Title Page
ABSTRACT
Contents
LIST OF ABBREVIATIONS 14
1. Introduction 16
2. Experimental 19
2.1. Reagents and Materials 19
2.2. Preparation of Biomass-derived Carbon-coated Needles 20
2.2.1. Hydrothermal Carbonization (HTC) using Withered Roses 20
2.2.2. Thermochemical Activation of Hydrochar (HC) 21
2.2.3. Fabrication of INME Needle with Polydimethylsiloxane (PDMS)/ Activated Hydrochar (AHC) Adsorbent 21
2.3. Characterization of RM, HC, AHC, and PDMS/AHC 22
2.3.1. Fourier Transform-Infrared Spectroscopy (FT-IR) 22
2.3.2. BET (Brunauer, Emmett, Teller) & Barrett-Joyner-Halenda (BJH) Measurement 23
2.3.3. Field Emission-Scanning Electron Microscope (FE-SEM) 23
2.3.4. Thermogravimetric Analysis (TGA) 23
2.4. Optimization of Experimental Conditions 23
2.4.1. Optimization of Reaction Conditions Using DOE Method 24
2.4.2. Optimization of Reaction Conditions for Hydrothermal Carbonization (HTC) of Dried roses Using DOE Method 24
2.4.3. Optimization of Reaction Conditions for Thermochemical Activation of Hydrochar (HC) Using DOE Method 25
2.4.4. Optimization of INME Conditions Using Manual Method 26
2.4.5. Analysis Conditions of Gas Chromatograph/ Mass Spectrometer (GC/MS) 27
2.5. Validation of Analysis Method 28
3. Results and Discussion 29
3.1. Characterization of RM, HC, AHC, and PDMS/AHC 29
3.1.1. Fourier Transform-Infrared Spectroscopy (FT-IR) 29
3.1.2. Field Emission-Scanning Electron Emission (FE-SEM) 30
3.1.3. BET (Brunauer, Emmett, Teller) & Barrett-Joyner-Halenda (BJH) Measurement 30
3.1.4. Thermogravimetric Analysis (TGA) of PDMS and PDMS/AHC 31
3.2. Optimization of Experimental Conditions 32
3.2.1. Optimization of Experimental Conditions for Hydrothermal Carbonization (HTC) of Raw material Using DOE Method 32
3.2.2. Optimization of Experimental Conditions for Thermochemical Activation of Hydrochar (HC) Using DOE Method 33
3.2.3. Optimization of HS-INME Conditions Using Manual Method 34
3.2.4. Optimization of HS-INME Conditions Using DOE Method 35
3.3. Validation of Analytical Method 36
3.4. Comparison of Extraction Efficiency 37
4. Conclusion 39
5. References 40
국문 요약 70
LIST OF PUBLICATIONS & PRESENTATIONS 72
Table 1. Physicochemical properties of target phthalates in this study 45
Table 2. Extraction parameters and optimized condition 46
Table 3. Gas chromatograph/mass spectrometer (GC/MS) conditions to analyze target phthalate standards 47
Table 4. Experimental design factors and levels of chosen variables for optimization of hydrothermal carbonization (HTC) conditions 48
Table 5. Experimental design matrix for optimization of hydrothermal carbonization (HTC) conditions 49
Table 6. Experimental design factors and levels of chosen variables for optimization of activation conditions 50
Table 7. Experimental design matrix for optimization of activation conditions 51
Table 8. MBN, IN prediction formula, calculated/actual value, and relative error obtained through DOE in optimization of hydrothermal carbonization and activation condition 52
Table 9. Experimental design factors and levels of chosen variables for INME-PDMS/AHC-GC/MS analysis 53
Table 10. Experimental design matrix for optimization of INME-PDMS/AHC conditions 54
Table 11. Peak area prediction formula, calculated/actual value, and relative error of each phthalate obtained through DOE in optimization of HS-INME-PDMS/AHC analysis condition 55
Table 12. Validation data of HS-INME using PDMS/AHC followed GC/MS (n=3); regression equation, linearity (r²), limit of detection (LOD), limit of quantification (LOQ), and dynamic range 56
Table 13. Validation data of HS-INME using PDMS/AHC followed GC/MS; recovery and reproducibility 57
Table 14. Extraction efficiency values of target phthalates 58
Figure 1. The manufacturing process of PDMS/AHC needle 59
Figure 2. A scheme of the Analysis of Phthalates using HS-INME-PDMS/AHC 60
Figure 3. FT-IR Spectrums of RM, HC, and AHC 61
Figure 4. SEM images (x3,500) of (A) RM, (B) HC, (C) AHC 62
Figure 5. (A) N₂ adsorption-desorption isotherms and (B) pore size distribution of RM, HC, and AHC 63
Figure 6. TGA curves of PDMS and PDMS/AHC 64
Figure 7. Optimization results of (A) hydrothermal carbonization and (B) thermochemical activation conditions using DOE 65
Figure 8. Optimization results of HS-INME conditions for the analysis of four phthalates 66
Figure 9. Response surface diagram of (A) methylene blue number (MBN) and (B) iodine number (IN) 67
Figure 10. Manual optimization of HS-INME condition 68
Figure 11. Response surface diagram of four phthalates and correlation among the saturation time, adsorption time, and desorption time 69