Chemistry of Diesel Fuels

315 Pages·2000·22.505 MB·\315

by  Chunsham Song (Author)

Chemistry o f Diesel Fuels

Chemistry o f Diesel F uels
Edited by
Chunshan Song
Department of Energy & Geo-Environmental

Engineering and A pplied C atalysis in Energy L aboratory

Pennsylvania State U niversity

University P ark, P A 16802, U SA

Chang S . Hsu
Corporate Research

Exxon Mobil Research & Engineering C o.

Route 22 East, Clinton Township

Annandale, NJ 0880 I , U SA

Isao Mochida
Institute o f A dvanced M aterial Study

Kyushu University,

Kasuga, Fukuoka 816-0811, Japan
Published in 2000 b y
Taylor & Francis
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New York, NY 10001
Published in G reat B ritain b y
Taylor & Francis
11 New F etter L ane
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Copyright © 2 000 b y T aylor & Francis
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All rights reserved. No part of t his book may be reprinted or reproduced or
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publisher.
Library o f C ongress C ataloging-in-Publication D ata
Chemistry of d iesel fuels / edited b y Chunshan Song, Chang S. H su, and Isao
Mochida.
p. cm. - (Applied energy technology series)
Includes bibliographical references and index.
ISBN 1-56032-845-2 (alk. Paper)
1. Diesel fuels. I. S ong, Chunshan. II. Hsu, C hang S . III. Mochida, Isao. IV.
Series.
TP343.C54 2000
665S384-dc21
00-036429
Contents
Contributors Xli
Preface XVll
Section 1 . Introduction
Chapter 1 . Introduction t o C hemistry o f D iesel Fuels 1
Chunshan Song
1.0 Introduction 1
2.0 Features o f Diesel E ngines 3
3.0 Properties o f Diesel Fuels 7
3.1 Cetane Number a nd C etane I ndex 7
3.2. Heating V alue, Density a nd V iscosity 10
3.3. Boiling R ange, Volatility a nd F lash P oint 13
3.4. Low-Temperature Characteristics 14
3.5. Sulfur C ontent 15
3.6. Stability 16
3.7. Other P roperties 16
4.0 Composition o f Diesel F uels 17
4.1. Type o f Diesel F uels 17
4.2. Molecular C omponents of Diesel F uels 18
5.0 Production o f Cleaner D iesel Fuel 21
5.1. Feed S tocks a nd P rocesses 21
5.2. Deep Desulfurization 24
5.3. Deep D earomatization 29
5.4 Application o f Noble Metal C atalyst 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 I mprovers 36
7.0 Diesel Emissions and A ftertreatment 36
7.1 NOx a nd P articulate M atters 36
7.2 Hydrocarbons a nd CO 37
7.3 Effects of Fuel Processing 38
7.4 Ways to Reduce Emissions 39
8.0 Alternative Diesel F uels 41
8.1 Middle Distillates f rom Synthesis G as 41
8.2 Dimethyl E ther 42
8.3 Biodiesel 43
8.4 Compressed Natural Gas 43
v
8.5 Liquefied P etroleum G as 44
8.6 Fuels for H ybrid V ehicles 45
9.0 Conclusion 46
10.0 Acknowledgments 46
11.0 References 47
Section I I. Characterization o f Diesel F uels
Chapter 2 . Molecular C haracterization o f D iesel Fuels Using
Modern Analytical Techniques 61
C. S. Hsu, G. J . D echert, D. J. Abbott,
M. W Genowitz a nd 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 C omposition o f Diesel Fuels 63
3.2 Qualitative A nalysis b y G C/MS 64
3.3 Trace A nalysis of Diesel P olars 66
3.4 Quantitative A nalysis by C hromatography 68
3.5 Compound T ype A nalysis b y M ass S pectrometry 71
3.6 Quantification b y G CIMS 73
4.0 Conclusions 74
5.0 References 74
Chapter 3 . Rapid D etailed Analysis of Transportation F uels
by GC-FIMS 77
Ripudaman M alhotra, Michael J . Coggiola,
Steve E . Young, Charles A. S pindt, Chang S amuel H su,
Gary J . Dechert, Parviz M . Rahimi a nd Y evgenia Briker
1.0 Introduction 77
2.0 Instrument M odification 79
3.0 Results and Discussion 81
3.1 Total Ion C hromatograms 81
3.2 Z-Series A nalysis 84
3.3 Analysis o f Dibenzothiophenes 86
3.4 Analysis o fIndoles 88
4.0 Conclusions 91
5.0 Acknowledgment 91
6.0 References 91
vi
Section I II. Production o f Clean D iesel F uels
Chapter 4. Catalytic Cracking of C6-C16 Paraffins and
Cycloparaffins o ver a Mesoporous Z eolite -
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 A nalyses o fthe S olid P roducts 95
2.4 Preparation o fH-MCM-22 95
2.5 Measurement o f Catalytic A ctivity 95
3.0 Results 96
3.1 Characterization o f 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 U se of H ydrocracking P rocess T o P roduce H igh
Quality D iesel O il F rom B razil's H igh N itrogen
Feedstocks 107
Donizeti A urelio S ilva Belato. Maria Regina R ezende
Oddone and Raissa M aria Cotta Ferreira da Silva
1.0 Introduction 107
2.0 Experiment and M ethodology 107
2.1. Pilot P lant, Feestocks C haracteristics a nd T ests Methods 107
3.0 Results and D iscussions 108
3.1 First-Step T ests Results 108
3.1.1 Kinetic Models 110
3.2 Second-Step P roducts Y ields a nd Quality 113
4.0 Conclusions 120
5.0 Acknowledgment 121
6.0 References 121
Chapter 6 . HzS and A romatic E ffects o n H ydrodesulfurization
of Dibenzothiophenes o ver C oMo/C C atalyst 123
Hamdy F arag. Isao Mochida and K inya Sakanishi
1.0 Introduction 123
2.0 Experimental 124
2.1 Chemicals 124
vii
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 ofH2S Self-Produced on HDS ofDBT
126
3.2 Effect of Naphthalene on HDS ofDBT 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 137
Chapter 7 . Novel Mesoporous C o-MoIMCM-41 Catalysts
for Deep Hydrodesulfurization o f D iesel Fuels 139
Chunshan Song, K. Madhusudan Reddy, Heather L eta,
Muneyoshi Yamada and N aoto Koizumi
1.0 Introduction 139
2.0 Experimental 140
3.0 Results and Discussion 141
3.1 Estimation of Acidity by n-BA TPD 141
3.2 In situ FT-IR of NO on C o-Mo Catalyst 144
3.3 DBT H DS over C o-Mo/MCM-41 147
3.4 DBT HDS over C o-Mo/A1203 151
3.5 Comparison ofCo-MoIMCM-41 with Co-Mo/AJz03 151
3.6 4-MDBT H DS overCo-Mo/MCM-41 152
4.0 Conclusion 152
5.0 Acknowledgment 153
6.0 References 153
Chapter 8 . Performance o f M o C atalysts S upported o n
Ti02-Based B inary S upports f or Distillate Fuel
Hydroprocessing 157
G. MuraU Dhar, Mohan S. Rana, S. K. Maity,
B. N. Srinivas, and T . S. R. Prasada Rao
1.0 Introduction 157
1.1 Role of S upport in Catalytic Reactions 158
2.0 Support E ffects in Hydrotreating C atalysts 159
2.1 y-AJz03 Support 159
2.2 Other Supports 161
3.0 Ti-Containing M ixed Oxides as Supports for Mo and CoMo 164
3.1 TiOz-AIz03 System 164
Vlll
3.2 Mode of Active Phase F onnation a nd Catalytic Action 167
3.3 Promotional Effect 168
3.4 Variation of Mo L oading 169
3.5 Ti02-Zr02 M ixed O xide Supported M o Catalysts 171
3.6 Ti02-Si02 Mixed O xide Supported M o Catalysts 175
3.7 Comparison o f Three T i-Containing O xide Supports 176
4.0 Conclusions 180
5.0 Acknowledgment 181
6.0 References 181
Chapter 9 . Preparation o f Surfactants f rom a Product o f
Diesel Fuel Biodesulfurization 187
Elaine A . Lange a nd Q un Lin
1.0 Introduction 187
2.0 Methodology 191
2.1 Surfactant Synthesis 191
2.2 Analysis and C haracterization 192
3.0 Results and D iscussion 192
3.1 Interfacial Properties 192
3.2 Effect o f Calcium I ons 195
3.3 Foaming B ehavior 196
4.0 Conclusion 197
5.0 Acknowledgment 197
6.0 References 197
Section I V. Additives for Diesel Fuels
Chapter 1 0. Synthesis o f Low Nitrogen Cetane I mprovers
from the Nitration o f R enewable F eedstocks 199
Mark H . Mason, Christopher fan, Zhi Chen, Rajan
Aggarwal, Joseph A. H eppert, and G alen 1 . 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 R eduction
Chapter 1 1. The E ffect of Dimethoxy M ethane F uel Additive o n
Particle E missions from a Light D uty D iesel Vehicle 213
Richard E . Chase, M. Matti M aricq, Edward W. Kaiser,
Diane H . Podsiadlik, and W alter 0. Siegl
1.0 Introduction 213
IX