4.1.1 Effect of Initial pH on Extraction Efficiency  48
4.1.2 D2EHPA/Kerosene at various ratios  49
4.1.3 Varying organic-to-aqueous (O/A) ratios  53
4.1.4 Influence of temperature on extraction  56
4.1.5 Kerosene Dissolution in the Aqueous Phase  58
4.2 Lithium Stripping Efficiency  58
4.3 Precipitation method  61
4.3.1 Water chemistry precipitation pattern prediction  61
4.3.2 Influence of initial lithium concentration  64
4.3.3 Temperature effects on lithium compound precipitation efficiency  68
5 Conclusions and recommendations  71
References  73

LIST OF TABLES

2.1 Regional variations in Li+, Na+, K+ concentrations and Na/Li, K/Li molar ratios of geothermal water and Seawater.  12
3.1 Experimental Materials.  34
3.2 Residual TOC concentration in acidified samples awaiting ICP analysis, and TOC removal efficiency.  37
3.3 Data on univalent cation concentrations in water samples from the geothermal power plant at VA KANG AN, Taitung, Taiwan.  38
3.4 0.45 μm and 0.22 μm filtration for lithium and sodium ion extration efficiency. (Triplicate Sample Analysis).40
4.1 Lithium extration efficiency in aqueous phase and pH change at different initial pH.  49

LIST OF FIGURES

2.1 Three types of geothermal power plants.  15
2.2 Technology adoption decision process.  27
2.3 Changes of D2EHPA in aqueous and organic phases during extraction
[29, 31].  28
2.4 XRD analysis of lithium phosphate at various reaction temperatures,
as provided by Emmanuel et al. [68]. (from Emmanuel et al. [68]’s
Electronic Supplementary Information).  32
3.1 The Research Framework and Conceptual Map.  34
3.2 Turbid appearance of acidified post-extraction samples (Before filtra-
tion); clear appearance of samples following filtration with a 0.22 μm
syringe filter (After filtration).  36
3.3 Extration batch experiments.  38
3.4 Lithium removal efficiency within 24 hours in batch experiments at 25°C
with an initial lithium concentration of 2.14 mg/L, sodium hydroxide
concentration of 0.008 M, and a total amount of 0.0028 moles of D2EHPA. 39
3.5 Stripping batch experiment.  44
3.6 Lithium extration efficiency within 17 hours in batch experiments at
60°C with an initial lithium concentration of 2.12 mg/L, sodium hy-
droxide concentration of 0.008 M, and a total amount of 0.0029 moles
of D2EHPA.  44
3.7 Chemical Precipitation batch experiment.  47
4.8 Influence of hydrochloric acid concentration in the stripping aqueous
phase on sodium stripping efficiency and concentration factor.  60
4.9 Trends in lithium precipitation efficiency via LiF precipitation titrated
with NaF as a function of SI. PHREEQC Modeling conditions: [LiCl]
= 0.115 M, pH range 3-12.  61
4.10 Trends in lithium precipitation efficiency via Li2CO3 precipitation titrated
with Na2CO3 as a function of SI. PHREEQC Modeling conditions: [LiCl]
= 5 M, pH range 3-8.  62
4.11 Trends in lithium precipitation efficiency via Li3PO4 precipitation titrated
with Na3PO4 as a function of SI. PHREEQC Modeling conditions: [LiCl]
= 0.115 M, pH range 9-13.  63
4.12 Relationship between Na/Li molar ratio and lithium phosphate precip-
itation efficiency. (Conditions: initial [Li] = 400 mg/L, SI = 3.77-4.37,
reaction time = 48 hrs)  66
4.13 Relationship between Na/Li molar ratio and lithium phosphate precip-
itation efficiency. (Conditions: initial [Li] = 520 mg/L, SI = 3.77-4.37,
reaction time = 48 hrs)  66
4.14 Relationship between Na/Li molar ratio and lithium phosphate precip-
itation efficiency. (Conditions: Initial [Li] = 800 mg/L, SI = 3.77-4.37,
reaction time = 48 hrs)  67
4.15 Effect of Na/Li molar ratio on lithium phosphate precipitation efficiency.
(Conditions: initial [Li] = 800 mg/L, SI = 4.17, reaction Time = 48 hrs)  67
4.16 Influence of temperature on lithium fluoride precipitation efficiency. (Conditions: initial Li = 805 mg/L, reaction time = 5 hrs, SI = 0.54-1.02, Na/Li molar ratio = 0.98-2.25)  69
4.17 Influence of temperature on Lithium phosphate precipitation efficiency. (Conditions: initial Li = 805 mg/L, reaction time = 5 hrs, SI = 4.35-4.83, Na/Li molar ratio = 1.22-3.56)  69

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