Multiphase Reactor Engineering for Clean and Low-Carbon Energy Applications

Yi Cheng is currently a Professor in the Department of Chemical Engineering at Tsinghua University. He has received several awards such as the first prize of Natural Science Award by the Ministry of Education of China and the first prize of Science and Technology Progress Award by China Petroleum and Chemical Industry Federation. He has written numerous articles and presented papers at many conferences. Fei Wei is currently a Professor in the Department of Chemical Engineering at Tsinghua University. He has been the head of Fluidization Lab of Tsinghua University (FLOTU) for 20 years, and received several top-level national awards in China. He has written numerous articles, book chapters and book chapters and presented papers at many conferences. Yong Jin is currently a Professor in the Department of Chemical Engineering at Tsinghua University and a Member of the Chinese Academy of Engineering. He has authored more than 300 published articles, numerous books and book chapters and presented papers at approximately 50 conferences.

Preface xiii

List of Contributors Xv

1 Novel Fluid Catalytic Cracking Processes 1
Jinsen Gao, Chunming Xu, Chunxi Lu Chaohe Yang, Gang Wang, Xingying Lan and Yongmin Zhang

1.1 FCC Process Description 1

1.2 Reaction Process Regulation for the Heavy Oil FCC 3

1.2.1 Technology Background 3

1.2.2 Principle of the Technology 3

1.2.3 Key Fundamental Research 4

1.2.4 Industrial Validation 7

1.3 Advanced Riser Termination Devices for the FCC Processes 10

1.3.1 Introduction 10

1.3.2 General Idea of the Advanced RTD System 11

1.3.3 Development of the External‐Riser FCC RTD Systems 12

1.3.4 Development of the Internal‐Riser FCC RTDs 15

1.3.5 Conclusions and Perspectives 18

1.4 An MZCC FCC Process 19

1.4.1 Technology Background 19

1.4.2 Reaction Principle for MZCC 19

1.4.3 Design Principle of MZCC Reactor 20

1.4.4 Key Basic Study 23

1.4.5 The Industry Application of MZCC 23

1.4.6 Prospectives 26

1.5 Two‐Stage Riser Fluid Catalytic Cracking Process 28

1.5.1 Preface 28

1.5.2 Reaction Mechanism of Heavy Oil in the Riser Reactor 29

1.5.3 The Proposed TSR FCC Process 32

1.5.4 The Industrial Application of the TSR FCC Technology 33

1.5.5 The Development of the TSR FCC Process 33

1.6 FCC Gasoline Upgrading by Reducing Olefins Content Using SRFCC Process 36

1.6.1 Research Background 36

1.6.2 Reaction Principle of Gasoline Upgrading 37

1.6.3 Design and Optimization on the Subsidiary Riser 38

1.6.4 Key Fundamental Researches 38

1.6.5 Industrial Applications of the SRFCC Process 42

1.6.6 Outlook 43

1.7 FCC Process Perspectives 44

References 45

2 Coal Combustion 49
Guangxi Yue, Junfu Lv and Hairui Yang

2.1 Fuel and Combustion Products 49

2.1.1 Composition and Properties of Fuel 49

2.1.2 Analysis of Compositions in the Fuel 50

2.1.3 Calorific Value of Fuel 50

2.1.4 Classifications of Coal 50

2.1.5 Combustion Products and Enthalpy of Flue Gas 51

2.2 Device and Combustion Theory of Gaseous Fuels 52

2.2.1 Ignition of the Gaseous Fuels 52

2.2.2 Diffusion Gas Burner 52

2.2.3 Fully Premixed‐Type Gas Burner 53

2.3 Combustion Theory of Solid Fuel 53

2.3.1 The Chemical Reaction Mechanism of Carbon Combustion 54

2.3.2 Carbon Combustion Reaction Process 54

2.4 Grate Firing of Coal 55

2.4.1 Coal Grate Firing Facilities 56

2.5 Coal Combustion in CFB Boiler 57

2.5.1 The Characteristic of Fluidized Bed 57

2.5.2 Combustion Characteristic of CFB Boiler 58

2.5.3 Development of Circulating Fluidized Bed Combustion Technology 58

2.5.4 Comparison Between Bubbling Fluidized bed and Circulating Fluidized Bed 59

2.6 Pulverized Coal Combustion 60

2.6.1 Furnace Type of Pulverized Coal Combustion 61

2.6.2 Circulation Mode of Water Wall 62

2.6.3 Modern Large‐Scale Pulverized Coal Combustion Technology 62

2.6.4 The International Development of the Supercritical Pressure Boiler 62

References 63

3 Coal Gasification 65
Qiang Li and Jiansheng Zhang

3.1 Coal Water Slurry 65

3.1.1 The Advantage of CWS 65

3.1.2 The Production of CWS 66

3.1.3 The Atomization of CWS 67

3.2 The Theory of Coal Gasification 70

3.2.1 Overview of Coal Gasification 70

3.2.2 The Main Reaction Processes of Coal Gasification 72

3.2.3 Kinetics of Coal Gasification Reaction 73

3.2.4 The Influencing Factors of Coal Gasification Reaction 77

3.3 Fixed Bed Gasification of Coal 79

3.3.1 The Principle of Fixed Bed Gasification 79

3.3.2 The Classification of Fixed Bed Gasification Technology 81

3.3.3 Typical Fixed Bed Gasification Technologies 81

3.3.4 The Key Equipment for Pressurized Fixed Bed Gasifier 85

3.3.5 The Application and Improvement of Pressurized Fixed Bed Gasifier in China 89

3.4 Fluid Bed Gasification of Coal 90

3.4.1 The Basic Principles of Fluidized Bed Gasification 90

3.4.2 Typical Technology and Structure of Fluidized Bed Gasification 91

3.5 Entrained Flow Gasification of Coal 98

3.5.1 The Principle of Entrained Flow Gasification Technology 98

3.5.2 Typical Entrained Gas Gasification Technologies 101

3.6 Introduction to the Numerical Simulation of Coal Gasification 112

3.6.1 The Numerical Simulation Method of Coal Gasification 112

3.6.2 Coal Gasification Numerical Simulation (CFD) Method 113

References 116

4 New Development in Coal Pyrolysis Reactor 119
Guangwen Xu, Xi Zeng, Jiangze Han and Chuigang Fan

4.1 Introduction 119

4.2 Moving Bed with Internals 121

4.2.1 Laboratory Tests at Kilogram Scale 122

4.2.2 Verification Tests at 100‐kg Scale 125

4.2.3 Continuous Pilot Verification 127

4.3 Solid Carrier FB Pyrolysis 129

4.3.1 Fundamental Study 130

4.3.2 Pilot Verification with Air Gasification 136

4.4 Multistage Fluidized Bed Pyrolysis 139

4.4.1 Experimental Apparatus and Method 139

4.4.2 Results and Discussion 141

4.5 Solid Carrier Downer Pyrolysis 145

4.5.1 Experimental Apparatus and Method 146

4.5.2 Results and Discussion 147

4.6 Other Pyrolysis Reactors 149

4.6.1 Solid Heat Carrier Fixed Bed 149

4.6.2 A Few Other New Pyrolysis Reactors 150

4.7 Concluding Remarks 153

Acknowledgments 153

References 153

5 Coal Pyrolysis to Acetylene in Plasma Reactor 155
Binhang Yan and Yi Cheng

5.1 Introduction 155

5.1.1 Background 155

5.1.2 Principles and Features of Thermal Plasma 156

5.1.3 Basic Principles of Coal Pyrolysis in Thermal Plasma 157

5.1.4 Development of Coal Pyrolysis to Acetylene Process 158

5.2 Experimental Study of Coal Pyrolysis to Acetylene 159

5.2.1 Experimental Setup 159

5.2.2 Typical Experimental Results 161

5.3 Thermodynamic Analysis of Coal Pyrolysis to Acetylene 164

5.3.1 Equilibrium Composition with/without Consideration of Solid Carbon 164

5.3.2 Validation of Thermodynamic Equilibrium Predictions 164

5.3.3 Effect of Additional Chemicals on Thermodynamic Equilibrium 165

5.3.4 Key Factors to Determine the Reactor Performance 166

5.3.5 Key Factors to Determine the Reactor Performance 168

5.4 Computational Fluid Dynamics‐Assisted Process Analysis and Reactor Design 171

5.4.1 Kinetic Models of Coal Devolatilization 171

5.4.2 Generalized Model of Heat Transfer and Volatiles Evolution Inside Particles 176

5.4.3 Cross‐Scale Modeling and Simulation of Coal Pyrolysis to Acetylene 180

5.5 Conclusion and Outlook 183

References 186

6 Multiphase Flow Reactors for Methanol and Dimethyl Ether Production 189
Tiefeng Wang and Jinfu Wang

6.1 Introduction 189

6.1.1 Methanol 189

6.1.2 Dimethyl Ether 189

6.2 Process Description 191

6.2.1 Methanol Synthesis 191

6.2.2 DME Synthesis 192

6.2.3 Reaction Kinetics 195

6.3 Reactor Selection 197

6.3.1 Fixed Bed Reactor 197

6.3.2 Slurry Reactor 198

6.4 Industrial Design and Scale‐Up of Fixed Bed Reactor 200

6.4.1 Types of Fixed Bed Reactors 200

6.4.2 Design of Large‐Scale Fixed Bed Reactor 201

6.5 Industrial Design and Scale‐Up of Slurry Bed Reactor 202

6.5.1 Flow Regime of the Slurry Reactor 202

6.5.2 Hydrodynamics of Slurry Bed Reactor 203

6.5.3 Process Intensification with Internals 203

6.5.4 Scale‐Up of Slurry Reactor 206

6.6 Demonstration of Slurry Reactors 213

6.7 Conclusions and Remarks 214

References 215

7 Fischer–Tropsch Processes and Reactors 219
Li Weng and Zhuowu Men

7.1 Introduction to Fischer–Tropsch Processes and Reactors 219

7.1.1 Introduction to Fischer–Tropsch Processes 219

7.1.2 Commercial FT Processes 219

7.1.3 FT Reactors 220

7.1.4 Historical Development of FT SBCR 221

7.1.5 Challenges for FT SBCR 222

7.2 SBCR Transport Phenomena 222

7.2.1 Hydrodynamics Characteristics 222

7.2.2 Mass Transfer 226

7.2.3 Heat Transfer 229

7.3 SBCR Experiment Setup and Results 231

7.3.1 Introduction to SBCR Experiments 231

7.3.2 Cold Mode and Instrumentation 234

7.3.3 Hot Model and Operation 247

7.4 Modeling of SBCR for FT Synthesis Process 249

7.4.1 Introduction 249

7.4.2 Model Discussion 250

7.4.3 Multiscale Analysis 256

7.4.4 Conclusion 258

7.5 Reactor Scale‐Up and Engineering Design 259

7.5.1 General Structures of SBCR 259

7.5.2 Internal Equipment 259

7.5.3 Design and Scale‐Up Strategies of SBCR 261

Nomenclature 262

References 263

8 Methanol to Lower Olefins and Methanol to Propylene 271
Yao Wang and Fei Wei

8.1 Background 271

8.2 Catalysts 272

8.3 Catalytic Reaction Mechanism 273

8.3.1 HP Mechanism 274

8.3.2 Dual‐Cycle Mechanism 274

8.3.3 Complex Reactions 275

8.4 Features of the Catalytic Process 275

8.4.1 Autocatalytic Reactions 275

8.4.2 Deactivation and Regeneration 276

8.4.3 Exothermic Reactions 278

8.5 Multiphase Reactors 278

8.5.1 Fixed Bed Reactor 279

8.5.2 Moving Bed Reactor 280

8.5.3 Fluidized Bed Reactor 281

8.5.4 Parallel or Series Connection Reactors 284

8.6 Industrial Development 286

8.6.1 Commercialization of MTO 286

8.6.2 Commercialization of MTP 288

References 292

9 Rector Technology for Methanol to Aromatics 295
Weizhong Qian and Fei Wei

9.1 Background and Development History 295

9.1.1 The Purpose of Developing Methanol to Aromatics Technology 295

9.1.2 Comparison of MTA with Other Technologies Using Methanol as Feedstock 297

9.2 Chemistry Bases of MTA 298

9.3 Effect of Operating Conditions 300

9.3.1 Effect of Temperature 300

9.3.2 Partial Pressure 302

9.3.3 Space Velocity of Methanol 302

9.3.4 Pressure 302

9.3.5 Deactivation of the Catalyst 303

9.4 Reactor Technology of MTA 304

9.4.1 Choice of MTA Reactor: Fixed Bed or Fluidized Bed 304

9.4.2 MTA in Lab‐Scale Fluidized Bed Reactor and the Comparison in Reactors with Different Stages 305

9.4.3 20 kt/a CFB Apparatus for MTA 306

9.4.4 Pilot Plant Test of 30 kt/a FMTA System 306

9.5 Comparison of MTA Reaction Technology with FCC and MTO System 310

References 311

10 Natural Gas Conversion 313
Wisarn Yenjaichon, Farzam Fotovat and John R. Grace

10.1 Introduction 313

10.2 Reforming Reactions 313

10.3 Sulfur and Chloride Removal 314

10.4 Catalysts 314

10.5 Chemical Kinetics 315

10.6 Fixed Bed Reforming Reactors 316

10.7 Shift Conversion Reactors 317

10.7.1 High‐Temperature WGS 317

10.7.2 Low‐Temperature WGS 317

10.8 Pressure Swing Adsorption 317

10.9 Steam Reforming of Higher Hydrocarbons 318

10.10 Dry (Carbon Dioxide) Reforming 318

10.11 Partial Oxidation (POX) 320

10.11.1 Homogeneous POX 321

10.11.2 Catalytic Partial Oxidation 321

10.12 Autothermal Reforming (ATR) 321

10.13 Tri‐Reforming 321

10.14 Other Efforts to Improve SMR 322

10.14.1 Fluidized Beds 323

10.14.2 Permselective Membranes 323

10.14.3 Sorbent‐Enhanced Reforming 325

10.15 Conclusions 326

References 326

11 Multiphase Reactors for Biomass Processing and Thermochemical Conversions 331
Xiaotao T. Bi and Mohammad S. Masnadi

11.1 Introduction 331

11.2 Biomass Feedstock Preparation 332

11.2.1 Biomass Drying 332

11.2.2 Biomass Torrefaction Treatment 333

11.3 Biomass Pyrolysis 336

11.3.1 Pyrolysis Principles and Reaction Kinetics 336

11.3.2 Multiphase Reactors for Slow and Fast Pyrolysis 338

11.3.3 Catalytic Pyrolysis of Biomass 342

11.3.4 Biomass‐to‐Liquid Via Fast Pyrolysis 342

11.4 Biomass Gasification 343

11.4.1 Principles of Biomass Gasification 343

11.4.2 Gasification Reactions Mechanisms and Models 344

11.4.3 Catalytic Gasification of Biomass 347

11.4.4 Multiphase Reactors for Gasification 349

11.4.5 Biomass Gasification Reactor Modeling 355

11.4.6 Downstream Gas Processing 356

11.4.7 Technology Roadmap and Recent Market Developments 357

11.5 Biomass Combustion 359

11.5.1 Principles of Biomass Combustion 359

11.5.2 Reaction Mechanisms and Kinetics 360

11.5.3 Multiphase Reactors for Combustion 361

11.5.4 Advanced Combustion Systems 363

11.5.5 Agglomeration, Fouling, and Corrosion 365

11.5.6 Future Technology Developments 365

11.6 Challenges of Multiphase Reactors for Biomass Processing 366

11.6.1 Fluidization of Irregular Biomass Particles 366

11.6.2 Feeding, Conveying of Biomass 366

11.6.3 Reactor Modeling, Simulation, and Scale‐Up 367

11.6.4 Economics of Commercial Biomass Conversion Systems 368

References 369

12 Chemical Looping Technology for Fossil Fuel Conversion with In Situ CO2 Control 377
Liang‐Shih Fan, Andrew Tong and Liang Zeng

12.1 Introduction 377

12.1.1 Chemical Looping Concept 377

12.1.2 Historical Development 379

12.2 Oxygen Carrier Material 381

12.2.1 Primary Material Selection 381

12.2.2 Iron‐Based Oxygen Carrier Development 382

12.3 Chemical Looping Reactor System Design 384

12.3.1 Thermodynamic Analysis 385

12.3.2 Kinetic Analysis 388

12.3.3 Hydrodynamic Analysis 392

12.4 Chemical Looping Technology Platform 396

12.4.1 Syngas Chemical Looping Process 397

12.4.2 Coal Direct Chemical Looping Process 398

12.4.3 Shale Gas-to-Syngas Process 399

12.5 Conclusion 400

References 401

Index 405