표제지
제출문
보고서 초록
요약문
SUMMARY
CONTENTS
목차
제1장 연구개발과제의 개요 48
제1절 연구개발의 목적 49
제2절 연구개발의 필요성 51
1. 기술 개발의 중요성·필요성 51
2. 폐 촉매 재생의 필요성 54
3. 촉매의 비활성화 요인 55
가. 촉매 fouling 55
나. 촉매 poisoning 56
다. 촉매의 thermal degradation 57
제3절 연구의 목표 및 내용 58
1. 최종목표 58
2. 연차별 주요 사업 내용 및 범위 58
제2장 국내외 기술개발 현황 59
제1절 국내외 기술 개발 60
1. 국외 관련기술의 현황 60
2. 국내 관련기술의 현황 60
3. 국내외 유사기술과의 차별성 61
제3장 연구개발수행 내용 및 결과 62
제1절 실험 63
1. 실험재료 및 방법 63
2. 실험 장치 및 방법 77
3. 촉매 특성조사 79
제2절 산업용 폐 촉매 81
1. Blank 실험 84
2. 귀금속 계열 폐 촉매 결과 85
가. Pd계 폐 촉매 85
(1) Pd-S 폐 촉매 91
(가) 산용액 전처리 영향 91
(나) 가스 전처리 영향 92
① 공기 전처리 영향 92
② 수소 전처리 영향 99
(다) XPS 104
(2) Pd-N-0.30 촉매 111
(가) 가스 전처리 영향 111
① 공기 전처리 영향 111
② 수소 전처리 영향 115
(나) XPS 120
나. Pt계 폐 촉매 131
(1) Pt-F 폐 촉매 131
(가) 산용액 전처리 영향 131
(나) 가스 전처리 영향 136
① 공기 전처리 영향 136
② 수소 전처리 영향 140
(2) Pt-S 폐 촉매 145
(가) 산용액 전처리 영향 145
(나) 가스 전처리 영향 145
(3) Pt-C 폐 촉매 151
(가) 가스 및 화학 전처리 영향 151
다. 벤젠, 톨루엔 그리고 자일렌의 반응성 비교 및 폐 촉매 혼합에 따른 VOCs 활성 157
3. 금속 산화물계 폐 촉매 163
가. ZnO-CuO 폐 촉매 167
(1) 가스 및 화학적 전처리 영향 167
나. NiO 폐 촉매 172
(1) 가스 및 화학적 전처리 영향 172
다. Ni-Mo-LD 및 Co-Mo-S 폐 촉매 178
(1) 가스 및 화학적 전처리 영향 178
라. Fe2₂O₃ 폐 촉매 183
(1) 가스 및 화학적 전처리 영향 183
마. Cu 폐 촉매 188
(1) 산용액 전처리 영향 188
(2) 가스 전처리 영향 194
바. 최적 전처리 조건 및 벤젠, 톨루엔 그리고 자일렌의 반응성 비교 202
4. 기타. 206
5. 결론 209
제3절 배기가스 정화용 폐 자동차 촉매 211
1. 폐 자동차 촉매 (H-S-13) 211
가. H-S-13 촉매의 물리화학적 특성 211
나. H-S-13 촉매의 전화율 실험 222
(1) 산수용액 전처리 영향 224
(2) 가스 전처리 영향 242
(가) 수소 및 공기 전처리 242
(3) 염기 수용액 및 세정액 전처리 252
다. 전처리 농도, 교반시간, 톨루엔 농도, 그리고 충진량에 따른 H-S-13 촉매의 활성 변화 258
라. 벤젠, 톨루엔 그리고 자일렌의 반응성 비교 263
마. 반응시간 266
바. 혼합효과 266
2. 배기가스 정화용 폐 자동차 촉매 (K-S-12, K-S-16, K-S-18) 271
가. K-S-12, K-S-16 그리고 K-S-18 촉매의 물리화학적 특성 271
나. K-S-12, K-S-16과 K-S-18의 촉매 전화율 실험 281
(1) 산수용액 전처리 영향 287
(가) K-S-12 촉매 287
(나) K-S-16 촉매 296
(다) K-S-18 촉매 304
다. 벤젠, 톨루엔 그리고 자일렌의 반응성 비교 311
3. 배기가스 정화용 폐 자동차 촉매 (K-P-20, K-C-28) 315
가. K-P-20과 K-C-28의 물리화학적 특성 315
나. K-C-20 과 K-P-28 촉매 전화율 실험 318
(1) 산수용액 전처리 영향 322
다. 벤젠, 톨루엔 그리고 자일렌의 반응성 비교 330
4. 기타 333
5. 결론 336
제4절 소규모 VOCs 발생원을 위한 소형 VOCs 처리장치 개발 338
1. 소형 VOCs 시스템 제작 338
2. 산업현장에서 발생하는 폐 촉매를 최적 재생기술로 처리 한 재생촉매를 이용한 소형 VOCs 처리장치 효율 조사 347
가. 귀금속 계열 폐 촉매 347
나. 금속산화물 계열 폐 촉매 348
3. 폐 자동차에서 발생하는 배출가스 정화용 폐 촉매의 최적 재생기술 및 재생촉매를 이용한 소형 VOCs 처리장치 효율 조사 357
4. 소형 VOCs 처리장치의 현장 적용을 위한 파일럿 테스트 360
5. 결론 366
제4장 목표 달성도 및 관련분야에의 기여도 367
제1절 목표 달성도 368
제2절 관련분야에의 기여도 369
제5장 연구개발결과의 활용계획 372
제6장 연구개발과정에서 수집한 해외과학기술정보 374
제7장 참고문헌 376
Table 1.1./2.1. Effect of VOCs 51
Table 1.2./2.2. Classification of VOCs control technologies 52
Table 1.3./2.3. General characteristics of control technologies 53
Table 3.1. The basic properties of the spent catalysts 65
Table 3.2. The basic properties of the spent TWC catalysts 66
Table 3.3. Physicochemical properties of toluene, benzene, and o-xylene 76
Table 3.4. BET specific surface area of the spent catalysts 82
Table 3.5. ICP analysis of the spent catalysts 83
Table 3.6. BET surface area of the acid-treated Pd-S catalysts 95
Table 3.7. BET surface area of the air-treated spent catalyst 98
Table 3.8. BET surface area of the hydrogen-treated Pd-S catalyst 102
Table 3.9. Binding energies (BEs) of the Pd 3d5/2(이미지참조) (eV) for Pd-S, air, and hydrogen-treated catalysts 108
Table 3.10. BET surface area of air-treated Pd-N-0.30 catalyst 114
Table 3.11. BET surface area of hydrogen-treated Pd-N-0.30 catalyst 118
Table 3.12. Binding energies (BEs) of the Pd 3d5/2(이미지참조) (eV) for Pd-N-0.30, air, and hydrogen treated catalysts 124
Table 3.13. Binding energies (BEs) of the Pd 3d5/2(이미지참조) (eV) of the Pd-N-0.30 129
Table 3.14. BET surface area of the acid treated Pt-F catalysts 135
Table 3.15. BET surface area of the air-treated Pt-F catalysts 139
Table 3.16. BET surface area of the hydrogen-treated Pt-F catalyst 143
Table 3.17. BET surface area of acid treated spent catalysts 148
Table 3.18. BET surface area of the physicochemical treated Pt-C catalyst 154
Table 3.19. Comparison of BTX conversion over the spent noble catalysts. 159
Table 3.20. BET surface area of the different spent transition metal catalysts. 165
Table 3.21. BET surface area of the physicochemical treated ZnO-CuO catalysts 171
Table 3.22. BET surface area of the physicochemical-treated NiO-10 catalyst 177
Table 3.23. BET surface area of Ni-Mo-LD and Co-Mo-S catalysts 182
Table 3.24. BET surface area of the physicochemical-treated Fe₂O₃ catalysts 184
Table 3.25. BET surface area and ICP analysis of the chemical-treated Cu catalysts 191
Table 3.26. BET surface area of the gas-treated Cu-F catalysts 198
Table 3.27. Binding energies of the Cu 2p for the spent Cu catalysts 201
Table 3.28. Comparison of BTX conversion over spent transition metal catalysts 205
Table 3.29. Basic properties of spent three-way automotive exhaust catalyst (H-S-13). 220
Table 3.30. Atom ratios of H-S-13 catalyst on ICP analyses 221
Table 3.31. pKa values of acid aqueous solutions 225
Table 3.32. Basic properties of the acid aqueous solution pretreated H-S-13 catalyst 233
Table 3.33. Atom ratios of acid aqueous solution pretreated H-S-13-F on ICP analyses 238
Table 3.34. Atom ratios of acid aqueous solution pretreated H-S-13-F on ICP analyses 239
Table 3.35. Basic properties of hydrogen pretreated H-S-13-F catalyst 245
Table 3.36. Basic properties of air pretreated H-S-13-F catalyst 247
Table 3.37. Basic properties of the basic aqueous solution and hexane pretreated H-S-13-F catalyst 254
Table 3.38. Comparison of BTX conversion over H-S-13-F catalyst. 265
Table 3.39. Basic properties of the K-S-12, K-S-16 and K-S-18 catalysts 274
Table 3.40. Atom ratios of K-S-12-F, K-S-16-F and K-S-18-F on ICP analyses 276
Table 3.41. Atom ratios of K-S-12-R, K-S-16-R and K-S-18-R on ICP analyses 277
Table 3.42. Basic properties of the acid aqueous solution pretreated K-S-12 catalysts 289
Table 3.43. Atom ratios of acid aqueous solution pretreated K-S-12-F on ICP analyses 292
Table 3.44. Atom ratios of acid aqueous solution pretreated K-S-12-F on ICP analyses 293
Table 3.45. Basic properties of the acid aqueous solution pretreated K-S-16 catalysts 298
Table 3.46. Atom ratios of acid aqueous solution pretreated K-S-16-F on ICP analyses 300
Table 3.47. Atom ratios of acid aqueous solution pretreated K-S-16-F on ICP analyses 301
Table 3.48. Basic properties of the acid aqueous solution pretreated K-S-18 catalyst 306
Table 3.49. Atom ratios of acid aqueous solution pretreated K-S-18-F on ICP analyses 308
Table 3.50. Atom ratios of acid aqueous solution pretreated K-S-18-F on ICP analyses 309
Table 3.51. Comparison of BTX conversion over K-S-12, K-S-16 and K-S-18 catalysts 313
Table 3.52. Basic properties of K-P-20 and K-C-28 catalysts 316
Table 3.53. Atom ratios of K-C-20 and K-P-28 catalysts on ICP analyses 319
Table 3.54. Basic properties of the acid aqueous solution pretreated K-P-20 326
Table 3.55. Basic properties of the acid aqueous solution pretreated K-C-28 327
Table 3.56. Comparison of BTX conversion over K-P-20 and K-C-28 catalysts 331
Table 3.57. Comparison of BTX conversion over the pretreated spent noble catalysts 353
Table 3.58. Comparison of BTX conversion over the pretreated transition metal catalysts 356
Table 3.59. Comparison of BTX conversion over the sulphuric acid aqueous treated H-S catalyst 359
Table 5.1./4.1. Emitted amount of VOCs in Korea. 372
Fig. 1.1./2.1. Automotive catalyst structural design including honeycomb support and mounting can [18]. 54
Fig. 3.1. Photographs of the spent catalysts.... 67
Fig. 3.2. Photographs of the spent catalysts.... 68
Fig. 3.3. Photographs of the spent catalysts.... 69
Fig. 3.4. Photographs of the spent catalysts.... 70
Fig. 3.5. Photographs of spent three-way automotive exhaust catalyst (H-S-13). 71
Fig. 3.6. Photographs of spent three-way automotive exhaust catalysts (K-S-12, K-S-16, and K-S-18). 72
Fig. 3.7. Photographs of spent three-way automotive exhaust catalyst (K-P-20). 73
Fig. 3.8. Photographs of spent three-way automotive exhaust catalyst (K-C-28). 74
Fig. 3.9. Photographs of spent three-way automotive exhaust catalyst for experimental study. 75
Fig. 3.10. Experimental apparatus for the catalytic oxidation of VOCs. 78
Fig. 3.11. TPR/TPO apparatus used in this study. 80
Fig. 3.12. Toluene conversion without catalyst as a function of reaction temperature.... 84
Fig. 3.13. Toluene conversion over the Pd-based catalysts as a function of reaction temperature. 87
Fig. 3.14. Toluene conversion as a function of temperature at the different loading of Pd 88
Fig. 3.15. Toluene conversion as a function of temperature at the different packing weights over the Pd-N-0.30 catalyst. 89
Fig. 3.16. Toluene conversion as a function of temperature at the different concentrations over the Pd-N-0.30 catalyst. 90
Fig. 3.17. Toluene conversion as a function of reaction temperature over the acid-treated Pd-S catalyst. 93
Fig. 3.18. XRD patterns measured for the acid-treated Pd-S catalyst. 94
Fig. 3.19. Toluene conversion as a function of reaction temperature over the air-treated Pd-1 catalyst. 96
Fig. 3.20. XRD patterns measured for the air-treated Pd-S catalyst. 97
Fig. 3.21. Toluene conversion as a function of reaction temperature over the hydrogen-treated Pd-S catalyst. 100
Fig. 3.22. XRD patterns measured for the hydrogen-treated Pd-S catalyst 101
Fig. 3.23. Toluene conversion as a function of temperature over the physicochemical-treated Pd-S catalyst. 103
Fig. 3.24. XPS spectra of the Pd-S catalyst:... 105
Fig. 3.25. XPS spectra of the hydrogen-treated Pd-S catalyst:... 106
Fig. 3.26. XPS spectra of the hydrogen-treated Pd-S catalyst after toluene oxidation 107
Fig. 3.27. TEM photographs of the air-treated Pd-S catalyst. 109
Fig. 3.28. TEM photographs of the hydrogen-treated Pd-S catalyst. 110
Fig. 3.29. Toluene conversion as a function of temperature over the air-treated Pd-N-0.30 catalyst. 112
Fig. 3.30. XRD patterns measured for the air-treated Pd-N-0.30 catalyst 113
Fig. 3.31. Toluene conversion as a function of temperature over the hydrogen-treated Pd-N-0.30 catalyst. 116
Fig. 3.32. XRD patterns measured for the hydrogen-treated Pd-N-0.30 catalyst 117
Fig. 3.33. Toluene conversion as a function of temperature over the physicochemical treated Pd-N-0.30 catalyst. 119
Fig. 3.34. XPS spectra of the Pd-N-0.30 catalyst:... 121
Fig. 3.35. XPS spectra of the hydrogen-treated Pd-N-0.30 catalyst:... 122
Fig. 3.36. XPS spectra of the hydrogen-treated Pd-N-0.30 catalyst after toluene oxidation 123
Fig. 3.37. TEM Photographs of the air-treated Pd-N-0.30 catalyst. 126
Fig. 3.38. TEM Photographs of the hydrogen-treated Pd-N-0.30 catalyst. 127
Fig. 3.39. Toluene conversion as a function of time over the Pd-N-0.30 catalyst. 128
Fig. 3.40. TPR profiles of the gas-treated Pd-N-0.30 catalyst. 130
Fig. 3.41. Toluene conversion as a function of reaction temperature over Pt-based catalysts. 132
Fig. 3.42. Toluene conversion as a function of temperature over the acid-treated Pt-F catalyst. 133
Fig. 3.43. XRD patterns measured for the acid-treated Pt-F catalyst 134
Fig. 3.44. Toluene conversion as a function of temperature over the air-treated Pt-F catalyst. 137
Fig. 3.45. XRD patterns measured for air pre-treated Pt-F catalyst. 138
Fig. 3.46. Toluene conversion as a function of temperature over hydrogen-treated Pt-F catalyst. 141
Fig. 3.47. XRD patterns measured for the hydrogen-treated Pt-F catalyst 142
Fig. 3.48. Toluene conversion as a function of temperature over the physico-chemical treated Pt-F catalyst. 144
Fig. 3.49. Toluene conversion as a function of temperature over the acid-treated Pt-S catalyst. 146
Fig. 3.50. XRD patterns measured for the acid treated Pt-S catalyst. 147
Fig. 3.51. Toluene conversion as a function of temperature over the physicochemical-treated Pt-S catalyst. 149
Fig. 3.52. XRD patterns measured for the gas-treated Pt-S catalyst. 150
Fig. 3.53. Toluene conversion as a function of temperature over the different physicochemical treated Pt-C catalyst. 152
Fig. 3.54. XRD patterns measured for the physicochemical-treated Pt-C catalyst 153
Fig. 3.55. SEM photographs of the physicochemical-treated Pt-C catalyst. 155
Fig. 3.56. TEM photographs of the physicochemical-treated Pt-C catalyst. 156
Fig. 3.57. BTX conversion as a function of temperature over the Pd-S and Pd-N-0.30 catalysts. 160
Fig. 3.58. BTX conversion as a function of temperature over the Pt-F, Pt-S and Pt-C catalysts. 161
Fig. 3.59. Toluene conversion as a function of temperature over the Pt-F, Pt-S/Pd-S, and Pt-C catalysts. 162
Fig. 3.60. Toluene conversion as a function of temperature over the different spent transition metal catalysts. 164
Fig. 3.61. TPR profiles of the different spent transition metal catalysts. 166
Fig. 3.62. Toluene conversion as a function of temperature over the gas-treated ZnO-CuO catalysts. 168
Fig. 3.63. Toluene conversion as a function of temperature over the chemical-treated ZnO-CuO catalysts. 169
Fig. 3.64. XRD peaks measured for the chemical treated ZnO-CuO catalysts 170
Fig. 3.65. Toluene conversion as a function of temperature over the NiO catalysts 173
Fig. 3.66. Toluene conversion as a function of temperature over the gas-treated NiO-10 catalysts. 174
Fig. 3.67. Toluene conversion as a function of temperature over chemical-treated NiO-10 catalysts. 175
Fig. 3.68. XRD patterns measured for the chemical-treated NiO-10 catalysts 176
Fig. 3.69. Toluene conversion as a function of temperature over physico-chemical treated Ni-Mo-LD and Co-Mo-S catalysts. 179
Fig. 3.70. XRD patterns measured for the physicochemical-treated Ni-Mo-LD and Co-Mo-S catalysts. 180
Fig. 3.71. SEM photos of the Ni-Mo-LD and Co-Mo-S catalysts. 181
Fig. 3.72. Toluene conversion as a function of temperature over the physicochemical treated Fe₂0₃ catalysts. 185
Fig. 3.73. XRD patterns measured for the acid, base, and hexane treated Fe₂O₃ catalyst 186
Fig. 3.74. TPR profiles of the chemical-treated Fe₂O₃ catalyst. 187
Fig. 3.75. Toluene conversion as a function of temperature over the acid and hexane treated Cu catalysts. 189
Fig. 3.76. XRD patterns measured for the acid and hexane treated Cu catalysts 190
Fig. 3.77. SEM photos of the parent, hexane and HNO₃ treated catalyst. 192
Fig. 3.78. TPR profiles of the chemical-treated Cu catalysts. 193
Fig. 3.79. Toluene conversion as a function of reaction temperature over the air-treated Cu catalysts (top) and XRD patterns measured for the same catalysts. 196
Fig. 3.80. Toluene conversion as a function of reaction temperature over the hydrogen-treated Cu catalysts (top) and XRD patterns measured for the same catalysts. 197
Fig. 3.81. H₂-TPR profiles of the hydrogen-treated Cu spent catalyst. 199
Fig. 3.82. XPS spectra of Cu 2p of the spent Cu catalyst. 200
Fig. 3.83. BTX conversion as a function of reaction temperature over the ZnO-CuO, NiO-10, and Ni-Mo-LD catalysts. 203
Fig. 3.84. BTX conversion as a function of reaction temperature over the Co-Mo-S, Fe₂O₃, and Cu-F catalysts. 204
Fig. 3.85. Adsorption equilibrium isotherms of benzene on SWCNT. 207
Fig. 3.86. Adsorption equilibrium isotherms of toluene on MCM-48. 208
Fig. 3.87. SEM images of the H-S-13 catalyst. 214
Fig. 3.88. SEM images of the H-S-13 catalyst. 215
Fig. 3.89. XRD pattern of the H-S-13 catalyst... 216
Fig. 3.90. TEM image of the H-S-13 catalyst. 217
Fig. 3.91. Nitrogen adsorption-desorption isotherms of H-S-13 catalyst at 77 K 218
Fig. 3.92. Pore size distributions determined by BJH method. 219
Fig. 3.93. Toluene conversion over H-S-13 catalyst as a function of reaction temperature. (Reaction condition: toluene concentration=1000 ppm, total flow rate=100 cc/min) 223
Fig. 3.94. Toluene conversion over seven different acid aqueous solution pretreated H-S-13-F as a function of reaction temperature. (Reaction condition: toluene concentration=1000 ppm, total flow rate=100 cc/min) 226
Fig. 3.95. Toluene conversion over seven different acid aqueous solution pretreated H-S-13-R as a function of reaction temperature. (Reaction condition: toluene concentration=1000 ppm, total flow rate=100 cc/min) 227
Fig. 3.96. XRD patterns measured for acid aqueous solution pretreated H-S-13-R (a Parent, b:HNO₃, c: H₂SO₄, d: CH₃COOH, e: H₃PO₄, f: HCI, g: C₂H₂O₄, h: C6H8O7(이미지참조), ○ 2MgO·2Al₂O·5SiO₂). 228
Fig. 3.97. TEM images of acid aqueous solution pretreated H-S-13-F catalyst. 234
Fig. 3.98. TEM images of acid aqueous solution pretreated H-S-13-F catalyst. 235
Fig. 3.99. TEM images of acid aqueous solution pretreated H-S-13-F catalyst. 236
Fig. 3.100. TEM images of acid aqueous solution pretreated H-S-13-F and H-S-13-F catalysts. 237
Fig. 3.101. Relative contaminant (top) and precious (bottom) metals atom ratios for parent (H-S-13-F) catalyst. 240
Fig. 3.102. TPR (top) and TPO (bottom) profiles of acid aqueous solution pretreated H-S-13-F and H-S-13-F catalysts. 241
Fig. 3.103. Toluene conversion as a function of temperature over hydrogen pretreated H-S-13-F catalyst. 244
Fig. 3.104. Toluene conversion as a function of temperature over air pretreated H-S-13-F catalyst. 246
Fig. 3.105. TEM images of hydrogen pretreated H-S-13-F catalyst. 248
Fig. 3.106. TEM images of hydrogen Pretreated H-S-13-F catalyst. 249
Fig. 3.107. TPR (top) and TPO (bottom) profiles of hydrogen pretreated H-S-13-F and H-S-13-F catalysts. 250
Fig. 3.108. TPR (top) and TPO (bottom) profiles of air pretreated H-S-13-F and H-S-13-F catalyst. 251
Fig. 3.109. Toluene conversion as a function of temperature over the basic aqueous solution and hexane pretreated H-S-13-F catalyst. 255
Fig. 3.110. XRD patterns measured for basic aqueous solution and hexane pretreated H-S-13-F catalyst... 256
Fig. 3.111. TPR (top) and TPO (bottom) profiles of basic aqueous solution and hexane Pretreated H-S-13-F and H-S-13-F catalyst. 257
Fig. 3.112. Comparison plot of toluene conversion over the acid aqueous solution, gas and acid aqueous solution + gas pretreated H-S-13-F catalyst. 260
Fig. 3.113. Effect of acid aqueous concentrations (a; H₂S0₄, b; CH₃COOH) and stirring time (c) on the toluene conversion. 261
Fig. 3.114. Effect of different loading amounts (top) and different inlet concentrations (bottom) on the toluene conversion. 262
Fig. 3.115. BTX conversion as a function of temperature over sulfuric acid aqueous solution pretreated H-S-13-F catalyst. 264
Fig. 3.116. Stability test of oxalic acid aqueous solution pretreated H-S-13-R catalyst for toluene oxidation. (Reaction condition: toluene concentration = 1000 ppm, total flow rate = 100 cc/min) 268
Fig. 3.117. Comparison of toluene oxidation for H-S-13-F, Pd, Pd/H-S-13-F and H-S-13-F/Pd catalysts. 269
Fig. 3.118. Comparison of toluene oxidation for H-S-13-F, Pt, Pt/H-S-13-F and H-S-13-F/Pt catalysts. 270
Fig. 3.119. XRD patterns for K-S-12, K-S-16, and K-S-18 catalysts (△ 2MgO·2Al₂O₃·5Si0₂). 275
Fig. 3.120. Relative ratios of Pb, S, P, Zn, Ca, Fe, Ni, Cu, and Cr remained over K-S-12 catalyst. 278
Fig. 3.121. Difference ratios of Pb, S, P, Zn, Ca, Fe, Ni, Cu, and Cr between front (F) and rear (R) parts. 279
Fig. 3.122. Relative ratios of Ce, Mg, Zr and Ba over K-S-12 catalyst (top) and Pt and Rh remained over K-S-12, K-S-16 and K-S-18 catalysts (bottom). 280
Fig. 3.123. Toluene conversion over K-S-12, K-S-16 and K-S-18 catalysts as a function of reaction temperature. (Reaction condition: toluene concentration=1000 ppm, total flow rate=100 cc/min) 283
Fig. 3.124. Toluene conversion over K-S-12, K-S-16 and K-S-18 catalysts as a function of reaction temperature. (Reaction condition: toluene concentration=1000 ppm, total flow rate=100 cc/min) 284
Fig. 3.125. TPR profiles of K-S-12, K-S-16 and K-S-18 catalysts. 285
Fig. 3.126. TPO profiles of K-S-12, K-S-16 and K-S-18 catalysts. 286
Fig. 3.127. Toluene conversion over seven different acid aqueous solution pretreated K-S-12 catalyst as a function of reaction temperature. (Reaction condition: toluene concentration=1000 ppm, total flow rate=100 cc/min) 291
Fig. 3.128. Relative precious atom ratios for parent (K-S-12-F) catalyst. 294
Fig. 3.129. Relative contaminant atom ratios for parent (K-S-12-F) catalyst. 295
Fig. 3.130. Toluene conversion over seven different acid aqueous solution pretreated K-S-16 catalyst as a function of reaction temperature. (Reaction condition: toluene concentration=1000 ppm, total flow rate=100 cc/min) 299
Fig. 3.131. Relative precious atom ratios for parent (K-S-16-F) catalyst. 302
Fig. 3.132. Relative contaminant atom ratios for parent (K-S-16-F) catalyst. 303
Fig. 3.133. Toluene conversion over seven different acid aqueous solution pretreated K-S-18 as a function of reaction temperature. (Reaction condition: toluene concentration=1000 ppm, total flow rate=100 cc/min) 307
Fig. 3.134. Relative precious (top) and contaminant atom (bottom) ratios for parent (K-S-18-F) catalyst. 310
Fig. 3.135. BTX conversion as a function of temperature over oxalic and sulfuric acid aqueous solution pretreated catalysts. 314
Fig. 3.136. XRD patterns of K-P-20 (top) and K-C-28 (bottom) catalysts (△ 2MgO·2Al₂O₃·5Si0₂). 317
Fig. 3.137. Relative precious (top) and contaminant atom (bottom) ratios for K-P-20 and K-C-28 catalysts. 320
Fig. 3.138. Toluene conversion over K-P-20 and K-C-28 catalysts as a function of reaction temperature. (Reaction condition: toluene concentration=1000 ppm, total flow rate=100 cc/min) 321
Fig. 3.139. Toluene conversion over seven different acid aqueous solution pretreated K-P-20 as a function of reaction temperature. (Reaction condition: toluene concentration=1000 ppm, total flow rate=100 cc/min) 324
Fig. 3.140. Toluene conversion over seven different acid aqueous solution pretreated K-C-28 as a function of reaction temperature. (Reaction condition: toluene concentration=1000 ppm, total flow rate=100 cc/min) 325
Fig. 3.141. Relative precious (top) and contaminant atom (bottom) ratios for parent (K-P-20-F) catalyst. 328
Fig. 3.142. Relative precious (top) and contaminant atom (bottom) ratios for parent (K-C-28-F) catalyst. 329
Fig. 3.143. BTX conversion as a function of temperature over oxalic and nitric acid aqueous solution pretreated K-P-20-F and K-C-28-F catalysts. 332
Fig. 3.144. Adsorption equilibrium isotherms (top) and adsorption energy distribution curves (bottom) of toluene on different pre-treated Pd-0.3. 334
Fig. 3.145. Adsorption equilibrium isotherms of benzene, toluene and xylene on DWCNT. 335
Fig. 3.146. Schematic diagram of VOC hydrid system. 341
Fig. 3.147. Schematic diagram of control panel. 342
Fig. 3.148. Detailed view of VOC hydrid system and control panel. 343
Fig. 3.149. View of main control monitor. 344
Fig. 3.150. Detailed view of main control monitor. 345
Fig. 3.151. A picture of small scale pilot type catalytic oxidation unit. 346
Fig. 3.152. Photographs of the spent catalysts... 350
Fig. 3.153. BTX conversion as a function of temperature over the hydrogen treated Pd-S catalyst. 351
Fig. 3.154. BTX conversion as a function of temperature over the hydrogen treated Pt-F catalyst. 352
Fig. 3.155. BTX conversion as a function of temperature over the nitric acid aqueous treated Fe₂O₃ catalyst. 354
Fig. 3.156. BTX conversion as a function of temperature over the hydrogen treated Cu-F catalyst. 355
Fig. 3.157. BTX conversion as a function of temperature over the sulphuric acid aqueous treated H-S catalyst. 358
Fig. 3.158. Calibration curves for the commercial application. 362
Fig. 3.159. Influence of total flow rate on BTX conversion over the sulphuric acid aqueous treated H-S catalyst. 363
Fig. 3.160. Influence of inlet concentrations on BTX conversion over the sulphuric acid aqueous treated H-S catalyst. 364
Fig. 3.161. Stability test of the sulphuric acid aqueous treated H-S catalyst of VOCs oxidation. 365