High-Energy-Density Fuels for Advanced Propulsion

Ji-Jun Zou, PhD, is the Department Head of Chemical Technology and Chair Professor at the School of Chemical Engineering and Technology in Tianjin University, China. He has received several awards including Technological Leading Scholar of 10000 Talent project (2017), and Changjiang Young Scholar by the Ministry of Education (2016). An Associate Editor of RSC Advances, he has also authored or coauthored more than 150 papers and 30 patents. Xiangwen Zhang, PhD, is the Director of Key Laboratory of advanced fuel and chemical propellant of Ministry of Education. His research interests include fuel processing technology and reaction engineering. He has authored/coauthored more than 300 papers and 30 patents. Lun Pan, PhD, is an Associate Professor whose research interests focus on the design and synthesis of functional photocatalysts; their related modulation of morphology, facets, and surface defects; and their applications in photocatalysis, such as in photocatalytic isomerization for synthesis of advanced fuels. He has published more than 50 papers and 20 patents.

• Preface xiiiAbout the Authors xvAcknowledgments xvii1 Introduction 1Ji‐Jun ZouReference 32 Development History and Basics of Aerospace Fuels 5Xiangwen Zhang and Tinghao Jia2.1 Introduction 52.2 General Properties and Requirements of Aerospace Fuels 62.2.1 Density 72.2.2 Low‐Temperature Fluidity 82.2.2.1 Viscosity 82.2.2.2 Freezing Point 102.2.3 Thermal Oxidation Stability 112.2.4 Prediction of Jet Fuel Performance 122.3 Development of Aerospace Fuels 122.3.1 Aviation Gas Turbine Engine Fuels (Petroleum Fuels) 122.3.2 Development of Russian Aerospace Fuels 152.3.3 High‐Thermal‐Oxidative‐Stability Fuels 152.3.4 Current Fuels 172.3.5 Future Fuels 192.4 High‐Energy‐Density Fuels 212.4.1 RJ‐4 212.4.2 RJ‐5 and Related Fuels 222.4.3 JP‐10, JP‐9, and RJ‐7 222.4.4 Strained and Diamondoid Fuels 252.4.5 Gelled Fuels 262.5 Non‐petroleum Fuels 272.5.1 F‐T Fuels 282.5.2 Bio‐aviation Fuels 282.5.3 Perspectives 31References 333 Design and Synthesis of High‐Density Polycyoalkane Fuels 39Ji‐Jun Zou and Chengxiang Shi3.1 Introduction 393.2 Cycloaddition 403.2.1 Reaction Pathway 403.2.2 Cycloaddition Catalysts 443.3 Hydrogenation 503.3.1 Hydrogenation of Dicyclopentadiene 503.3.1.1 Hydrogenation Mechanism 503.3.1.2 Hydrogenation Catalysts 513.3.1.3 Hydrogenation Kinetics 543.3.2 Hydrogenation of Tricyclopentadiene 673.3.2.1 Hydrogenation Mechanism 673.3.2.2 Hydrogenation Catalysts 693.3.2.3 Hydrogenation Kinetics 703.4 Isomerization 743.4.1 Isomerization of Tetrahydrodicyclopentadiene 743.4.2 Isomerization of Tetrahydrotricyclopentadiene 813.5 Other Reactions and Procedures 903.5.1 Alternative Isomerization–Hydrogenation Synthesis 903.5.2 One‐Step Synthesis of exo‐Tetrahydrodicyclopentadiene 95References 974 Design and Synthesis of High‐Density Diamondoid Fuels 101Lun Pan and Jiawei Xie4.1 Introduction 1014.2 Synthesis of Alkyl Diamondoids via Acid‐Catalyzed Rearrangement 1024.3 Synthesis of Alkyl Diamondoids via IL‐Catalyzed Rearrangement 1124.3.1 Rearrangement of Tetrahydrotricyclopentadiene 1144.3.2 Rearrangement of Tetrahydrodicyclopentadiene 1204.3.3 Rearrangement of Other Polycycloalkanes 1274.3.4 Rearrangement of Biomass‐Derived Hydrocarbons 1344.4 Synthesis of Alkyl Diamondoids via Zeolite‐Catalyzed Rearrangement 1354.5 Alkylation and Other Chemical Synthesis Methods 1384.6 Basic Properties of Alkyl Diamondoids 142References 1445 Design and Synthesis of High‐Energy Strained Fuels 149Ji‐Jun Zou, Junjian Xie, Yakun Liu, and Chi Ma5.1 Introduction 1495.2 Quadricyclane Fuel 1495.2.1 Properties and Synthesis of Quadricyclane 1495.2.2 Homogeneous Photosensitizers 1525.2.2.1 Triplet Sensitizer 1525.2.2.2 Transition‐Metal‐Compound‐Based Sensitizer 1535.2.3 Heterogeneous Photocatalysis 1555.2.3.1 Zinc and Cadmium Oxides and Sulfides 1555.2.3.2 Modified Zeolites 1555.2.3.3 Metal‐Doped TiO2 1565.2.3.4 Ti‐Containing MCM‐41 1615.2.3.5 Combination of Metal Doping and Framework Ti Species 1645.2.3.6 Mechanism of Heterogeneous Photocatalysis 1675.2.4 Utilization of Quadricyclane 1685.3 Cyclopropane Fuel 1705.3.1 Organometallic Carbenoid‐Mediated Cyclopropanation 1705.3.1.1 Zinc Carbenoid‐Mediated Cyclopropanation 1715.3.1.2 Samarium Carbenoid‐Mediated Cyclopropanation 1745.3.1.3 Lithium Carbenoid‐Mediated Cyclopropanation 1755.3.1.4 Metallic Aluminum Carbenoid‐Mediated Cyclopropanation 1775.3.2 Transition Metal Carbene‐Mediated Cyclopropanation 1815.3.2.1 Diazomethane System 1835.3.2.2 Copper Catalytic System 1855.3.2.3 Other Transition Metal Catalyst Systems 1875.3.3 Other Cyclopropanation Methods 1905.3.4 Fuel Synthesis and Mechanism 1905.3.4.1 Cyclopropanation of endo‐DCPD with Monomeric IZnCH2I in Gas Phase 1935.3.4.2 Cyclopropanation of endo‐DCPD with Monomeric IZnCH2I in Diethyl Ether Solvent 1975.3.4.3 Cyclopropanation of endo‐DCPD with (ICH2)2Zn in Diethyl Ether Solvent 2015.4 Spiro and Caged Fuels 2025.4.1 Spiro‐Fuels 2035.4.2 PCU Monomer, Dimers, and Derivatives 2095.4.2.1 PCU Monomer 2095.4.2.2 PCU Dimers 2105.4.2.3 PCU Derivatives 2145.4.3 Cubane and Derivatives 2185.4.4 Other Caged Fuels 222References 2246 Design and Synthesis of High‐Density Fuels from Biomass 241Ji‐Jun Zou and Genkuo Nie6.1 Introduction 2416.2 Carbon‐Increasing Reaction Strategies 2446.2.1 Chain and Ring Increasing by Hydroxyalkylation and Alkylation 2446.2.1.1 Synthesis of Branched Monocyclic Hydrocarbons by Hydroxylalkylation and Alkylation 2506.2.1.2 Synthesis of Branched Monocyclic Hydrocarbons by Alkylation 2526.2.1.3 Synthesis of Branched Multicyclic Hydrocarbons by Alkylation 2546.2.2 Chain and Ring Increasing by Aldol Condensation 2566.2.2.1 Synthesis of Branched Monocyclic and Multicyclic Hydrocarbons by Aldol Condensation 2566.2.2.2 Catalyst Design in the Synthesis of Bi‐ to Tetra‐Five/Six‐Membered Ring Hydrocarbons 2606.2.3 Ring Increasing by Diels–Alder Cycloaddition 2606.2.3.1 Synthesis of Multicyclic Hydrocarbons Using Terpinenes 2626.2.3.2 Synthesis of Branched Multicyclic Hydrocarbons Using 2‐MF 2656.2.3.3 Synthesis of Branched Monocyclic Hydrocarbons Using Diacetone Alcohol 2676.2.3.4 Synthesis of JP‐10 Using Furfuryl Alcohol 2676.2.4 Ring Increasing by Oligomerization 2676.2.4.1 Synthesis of Multicyclic Hydrocarbons Using Pinene 2696.2.4.2 Synthesis of Multicyclic Hydrocarbons Using Cyclenes 2716.2.5 Ring Increasing by Combined Reactions 2726.2.5.1 Robinson Annulation 2726.2.5.2 Reductive Coupling 2746.2.5.3 Guerbet Reaction 2756.2.6 Fused Cycle Constructing by Skeleton Rearrangement 2756.2.7 Integrated Reaction Strategies 2776.2.7.1 Dual‐Bed Catalyst System 2786.2.7.2 One‐Pot Reaction 2796.2.7.3 Multistep Coupling Reaction 2806.2.7.4 Cellulose Co‐conversion with Polyethylene via Catalytically Combined Processes 283References 2837 Design and Synthesis of Nanofluid Fuels 291Lun Pan, Xiu‐Tian‐Feng E, Jinwen Cao, and Kang Xue7.1 Introduction 2917.2 Synthesis and Properties of Nanofluid Fuels 2927.2.1 Single‐Step Methods 2937.2.1.1 Physical Methods 2937.2.1.2 Chemical Methods 2997.2.2 Two‐Step Methods 3037.3 Methods to Evaluate Stability of Nanofluids 3057.3.1 Sedimentation Photograph Capturing 3057.3.2 Sedimentation Balance Method 3057.3.3 Centrifugation Method 3057.3.4 ζ‐Potential Measurement 3067.3.5 UV–Vis Spectrophotometer 3087.3.6 Light Scattering Method 3107.3.7 Three‐Omega Method 3107.4 Approaches to Enhance Stability of Nanofluids 3107.4.1 Mechanical Mixing 3117.4.2 pH Control 3127.4.3 Surfactants 3137.4.4 Surface Modification 3137.5 Typical High‐Energy Nanofluid Fuels 3157.5.1 Boron‐Based Nanofluids 3157.5.1.1 Preparation of Stable Boron‐in‐Jet Fuel Nanofluids 3167.5.1.2 Dispersion of Boron‐Based Nanofluids 3177.5.2 Aluminum‐Based Nanofluids 3207.6 Physical Properties of Nanofluid Fuels 3227.6.1 Density and Energy 3227.6.2 Viscosity 3237.6.3 Surface tension 3287.6.4 Latent Heat of Vaporization 3297.6.5 Combustion Characteristics 3317.6.6 Evaporation Characteristics 3377.7 Formulation and Synthesis of Gelled Fuels 3417.7.1 Gel Formulation 3417.7.2 Gel Preparation and Gelation Mechanism 3467.8 Rheological Behavior 3487.9 Atomization Behavior 3527.10 Combustion Behavior 356References 3618 Design and Synthesis of Green Hypergolic Ionic Liquid Fuels 377Xiangwen Zhang and Yong‐Chao Zhang8.1 Introduction 3778.2 Development History of Hypergolic Ionic Liquids 3788.3 Physicochemical Properties of Hypergolic Ionic Liquids 3798.3.1 Thermal Properties 3798.3.2 Density 3808.3.3 Viscosity 3808.3.4 Heat of Formation 3808.3.5 Ignition Delay Time 3818.3.6 Specific Impulse 3828.4 Hypergolic Ionic Liquids 3828.4.1 Hypergolic Ionic Liquids Based on Dicyanamide Anions 3828.4.2 Hypergolic Ionic Liquids Based on Nitrocyanamide Anions 3978.4.3 Hypergolic Ionic Liquids Based on Boronium‐Based and B─H Bond‐Rich Anions 4028.4.4 Hypergolic Ionic Liquids Based on Other Anions 421References 4319 Combustion Properties of Fuels and Methods to Improve Them 437Lun Pan and Xiu‐Tian‐Feng E9.1 Introduction 4379.2 Typical Equipment Used in Combustion Experiment 4399.2.1 Rapid Compressor 4399.2.2 Shock Tube 4419.2.2.1 Heated Shock Tube 4419.2.2.2 Aerosol Shock Tube 4419.2.3 Hot Plate 4469.2.4 Laser Ignition 4479.2.5 Constant‐Volume Strand Burner 4479.3 Combustion and Ignition Characters 4509.3.1 Ignition Probability 4509.3.2 Ignition Temperature 4509.3.3 Ignition Delay Time 4539.3.4 Combustion Rate 4559.4 Methods to Enhance Ignition and Combustion 4589.4.1 Effect of NP Concentration on Ignition and Combustion 4589.4.2 Effect of Surfactants or Dispersants on Ignition and Combustion 4619.4.3 Effect of Nanoparticle Characteristics on Ignition and Combustion 4629.5 Combustion Mechanism of Nanofluid Fuels 464References 470Index 475