Title Page
ABSTRACT
국문 초록
PREFACE
Contents
CHAPTER 1. INTRODUCTION 17
CHAPTER 2. EXPERIMENTAL 24
2.1. Feedstock and characterization. 24
2.2. Catalyst preparation 25
2.3. Catalyst characterization 26
2.4. Catalytic activity tests and product analysis 27
2.5. Deactivation and regeneration tests 30
CHAPTER 3. RESULTS AND DISCUSSION 32
3.1. Feedstock properties 32
3.2. Catalyst properties 41
3.3. Catalytic activity 49
3.3.1. Effect of phosphorus modification and steam treatment on product distribution 49
3.3.2. Effect of catalytic cracking and thermal cracking on product distribution 53
3.3.3. Effect of reaction temperature on product distribution 58
3.3.4. Effect of WHSV on product distribution 60
3.3.5. Effect of feedstock type on product distribution 62
3.4. Deactivation and regeneration tests 67
3.5. Model feed tests 71
CHAPTER 4. CONCLUSIONS 79
REFERENCES 81
Table 1. Physicochemical properties, heating value, and chemical composition of crude WPPO. 35
Table 2. Metal concentration of crude WPPO obtained using inductively coupled plasma-atomic emission spectroscopy (ICP-AES). 36
Table 3.1. Boiling point distribution of crude WPPO. 37
Table 3.2. The components of crude WPPO based on the boiling point distribution. 38
Table 4. The PIONA components of crude WPPO (P: paraffin, I: iso-paraffin, O: olefin, N: naphthene, A: aromatic). 39
Table 5. The PIONA components of Naphtha (P: paraffin, I: iso-paraffin, O: olefin, N: naphthene, A: aromatic). 40
Table 6. Physicochemical properties of four types of catalysts (ms-HZSM5, ms-HZSM5-S, ms-P-HZSM5, and ms- P-HZSM5-S) employed in this study. 48
Table 7. Yields of products (wt%) obtained via thermal cracking and catalytic cracking of four types of catalysts (feed, WPPO; catalyst, ms-HZSM5, ms-HZSM5-S, ms-P-HZSM5, and ms-P-HZSM5-S; catalyst weight=3 g,... 52
Table 8. The PIONA components of products obtained via thermal cracking (feed, WPPO; Temperature=680 ℃, WHSV=16 h⁻¹). 56
Table 9. The PIONA components of products obtained via catalytic cracking (feed, WPPO; catalyst, ms-P-HZSM5-S, Temperature=680 ℃, WHSV=16 h⁻¹). 57
Table 10. The PIONA components of products obtained via thermal cracking (feed, Naphtha; Temperature=680 ℃, WHSV=16 h⁻¹). 65
Table 11. The PIONA components of products obtained obtained via cracking catalytic cracking (feed, Naphtha; catalyst, ms-P-HZSM5-S, Temperature=680 ℃,... 66
Table 12. Physicochemical properties of spent catalyst obtained after the ninth run and regenerated catalyst. 70
Table 13. Yields of products (wt%) obtained via thermal cracking and catalytic cracking using various alkanes, alkenes, and alkane-alkene mixtures of (a) C₆ hydrocarbon and (b) C₁₂ hydrocarbon as feedstocks (catalyst, ms-P-... 76
Table 14. Yields of products (wt%) obtained via thermal cracking and catalytic cracking using various alkanes, alkenes, and alkane-alkene mixtures of (a) C₆... 77
Table 15. Yields of products (wt%) obtained via catalytic cracking with ms-P-HZSM5-S using different one-ring aromatic compounds as feedstocks (catalyst weight=3 g; Temperature=680 ℃; WHSV=16 h⁻¹). 78
Figure 1. Schematic diagram of the process for producing light olefins using waste plastic in the Petrochemical industry. 20
Figure 2. Schematic diagram of Micro-Activity Test (MAT) unit. 29
Figure 3. Liquid compositions based on gas chromatograms of the crude WPPO feedstock (P: paraffin, O: olefin, BNZ: benzene, TOL: toluene, EBZ: ethylbenzene, XYL: xylene, STR: styrene). 34
Figure 4. Scanning elctron microscopy (SEM) images and particle size distribution (PSD) curves of (a) ms-HZSM5 and (b) ms-P-HZSM5. 44
Figure 5. The X-ray diffraction (XRD) patterns of ms-HZSM5, ms-HZSM5-S, ms-P-HZSM5, and ms-P-HZSM5-S. 45
Figure 6. Temperature-programmed-desorption of ammonia (NH₃-TPD) profiles of ms-HZSM5, ms-HZSM5-S, ms-P-HZSM5, and ms-P-HZSM5-S. 46
Figure 7. Fourier transform infrared spectroscopy (FTIR) of pyridine-adsorption of ms-HZSM5, ms-HZSM5-S, ms-P-HZSM5, and ms-P-HZSM5-S. 47
Figure 8. Main product yields (wt%) obtained via thermal cracking and catalytic cracking of four types of catalysts (feed, WPPO, catalyst, ms-HZSM5, ms-HZSM5-... 51
Figure 9. Paraffins iso-paraffins, olefins, naphthenes, and aromatics (PIONA) quantification of WPPO feedstock and products obtained via thermal cracking and catalytic cracking (feed, WPPO, catalyst, ms-P-HZSM5-S; catalyst... 54
Figure 10. Liquid compositions based on gas chromatograms of the (a) WPPO feedstock, (b) thermal cracking product, and (c) catalytic cracking product (feed, WPPO, catalyst, ms-P-HZSM5-S; catalyst weight=3 g,... 55
Figure 11. Main product yields (wt%) obtained via (a) thermal cracking and (b) catalytic cracking at different temperatures (feed, WPPO, catalyst, ms-P-HZSM5-S;... 59
Figure 12. Main product yields (wt%) obtained via catalytic cracking at different WHSV (feed, WPPO, catalyst, ms-P-HZSM5-S; catalyst weight=1-12 g,... 61
Figure 13. Yields of products (wt%) obtained through thermal and catalytic cracking using WPPO or Naphtha as the feedstock (catalyst, ms-P-HZSM5-S; catalyst weight=3 g, Temperature=680 ℃, WHSV=16 h⁻¹). 64
Figure 14. Product yields (wt%) monitored during repetitive catalytic cracking tests and those obtained using the regenerated catalyst (feed, WPPO, catalyst, ms-... 69
Figure 15. Main product yields (wt%) and conversion obtained via thermal cracking and catalytic cracking using various alkanes, alkenes, and alkane-alkene mixtures (a)... 74
Figure 16. The suggested mechanism for the initial steps in the cracking reaction of linear alkane and linear alkene in WPPO. 75