[표지]
제출문
보고서 요약서
요약문
SUMMARY
Contents
목차
제1장 연구개발과제의 개요 28
제2장 국내외 연구개발 현황 29
1. 국내외 SI 공정 개발 개요 29
2. 국내외 SI 공정 실증 개발 30
제3장 연구개발수행 내용 및 결과 34
제1절 상압 및 가압 반회분식 분젠반응 34
1. 서론 34
2. 상압 조건에서 HIx 용액을 이용한 분젠 반응을 특성 37
3. 가압 조건에서 Hlx 용액을 이용한 분젠 반응의 특성 48
제2절 가압 연속식 분젠 반응 63
1. 서론 63
2. 연구개발 수행내용 및 결과 63
3. 소결 71
제3절 황산상/HIx 상분리 장치 72
1. 전도도의 측정을 통한 상분리 방법의 개선 제안 72
2. 3개 전도도 장치를 이용한 상분리 모사 실험 및 전도도 측정 78
3. 소결 84
제4절 HIx 정제기 86
1. 서론 86
2. 연구 개발 수행 내용 및 결과 86
3. 소결 88
제5절 황산 정제, 농축 및 분해기 89
1. 서론 89
2. 황산분해공정의 개요 89
3. 황산정제기 개선연구 92
4. SiC 기반 황산촉매의 개선연구 131
제6절 HIx 용액 물성 측정 및 상관관계식 154
1. HIx 열용량 측정 154
2. Hlx 물성 상관관계 159
3. 소결 163
제7절 SEC3 증류탑 및 열교환기 기초 계산 164
1. 증류탑 설계를 위한 공정흐름 및 물질 수지 164
2. 증류탑 및 열교환기 계산 166
3. 소결 180
4. Aspen plus input summary 180
제8절 HI분해기 효율향상 191
1. 서론 191
2. 연구개발 수행 내용 및 결과 191
3. 소결 201
제9절 개선된 Lab scale 분젠 반응 공정 설계, 건설 및 운전 203
1. 서론 203
2. 개선된 SEC1 P&ID 및 주요 장치 도면 204
3. 개선된 SEC1 운전 절차 208
4. 개선된 SEC1 운전 결과 210
제10절 1Nm³/h 수소생산 SI 실험 설비의 물질수지 및 P&ID 214
1. 서론 214
2. 물질수지 및 P&ID 216
제4장 목표달성도 및 관련분야에의 기여도 250
제5장 연구개발 결과의 활용계획 256
제6장 연구개발과정에서 수집한 해외과학기술정보 257
제7장 참고문헌 261
Table 3.2.1. Effects of amounts of SO₂gas on pressurized continuous Bunsen reaction 66
Table 3.2.2. Effects of partial pressure of SO₂gas on pressurized continuous Bunsen products 67
Table 3.2.3. The variation of molar ratio of HIx or total phase according to the elapsed time after the Bunsen reaction 70
Table 3.3.1. measured conductivity(mS/cm) of HIx solution with varying composition and temperature. 82
Table 3.3.2. measured conductivity(mS/cm) of H₂SO₄solution with varying composition and temperature. 83
Table 3.5.1. Specifications for a bench-scale sulfuric acid separator 94
Table 3.5.2. Measurement of sectional temperatures in the sulfuric acid separator 99
Table 3.5.3. Separation of H₂SO₄/HI/I₂mixture with various feeding rates in... 114
Table 3.5.4. Separation of H₂SO₄/HI/I₂mixture with various feeding rates in C-type sulfuric acid separator 118
Table 3.5.5. Separation of H₂SO₄-phase from a bench-scale Bunsen reaction with various feeding rates in C-type sulfuric acid separator 124
Table 3.5.6. BET analysis of Pt-N/SiC catalysts prepared different oxygen condition 139
Table 3.5.7. XRF analysis of Pt-N/SiC catalysts prepared different oxygen condition 140
Table 3.5.8. BET surface area, pore volume, average pore diameter and amount of metal loading of the SiC supports and pristine Pt/SiC catalysts. 145
Table 3.5.9. Binding energies of C1s, Si2p and Pt on the pristine Pt/SiC... 147
Table 3.5.10. BET surface area, pore volume, average pore diameter and amount of metal loading of the Spent Pt/SiC catalysts. 150
Table 3.6.1. HIx compositions prepared for the heat capacity measurement 155
Table 3.6.2. The measured heat capacity of HIx A ~ HIx F 157
Table 3.6.3. The measured heat capacity of HIx 1 ~ HIx 4 157
Table 3.6.4. parameters of the heat capacity correlation equation(1) 158
Table 3.6.5. Parameters of the density correlation equation (2) for HIx 160
Table 3.6.6. Parameters of the viscosity correlation equation (4) for HIx 161
Table 3.6.7. Parameters of the thermal conductivity correlation equation (6) for HIx 162
Table 3.6.8 Parameters of the heat capacity correlation equation... 163
Table 3.7.1. Preliminary process calculation results in the vicinity of HIx distillation column in SEC3 165
Table 3.9.1. Specifications of the important reactor and vessels. 208
Table 3.10.1. Unit and pipe construction materials chosen according to the... 215
Fig. 2.4.1. 200 L/h SI process facility under construction in JAEA. 31
Fig. 2.4.2. SI process development plan of Japan. 31
Fig. 2.4.3. SI process development plan of China. 32
Fig. 2.4.4. ENEA SI laboratory. 33
Fig. 3.1.1. Schematic flow diagram of sulfur-iodine cycle for thermochemical... 35
Fig. 3.1.2. Schematic diagram of experimental apparatus for Bunsen... 38
Fig. 3.1.3. The amounts of products in global system after... 39
Fig. 3.1.4. Variation in amounts of components in global system after Bunsen reaction with different operating temperature; HI/I₂/H₂O feed molar ratio=1/2.5/7.0. 40
Fig. 3.1.5. The amounts of H₂SO₄phase and distribution... 40
Fig. 3.1.6. The amounts of impurities in each phase after... 41
Fig. 3.1.7. The amounts of products in global system after Bunsen reaction with different initial I₂/HI molar ratio at 333 K; H₂O/HI feed molar ratio=6.17. 43
Fig. 3.1.8. Variation in amounts of components after Bunsen reaction with different initial I₂/HI molar ratio at 333 K; H₂O/HI feed molar ratio=6.17. 43
Fig. 3.1.9. The amounts of H₂SO₄phase and distribution ratio of H₂O into H₂SO₄phase after Bunsen reaction with different initial I₂/HI molar ratio at 333 K; H₂O/HI feed molar ratio=6.17. 44
Fig. 3.1.10. The amounts of impurities in each phase after Bunsen reaction with different initial I₂/HI molar ratio at 333 K; H₂O/HI feed molar ratio=6.17. 44
Fig. 3.1.11. The amounts of products in global system 45
Fig. 3.1.12. The variation in amounts of components... 46
Fig. 3.1.13. The amounts of H₂SO₄phase and distribution... 46
Fig. 3.1.14. The amounts of impurities in each phase after Bunsen reaction with different initial H₂O/HI molar ratio at 333 K; I₂/HI feed molar ratio=2.5. 47
Fig. 3.1.15. Schematic diagram of experimental apparatus for... 49
Fig. 3.1.16. Variation of HIx phase composition with time on stream at 333 K; HI/I₂/H₂O feed molar ratio=1/2.5/7.0, operating pressure=3 atm. 50
Fig. 3.1.17. The amounts of products in HIx phase with different operating pressure at 333 K; HI/I₂/H₂O feed molar ratio=1/2.5/7.0. 50
Fig. 3.1.18. The variation in amounts of components in... 51
Fig. 3.1.19. H₂SO₄/HI molar ratio in HIx phase with different operating pressure at 333 K; HI/I₂/H₂O feed molar ratio=1/2.5/7.0. 52
Fig. 3.1.20. The amounts of H₂SO₄phase and distribution.... 52
Fig. 3.1.21. H₂O/HI and I₂/HI molar ratios in HIx... 54
Fig. 3.1.22. Variation in amounts of components in HIx phase with different temperature and operating pressure; HI/I₂/H₂O feed molar ratio=1/2.5/7.0. 54
Fig. 3.1.23. H₂SO₄/HI molar ratio in HIx phase with different temperature and operating pressure; HI/I₂/H₂O feed molar ratio=1/2.5/7.0. 55
Fig. 3.1.24. The amount of H₂SO₄phase with different temperature and operating pressure; HI/I₂/H₂O feed molar ratio=1/2.5/7.0. 55
Fig. 3.1.25. Distribution ratio of H₂O into H₂SO₄phase... 56
Fig. 3.1.26. H₂O/HI and I₂/HI molar ratios in HIx phase with different initial I₂/HI molar ratio and operating pressure at 333 K; H₂O/HI feed molar ratio=7. 57
Fig. 3.1.27. Variation in amounts of components in HIx phase with different initial I₂/HI molar ratio and operating pressure at 333 K; H₂O/HI feed molar ratio=7. 57
Fig. 3.1.28. H₂SO₄/HI molar ratio in HIx phase with different initial I₂/HI molar ratio and operating pressure at 333 K; H₂O/HI feed molar ratio=7. 58
Fig. 3.1.29. The amount of H₂SO₄phase and... 58
Fig. 3.1.30. H₂O/HI and I₂/HI molar ratios in HIx phase 59
Fig. 3.1.31. Variation in amounts of components in ... 60
Fig. 3.1.32. The amount of H₂SO₄phase and... 60
Fig. 3.1.33. Solubility of I₂with different initial... 61
Fig. 3.2.1. Schematic diagram of experimental apparatus for pressurized... 65
Fig. 3.2.2. Photograph of Bunsen reactor. 67
Fig. 3.2.3. Plane photograph of vial with Bunsen... 68
Fig. 3.2.4. The variation of the concentration of H₂SO₄in Bunsen products after 12 h at room temperature. 69
Fig. 3.2.5. The variation of the concentration of HI in Bunsen products after 12 h at room temperature. 69
Fig. 3.2.6. The variation of the concentration of I₂in Bunsen products after 12 h at room temperature. 70
Fig. 3.3.1. conceptual drawing of the induced conductivity meter. 73
Fig. 3.3.2. Conducivity of H₂SO₄solution with different ratio of... 74
Fig. 3.3.3. Conducivity of H₂SO4 solution with different ratio of H₂O/H₂SO₄... 74
Fig. 3.3.4. Conducivity of HIx solution with different ratio of I₂/HI at... 75
Fig. 3.3.5. Control conception of a phase separator for water/oil. 76
Fig. 3.3.6. Valve control scheme in case of sulfuric acid phase and HIx interface placed between CI102 and CI103 76
Fig. 3.3.7. Valve control scheme in case of sulfuric acid phase and HIx interface placed between CI101 and CI102 77
Fig. 3.3.8. Valve control scheme in case of sulfuric acid phase and HIx interface placed below CI103 77
Fig. 3.3.9. Valve control scheme that the CI101 and CI102 control the H₂SO₄... 78
Fig. 3.3.10. Phase separation between... 79
Fig. 3.3.11. A picture of conductivity... 80
Fig. 3.3.12. Phase separation control... 81
Fig. 3.3.13. Phase separation control simulation unit test photograph 82
Fig. 3.3.14. Conductivity of HIx solution... 83
Fig. 3.3.15. Conductivity of HIx solution with... 84
Fig. 3.4.1. The image of HI purification... 87
Fig. 3.4.2. The influence of temperature on the removal efficiency for... 88
Fig. 3.4.3. The influence of N₂flow rate on the removal efficiency... 88
Fig. 3.5.1. Block diagram of sulfuric acid decomposition section in SI-cycle... 90
Fig. 3.5.2. Conceptual diagram of a bench-scale sulfuric acid decomposition process 91
Fig. 3.5.3. Conceptual design of a bench-scale sulfuric acid... 93
Fig. 3.5.4. Variation of inside temperatures in a bench-scale sulfuric acid separator 94
Fig. 3.5.5. Lab-scale sulfuric acid separator(A-type: ID 30mm, Pyrex column) 96
Fig. 3.5.6. Lab-scale sulfuric acid separator(B-type: ID 60mm, Pyrex column) 97
Fig. 3.5.7. Lab-scale sulfuric acid separator with a long column(column OD 30... 98
Fig. 3.5.8. Temperature profiles in the sections of sulfuric acid separator... 100
Fig. 3.5.9. Separation of H₂SO₄/HI/I₂mixture in the A-type sulfuric acid... 102
Fig. 3.5.10. Separation of H₂SO₄/HI/I₂mixture in the A-type sulfuric acid... 103
Fig. 3.5.11. Colors of aq. H₂SO₄in the reboiler and packing materials of the 103
Fig. 3.5.12. Molar ratio of I₂/HI in the top vent gas from the sulfuric... 103
Fig. 3.5.13. Separation of H₂SO₄/HI/I₂mixture in the A-type sulfuric acid... 104
Fig. 3.5.14. Molar ratio of I₂/HI in the top vent gas from the sulfuric acid... 105
Fig. 3.5.15. Separation of H₂SO₄/HI/I₂mixture in the A-type sulfuric acid... 106
Fig. 3.5.16. Separation of H₂SO₄/HI/I₂mixture in the A-type sulfuric acid... 106
Fig. 3.5.17. I₂remaining in sulfuric acid in the reboiler and packing materials... 107
Fig. 3.5.18. UV-Vis analysis of I₂remaining in sulfuric acid in the... 107
Fig. 3.5.19. Molar ratio of I₂/HI in the top vent gas from the sulfuric acid separator... 107
Fig. 3.5.20. Variation of I₂/HI molar ratio in the top vent gas from the... 108
Fig. 3.5.21. Lab-scale sulfuric acid separator with a short column(column OD... 109
Fig. 3.5.22. Separation of H₂SO₄/HI/I₂mixture in the B-type sulfuric acid separator... 110
Fig. 3.5.23. Separation of H₂SO₄/HI/I₂mixture in the B-type sulfuric acid... 112
Fig. 3.5.24. Separation of H₂SO₄/HI/I₂mixture in the B-type sulfuric acid... 113
Fig. 3.5.25. Variation of I₂/HI molar ratio in the top vent gas from the sulfuric... 115
Fig. 3.5.26. Separation of H₂SO₄/HI/I₂mixture in the B-type sulfuric acid separator... 115
Fig. 3.5.26. Separation of H₂SO₄/HI/I₂mixture in the B-type sulfuric acid separator... 116
Fig. 3.5.27. Sulfuric acid separator with a large-diameter column(OD mm,... 117
Fig. 3.5.28. Temperature profile example of H₂SO₄/HI/I₂separation in the... 118
Fig. 3.5.29. Separation of H₂SO₄/HI/I₂mixture in the C-type sulfuric acid separator... 119
Fig. 3.5.29. Separation of H₂SO₄/HI/I₂mixture in the C-type sulfuric acid separator... 120
Fig. 3.5.29. Separation of H₂SO₄/HI/I₂mixture in the C-type sulfuric acid separator... 121
Fig. 3.5.30. Separation of high-HI/I₂concentration mixture in the C-type... 123
Fig. 3.5.31. Separation of H₂SO₄-phase of a bench-scale Bunsen reaction in the... 124
Fig. 3.5.31. Separation of H₂SO₄-phase of a bench-scale Bunsen reaction in the... 125
Fig. 3.5.31. Separation of H₂SO₄-phase of a bench-scale Bunsen reaction in the... 126
Fig. 3.5.32. Separation of H₂SO₄-phase of a bench-scale Bunsen reaction in the 127
Fig. 3.5.33. H₂SO₄/HI/I₂separation system having dual supply of H₂SO₄/HI/I₂... 128
Fig. 3.5.34. Separation of H₂SO₄/HI/I₂mixture with additional supply of... 129
Fig. 3.5.35. Scheme of SiC hollow sphere preparation 134
Fig. 3.5.36. schematic diagram of sulfuric acid decomposer. 135
Fig. 3.5.37. Effects of O₂partial pressure in calcining the catalysts. 137
Fig. 3.5.38. Stability test of the Pt/SiC-50 (Cl, 2% O₂) catalyst. 137
Fig. 3.5.39. Effects of GHSV with the Pt-Cl/SiC (5% O₂... 138
Fig. 3.5.40. XRD patterns of the Pt-Cl/SiC catalysts calcined at the different O₂partial pressure 139
Fig. 3.5.41. Activity of the Pt-N/SiC catalysts prepared at different O₂partial pressure 140
Fig. 3.5.42. Stability of the Pt/SiC-34(N, 5%O₂) catalyst 141
Fig. 3.5.43. XRD patterns of SiC supports and pristine Pt/SiC catalysts:(a)... 144
Fig. 3.5.44. TEM and SAED images as well as Pt particle size... 145
Fig. 3.5.45. Binding energies of C1s, Si2p, and Pt4f peaks (a1, a2.... 146
Fig. 3.5.46. Stability data for the temperature-dependent catalytic activity... 149
Fig. 3.5.47. XRD patterns of spent (a) Pt/SiC-I, (b) Pt/SiC-AI, (c) Pt/SiC-P... 150
Fig. 3.5.48. TEM and SAED images as well as Pt particle ... 151
Fig. 3.5.49. XRD Patterns of Spent (a) Pt/SiC-I, (b)... 151
Fig. 3.6.1. Comparative result between the measured heat capacity of the deionized water... 155
Fig. 3.6.2. Comparative result between the measured heat capacity of... 158
Fig. 3.6.3. Comparative result between the measured heat capacity of... 159
Fig. 3.6.4. Comparative result between the measured density of the HIx solution and the correlation equation(2). 161
Fig. 3.7.1. Process flow diagram in the vicinity of HIx... 164
Fig. 3.7.2. Process flow diagram and mass balance in the vicinity of HIx distillation column in SEC3 165
Fig. 3.7.3. Process flow diagram of Aspen plus in the... 166
Fig. 3.7.4. Calculation conditions for the HIx distillation column 167
Fig. 3.7.5. Feed and product stage set-up 167
Fig. 3.7.6. Calculation results of the HIx distillation column 168
Fig. 3.7.7. Calculation results of the reboiler 168
Fig. 3.7.8. Calculation results of the condenser 169
Fig. 3.7.9. The calculated profile of the HIx distillation column. 169
Fig. 3.7.10. Liquid(left, a) and vapor(right, b) compositions in the HIx distillation column 170
Fig. 3.7.11. Temperature profile in the HIx distillation column 170
Fig. 3.7.12. Temperature difference profile in the HIx distillation column 171
Fig. 3.7.13. Liquid composition profile in the HIx distillation column 171
Fig. 3.7.14. Vapor composition profile in the HIx distillation column 172
Fig. 3.7.15. Temperature sensitivity profile in the HIx distillation column 172
Fig. 3.7.16. Calculation conditions for a heat exchanger 175
Fig. 3.7.17. Shell side parameters of a heat exchanger 175
Fig. 3.7.18. Tube side parameters of a heat exchanger 176
Fig. 3.7.19. Baffle type and parameters of a heat exchanger 176
Fig. 3.7.20. Nozzles size of a heat exchanger 176
Fig. 3.7.21. Summary results of the calculated heat exchanger 177
Fig. 3.7.22. The detail calculated results of a heat exchanger 177
Fig. 3.7.23. The detail calculated results of shell side of a heat exchanger 178
Fig. 3.7.24. The detail calculated results of tube side of a heat exchanger 178
Fig. 3.7.25. Calculated pressure drop in a heat exchanger 179
Fig. 3.7.26. The detail calculated results of baffles in a heat exchanger 179
Fig. 3.8.1. Schematic diagram for catalytic HI decomposition... 193
Fig. 3.8.2. HI decomposition according to the... 197
Fig. 3.8.3. HI decomposition according to the loaded Nickel... 198
Fig. 3.8.4. HI decomposition of three step according to the different... 200
Fig. 3.8.5. Non-isothermal analysis result of NiI₂. 201
Fig. 3.9.1. P&ID of the improved lab. scale SEC1 facility 204
Fig. 3.9.2. P&ID of the improved lab. scale SEC1-SEC3 interface facility 205
Fig. 3.9.3. T100, T101, T103 construction drawings 205
Fig. 3.9.4. T102 construction drawings 206
Fig. 3.9.5. S101 construction drawings 206
Fig. 3.9.6. S102 construction drawings 207
Fig. 3.9.7. Constructed units and piping utilization of PTFE linig, Zr tube and welding connections. 207
Fig. 3.9.8 .Improved SEC1 construction and operation photographs 211
Fig. 3.9.9. SO₂gas phase diminished at the outlet of Bunsen reactor 211
Fig. 3.9.10. The initial and steady operation results of the phase separator. 212
Fig. 3.9.11. A photograph of the control monitor on sulfuric acid phase separation... 213
Fig. 3.10.1. SEC1 PFD 216
Fig. 3.10.2. SEC2 PFC 218
Fig. 3.10.3. SEC3 PFD 220
Fig. 3.10.4. P&ID symbols and code description 221
Fig. 3.10.5. SEC1 P&ID 221
Fig. 3.10.6. SEC2 P&ID 227
Fig. 3.10.7. SEC3 ED part P&ID 235
Fig. 3.10.8. SEC3 HI distillation and decomposition part 236