Title Page
Abstract in Korean
Abstract in English
Contents
Nomenclature 13
1. Introduction 14
1.1. Background 14
1.2. Carbon capture and utilization & Storage (CCUS) 17
1.2.1. Carbon capture and Storage (CCS) 19
1.2.2. Carbon Capture and Utilization (CCU) 20
2. Literature Review 21
2.1. Methanol synthesis 21
2.1.1. Conventional method 24
2.1.2. CO₂ hydrogenation 26
2.1.3. Syngas hydrogenation 28
2.2. Dimethyl carbonate (DMC) synthesis 31
2.2.1. Conventional method 33
2.2.2. Oxidative carbonylation of methanol 34
2.2.3. Transesterification of cyclic carbonate 36
2.2.4. Direct conversion of methanol and CO₂ 37
3. Method 41
3.1. Process simulation 41
3.1.1. Methanol synthesis 42
3.1.2. Co-production of methanol and ammonia 49
3.1.3. Production of dimethyl carbonate using CO₂ and methanol 52
3.2. Economic analysis 59
3.2.1. Economic assumptions 59
3.2.2. Capital expenditure (CAPEX) estimation 61
3.2.3. Operational expenditure (OPEX) estimation 65
4. Results and Discussion 68
4.1. Process simulation 68
4.1.1. Methanol synthesis 68
4.1.2. Co-production of methanol and ammonia 71
4.1.3. Production of dimethyl carbonate using CO₂ and methanol 76
4.2. Heat integration 96
4.2.1. Methanol synthesis 96
4.2.2. Co-production of methanol and ammonia 97
4.2.3. Production of dimethyl carbonate using CO₂ and methanol 98
4.3. Economic analysis 101
4.3.1. Methanol synthesis 101
4.3.2. Co-production of methanol and ammonia 104
4.3.3. Production of dimethyl carbonate using CO₂ and methanol 107
4.4. Sensitivity analysis 112
4.4.1. Methanol synthesis 112
4.4.2. Co-production of methanol and ammonia 114
4.4.3. Production of dimethyl carbonate using CO₂ and methanol 116
5. Conclusion 120
6. Reference 122
Table 1. The CO₂ sources in various industries 16
Table 2. Kinetic parameters of Equation (19) to (21) 45
Table 3. Adsorption and equilibrium constants for driving force term 46
Table 4. Adsorption constants in the adsorption term of Graaf's model 47
Table 5. Economic assumption in this paper 60
Table 6. CAPEX distribution 64
Table 7. OPEX distribution 66
Table 8. The key stream data of methanol synthesis 69
Table 9. The key stream data of co-production of methanol and ammonia 72
Table 10. The key stream data of direct synthesis of DMC (Case 1) 78
Table 11. The key stream data of direct synthesis of DMC (Case 2) 85
Table 12. The key stream data of direct synthesis of DMC (Case 3) 89
Table 13. The column specification of direct synthesis of DMC (Case 1) 93
Table 14. The column specification of direct synthesis of DMC (Case 2) 94
Table 15. The column specification of direct synthesis of DMC (Case 3) 95
Table 16. Utility usage for each equipment of methanol synthesis 102
Table 17. Utility usage for each equipment of co-production of methanol and ammonia 105
Table 18. Utility usage for direct synthesis of DMC (Case 1) 108
Table 19. Utility usage for direct synthesis of DMC (Case 2) 109
Table 20. Utility usage for direct synthesis of DMC (Case 3) 110
Figure 1. The global CO₂ emissions chart from 1900 to 2021 15
Figure 2. The concept of CCUS technology 18
Figure 3. The global methanol supply and demand chart 22
Figure 4. The global methanol demand in various industries 23
Figure 5. The scheme of Lurgi process 25
Figure 6. The composition of byproducts from iron production plant 29
Figure 7. The annual electric vehicle battery demand by regions 32
Figure 8. The PFD of oxidative carbonylation of methanol 35
Figure 9. The PFD of the direct synthesis of DMC with dehydrating agent 39
Figure 10. The PFD of methanol production based on [40] 43
Figure 11. The PFD of co-production of methanol and ammonia 50
Figure 12. The PFD of Direct synthesis with 2-cyanopyridine 53
Figure 13. The Txy diagram of methanol and DMC 55
Figure 14. The Txy diagram of water and DMC 56
Figure 15. The PFD of the direct synthesis of DMC with 2CP of Case 2 (methanol : CO₂=10 : 4 in kmol/hr) 83
Figure 16. The energy analysis of methanol synthesis and co-production of methanol and ammonia 99
Figure 17. The energy analysis of direct synthesis of DMC for all cases 100
Figure 18. TAC distribution chart for methanol synthesis 103
Figure 19. TAC distribution chart for co-production of methanol and ammonia 106
Figure 20. TAC distribution chart for direct synthesis of DMC for Case 1 111
Figure 21. Sensitivity analysis results for methanol synthesis 113
Figure 22. Sensitivity analysis results for co-production of methanol and ammonia 115
Figure 23. Sensitivity analysis results for direct synthesis of DMC (Case 1) 117
Figure 24. Sensitivity analysis results for direct synthesis of DMC (Case 2) 118
Figure 25. Sensitivity analysis results for direct synthesis of DMC (Case 3) 119