臺灣博碩士論文加值系統

對苯二甲酸是一種常用於化學工業之塑膠原料，在對苯二甲酸製程過程中所排
放的廢水中包含大量的對苯二甲酸與其他有機酸，所以如何回收有經濟價值的對苯
二甲酸極具實際意義。本研究之目的是使用活性碳進行吸附分離廢水中的苯甲酸及
對苯二甲酸，在實驗部分，單成分與雙成分吸附實驗在批式及固定床中進行，其中
溫度對活性碳吸附的影響將被探討。批式實驗結果顯示，苯甲酸的吸附量高於對苯
二甲酸，而吸附量會隨著溫度越高而下降，對苯二甲酸的活化能高於苯甲酸的活化
能。在固定床實驗方面，對苯二甲酸會比苯甲酸提早貫穿，因此在苯甲酸還沒貫穿
之前，只含有對苯二甲酸的出流水，可以進而有效的回收。氫氧化鈉無法有效地再
生活性碳，因此未來應探討其他有效的再生方法。

Terephthalic acid (TPA) is commonly used as a plastic raw material in chemical
industry. The wastewater discharged from terephthalic acid manufacturing process contains a large quantity of terephthalic acid and other organic acids, so how to recover the contained terephthalic acid is of practical interest. This study aimed at investigating the adsorptive separation of benzoic acid and terephthalic acid by activated carbon from simulated TPA wastewater. Experimentally, single component and binary component wastewaters were adsorbed by activated carbon in batch tests and fixed bed operations.
The effects of wastewater temperature for activated carbon adsorption were studied. The batch results showed that the adsorption capacity for benzoic acid was higher than that for terephthalic acid and all the adsorption capacity decreased with increasing temperature. The activated energy of terephthalic acid adsorption was higher than that of benzoic acid. In the fixed bed test, terephthalic acid was found to breakthrough earlier than benzoic acid, so that terephthalic acid could be recovered from the effluent before benzoic acid breakthroughed. Sodium hydroxide could not effectively regenerate the activated carbon. Therefore, other effective regeneration method should be further studied in the future.

TABLE OF CONTENTS
ACKNOWLEDGMENTS i
ABSTRACT (English) ii
ABSTRACT (Chinese) iii
TABLE OF CONTENTS iv
LIST OF TABLES vi
LIST OF FIGURES vii
CHAPTER 1 INTRODUCTION 1
1.1 Background 1
1.2 Objectives and Scope 1
CHAPTER 2 LITERATURE SURVEY 3
2.1 Terephthalic Acid Wastewater 3
2.1.1 Wastewater Sources 3
2.1.2 Treatment Technologies 3
2.2 Activated Carbon Adsorption 8
2.3 Adsorption Isotherm 9
2.4 Adsorption Kinetics 12
2.5 Fixed Bed Operation 14
CHAPTER 3 EXPERIMENTAL 16
3.1 Chemicals and Equipment 16
3.1.1 Chemicals 16
3.1.2 Equipment 16
3.2 Procedures 17
3.2.1 Activated Carbon Pretreatment 17
3.2.2 The UV Calibration Curve 17
3.2.3 HPLC Calibration Curve 28
3.2.4 Adsorption Isotherm Experiment 32
3.2.5 Adsorption Kinetic Experiment 36
3.2.6 Column Experiment 37
CHAPTER 4 RESULTS AND DISCUSSION 40
4.1 Adsorption Isotherm Tests 40
4.1.1 Single Component Adsorption 40
4.1.2 Binary Component Adsorption 45
4.1.3 Temperature Effect 45
4.2 Adsorption Kinetic Tests 53
4.2.1 Adsorption Kinetics 53
4.2.2 Activation Energy 62
4.3 Column Tests 69
4.3.1 Single Component Column Tests 69
4.3.2 Binary Component Column Tests 74
4.3.3 NaOH Desorption 77
CHAPTER 5 CONCLUSIONS 81
REFERENCES 83



LIST OF TABLES
2.1 Composition of TPA wastewater at pH 11 4
2.2 Properties of terephthalic acid and benzoic acid 5
2.3 Adsorption isotherm models for single component system 11
2.4 Adsorption isotherm models for multi-component system 15
3.1 Properties of the activated carbon used in this study 18
3.2 UV calibration parameters for BA and TPA solution at pH 11 23
3.3 UV calibration parameters for TPA in 0.5N NaOH solution 24
3.4 UV calibration parameters for TPA/BA system at pH 11 29
3.5 Regression results of HPLC calibration curve for BA and TPA 33
4.1 Parameters of adsorption isotherm models for BA at pH 11 and 25℃ 43
4.2 Parameters of adsorption isotherm models for TPA at pH 11 and 25℃ 44
4.3 Model parameters of binary adsorption isotherm at pH 11 and 25℃ 49
4.4 Model parameters of adsorption isotherm for BA at pH 11 50
4.5 Model parameters of adsorption isotherm for TPA at pH 11 51
4.6 Model parameters of binary adsorption isotherm at pH 11 52
4.7 Parameters of adsorption kinetic models for BA and TPA at pH11 and
25℃ 57
4.8 Parameters of Pseudo second order models for BA and TPA at different
temperatures 63
4.9 The activation energies for BA and TPA 66
4.10 Experimental condition of BA column test at pH 11 and 25℃ 70
4.11 Experimental condition of TPA column test at pH 11 and 25℃ 71
4.12 Experimental condition of binary system column test at pH 11 and 25℃ 75

LIST OF FIGURES
2.1 The structures of terephthalic acid and benzoic acid 6
3.1 The UV absorbance spectrum of benzoic acid at pH 11 19
3.2 The UV absorbance spectrum of terephthalic acid at pH 11 20
3.3 The UV absorbance spectrum of terephthalic acid in 0.5N NaOH solution 21
3.4 The UV calibration curve of benzoic acid at pH 11 25
3.5 The UV calibration curve of terephthalic acid at pH 11 26
3.6 The UV calibration curve of terephthalic acid in 0.5N NaOH solution 27
3.7 Comparison of measured and predicted absorbances for BA/TPA system 30
3.8 The HPLC spectrum for BA and TPA 31
3.9 The HPLC calibration curve of benzoic acid 34
3.10 The HPLC calibration curve of terephthalic acid 35
3.11 Schematic diagram for the column experiment apparatus 38
4.1 Adsorption kinetics of BA and TPA at pH 11 and 25℃ 41
4.2 Experimental adsorption isotherms of BA and TPA at pH 11 and 25℃ 42
4.3 Experimental adsorption isotherm of BA compared with the Radke-
Prausnitz model 46
4.4 Experimental adsorption isotherm of TPA compared with the Sips model 47
4.5 Experimental adsorption isotherm of BA and TPA mixture compared with
the extended Langmuir model 48
4.6 Experimental adsorption isotherm of BA at varying temperatures
compared with the Freundlich model 54
4.7 Experimental adsorption isotherm of TPA at varying temperatures
compared with the Freundlich model 55
4.8 Experimental adsorption isotherm of the BA/TPA mixture at varying
temperatures compared with the extended Langmuir model 56
4.9 Experimental adsorption kinetic curve of BA compared with the pseudo
first-order model 58
4.10 Experimental adsorption kinetic curve of BA compared with the pseudo
second-order model 59
4.11 Experimental adsorption kinetic curve of TPA compared with the pseudo
first-order model 60
4.12 Experimental adsorption kinetic curve of TPA compared with the pseudo
second-order model 61
4.13 Experimental adsorption kinetic curve of BA at varying temperatures
compared with the pseudo second-order model 64
4.14 Experimental adsorption kinetic curve of TPA at varying temperatures
compared with the pseudo second-order model 65
4.15 The relationship between rate constant and temperature for BA 67
4.16 The relationship between rate constant and temperature for TPA 68
4.17 Breakthrough curve of BA and effluent pH of column test at 25℃ 72
4.18 Breakthrough curve of TPA and effluent pH of column test at 25℃ 73
4.19 Breakthrough curves of binary components and effluent pH at 25℃ 76
4.20 Desorption curve of BA by 0.5N NaOH at 25℃ 78
4.21 Desorption curve of TPA by 0.5N NaOH at 25℃ 79
4.22 Desorption curves of the binary components by 0.5N NaOH at 25℃ 80

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