Contributors .................................................. xii
Preface ...................................................... xvii
Section I. Introduction
Chapter 1. Introduction to Chemistry of Diesel Fuels ............ 1
Chunshan Song
1.0 Introduction ............................................... 1
2.0 Features of Diesel Engines ................................. 3
3.0 Properties of Diesel Fuels ................................. 7
3.1 Cetane Number and Cetane Index ............................. 7
3.2 Heating Value, Density and Viscosity ...................... 10
3.3 Boiling Range,Volatility and Flash Point .................. 13
3.4 Low-Temperature Characteristics ........................... 14
3.5 Sulfur Content ............................................ 15
3.6 Stability ................................................. 16
3.7 Other Properties .......................................... 16
4.0 Composition of Diesel Fuels ............................... 17
4.1 Type of Diesel Fuels ...................................... 17
4.2 Molecular Components of Diesel Fuels ...................... 18
5.0 Production of Cleaner Diesel Fuel ......................... 21
5.1 Feed Stocks and Processes ................................. 21
5.2 Deep Desulfurization ...................................... 24
5.3 Deep Dearomatization ...................................... 29
5.4 Application of Noble Metal Catalyst ....................... 30
6.0 Diesel Fuel Additives ..................................... 32
6.1 Stabilizers ............................................... 33
6.2 Cold Flow Improvers ....................................... 33
6.3 Cetane Improvers .......................................... 34
6.4 Combustion Improvers ...................................... 36
7.0 Diesel Emissions and Aftertreatment ....................... 36
7.1 NOx and Particulate Matters ............................... 36
7.2 Hydrocarbons and CO ....................................... 37
7.3 Effects of Fuel Processing ................................ 38
7.4 Ways to Reduce Emissions .................................. 39
8.0 Alternative Diesel Fuels .................................. 41
8.1 Middle Distillates from Synthesis Gas ..................... 41
8.2 Dimethyl Ether ............................................ 42
8.3 Biodiesel ................................................. 43
8.4 Compressed Natural Gas .................................... 43
8.5 Liquefied Petroleum Gas ................................... 44
8.6 Fuels for Hybrid Vehicles ................................. 45
9.0 Conclusion ................................................ 46
10.0 Acknowledgments ........................................... 46
11.0 References ................................................ 47
Section II Characterization of Diesel Fuels
Chapter 2 Molecular Characterization of Diesel Fuels Using
Modern Analytical Techniques ........................ 61
C.S. Hsu, G.J. Dechert, D.J. Abbott, M.W. Genowitz
and R. Barbour
1.0 Introduction .............................................. 61
2.0 Experiment ................................................ 62
2.1 Materials ................................................. 62
2.2 Instrumentation ........................................... 62
3.0 Results and Discussion .................................... 63
3.1 Bulk Composition of Diesel Fuels .......................... 63
3.2 Qualitative Analysis by GC/MS ............................. 64
3.3 Trace Analysis of Diesel Polars ........................... 66
3.4 Quantitative Analysis by Chromatography ................... 68
3.5 Compound Type Analysis by Mass Spectrometry ............... 71
3.6 Quantification by GC/MS ................................... 73
4.0 Conclusions ................................................ 74
5.0 References ................................................ 74
Chapter 3 Rapid Detailed Analysis of Transportation Fuels
by GC-FIMS .......................................... 77
Ripudaman Malhotra, Michael J. Coggiola, Steve E.
Young, Charles A. Spindt, Chang Samuel Hsu, Gary
J. Dechert, Parviz M. Rahimi and Yevgenia Briker
1.0 Introduction .............................................. 77
2.0 Instrument Modification ................................... 79
3.0 Results and Discussion .................................... 81
3.1 Total Ion Chromatograms ................................... 81
3.2 Z-Series Analysis ......................................... 84
3.3 Analysis of Dibenzothiophenes ............................. 86
3.4 Analysis of Indoles ....................................... 88
4.0 Conclusions ............................................... 91
5.0 Acknowledgment ............................................ 91
6.0 References ................................................ 91
Section III. Production of Clean Diesel Fuels
Chapter 4. Catalytic Cracking of C6-C16 Paraffins and
Cycloparaffins over a Mesoporous Zeolite -
Unstacked H-MCM-22 .................................. 93
Isao Mochida, Teruyuki Nagayoshi, Seiichiro
Eguchi, Kinya Sakanishi, and D. Duayne Whitehurst
1.0 Introduction .............................................. 93
2.0 Experimental .............................................. 94
2.1 Materials ................................................. 94
2.2 Zeolite Synthesis ......................................... 94
2.3 Structural Analyses of the Solid Products ................. 95
2.4 Preparation of H-MCM-22 ................................... 95
2.5 Measurement of Catalytic Activity ......................... 95
3.0 Results ................................................... 96
3.1 Characterization of MCM-22 ................................ 96
3.2 Catalytic Activity of MCM-22 .............................. 99
4.0 Discussion ............................................... 103
5.0 Conclusions .............................................. 104
6.0 References ............................................... 105
Chapter 5. The Use of Hydrocracking Process To Produce High
Quality Diesel Oil From Brazil's High Nitrogen
Feedstocks ......................................... 107
Donizeti Aurelio Silva Belato, Maria Regina
Rezende Oddone and Raissa Maria Cotta Ferreira da
Silva
1.0 Introduction ............................................. 107
2.0 Experiment and Methodology ............................... 107
2.1 Pilot Plant, Feestocks Characteristics and Tests
Methods .................................................. 107
3.0 Results and Discussions .................................. 108
3.1 First-Step Tests Results ................................. 108
3.1.1 Kinetic Models .................................... 110
3.2 Second-Step Products Yields and Quality .................. 113
4.0 Conclusions .............................................. 120
5.0 Acknowledgment ........................................... 121
6.0 References ............................................... 121
Chapter 6. H2S and Aromatic Effects on Hydrodesulfurization
of Dibenzothiophenes over CoMo/C Catalyst ......... 123
Hamdy Farag, Isao Mochida and Kinya Sakanishi
1.0 Introduction ............................................. 123
2.0 Experimental ............................................. 124
2.1 Chemicals ................................................ 124
2.2 Catalyst Preparation ..................................... 124
2.3 Catalyst Sulfidation ..................................... 125
2.4 Catalytic Activity ....................................... 125
2.5 Analysis ................................................. 125
3.0 Results .................................................. 126
3.1 Effect of H2S Self-Produced on HDS of DBT ................ 126
3.2 Effect of Naphthalene on HDS of DBT ...................... 128
3.3 Effect of H2S Self-Produced on HDS of 4,6-DMDBT .......... 131
3.4 Effect of Naphthalene on HDS of 4,6-DMDBT ................ 133
4.0 Discussion ............................................... 136
5.0 Conclusions .............................................. 137
6.0 References ............................................... 131
Chapter 7. Novel Mesoporous Co-Mo/MCM-41 Catalysts for Deep
Hydrodesulfurization of Diesel Fuels .............. 139
Chunshan Song, K. Madhusudan Reddy, Heather Leta,
Muneyoshi Yamada and Naoto Koizumi
1.0 Introduction ............................................. 139
2.0 Experimental ............................................. 140
3.0 Results and Discussion ................................... 141
3.1 Estimation of Acidity by n-B A TPD ....................... 141
3.2 In situ FT-IRofNO on Co-Mo Catalyst ...................... 144
3.3 DBT HDS over Co-Mo/MCM-41 ................................ 147
3.4 DBT HDS over Co-Mo/Al2O3 ................................. 151
3.5 Comparison of Co-Mo/MCM-41 with Co-Mo/Al2O3 .............. 151
3.6 4-MDBT HDS over Co-Mo/MCM-41 ............................. 152
4.0 Conclusion ............................................... 152
5.0 Acknowledgment ........................................... 153
6.0 References ............................................... 153
Chapter 8. Performance of Mo Catalysts Supported on Ti02-
Based Binary Supports for Distillate Fuel
Hydroprocessing .................................... 157
G. Murali Dhar, Mohan S. Rana, S.K. Maity,
B.N. Srinivas, and T.S.R. Prasada Rao
1.0 Introduction ............................................. 157
1.1 Role of Support in Catalytic Reactions ................... 158
2.0 Support Effects in Hydrotreating Catalysts ............... 159
2.1 γ-Al2O3 Support .......................................... 159
2.2 Other Supports ........................................... 161
3.0 Ti-Containing Mixed Oxides as Supports for Mo and CoMo ... 164
3.1 TiO2-Al2O3 System ........................................ 164
3.2 Mode of Active Phase Formation and Catalytic Action ...... 167
3.3 Promotional Effect ....................................... 168
3.4 Variation of Mo Loading .................................. 169
3.5 TiO2-ZrO2 Mixed Oxide Supported Mo Catalysts ............. 171
3.6 TiO2-SiO2 Mixed Oxide Supported Mo Catalysts ............. 175
3.7 Comparison of Three Ti-Containing Oxide Supports ......... 176
4.0 Conclusions .............................................. 180
5.0 Acknowledgment ........................................... 181
6.0 References ............................................... 181
Chapter 9. Preparation of Surfactants from a Product of
Diesel Fuel Biodesulfurization ..................... 187
Elaine A. Lange and Qun Lin
1.0 Introduction ............................................. 187
2.0 Methodology .............................................. 191
2.1 Surfactant Synthesis ..................................... 191
2.2 Analysis and Characterization ............................ 192
3.0 Results and Discussion ................................... 192
3.1 Interfacial Properties ................................... 192
3.2 Effect of Calcium Ions ................................... 195
3.3 Foaming Behavior ......................................... 196
4.0 Conclusion ............................................... 197
5.0 Acknowledgment ........................................... 197
6.0 References ............................................... 197
Section IV. Additives for Diesel Fuels
Chapter 10. Synthesis of Low Nitrogen Cetane Improvers
from the Nitration of Renewable Feedstocks ........ 199
Mark H. Mason, Christopher Yan, Zhi Chen, Rajan
Aggarwal, Joseph A. Heppert, and Galen J. Suppes
1.0 Introduction ............................................. 199
2.0 Experimental ............................................. 201
3.0 Results and Discussion ................................... 204
4.0 Conclusion ............................................... 210
5.0 Acknowledgments .......................................... 211
6.0 References ............................................... 211
Section V. Emissions and Reduction
Chapter 11. The Effect of Dimethoxy Methane Fuel Additive
on Particle Emissions from a Light Duty Diesel
Vehicle ........................................... 213
Richard E. Chase, M. Matti Maricq, Edward
W. Kaiser, Diane H. Podsiadlik, and Walter
O. Siegl
1.0 Introduction ............................................. 213
2.0 Experiment ............................................... 214
3.0 Results and Discussion ................................... 215
3.1 Filter Measurement ....................................... 215
3.2 Gaseous Emissions ........................................ 217
3.3 Particle Size Measurements ............................... 217
4.0 Conclusion ............................................... 224
5.0 Acknowledgment ........................................... 225
6.0 References ............................................... 225
Chapter 12. The Role of Hydrocarbon Reductant in Metal
Loaded Zeolite DeNO, Catalysis .................... 227
Noline C. Clark, Jon A. Rau, Kevin C. Ott, and
Mark Т. Paffett
1.0 Introduction ............................................. 227
2.0 Experiment ............................................... 228
3.0 Results .................................................. 229
3.1 Cu/Zeolite ............................................... 229
3.2 Fe/Zeolite ............................................... 230
3.3 Co/Zeolite ............................................... 231
4.0 Discussion and Conclusions ............................... 233
5.0 Acknowledgment ........................................... 235
6.0 References ............................................... 236
Chapter 13. Distribution of PAHs in Burn Residue and Soot
Samples and Differentiation of Pyrogenic and
Petrogenic PAHs. The 1994 and 1997 Mobile Burn
Study ............................................. 237
Zhendi Wang, M. Fingas, M. Landriault,
L. Sigouin, and P. Lambert
1.0 Introduction ............................................. 237
2.0 Methodology .............................................. 239
2.1 Diesel, Bum Residue and Soot Samples ..................... 239
2.2 Sample Preparation ....................................... 239
2.3 Gas Chromatography/Mass Spectrometry Analysis ............ 240
3.0 Results and Discussion ................................... 241
3.1 Distribution of Target PAHs in Diesel and Burn Residue ... 241
3.2 PAH Fingerprints of Soot Samples ......................... 244
3.3 Determination of Destruction Efficiencies of Diesel
PAHs ..................................................... 248
3.4 Differentiation of Pyrogenic PAHs from Petrogenic PAHs ... 249
4.0 Conclusion ............................................... 251
5.0 References ............................................... 252
Chapter 14 The Use of Oxygenated Diesel Fuels for Reduction
of Particulate Emissions from a Single-Cylinder
Indirect Injection Engine .......................... 255
Howard S. Hess, Melissa A. Roan, Sumeet Bhalla,
Suchada Butnark, Vlad Zarnescu, André L. Boehman,
Peter J.A. Tijm and Francis J. Waller
1.0 Introduction ............................................. 255
2.0 Experiment ............................................... 256
3.0 Results and Discussion ................................... 259
4.0 Conclusion ............................................... 266
5.0 Acknowledgments .......................................... 267
6.0 References ............................................... 267
Chapter 15 Catalytic Activity of Alkali Metal Salts
Supported on Perovskite Type Oxide for
Carbonaceous Materials Combustion .................. 269
Isao Mochida, Tatsuro Miyazaki and Kinya
Sakanishi
1.0 Introduction ............................................. 269
2.0 Experimental ............................................. 270
2.1 Sample Preparation ....................................... 270
2.2 Combustion Equipment ..................................... 270
3.0 Results and Discussion ................................... 271
3.1 Carbon Conversion Catalyzed by K2CO3 Supported on
Several Supports ......................................... 271
3.2 Influences of Catalyst Amount to Carbon on the
Combustion ............................................... 273
3.3 Elution of Active Species ................................ 274
3.4 Range for Catalyst Travel ................................ 274
3.5 Influential Factors on the Catalytic Activity ............ 276
3.6 Catalytic Activities of Potassium Sulfate and Chloride
Supported on LSCMP ....................................... 276
3.7 Decomposition of KCl and K2SO4 on LSCMP .................. 277
3.8 Analysis of Potassium Salts before and after
Combustion ............................................... 278
3.9 Reactivities of Several Carbonaceous Materials ........... 279
4.0 Conclusions .............................................. 287
5.0 References ............................................... 288
Author Index .................................................. 289
Subject Index ................................................. 290
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