Describing novel developments as well as established methods, the authors start with the evaluation of different oxygen carriers and subsequently illuminate various technological concepts for the energy conversion process. They then go on to discuss the potential for commercial applications in gaseous, coal, and fuel combustion processes in industry.
The result is an invaluable source for every scientist in the field, from inorganic chemists in academia to chemical engineers in industry.
Table of Contents
Preface xiii
Section 1 Chemical Looping Process Concepts 1
1 TheMoving Bed Fuel Reactor Process 3
Andrew Tong,Mandar V. Kathe, DaweiWang, and Liang-Shih Fan
1.1 Introduction 3
1.2 Modes of Moving Bed Fuel Reactor Operation 4
1.2.1 Counter-Current Moving Bed Fuel Reactor: 5
1.2.2 Co-current Moving Bed Fuel Reactor 8
1.3 Chemical Looping Reactor System Design Considerations for Moving Bed Fuel Reactors 10
1.3.1 Mass Balance and Solids Circulation Rate 10
1.3.2 Heat Management 11
1.3.3 Sizing of Reactors 12
1.3.4 Sizing of the Air Reactor 13
1.3.5 Gas Sealing 13
1.3.6 Solids Circulation Control 14
1.3.7 Process Pressure Balance 17
1.4 Counter-Current Moving Bed Fuel Reactor Applications in Chemical Looping Processes 18
1.4.1 Counter-Current Moving Bed Fuel Reactor Modeling 18
1.4.2 Syngas Chemical Looping Process 20
1.4.3 Coal Direct Chemical Looping Process Development 23
1.5 Co-current Moving Bed Fuel Reactor Applications in Chemical Looping Processes 27
1.5.1 Coal to Syngas Chemical Looping Process 27
1.5.2 Methane to Syngas Chemical Looping Process 29
1.5.3 CO2 Utilization Potential 31
1.5.4 MTS Modularization Strategy 32
1.6 Concluding Remarks 36
References 37
2 Single and Double Loop Reacting Systems 41
JustinWeber
2.1 Introduction 41
2.2 Reactor Types 43
2.2.1 Fluid Beds 45
2.2.2 Spouted Beds 45
2.2.3 Risers 46
2.3 Gas Sealing and Solids Control 47
2.4 Single Loop Reactors 48
2.5 Double (or More) Loop Reactors 48
2.6 Solid Fuel Reactors 50
2.6.1 Volatiles 50
2.6.2 Carbon Leakage 51
2.6.3 Ash Separation 52
2.7 Pressurized Reactors 52
2.8 Solid Circulation Rate 53
2.9 Lessons Learned 55
2.9.1 Solids and Pressure Balance Control 55
2.9.2 Solids in Reactor Exhaust 56
2.9.3 Condensation in Exhaust 56
2.9.4 Self-Fluidization 57
2.9.5 Cyclones 57
2.10 Summary 58
Acknowledgements 58
References 58
3 Chemical Looping Processes Using Packed Bed Reactors 61
Vincenzo Spallina, Fausto Gallucci, andMartin van Sint Annaland
3.1 Introduction 61
3.2 Oxygen Carriers for Packed Bed Reactor 63
3.3 Chemical Looping Combustion 65
3.4 Chemical Looping Reforming 73
3.5 Other Chemical Looping Processes 78
3.5.1 Chemical Looping for H2 Production 78
3.5.2 Cu-Ca Process for Sorption Enhanced Reforming 84
3.6 Conclusions 86
Nomenclature 87
References 88
4 Chemical Looping with Oxygen Uncoupling (CLOU) Processes 93
Kevin J.Whitty, JoAnn S. Lighty, and TobiasMattisson
4.1 Introduction 93
4.2 Fundamentals of the CLOU Process 95
4.2.1 CLOU Oxygen Carriers 97
4.2.2 CLOU Oxygen Carrier Oxidation 98
4.2.3 CLOU Oxygen Carrier Reduction (“Uncoupling”) 99
4.3 CLOU Reactor Design 100
4.3.1 Fuel Flow and Overall Balances 101
4.3.2 Energy Considerations 102
4.3.3 Air Reactor Design 103
4.3.4 Fuel Reactor Design 106
4.3.5 Loop Seal Design 107
4.3.6 Sulfur 109
4.4 Status of CLOU Technology Development 110
4.4.1 Laboratory-Scale CLOU Testing 110
4.4.2 Development-Scale and Pilot-Scale Systems 111
4.5 Future Development of CLOU Technology 118
References 119
5 Pressurized Chemical Looping Combustion for Solid Fuel 123
Liangyong Chen, Zhen Fan, Rui Xiao, and Kunlei Liu
5.1 Introduction 123
5.2 Coal-Based Pressurized Chemical Looping Combustion Combined Cycle 124
5.2.1 Concept 124
5.2.2 Process of the Direct Coal-Fueled PCLC Developed by UK-CAER 125
5.2.3 Process of the Direct Coal-Fueled PCLC at SEU, China 127
5.3 Fundamentals and Experiments of Pressurized Chemical Looping Combustion 128
5.3.1 Transient Oxidation of Magnetite to Hematite in PCLC 128
5.3.2 The Solid Behaviors in the Solid-Fueled PCLC (Fuel Reactor Side) 129
5.3.2.1 Materials 129
5.3.2.2 Experiment Setup 130
5.3.2.3 In situ Gasification 133
5.3.2.4 Combustion Efficiency 136
5.4 Direct Coal-Fueled PCLC Demonstration in Laboratory Scale 139
5.4.1 100 kWth PCLC Facility at SEU, China 139
5.4.2 50 kWth PCLC Unit at UK-CAER 142
5.5 Tech-economic Analysis 143
5.5.1 Technical Performance Evaluation on the Direct Coal-Fueled PCLC-CC 143
5.5.1.1 Combined Cycle 145
5.5.1.2 PCLC Unit 145
5.5.1.3 Physical Properties 145
5.5.1.4 Case Study 146
5.5.1.5 Optimization of Plant Configuration 148
5.5.2 Performance of the UK-CAER’s PCLC-CC Plant 148
5.6 Technical Gaps and Challenges 155
References 157
Section 2 Oxygen Carriers 159
6 Regenerable, Economically Affordable Fe2O3-Based Oxygen Carrier for Chemical Looping Combustion 161
Hanjing Tian, Ranjani Siriwardane, Esmail R.Monazam, and RonaldW. Breault
6.1 Introduction 161
6.2 Primary Oxide Selection 162
6.3 Supported Single Oxides 166
6.4 Natural Oxide Ores 170
6.5 Supported Binary Oxides System 173
6.5.1 Thermodynamic Analysis of CuO-Fe2O3 Phases 173
6.5.2 Decomposition-Oxidation Cycle of Chemical Looping Oxygen Uncoupling 174
6.5.3 Coal Chemical Looping Combustion 174
6.5.4 Chemical Looping Combustion with Methane as Fuel 177
6.5.5 Bulk Phase and Oxidation State Analysis of Mixed CuO- Fe2O3 System 180
6.5.6 Synergetic Reactivity-Structure of CuO- Fe2O3 Oxygen Carriers 182
6.6 Kinetic Networks of Fe2O3-based Oxygen Carriers 185
6.7 50-kWth Methane/Air Chemical Looping Combustion Tests 191
References 195
7 Oxygen Carriers for Chemical-Looping with Oxygen Uncoupling (CLOU) 199
Tobias Mattisson and Kevin J.Whitty
7.1 Introduction 199
7.2 Thermodynamics of CLOU 202
7.2.1 Equilibrium Partial Pressure of O2 202
7.2.2 Thermal Considerations 207
7.3 Overview of Experimental Investigations of CLOU Materials 208
7.3.1 Copper Oxide 209
7.3.2 Combined and Mixed Oxides 210
7.3.3 Naturally Occurring Oxygen Carriers 216
7.4 Kinetics of Oxidation and Reduction of Oxygen Carriers in CLOU 217
7.5 Conclusions 219
Acknowledgment 219
References 220
8 Mixed Metal Oxide-Based Oxygen Carriers for Chemical Looping Applications 229
Fanxing Li, Nathan Galinsky, and Arya Shafieharhood
8.1 Overview 229
8.2 Mixed Oxides for Chemical Looping with Oxygen Uncoupling (CLOU) 232
8.3 Mixed Oxides for iG-CLC 235
8.4 Mixed Oxides for Chemical Looping Reforming (CLR) 241
8.4.1 Chemical Looping Reforming 241
8.4.2 Monometallic Redox Catalysts for CLR 242
8.5 Redox Catalyst Improvement Strategies 244
8.6 Mixed Oxides for Other Selective Oxidation Applications 247
8.6.1 Oxidative Coupling of Methane 248
8.6.2 Oxidative Dehydrogenation (ODH) of Ethane 249
8.7 Toward Rationalizing the Design of Mixed Metal Oxides 250
8.8 Future Directions 251
References 252
9 Oxygen Carrier Structure and Attrition 263
Nathan Galinsky, Samuel Bayham, EsmailMonazam, and RonaldW. Breault
9.1 Introduction 263
9.2 Oxygen Carrier Structure 264
9.2.1 Unsupported Oxygen Carriers 264
9.2.1.1 Surface 264
9.2.1.2 Structure 266
9.2.1.3 Gas Pores and Diffusion 269
9.2.1.4 Ilmenite 270
9.2.2 Supported Oxygen Carriers 271
9.2.2.1 Copper Oxides 271
9.2.2.2 Iron Oxides 272
9.3 Attrition 275
9.3.1 Sources of Attrition 276
9.3.2 Solids Properties Relevant to Attrition 278
9.3.2.1 Hardness 279
9.3.2.2 Fracture Toughness 281
9.3.3 Mechanistic Modeling of Attrition 283
9.3.3.1 Attrition due to Wear (Abrasion) 283
9.3.3.2 Impact Attrition 285
9.4 Attrition Modeling 285
9.4.1 Unsteady-State Models 286
9.4.2 Steady-State Models 287
9.4.3 System Modeling 288
9.5 Experimental Testing 289
9.5.1 Nanoindentation 289
9.5.2 Fluidized Beds 291
9.5.3 Impact Testing 292
9.5.4 Jet Cup 293
References 295
Section 3 Commercial Design Studies of CLC Systems 303
10 Computational Fluid Dynamics Modeling and Simulations of Fluidized Beds for Chemical Looping Combustion 305
Subhodeep Banerjee and Ramesh K. Agarwal
10.1 Introduction 305
10.2 Reactor-Level Simulations of CLC Using CFD 308
10.3 Governing Equations 310
10.4 Eulerian-Lagrangian Simulation of a Spouted Fluidized Bed in a CLC Fuel Reactor with Chemical Reactions 313
10.5 Spouted Fluidized Bed Simulation Results 316
10.6 Eulerian-Lagrangian Simulation of a Binary Particle Bed in a Carbon Stripper 319
10.7 Binary Particle Bed Simulation Results 324
10.8 Summary and Conclusions 328
References 328
11 Calcium- and Iron-Based Chemical Looping Combustion Processes 333
RobertW. Stevens Jr., Dale L. Keairns, Richard A. Newby, and Mark C.Woods
11.1 Introduction 333
11.2 CLC Plant Design, Modeling, and Cost Estimation Bases 334
11.2.1 Design Basis 334
11.2.2 Cost Estimation Basis 335
11.2.3 Reactor Modeling Basis 336
11.3 Chemical Looping Combustion Reference Plant Descriptions 337
11.3.1 General CLC Power Plant Configuration 338
11.3.2 Reference Plant Stream Conditions 341
11.4 Chemical Looping Combustion Reference Plant Performance 342
11.5 Chemical Looping Combustion Reference Plant Cost 352
11.6 Chemical Looping Combustion Reference Plant Performance and Cost Sensitivities 360
11.6.1 Reactor Temperature Sensitivity 362
11.6.2 Reactor Velocity Sensitivity 365
11.6.3 Carbon Gasification Efficiency Sensitivity 367
11.6.4 Reducer Oxygen Carrier Conversion Sensitivity 368
11.6.5 COE Sensitivity to Oxygen Carrier Makeup Rate and Price 370
11.6.6 COE Sensitivity to Char-Oxygen Carrier Separator Cost 371
11.7 Summary and Conclusions 372
References 375
12 Simulations for Scale-Up of Chemical Looping with Oxygen Uncoupling (CLOU) Systems 377
JoAnn S. Lighty, Zachary T. Reinking, andMatthew A. Hamilton
12.1 Introduction 377
12.2 Process Modeling 377
12.2.1 Background 377
12.2.2 Aspen Plus Modeling 378
12.2.3 Other Approaches to Material and Energy Balance Determinations 383
12.2.4 Autothermal Operation 385
12.2.5 Using Process Modeling for Steam Production Estimates 385
12.2.6 Summary 386
12.3 Computational Fluid Dynamic Simulations 387
12.3.1 Background 387
12.3.2 Summary of the Literature 388
12.3.3 Conclusions 394
References 394
Section 4 Other Chemical Looping Processes 397
13 Calcium Looping Carbon Capture Process 399
Yiang-Chen Chou,Wan-Hsia Liu, and Heng-Wen Hsu
13.1 Introduction 399
13.1.1 Fundamental Principles of Calcium Looping Process 399
13.1.2 Thermodynamics and Reaction Equilibrium of CaO and CaCO3 402
13.2 Current Status of Calcium Looping Process 404
13.2.1 Kilowatt-Scale Calcium Looping Facility 404
13.2.2 Megawatt-Scale Calcium Looping Plant 410
13.3 Strategies for Enhancing Sorbent Recyclability and Activity 415
13.3.1 Synthesis of CaO Sorbent from Inorganic or Organometallic Precursors 417
13.3.2 Incorporation of Dopant or Inert Stabilizer with Calcium-Based Sorbents 418
13.3.3 Sorbent Reactivation Through Additional Processing 423
References 428
14 Chemical Looping of Low-Cost MgO-Based Sorbents for CO2 Capture in IGCC 435
Hamid Arastoopour and Javad Abbasian
14.1 Introduction 435
14.2 MgO-Based Sorbent 438
14.3 Reaction Model for Carbon Capture and Regeneration 443
14.4 CFD Simulations of the Regenerative Carbon Dioxide Capture Process 447
14.4.1 Two-dimensional Simulation of the Regenerator and the Carbonator in the CFB Loop 447
14.4.2 Three-dimensional Simulation of Carbon Capture and Regeneration in the Absorber and Regenerator Reactors 450
14.5 Preliminary Economic Assessment 452
Acknowledgment 457
References 457
Index 461
