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신·재생에너지 기술개발사업 최종(완료)보고서 제출서
제출문
요약문
SUMMARY
CONTENTS
목차
제1장 연구개발과제의 개요 29
제1절 연구 개발의 목적 29
제2절 필요성 및 범위 31
1. 기술적 측면 31
2. 산업, 경제적 측면 33
3. 정책적 측면 34
제2장 국내 외 연구 동향 35
제1절 국내 기술 현황 35
제2절 국외 개발 현황 36
제3장 연구개발수행 내용 및 결과 39
제1절 유동층 반응 시스템 39
1. 유동층 반응기에서 카본 블랙 촉매를 이용한 메탄의 촉매분해에 의한 수소 생산 39
2. 유동층 반응기에서 카본 블랙 촉매를 이용한 프로판의 촉매분해에 의한 수소 생산 89
3. 유동층 반응기에서 N330 카본 블랙 촉매를 이용한 프로판을 포함한 메탄의 촉매 분해에 의한 수소 제조 128
4. Scale-up 반응기에서의 카본 블랙 촉매를 이용한 메탄의 촉매 분해에 의한 수소 생산 160
5. Pilot plant에서의 카본 블랙 촉매를 이용한 메탄의 촉매 분해에 의한 수소 생산 177
제2절 미소 반응기를 이용한 촉매 특성 연구 210
1. 카본 블랙 촉매를 이용한 메탄 분해에 의한 수소 생산 210
2. 아세틸렌 흡착을 통한 카본 블랙의 활성점 연구 252
3. 카본 블랙 촉매를 이용한 에탄분해에 의한 수소 생산 274
4. 카본 블랙 촉매 상에서 에탄이 포함된 메탄 분해에 의한 수소 생산 318
제3절 LPG 분해 실험 361
1. LPG 촉매 분해반응 실험 361
2. 프로판 분해 369
3. 부탄 분해 389
4. 프로판-부탄 혼합가스 분해 422
5. 상용 LPG 분해 441
6. 반응물 변화에 따른 탄화 수소 분해 반응 462
제4절 카본 블랙 재활용 474
1. 메탄 분해용 탄소 촉매의 물성 연구 474
2. 카본 블랙의 고무 충진제 연구 500
3. 표면 처리된 카본 블랙/고분자의 전자파 차폐 특성 549
제5절 반응기 열전달 개선 및 공정 simulation 584
1. 수치 해석 모델 및 이의 활용 프로세스 수립 584
2. 여천 Pilot plant 시뮬레이션 수행 587
3. 반응기 형상의 제안 591
4. Double Jacket External heating 방식 반응기의 주요 특징 591
5. Internal heating and external reheat 방식 반응기의 주요 특징 591
6. Helical fin type 반응기의 형상과 주요 특징 594
7. HRS 방식의 고온 유동층 화학반응기의 시뮬레이션 결과 598
8. 경계조건 확보를 위한 실험 수행 600
제4장 목표달성도 및 관련 분야에의 기여도 605
제1절 목표달성도 605
제2절 관련 분야에의 기여도 608
제5장 연구 개발 결과와 활용계획 618
제6장 연구 개발과정에서 수집한 해외과학기술정보 619
제7장 참고 문헌 622
제1절 유동층 반응 시스템 622
제2절 미소 반응기를 이용한 카본 블랙 촉매 특성 연구 625
제3절 LPG 분해 실험 628
제4절 카본 블랙 재활용 631
제5절 반응기 열전달 개선 및 공정 simulation 634
Appendix - High Purity Hydrogen PSA 637
Table 1. 국내 특허 현황 36
Table 2. 국외 특허 현황 38
Table 1-1. 실험에 사용한 카본블랙의 물리 화학적 특성. 40
Table 1-2. 실험에 사용한 카본블랙의 반응차수 및 활성화 에너지. 68
Table 1-3. 반응 후 카본블랙의 물리 화학적 특성 변화 81
Table 1-4. 카본블랙 분류 91
Table 1-5. 실험에 사용한 카본블랙의 물리 화학적 특성. 128
Table 1-6. quartz 반응기와 scale-up 반응기의 차이점. 161
Table 1-7. quartz 반응기, scale-up 반응기 & pilot plant 비교 179
Table 1-8. Composition of reactant 184
Table 2-1. Carbon blacks used in the experiment 212
Table 2-2. Reaction orders and activation energies for rubber & specialty blacks 231
Table 2-3. Methane and ethane flow rates and feed composition 319
Table 2-4. Contribution by methane and ethane decomposition to H₂ production(Basis : 100 mol CH₄ fed, ethane/methane = 5/95) 332
Table 2-5. Contribution by methane and ethane decomposition to H₂ production (Basis : 100 mol CH₄ fed, ethane/methane = 10/90) 341
Table 2-6. Contribution by methane and ethane decomposition to H₂ production (Basis : 100 mol CH₄ fed, ethane/methane = 15/85) 350
Table 3-1. Commercially available carbon based catalysts in the decomposition of hydrocarbon. 363
Table 3-2. Comparison of product distribution, conversion, and hydrogen yield over various carbon-based catalysts at 750 ℃. 376
Table 3-3. Variation of conversion and product distribution as function of time on stream over activated carbon and carbon black catalysts at 750 ℃ 386
Table 3-4. Product distributions (mol %) in thermal decomposition of n-butane. 400
Table 3-5. Product distributions (mol %) in catalytic decomposition of n-butane. 401
Table 3-6. Composition of commercial LPG. 441
Table 3-7. Conversion of methane for hydrogen sulfide concentration. in the methane decomposition. 464
Table 3-8. Conversion of methane for hydrogen sulfide concentration. in the methane decomposition. 468
Table 4-1. Properties of Raw Carbon Black Used as Catalysts for Methane Decomposition 479
Table 4-2. Properties of N330 (Crushed Pellet) Black with Different Weight Gain before and after Reaction 479
Table 4-3. Pore Analyses of Carbon Black Samples before and after Reaction 480
Table 4-4. Properties of N330-f Black before and after Reaction for 8 hr with different weight Gain 480
Table 4-5. Properties of HI-900L black before and after reaction at 850℃ for 8 hr with different weight gain 483
Table 4-6. Properties of carbon nanofibers used as methane decomposition catalysts. 491
Table 4-7. BET surface area and mass of carbon catalysts with methane decomposition at different conditions 495
Table 4-8. Compounding formulations of composites 506
Table 4-9. Properties of N330(F) carbon blacks before and after reaction 507
Table 4-10. Properties of carbon blacks before and after surface modification 525
Table 4-11. Properties of N330(F) carbon blacks treated by CO₂ activation 541
Table 4-12. Surface resistivity of SBR rubber composites as a function of loading ratio 542
Table 4-13. Properties of carbon blacks before and after acid and alkali treatments 555
Table 4-14. Properties of carbon blacks before and after heat treatments 560
Table 4-15. Properties of N330(F) Carbon Blacks Treated by CO₂ Activation 564
Table 4-16. Variations of the electrical properties of carbon blacks and their PVA coating materials with different chemical treatments 569
Table 4-17. Variations of the electrical properties of carbon blacks and their PVA coating materials with different heat treatment temperature 569
Table 4-18. Variations of the electrical properties of carbon blacks and their PVA coating materials before and after CO₂ activation 570
Table 4-19. Variations of the electrical properties of carbon blacks and their PVDF coating materials with different chemical treatments 576
Table 4-20. Variations of the electrical properties of carbon blacks and their PVDF coating materials with different heat treatment temperature 576
Table 4-21. Variations of the electrical properties of carbon blacks and their PVDF coating materials before and after CO₂ activation 577
Table 4-22. Variations of the electrical properties of carbon blacks and their PVDF/PVP coating materials with different ratios 582
Figure 1-1. Pressure Drop Measurement. 41
Figure 1-2. Schematic of fluidized bed reactor system. 43
Figure 1-3. Minimum fluidization velocity of carbon black(N330). 45
Figure 1-4. Minimum fluidization velocity of carbon black(HI-900L). 46
Figure 1-5. Minimum fluidization velocity of carbon black(HI-20L). 47
Figure 1-6. Minimum fluidization velocity of carbon black(HI-170). 48
Figure 1-7. Minimum fluidization velocity of carbon black(Ketjen black EC-600JD). 49
Figure 1-8. CH₄ conversion vs. time over CB(HI-170) with different reaction temperature (Experiment Conditions : Cat. loading 100 g, Gas Velocity 1.0 Umf).(이미지참조) 51
Figure 1-9. CH₄ decomposition rate vs. time over CB(HI-170) with different reaction temperature (Experiment Conditions : Cat. loading 100 g, Gas Velocity 1.0 Umf).(이미지참조) 52
Figure 1-10. CH₄ conversion vs. time over carbon blacks with different reaction temperature (Experiment Conditions : Cat. loading 100 g, Gas Velocity 1.0 Umf).(이미지참조) 53
Figure 1-11. CH₄ conversion vs. time over CB(N330) with different gas velocity (Experiment Conditions : Cat. loading 100 g, Reaction Temp. 850 ℃). 55
Figure 1-12. CH₄ decomposition rate vs. time over CB(N330) with different gas velocity (Experiment Conditions : Cat. loading 100 g, Reaction Temp. 850 ℃). 56
Figure 1-13. CH₄ conversion vs. time over carbon blacks with different gas velocity (Experiment Conditions : Cat. loading 100 g, Reaction Temp. 850 ℃). 57
Figure 1-14. CH₄ decomposition rate vs. time over carbon blacks with different gas velocity (Experiment Conditions : Cat. loading 100 g, Reaction Temp. 850 ℃). 58
Figure 1-15. CH₄ conversion vs. time over carbon blacks with different surface area (Experiment Conditions : Cat. loading 100 g, Reaction Temp. 900 ℃). 60
Figure 1-16. CH₄ conversion vs. surface area over carbon blacks (Experiment Conditions : Cat. loading 100 g, Reaction Temp. 900 ℃). 61
Figure 1-17. CH₄ decomposition rate vs. time over carbon blacks with different surface area (Experiment Conditions : Cat. loading 100 g, Reaction Temp. 900 ℃). 62
Figure 1-18. CH₄ decomposition vs. surface area over carbon blacks (Experiment Conditions : Cat. loading 100 g, Reaction Temp. 900 ℃). 63
Figure 1-19. CH₄ conversion vs. time over CB(N330) with different catalyst loading (Experiment Conditions : Gas. velocity 1.0 Umf, Reaction Temp. 900 ℃)(이미지참조) 65
Figure 1-20. CH₄ conversion vs. time over CB(N330) with different catalyst loading (Experiment Conditions : Gas. velocity 1.0 Umf, Reaction Temp. 900 ℃)(이미지참조) 66
Figure 1-21. Arrhenius plot for methane decomposition over carbon blacks(rubber black, conductive black). 69
Figure 1-22. Arrhenius plot for methane decomposition over conductive carbon black(HI-black). 70
Figure 1-23. CH₄ conversion vs. time over CB(N330) (Experiment Conditions : Cat. loading 100 g, Gas Velocity 1.0 Umf).(이미지참조) 73
Figure 1-24. Minimum fluidization velocity of used carbon black(N330). 74
Figure 1-25. CH₄ conversion vs. time over CB(N330) with used catalyst (Experiment Conditions : Cat. loading 100 g, Gas Velocity 1.0 Umf).(이미지참조) 75
Figure 1-26. CH₄ decomposition rate vs. time over CB(N330) with used catalyst (Experiment Conditions : Cat. loading 100 g, Gas Velocity 1.0 Umf).(이미지참조) 76
Figure 1-27. CH₄ conversion and carbon deposit vs. time over CB(N330) (Experiment Conditions : Cat. loading 100 g, Reaction Temp.850 ℃). 78
Figure 1-28. The specific carbon deposition(Wc) at activity stabilization vs. surface area of fresh carbon blacks (Experiment Conditions : Cat. loading 100 g, Reaction Temp. 850 ℃)(이미지참조) 79
Figure 1-29. SEM images for carbon black(HI-900L). 82
Figure 1-30. SEM images for carbon blacks(HI-170). 83
Figure 1-31. TEM images for carbon black(N330). 84
Figure 1-32. TEM images for carbon black(HI-900L). 85
Figure 1-33. TEM images for carbon blacks. 86
Figure 1-34. TEM images for carbon black(Ketjen black EC 600JD) 87
Figure 1-35. Schematic of fluidized bed reactor system 92
Figure 1-36. C₃H8 conversion over various carbon blacks at different temperature(이미지참조) 96
Figure 1-37. C₃H6 selectivity over various carbon blacks at different temperature(이미지참조) 97
Figure 1-38. C₂H6 selectivity over various carbon blacks at different temperature(이미지참조) 98
Figure 1-39. C₂H₄ selectivity over various carbon blacks at different temperature(이미지참조) 99
Figure 1-40. CH₄ selectivity over various carbon blacks at different temperature(이미지참조) 100
Figure 1-41. C(s) selectivity over various carbon blacks at different temperature 101
Figure 1-42. H₂ yield over various carbon blacks at different temperature 102
Figure 1-43. The effect of reaction temperature on gas composition(N330(F)) 103
Figure 1-44. C₃H8 conversion over carbon black at different gas velocity(N330(F))(이미지참조) 106
Figure 1-45. The effect of gas velocity on gas composition(N330(F)) 107
Figure 1-46. C₃H8 decomposition rate over carbon black at different gas velocity(N330(F))(이미지참조) 108
Figure 1-47. H₂ yield over carbon black at different gas velocity(N330(F)) 109
Figure 1-48. C₃H8 conversion over carbon black at different catalyst loading(N330(F))(이미지참조) 111
Figure 1-49. H₂ yield over carbon black at different catalyst loading(N330(F)) 112
Figure 1-50. Specific surface area of C in the reactor vs. the mass of deposited carbon per mass of fresh carbon blacks (rubber & color black) 114
Figure 1-51. Specific surface area of C in the reactor vs. the mass of deposited carbon per mass of fresh carbon blacks 115
Figure 1-52. Relative specific surface area of the whole C in the reactor vs. the mass of deposited carbon per mass of fresh carbon blacks 116
Figure 1-53. Secondary particle size of carbon black vs. the mass of deposited carbon per mass of fresh & used carbon black(N330(F)) 118
Figure 1-54. TEM images of fresh and used N330(F) : (a) fresh N330(F), (b) 600℃, 8 h, Wc=0.165, m (c) 700℃, 8 h, Wc=0.541, (d) 800℃-2Umf, 8 h, Wc=1.370(이미지참조) 121
Figure 1-55. TEM images of fresh and used Raven900(F) : (a) fresh Raven(F), (b) 700℃, 8 h, Wc=0.427, (c) 800℃, 8 h, Wc=1.042(이미지참조) 123
Figure 1-56. TEM images of fresh and used EC-600JD(F) : (a) fresh EC-600JD(F), (b) 700℃, 8 h, Wc=0.804, (c) 800℃, 8 h, Wc=2.163(이미지참조) 124
Figure 1-57. TEM images of fresh and used HI-20L(F) : (a) fresh HI-20L(F), (b) 800℃, 8 h, Wc=0.912(이미지참조) 125
Figure 1-58. TEM images of fresh and used HI-170(F) : (a) fresh HI-170(F), (b) 700℃, 8 h, Wc=0.098(이미지참조) 126
Figure 1-59. Schematic of fluidized bed reactor system. 130
Figure 1-60. CH₄ Conversion vs. time over carbon black(N330) with different reaction temperature (반응 가스 내 CH₄, C₃H8 비율 : 9:1)(이미지참조) 134
Figure 1-61. CH₄ Conversion vs. time over carbon black(N330) with different gas velocity (반응 가스 내 CH₄, C₃H8 비율 : 9:1)(이미지참조) 135
Figure 1-62. CH₄ decomposition rate vs. time over carbon black(N330) with different gas velocity (반응 가스 내 CH₄, C₃H8 비율 : 9:1)(이미지참조) 136
Figure 1-63. CH₄ Conversion vs. time over carbon black(N330) with different catalyst loading (반응 가스 내 CH₄, C₃H8 비율 : 9:1)(이미지참조) 137
Figure 1-64. Aggregates size of used carbon black vs. Wc (반응 가스 내 CH₄, C₃H8 비율 : 9:1)(이미지참조) 140
Figure 1-65. Aggregates size of used carbon black and Wc vs. different reaction temperature (반응 가스 내 CH₄, C₃H8 비율 : 9:1)(이미지참조) 141
Figure 1-66. Aggregates size of used carbon black and Wc vs. different gas velocity (반응 가스 내 CH₄, C₃H8 비율 : 9:1)(이미지참조) 142
Figure 1-67. Aggregates size of used carbon black and Wc vs. different catalyst loading (반응 가스 내 CH₄, C₃H8 비율 : 9:1)(이미지참조) 143
Figure 1-68. Specific surface area vs. Wc (반응 가스 내 CH₄, C₃H8 비율 : 9:1)(이미지참조) 145
Figure 1-69. TEM image of fresh carbon black(N330) 148
Figure 1-70. Hess-Ban-Heidenreich model of carbon black structure[Harris, 1999] 149
Figure 1-71. TEM images of used carbon black(N330) (a) Experiment condition : temperature 900 ℃, gas velocity 1 Umf, catalyst loading 200 g, Wc 0.1260...(이미지참조) 150
Figure 1-72. TEM images of used carbon black(N330) (a) Experiment condition : temperature 900 ℃, gas velocity 1 Umf, catalyst loading 100 g, Wc 0.1940...(이미지참조) 151
Figure 1-73. TEM images of used carbon black(N330) (a) Experiment condition : temperature 850 ℃, gas velocity 1 Umf, catalyst loading 100 g, Wc 0.1430, × 200.000...(이미지참조) 152
Figure 1-74. TEM images of used carbon black(N330) Experiment condition : temperature 850 ℃, gas velocity 3 Umf, catalyst loading 100 g, Wc 0.2890, × 500.000(이미지참조) 153
Figure 1-75. TEM images of used carbon black(N330) Experiment condition : temperature 875 ℃, gas velocity 1 Umf, catalyst loading 100 g, Wc 0.1520, × 500.000(이미지참조) 154
Figure 1-76. CH₄ Conversion vs. mol. fraction of reaction temperature with different mol. fraction of C₃H8(이미지참조) 157
Figure 1-77. Production rate of H₂ vs. reaction temperature (Experiment condition : catalyst loading 100 g, gas velocity 1 Umf)(이미지참조) 158
Figure 1-78. Schematic of scale-up reactor system. 162
Figure 1-79. Image of scale-up reactor system. 163
Figure 1-80. CH₄ Conversion & Production rate of H₂ vs. Gas velocity (Reaction condition : Temperature 930 ℃, Catalyst loading 600 g) 165
Figure 1-81. CH₄ Conversion & Production rate of H₂ vs. Reaction Temperature (Reaction condition : Gas velocity 3 Umf, Catalyst loading 600 g)(이미지참조) 166
Figure 1-82. CH₄ Conversion vs. experiment condition 168
Figure 1-83. 반응기 주입구 형태 169
Figure 1-84. CH₄ Conversion vs. reaction condition over carbon balck 170
Figure 1-85. Production rate of H₂ vs. reaction condition over carbon black 171
Figure 1-86. CH₄ Conversion vs. Pressure with different reaction temperature 174
Figure 1-87. Production rate of H₂ vs. Pressure with different reaction temperature 175
Figure 1-88. Images of pilot plant 180
Figure 1-89. Schematic of pilot pant 181
Figure 1-90. Images of distributor 182
Figure 1-91. Images of back-pressure regulator 183
Figure 1-92. G/C raw data of reactant 184
Figure 1-93. CH₄ Conversion over carbon black with different reaction temperature 186
Figure 1-94. Production rate of H₂ over carbon balck with different reaction temperature (원료 내 수소 미포함) 187
Figure 1-95. Production rate of H₂ over carbon balck with different reaction temperature (원료 내 수소 포함) 188
Figure 1-96. CH₄ Conversion over carbon black with different gas velocity 191
Figure 1-97. Production rate of H₂ over carbon balck with different gas velocity (원료 내 수소 미포함) 192
Figure 1-98. Production rate of H₂ over carbon balck with different gas velocity (원료 내 수소 포함) 193
Figure 1-99. 반응기 하부에 설치된 furnace 195
Figure 1-100. Furnace 설치 전, 후의 CH₄ Conversion 196
Figure 1-101. Furnace 설치 전, 후의 반응기 내부 temperature profile 197
Figure 1-102. Tuyere distributor 199
Figure 1-103. 분산판 형태에 따른 CH₄ Conversion 200
Figure 1-104. 분산판 형태에 따른 Production rate of H₂ (원래 내 수소 포함) 201
Figure 1-105. CH₄ Conversion and Production rate of H₂ (Reaction condition : Temperature 950 ℃, Catalyst loading 15 kg, Gas velocity 2 Umf)(이미지참조) 203
Figure 1-106. CH₄ Conversion and Production rate of H₂ (Reaction condition : Temperature 950 ℃, Catalyst loading 15 kg, Gas velocity 3 Umf)(이미지참조) 204
Figure 1-107. PSA System 206
Figure 1-108. 열교환기 207
Figure 1-109. G/C raw data 208
Figure 2-1. Schematic diagram of reactor system. 213
Figure 2-2. CH₄ conversion vs. time in the absence of carbon black without and with rock wool in the reactor (CH₄ flow rate=25 cm³(STP)/min).(이미지참조) 217
Figure 2-3. Arrhenius plot for homogeneous gas-phase methane decomposition. 218
Figure 2-4. CH₄ conversion vs. time over carbon black. (temp.=1123 K, VHSV=15.0 L/gCB·h)(이미지참조) 220
Figure 2-5. CH₄ conversion vs. time over pelletized rubber blacks (temp.=1223 K, VHSV=15,000 cm³/h·g-cat). 221
Figure 2-6. Methane conversion over CBs vs. time (temperature = 1173 K, VHSV = 15,000 cm³/h·g-cat). 222
Figure 2-7. Methane conversion over CBs vs. time (temperature = 1123 K, VHSV = 15,000 cm³/h·g-cat). 223
Figure 2-8. Rate of CH₄ decomposition vs. specific surface area of pelletized rubber blacks (temp.=1223 K, VHSV=15,000 cm³/h·g-cat). 225
Figure 2-9. Rate of methane decomposition over CBs against the specific surface area of fresh CBs (temperature = 1123 K, VHSV = 15,000 cm³/h·g-cat). 226
Figure 2-10. Rate of methane decomposition over carbon blacks as a function of methane partial pressure(temp.=1173 K, VHSV=15.0 L/gCB·h).(이미지참조) 228
Figure 2-11. Rate of CH₄ decomposition as a function of CH₄ partial pressure over DCC-N103(P) and DOC-N330(P) (temp.=1173 K). 229
Figure 2-12. Rate of methane decomposition over specialty blacks as a function of methane partial pressure (temperature = 1173 K). 230
Figure 2-13. CH₄ conversion vs. time over DCC-N103(P) at different temperatures (VHSV = 15,000 cm³/h·g-cat). 234
Figure 2-14. CH₄ conversion vs. time over DCC-N330(F) at different temperatures. (VHSV = 15.0 L/gh) 235
Figure 2-15. CH₄ conversion vs. time over BP-2000 at different temperatures. (VHSV = 15.0 L/gh) 236
Figure 2-16. Arrhenius plot for CH₄ decomposition over DCC-N103(P) and DCC-N330(P) (VHSV = 15,000 cm³/h·g-cat a is the reaction order). 237
Figure 2-17. Arrhenius plot for methane decomposition over specialty blacks (VHSV = 15,000 cm³/h·g-cat; α = the reaction order in Table 2-2). 238
Figure 2-18. Specific BET SA of the product carbon vs. the mass of deposited carbon per mass of fresh N330(F) and BP-2000. 240
Figure 2-19. Relative total SA of the whole carbon in the reactor vs. the mass of deposited carbon per mass of fresh N330(F) and BP-2000. 241
Figure 2-20. SEM images for fresh carbon blacks. 243
Figure 2-21. SEM images of after reaction(VHSV=15.0 L/g·h) 244
Figure 2-22. TEM images of N330(F) 246
Figure 2-23. TEM images of BP-2000 247
Figure 3-24. TEM images of HI-20L, HI-900L and EC-600JD 248
Figure 2-25. Schematic diagram for C₂H₂ adsorption/TPD on carbon blacks. 254
Figure 2-26. TCD responses from acetylene pulse injection for N330(P) at different adsorption temperature. 257
Figure 2-27. Effect of temperature on physical and activated adsorption 258
Figure 2-28. TCD responses from acetylene pulse injection for EC-600JD at different adsorption temperature. 259
Figure 2-29. CH₄ decomposition rate vs. cumulative C₂H₂ adsorption at 773 K on various carbon blacks (correlation coefficient r² and slope [mol CH₄/mol C₂H₂·min] = 0.806 and 0.424 for 773/1123 K data, 0.792 and... 261
Figure 2-30. CH₄ decomposition rate vs. C₂H₂ consumption at 873 K for cach pulse on various carbon blacks (correlation coefficient r² and slope [mol CH₄/mol C₂H₂·min] = 0.814 and 1.074 for 873/1123 K data, 0.792 and... 262
Figure 2-31. Mass spectroscopy responses of C₂H₂ and H₂ from acetylene pulse injections at 773 K in the presence of N330(P) saturated with chemisorbed C₂H₂ and from subsequent TPD. 265
Figure 2-32. Mass spectroscopy responses of C₂H₂ and H₂ from acetylene pulse injections at 873 K in the presence of N330(P) having exposed to about 30 C₂H₂ pulses and from subsequent TPD. 266
Figure 2-33. A scheme for cumulative C₂H₂ chemisorption processes at 773 K. 269
Figure 2-34. A scheme for constant C₂H₂ consumption processes at 773 K (the numbers inside 6-member rings are the count of injections). 270
Figure 2-35. A scheme for C₂H₂ chemisorption processes involving zigzag face and corner. 271
Figure 2-36. A scheme for C₂H₂ chemisorption processes on zigzag face. 272
figure 2-37. Schematic diagram for C₂H6 decomposition on carbon blacks.(이미지참조) 276
Figure 3-38. C₂H6 conversion over various rubber-grade carbon blacks at different temperature (VHSV = 15,000 cm³/h·gCB).(이미지참조) 280
Figure 2-39. C₂H₄ selectivity over various rubber-grade carbon blacks at different temperature (VHSV = 15,000 cm³/h·gCB).(이미지참조) 281
Figure 2-40. CH₄ selectivity over various rubber-grade carbon blacks at different temperature (VHSV = 15,000 cm³/h·gCB).(이미지참조) 282
Figure 2-41. C(s) selectivity over various rubber-grade carbon blacks at different temperature (VHSV = 15,000 cm³/h·gCB).(이미지참조) 283
Figure 2-42. H₂ yield over various rubber-grade carbon blacks at different temperature (VHSV = 15,000 cm³/h·gCB).(이미지참조) 284
Figure 2-43. C₂H6 conversion over various specialty carbon blacks at different temperature (VHSV = 15,000 cm³/h·gCB).(이미지참조) 287
Figure 2-44. C₂H₄ selectivity over various specialty carbon blacks at different temperature (VHSV = 15,000 cm³/h·gCB).(이미지참조) 288
Figure 2-45. CH₄ selectivity over various specialty carbon blacks at different temperature (VHSV = 15,000 cm³/h·gCB).(이미지참조) 289
Figure 2-46. C(s) selectivity over various specialty carbon blacks at different temperature (VHSV = 15,000 cm³/h·gCB).(이미지참조) 290
Figure 2-47. H₂ yield over various specialty carbon blacks at different temperature (VHSV = 15,000 cm³/h·gCB).(이미지참조) 291
Figure 2-48. C₂H6 conversion and CH₄ selectivity at 1,023 K vs. specific surface areas of carbon blacks (VHSV = 15,000 cm³/h·gCB).(이미지참조) 292
Figure 2-49. C₂H₄selectivity, C(s) selectivity and H₄ yield at 1,023 K vs. specific surface areas of carbon blacks (VHSV = 15,000 cm³/h·gCB).(이미지참조) 293
Figure 2-50. Ethane conversion and methane selectivity in long-term tests with N330(F) and BP-2000 at 1073 K (VHSV = 15,000 cm³/h·gCB).(이미지참조) 295
Figure 2-51. Ethane selectivity and hydrogen yield in long-term tests with N330(F) and BP-2000 at 1073 K (VHSV = 15,000 cm³/h·gCB).(이미지참조) 296
Figure 2-52. Specific surface area of the whole carbon vs. the mass of deposited carbon per mass of original CB. 299
Figure 2-53. Relative total surface area of the whole carbon in the reactor vs. the mass of deposited carbon per mass of original CB. 300
Figure 2-54. SEM images for fresh carbon blacks. 306
Figure 2-55. SEM images of N330(P) after ethane decomposition reaction at 1,073 K (VHSV = 15,000 cm³/h·gCB).(이미지참조) 307
Figure 2-56. SEM images of N330(F) after ethane decomposition reaction at 1,073 K (VHSV = 15,000 cm³/h·gCB).(이미지참조) 308
Figure 2-57. SEM images of BP-2000 after ethane decomposition reaction at 1,073 K (VHSV = 15,000 cm³/h·gCB).(이미지참조) 309
Figure 2-58. TEM images for fresh carbon blacks. 312
Figure 2-59. TEM images of N330(F) after ethane decomposition reaction at 1.073 K (VHSV = 15,000 cm³/h·gCB).(이미지참조) 313
Figure 2-60. TEM images of N330(P) after ethane decomposition reaction for 2 hours (VHSV = 15,000 cm³/h·gCB).(이미지참조) 315
Figure 2-61. TEM images of BP-2000 after ethane decomposition reaction for 2 hours (VHSV = 15,000 cm³/h·gCB).(이미지참조) 316
Figure 2-62. Schematic diagram of the apparatus for C₂H6-containing CH₄ decomposition on carbon blacks.(이미지참조) 320
Figure 2-63. C₂H6 conversion over various carbon blacks at different temperatures (ethane/methane = 5/95, VHSV = 18,000 cm³ CH₄/h·gCB).(이미지참조) 324
Figure 2-64. C₂H₄ yield over various carbon blacks at different temperatures (ethane/methane = 5/95, VHSV = 18,000 cm³ CH₄/h·gCB).(이미지참조) 326
Figure 2-65. Apparent CH₄ conversion over various carbon blacks at different temperatures (ethane/methane = 5/95, VHSV = 18,000 cm³ CH₄/h·gCB).(이미지참조) 328
Figure 2-66. H₂ yield over various carbon blacks at different temperatures (ethane/methane = 5/95, VHSV = 18,000 cm³ CH₄/h·gCB).(이미지참조) 329
Figure 2-67. C(s) yield over various carbon blacks at different temperatures (ethane/methane = 5/95, VHSV = 18,000 cm³ CH₄/h·gCB).(이미지참조) 330
Figure 2-68. C₂H6 conversion over various carbon blacks at different temperatures (ethane/methane = 10/90, VHSV = 18,000 cm³ CH₄/h·gCB).(이미지참조) 334
Figure 2-69. C₂H₄ yield over various carbon blacks at different temperatures (ethane/methane = 10/90, VHSV = 18,000 cm³ CH₄/h·gCB).(이미지참조) 336
Figure 2-70. Apparent CH₄conversion over various carbon blacks at different temperatures (ethane/methane = 10/90, VHSV = 18,000 cm³ CH₄/h·gCB).(이미지참조) 337
Figure 2-71. H₂ yield over various carbon blacks at different temperatures (ethane/methane = 10/90, VHSV = 18,000 cm³ CH₄/h·gCB).(이미지참조) 339
Figure 2-72. C(s) yield over various carbon blacks at different temperatures (ethane/methane = 10/90, VHSV = 18,000 cm³ CH₄/h·gCB).(이미지참조) 340
Figure 2-73. C₂H6 conversion over various carbon blacks at different temperatures (ethane/methane = 15/85, VHSV = 18,000 cm³ CH₄/h·gCB).(이미지참조) 345
Figure 2-74. C₂H₄ yield over various carbon blacks at different temperatures (ethane/methane = 15/85, VHSV = 18,000 cm³ CH₄/h·gCB).(이미지참조) 346
Figure 2-75. Apparent CH₄ conversion over various carbon blacks at different temperatures (ethane/methane = 15/85, VHSV = 18,000 cm³ CH₄/h·gCB).(이미지참조) 347
Figure 2-76. H₂ yield over various carbon blacks at different temperatures (ethane/methane = 15/85, VHSV = 18,000 cm³ CH₄/h·gCB).(이미지참조) 348
Figure 2-77. C(s) yield over various carbon blacks at different temperatures (ethane/methane = 15/85, VHSV = 18,000 cm³ CH₄/h·gCB).(이미지참조) 349
Figure 2-78. CH₄ conversion in CH₄-only decomposition (VHSV = 15,000 cm³ CH₄/h·gCB) and C₂H6-containing CH₄ decomposition (ethane/methane = 5/95; VHSV = 18,947 cm³ CH₄/h·gCB) over various carbon blacks at...(이미지참조) 352
Figure 2-79. Concentration(in mol%) of C₂H₄ in the effluent vs. apparent CH₄ conversion 355
Figure 2-80. TEM images of N330(F) after C₂H6-containing CH₄ decomposition for 2 hours (ethane/methane = 5/95).(이미지참조) 357
Figure 2-81. TEM images of N330(F) after C₂H6-containing CH₄ decomposition for 2 hours(ethane/methane = 10/90).(이미지참조) 358
Figure 2-82. TEM images of N330(F) after C₂H6-containing CH₄ decomposition for 2 hours (ethane/methane = 15/85).(이미지참조) 359
Figure 3-1. LPG decomposition Process. 362
Figure 3-2. The schematic diagram for LPG decomposition. 366
Figure 3-3. The schematic diagram for LPG decomposition with using Cahn balance(TGA). 367
Figure 3-4. Cahn balance(TGA). 368
Figure 3-5. Gas composition in thermodynamic equilibrium of the propane decomposition process. 371
Figure 3-6. Product distribution for non-catalytic thermal cracking of propane as a function of reactor temperature. 372
Figure 3-7. Mass spectrometer signal of C₃H8 for non-catalytic thermal and catalytic decomposition of propane.(이미지참조) 373
Figure 3-8. Mass spectrometer signal of H₂ for non-catalytic thermal and catalytic decomposition of propane. 374
Figure 3-9. Product distribution from catalytic and thermal cracking of propane as a function of temperature. 379
Figure 3-10. The formation of hydrocarbons at 700 ℃ in the hydrogenation of carbon deposited from propane catalytic cracking 380
Figure 3-11. XRD analysis of carbon catalysts by propane decomposition. 381
Figure 3-12. The amount of carbon deposited from propane over BP-1100 catalyst. 382
Figure 3-13. Product distribution and conversion over BP-1100 catalyst at 950 ℃. 385
Figure 3-14. Product distribution and conversion over DCC-N330 catalyst at 750 ℃. 388
Figure 3-15. Conversion of butane over the carbon black based catalysts. 399
Figure 3-16. Effect of temperature on conversion in the thermal and catalytic decomposition of butane. 402
Figure 3-17. Effect of temperature on the product distribution in the catalytic and thermal decomposition. 403
Figure 3-18. Effect of temperature on conversion and products in the thermal and catalytic decomposition of butane. 404
Figure 3-19. Product distribution in catalytic decomposition of butane. 405
Figure 3-20. Hydrogen productivity with temperature in the thermal and catalytic decomposition of butane. 406
Figure 3-21. Distribution of the various products in catalytic decomposition of butane at 700 ℃. 407
Figure 3-22. Products Distribution by thermal and catalytic Decomposition of butane at 1100 ℃. 408
Figure 3-23. Effect of space velocity on butane conversion and product distribution in catalytic decomposition of butane. 409
Figure 3-24. Effect of temperature on the butane conversion in the catalytic decomposition of butane. 410
Figure 3-25. Arrhenius plot with the volume expansion in catalytic decomposition of butane. 411
Figure 3-26. Distribution of H₂ and CH₄ as the product in the catalytic decomposition of butane with temperature. 412
Figure 3-27. Carbon deposited reactor by thermal and catalytic decomposition of butane. 415
Figure 3-28. SEM images of the carbon black catalysts. 416
Figure 3-29. TEM images of the carbon black catalysts. 417
Figure 3-30. XRD analysis of fresh and used carbon black. 419
Figure 3-31. Products distribution for the mixing ratio of propane and butane in the catalytic decomposition at 700 ℃. 424
Figure 3-32. Comparison of hydrogen production for reactants. 425
Figure 3-33. Conversion of propane and butane by thermal and catalytic propane-butane mixed gas decomposition. 430
Figure 3-34. Distribution of product with temperature in the thermal and catalytic decomposition. 431
Figure 3-35. Hydrogen productivity with temperature in the thermal and catalytic decomposition of propane-butane mixed gas. 432
Figure 3-36. Hydrogen productivity with temperature in the catalytic decomposition of propane-butane mixed gas 433
Figure 3-37. Distribution of products by catalytic decomposition at 1000 ℃, 1100 ℃. 434
Figure 3-38. Catalytic decomposition for mixed propane-butane with reaction time of carbon black. 435
Figure 3-39. Arrhenius plot with the reaction temperature in catalytic decomposition of mixed propane-butane. 436
Figure 3-40. Effect of space velocity on the product distribution in the catalytic decomposition of propane-butane at 700 ℃. 437
Figure 3-41. TEM images of the carbon black catalysts. 440
Figure 3-42. Effect of temperature on the product distribution in the catalytic and thermal decomposition of LPG(1). 446
Figure 3-43. Effect of temperature on the product distribution in the catalytic and thermal decomposition of LPG(2). 447
Figure 3-44. Reactants decomposition with temperature in the thermal and catalytic decomposition of LPG. 448
Figure 3-45. Effect of reaction temperature for hydrogen production by PLG decomposition. 449
Figure 3-46. Hydrogen yield by the catalytic decomposition of LPG. 450
Figure 3-47. hydrogen production measured by mass spectrometer with respect to time in the thermal and catalytic decomposition of LPG. 451
Figure 3-48. Products Distribution by thermal and catalytic Decomposition of LPG at 1100 ℃. 452
Figure 3-49. Long-term test of LPG by carbon catalyst. 453
Figure 3-50. Effect of space velocity for LPG catalytic decomposition. 455
Figure 3-51. SEM images of the products carbon by thermal decomposition. 458
Figure 3-52. SEM images of the carbon black catalysts by catalytic decomposition. 459
Figure 3-53. TEM images of the carbon black catalysts. 461
Figure 3-54. Effect of hydrogen sulfide for methane catalytic decomposition. 465
Figure 3-55. EDX analysis of carbon black catalysts for hydrogen sulfide concentration in the methane decomposition. 466
Figure 3-56. Effect of hydrogen sulfide for propane catalytic decomposition. 467
Figure 3-57. Effect of hydrogen for methane catalytic decomposition. 471
Figure 3-58. Effect of carbon monoxide for methane catalytic decomposition. 472
Figure 3-59. Effect of carbon monoxide for propane catalytic decomposition. 473
Figure 4-1. XRD image of N330(P) blacks. 481
Figure 4-2. Pore distribution of N330(P) before and after reaction at 850℃, 1 Umf.(이미지참조) 482
Figure 4-3. Particle size distribution of N330(F) before and after reaction for 8 hr. 484
Figure 4-4. Pore distribution of N330(F) before and after reaction at 850℃, 4 Umf for 8 hr.(이미지참조) 485
Figure 4-5. SEM images of N330(F) before (a), and after reaction (b) at 850℃, 4Umf for 8 hr.(이미지참조) 486
Figure 4-6. Particle size distribution of HI-900L black 487
Figure 4-7. Pore distribution of HI-900L before and after reaction at 850 ℃, 1 Umf for 8 hr(이미지참조) 488
Figure 4-8. Summary of various properties of N330(F) and HI-900L black with methane decomposition. 489
Figure 4-9. SEM image of carbon nanofibers used as methane decomposition catalysts. 492
Figure 4-10. Methane conversion vs. time over different carbon catalysts. 493
Figure 4-11. SEM images of carbon nanofibers reacted at 900℃ for 5 hr. 496
Figure 4-12. Methane conversion vs. time over carbon nanofibers at different temperatures. 497
Figure 4-13. Conversion vs. time over N330 carbon black with different temperatures. 498
Figure 4-14. Methane conversion vs. time over carbon nanofibers without metal catalyst at 850℃ for 5 hr. 499
Figure 4-15. HR-TEM image of N330(F) after methane decomposition. 508
Figure 4-16. SEM images of (a) raw N330(F), (b) N330(F)-m with weight gain 9% and (c) N330(F)-p with weight gain 28% (×10,000). 509
Figure 4-17. SEM images of (a) raw N330(F), (b) N330(F)-m with weight gain 9% and (c) N330(F)-p with weight gain 28% (×300,000). 511
Figure 4-18. Mechanical properties of NBR rubber composites as a function of loading ratio (NBR filled by raw N330(F), N330(F)-m with weight gain 9% and... 513
Figure 4-19. Mechanical properties of NBR rubber composites as a function of loading ratio (NBR filled by raw N330(F), N330(F)-[m/p] with weight gain 5% and 15%). 515
Figure 4-20. Surface resistivity of NBR rubber composites versus loading ratio. 517
Figure 4-21. Mechanical properties of SBR rubber composites as a function of loading ratio(SBR filled by raw N330(F), N330(F)-m with weight gain 9% and N330(F)-p with weight gain 28%). 518
Figure 4-22. SEM images of raw N330(F) SBR composites with loading ratio (a) 20 phr and (b) 60 phr (×50,000). 520
Figure 4-23. SEM images of (a) raw N330(F), (b) N330(F)-B and (c) N330(F)-A (×10,000). 526
Figure 4-24. SEM images of (a) raw N330(F), (b) N330(F)-B and (c) N330(F)-A (×300,000). 528
Figure 4-25. Tensile strength and elongation versus loading ratio for composites filled by raw N330(F) and N330(F)-H. 530
Figure 4-26. Tensile strength and elongation versus loading ratio for composites filed by raw N330(F), N330(F)-B and N330(F)-A. 531
Figure 4-27. FT-IR graphs of N330(F) black before and after chemical modification. 532
Figure 4-28. SEM images of N330(F)-H black/SBR composites with loading ratio at (a) 20 phr and (b) 60 phr (×50,000). 533
Figure 4-39. Modulus at 300 % strain versus loading ratio of various carbon blacks. 534
Figure 4-30. Pore distribution of N330(F) before and after CO₂ activation at different conditions. 543
Figure 4-31. HR-TEM images of (a) N330(F)-CO₂-74% and (b) N330(F)-CO₂-57 % (×300,000) 544
Figure 4-32. SEM images of (a) raw N330(F) and (b) N330(F)-CO₂-74 % (×300,000) 545
Figure 4-33. ATR-FTIR spectra of N330(F) before and after CO₂ activation at different conditions. 546
Figure 4-34. Mechanical properties of SBR rubber composites as a function of loading ratio (SBR filled by raw N330(F) and N330(F)-CO₂... 547
Figure 4-35. Transmitted power density in EMI shielding as a function of frequency measured in the 0-6000 MHz range of (a) SBR rubber composites having activated carbon black with 74% yield at various... 548
Figure 4-36. Apparatus for measurement of resistivity. 553
Figure 4-37. SEM images of (a) raw N330(F), (b) N330(F)-HNO₃ and (c) N330(F)-NaOH (×100,000). 556
Figure 4-38. SEM images of (a) raw N330(F), (b) N330(F)-HNO₃ and (c) N330(F)-NaOH (×300,000). 557
Figure 4-39. ATR-FTIR spectra of N330(F) before and after chemical treatments. 558
Figure 4-40. SEM images of (a) raw N330(F), (b) N330(F)-800, and (c) N330(F)-1000, (d) N330(F)-1200 (×300,000). 561
Figure 4-41. ATR-FTIR spectra of N330(F) before and after heat treatments. 562
Figure 4-42. SEM images of (a) raw N330(F) and (b) N330(F)-CO₂-68% (×300,000). 565
Figure 4-43. ATR-FTIR spectra of N330(F) before and after CO₂ activation at different conditions. 566
Figure 4-44. EMI Shielding effectiveness of chemical treated carbon blacks filled PVA coating materials. 571
Figure 4-45. EMI Shielding effectiveness of heat treated carbon blacks filled PVA coating materials. 572
Figure 4-46. EMI Shielding effectiveness of carbon blacks filled PVA coating materials before and after CO₂ activation. 573
Figure 4-47. EMI Shielding effectiveness of chemical treated carbon blacks filled PVDF coating materials. 578
Figure 4-48. EMI Shielding effectiveness of heat treated carbon blacks filled PVDF coating materials. 579
Figure 4-49. EMI Shielding effectiveness of CO₂ activated carbon blacks filled PVDF coating materials. 580
Figure 4-50. EMI Shielding effectiveness of carbon blacks filled PVDF, PVP and PVDF/PVP mixtures coating materials. 583
Figure 5-1. 해석모델의 계산수행(node 수 15만개) 585
Figure 5-2. 반응기 유로 내부에서의 유동현상 시뮬레이션 결과 586
Figure 5-3. Double jacket external heating. 588
Figure 5-4. Pilot plant 반응기 내부 온도분포(CH₄ 입구-출구 중심부) 589
Figure 5-5. Pilot plant 압력분포(CH₄ 입구-출구 중심부) 590
Figure 5-6. Internal heating and external reheat. 593
Figure 5-7. Helical Type Fin을 적용한 고온 유동층 화학반응기의 시뮬레이션 결과 595
Figure 5-8. Helical Type Fin 방식 반응기의 온도분포(입구-출구 중심축) 596
Figure 5-9. Helical Type Fin 방식 반응기의 압력분포(입구-출구 중심축) 597
Figure 5-10. HRS 방식의 고온 유동층 화학반응기의 시뮬레이션 결과(온도,K) 599
Figure 5-11. 유동층 반응기 분산판 601
Figure 5-12. 반응기 내부유입 유량 및 압력 측정장치 602
Figure 5-13. 싸이클론 및 데이터 수집장치 603
Figure 5-14. 데이터 수집장치 604