This is the fifth volume in a series of books focusing on natural gas engineering, focusing on the extraction and disposal of acid gas. This volume includes information for both upstream and downstream operations, including chapters on modeling, carbon capture, chemical and thermodynamic models, and much more.

Written by some of the most well-known and respected chemical and process engineers working with natural gas today, the chapters in this important volume represent the most cutting-edge and state-of-the-art processes and operations being used in the field. Not available anywhere else, this volume is a must-have for any chemical engineer, chemist, or process engineer working with natural gas.

There are updates of new technologies in other related areas of natural gas, in addition to the extraction and disposal of acid gas, including testing, reservoir simulations, acid gas injection, and natural gas hydrate formations. Advances in Natural Gas Engineering is an ongoing series of books meant to form the basis for the working library of any engineer working in natural gas today. Every volume is a must-have for any engineer or library.

Ying (Alice) Wu is currently the President of Sphere Technology Connection Ltd. (STC) in Calgary, Canada. From 1983 to 1999 she was an Assistant Professor and Researcher at Southwest Petroleum Institute (now Southwest Petroleum University, SWPU) in Sichuan, China. She received her MSc in Petroleum Engineering from the SWPU and her BSc in Petroleum Engineering from Daqing Petroleum University in Heilongjiang, China.

John J. Carroll, PhD, PEng is the Director, Geostorage Process Engineering for Gas Liquids Engineering, Ltd. in Calgary, Canada. Dr. Carroll holds bachelor and doctoral degrees in chemical engineering from the University of Alberta, Edmonton, Canada, and is a registered professional engineer in the provinces of Alberta and New Brunswick in Canada. His fist book, Natural Gas Hydrates: A Guide for Engineers, is now in its second edition, and he is the author or co-author of 50 technical publications and about 40 technical presentations.

Weiyao Zhu is Professor at University of Science & Technology Beijing in China and Adjunct Professor in State Key Lab of Enhanced Oil and Gas Recovery at the Northeast Petroleum University. He has published more than 100 technical papers and an author of 6 technical books. His research focus is on fluid mechanics in porous media, the theory and application of the multiphase flow for resource exploitation, new energy development, environmental fluid mechanics, and reservoir simulation.

Preface xv

1 Rate-Base Simulations of Absorption Processes; Fata Morgana or Panacea? 1
P.J.G. Huttenhuis and G.F. Versteeg

1.1 Introduction 1

1.2 Procede Process Simulator (PPS) 2

1.3 Mass Transfer Fundamentals 3

1.4 CO2 Capture Case 8

1.5 Conclusions and Recommendations 15

References 16

2 Modelling in Acid Gas Removal Processes 17
Alan E. Mather

2.1 Introduction 17

2.2 Vapour-Liquid Equilibria 18

2.3 Modelling 21

2.3.1 Empirical Models 22

2.3.2 Activity Coefficient Models 22

2.3.3 Two (and more) Solvent Models 23

2.3.4 Single Solvent Models 24

2.3.5 Equation of State Models 24

2.4 Conclusions 25

References 26

3 Thermodynamic Approach of CO2 Capture, Combination of Experimental Study and Modeling 29
Karine Ballerat-Busserolles, Alexander R. Lowe, Yohann Coulier, and J.-Y. Coxam

3.1 Introduction 30

3.2 Thermodynamic Model 31

3.3 Carbon Dioxide Absorption in Aqueous Solutions of Alkanolamines 32

3.4 Conclusion 35

References 36

4 Employing Simulation Software for Optimized Carbon Capture Process 39
Wafa Said-Ibrahim, Irina Rumyantseva, and Manya Garg

4.1 Introduction 40

4.2 Acid Gas Cleaning – Process and Business Goals 40

4.3 Modeling Gas Treating in Aspen HYSYSR 42

4.3.1 Inbuilt Thermodynamics 43

4.3.2 Rate-Based Distillation in Aspen HYSYS 44

4.4 Conclusion 45

References 46

5 Expectations from Simulation 47
R. Scott Alvis, Nathan A. Hatcher, and Ralph H. Weiland

5.1 Introduction 48

5.2 Realism 48

5.2.1 Conclusion 1 49

5.2.2 Conclusion 2 50

5.2.3 Conclusion 3 50

5.2.4 Conclusion 4 51

5.3 Reliability of Simulation Data: What’s Data and What’s Not 52

5.3.1 Conclusion 5 54

5.3.2 Conclusion 6 54

5.3.3 Conclusion 7 55

5.3.4 Conclusion 8 55

5.4 Case Studies 56

5.4.1 Hellenic Petroleum Refinery Revamp 56

5.4.2 Treating a Refinery Fuel Gas 58

5.4.3 Carbon Dioxide Removal in an LNG Unit 60

5.4.4 Tail Gas Treating 65

5.5 Concluding Remarks 67

References 67

6 Calorimetry in Aqueous Solutions of Demixing Amines for Processes in CO2 Capture 69
Karine Ballerat-Busserolles, Alexander R. Lowe, Yohann Coulier, and J.-Y. Coxam

6.1 Introduction 70

6.2 Chemicals 72

6.3 Liquid-Liquid Phase Equilibrium 73

6.4 Mixing Enthalpies of {Water-Amine} and {Water-Amine-CO2} 75

6.4.1 Excess Enthalpies 77

6.4.2 Enthalpies of Solution 78

6.5 Acknowledgements 79

References 79

7 Speciation in Liquid-Liquid Phase-Separating Solutions of Aqueous Amines for Carbon Capture Applications by Raman Spectroscopy 81
O. Fandiño, M. Yacyshyn, J.S. Cox, and P.R. Tremaine

7.1 Introduction 81

7.2 Experimental 84

7.2.1 Materials 84

7.2.2 Sample Preparation 84

7.2.3 Raman Spectroscopic Measurements 85

7.2.4 Methodology Validation 86

7.2.5 Laser Selection Optimization 86

7.3 Results and Discussion 87

7.3.1 Ammonium Carbamate System 87

7.3.2 Methylpiperidine Band Identification 88

7.3.3 (N-methylpiperidine + Water + CO2) System 89

7.3.4 (2-methylpiperidine + Water + CO2) System 90

7.3.5 (4-methylpiperidine + Water + CO2) System 91

7.4 Conclusions 91

7.5 Acknowledgements 92

References 93

8 A Simple Model for the Calculation of Electrolyte Mixture Viscosities 95
Marco A. Satyro and Harvey W. Yarranton

8.1 Introduction 95

8.2 The Expanded Fluid Viscosity Model 98

8.3 Results and Discussion 99

8.3.1 EF Model for Salts Neglecting Dissociation 100

8.3.2 EF Model for Ionic Species 102

8.4 Conclusions 104

References 104

9 Phase Equilibria Investigations of Acid Gas Hydrates: Experiments and Modelling 107
Zachary T. Ward, Robert A. Marriott, and Carolyn A. Koh

9.1 Introduction 107

9.2 Experimental Methods 108

9.3 Results and Discussion 110

9.4 Conclusions 112

9.5 Acknowledgements 112

References 112

10 Thermophysical Properties, Hydrate and Phase Behaviour Modelling in Acid Gas-Rich Systems 115
Antonin Chapoy, Rod Burgass, Bahman Tohidi, Martha Hajiw, and Christophe Coquelet

10.1 Introduction 116

10.2 Experimental Setups and Procedures 117

10.2.1 Saturation and Dew Pressure Measurements and Procedures 117

10.2.2 Hydrate Dissociation Measurements and Procedures 119

10.2.3 Water Content Measurements and Procedures 120

10.2.4 Viscosity and Density Measurements and Procedures 120

10.2.5 Frost Point Measurements and Procedures 120

10.2.6 Materials 121

10.3 Thermodynamic and Viscosity Modelling 122

10.3.1 Fluid and Hydrate Phase Equilibria Model 122

10.4 Results and Discussions 128

10.5 Conclusions 136

10.6 Acknowledgements 136

References 136

11 “Self-Preservation” of Methane Hydrate in Pure Water and (Water + Diesel Oil + Surfactant) Dispersed Systems 141
Xinyang Zeng, Changyu Sun, Guangjin Chen, Fenghe Zhou, and Qidong Ran

11.1 Introduction 142

11.2 Experiments 142

11.2.1 Material 142

11.2.2 Apparatus 143

11.2.3 Experimental Procedure 146

11.3 Results and Discussion 146

11.3.1 Self-Preservation Effect without Surfactant in Low Water Cut Oil-Water Systems 146

11.3.2 Self-Preservation Effect without Surfactant in High Water Cut Oil-Water Systems 148

11.3.3 The Effect of Different Surfactants on Self-Preservation Effect in Different Water Cut Oil-Water Systems 149

11.4 Conclusions 151

11.5 Acknowledgement 151

References 151

12 The Development of Integrated Multiphase Flash Systems 153
Carl Landra, Yau-Kun Li, and Marco A. Satyro

12.1 Introduction 154

12.2 Algorithmic Challenges 155

12.3 Physical-Chemical Challenges 156

12.4 Why Solids? 156

12.5 Equation of State Modifications 157

12.6 Complex Liquid-Liquid Phase Behaviour 160

12.7 Hydrate Calculations 162

12.7 Conclusions and Future Work 165

References 167

13 Reliable PVT Calculations – Can Cubics Do It? 169
Herbert Loria, Glen Hay, Carl Landra, and Marco A. Satyro

13.1 Introduction 169

13.2 Two Parameter Equations of State 171

13.3 Two Parameter Cubic Equations of State Using Volume Translation 172

13.4 Three Parameter Cubic Equations of State 175

13.5 Four Parameter Cubic Equations of State 177

13.6 Conclusions and Recommendations 177

References 180

14 Vapor-Liquid Equilibria Predictions of Carbon Dioxide + Hydrogen Sulfide Mixtures using the CPA, SRK, PR, SAFT, and PC-SAFT Equations of State 183
M. Naveed Khan, Pramod Warrier, Cor J. Peters, and Carolyn A. Koh

14.1 Introduction 184

14.2 Results and Discussion 185

14.3 Conclusions 188

14.4 Acknowledgements 188

References 188

15 Capacity Control Considerations for Acid Gas Injection Systems 191
James Maddocks

15.1 Introduction 191

15.2 Requirement for Capacity Control 192

15.3 Acid Gas Injection Systems 196

15.4 Compressor Design Considerations 197

15.5 Capacity Control in Reciprocating AGI Compressors 199

15.6 Capacity Control in Reciprocating Compressor/PD Pump Combinations 213

15.7 Capacity Control in Reciprocating Compressor/Centrifugal Pump Combinations 215

15.8 Capacity Control When Using Screw Compressors 215

15.9 Capacity Control When Using Centrifugal Compression 218

15.10 System Stability 219

15.11 Summary 220

Reference 220

16 Review and Testing of Radial Simulations of Plume Expansion and Confirmation of Acid Gas Containment Associated with Acid Gas Injection in an Underpressured Clastic Carbonate Reservoir 221
Alberto A. Gutierrez and James C. Hunter

16.1 Introduction 222

16.2 Site Subsurface Geology 223

16.2.1 General Stratigraphy and Structure 224

16.2.2 Geology Observed in AGI #1 and AGI #2 227

16.3 Well Designs, Drilling and Completions 227

16.3.1 AGI #1 228

16.3.2 AGI #2 231

16.4 Reservoir Testing and Modeling 232

16.4.1 AGI #1 233

16.4.2 Linam AGI #2 233

16.4.3 Comparison of Reservoir between Wells 234

16.4.4 Initial Radial Model and Plume Prediction 234

16.4.5 Confirmation of Plume Migration Model and

Integrity of Caprock 236

16.5 Injection History and AGI #1 Responses 236

16.6 Discussion and Conclusions 238

References 241

17 Three-Dimensional Reservoir Simulation of Acid Gas Injection in Complex Geology – Process and Practice 243
Liaqat Ali and Russell E. Bentley

17.1 Introduction 244

17.2 Step by Step Approach to a Reservoir Simulation Study for Acid Gas Injection 245

17.3 Seismic Data and Interpretation 245

17.4 Geological Studies 246

17.5 Petrophysical Studies 246

17.6 Reservoir Engineering Analysis 247

17.7 Static Modeling 247

17.8 Reservoir Simulation 248

17.9 Case History 249

17.10 Injection Interval Structure and Modeling 249

17.11 Petrophysical Modeling and Development of Static Model 250

17.12 Injection Zone Characterization 251

17.13 Reservoir Simulation 253

17.14 Summary and Conclusions 256

References 257

18 Production Forecasting of Fractured Wells in Shale Gas Reservoirs with Discontinuous Micro-Fractures 259
Qi Qian, Weiyao Zhu, and Jia Deng

18.1 Introduction 260

18.2 Multi-Scale Flow in Shale Gas Reservoir 261

18.2.1 Multi-scale Nonlinear Seepage Flow Model of Shale Gas Reservoir 261

18.2.2 Adsorption – Desorption Model of Shale Gas Reservoir 263

18.3 Physical Model and Solution of Fractured Well of Shale Gas Reservoir 264

18.3.1 The Dual Porosity Spherical Model with Micro-Fractures Surface Layer 264

18.3.2 The Establishment and Solvement of Seepage Mathematical Model 266

18.4 Analysis of Influencing Factors of Sensitive Parameters 273

18.5 Conclusions 277

18.6 Acknowledgements 278

References 278

19 Study on the Multi-Scale Nonlinear Seepage Flow Theory of Shale Gas Reservoir 281
Weiyao Zhu, Jia Deng, and Qi Qian

19.1 Introduction 282

19.2 Multi-Scale Flowstate Analyses of the Shale Gas Reservoirs 283

19.3 Multi-Scale Nonlinear Seepage Flow Model in Shale Gas Reservoir 285

19.3.1 Nonlinear Seepage Flow Model in Nano-Micro Pores 285

19.3.2 Multi-Scale Seepage Model Considering of Diffusion, Slippage 288

19.3.3 Darcy Flow in Micro Fractures and Fractured Fractures 289

19.4 Transient Flow Model of Composite Fracture Network System 291

19.5 Production Forecasting 294

19.6 Conclusions 298

19.7 Acknowledgements 299

References 299

20 CO2 EOR and Sequestration Technologies in PetroChina 301
Yongle Hu, Xuefei Wang, and Mingqiang Hao

20.1 Introduction 302

20.2 Important Progress in Theory and Technology 302

20.2.1 The Miscible Phase Behaviour of Oil-CO2 System 302

20.2.2 CO2 Flooding Reservoir Engineering Technology 304

20.2.3 Separated Layer CO2 Flooding, Wellbore Anti-Corrosion and High Efficiency Lift Technology 306

20.2.4 Long Distance Pipeline Transportation and Injection Technology 306

20.2.5 Produced Fluid Treatment for CO2 Flooding and Cycling Gas Injection Technology 306

20.2.6 CO2 Flooding Reservoir Monitoring, Performance Analysis Technology 307

20.2.7 Potential Evaluation for CO2 Flooding and Storage 308

20.3 Progress of Pilot Area 311

20.3.1 Block Hei59 312

20.3.2 Block Hei79 313

20.4 Conclusions 315

20.5 Acknowledgements 316

References 317

21 Study on the Microscopic Residual Oil of CO2 Flooding for Extra-High Water-Cut Reservois 319
Zengmin Lun, Rui Wang, Chengyuan Lv, Shuxia Zhao, Dongjiang Lang, and Dong Zhang

21.1 Introduction 319

21.2 Overview of CO2 EOR Mechanisms for Extra High Water Cut Reservoirs 320

21.3 Experimental Microscopic Residual Oil Distribution of CO2 Flooding for Extra High Water Cut Reservoirs 321

21.3.1 NMR Theory 321

21.3.2 In situ NMR Test for Water Flooding and CO2 Flooding 322

21.4 Displacement Characteristics of CO2 Flooding and Improve Oil Recovery Method for Post CO2 Flooding 325

21.4.1 CO2 Displacement Characteristics for Extra High Water Cut Reservoirs 325

21.4.2 Improved Oil Recovery for Post CO2 Flooding 326

21.5 Conclusions 327

References 328

22 Monitoring of Carbon Dioxide Geological Utilization and Storage in China: A Review 331
Qi Li, Ranran Song, Xuehao Liu, Guizhen Liu, and Yankun Sun

22.1 Introduction 332

22.2 Status of CCUS in China 332

22.3 Monitoring of CCUS 336

22.3.1 Monitoring Technology at Home and Abroad 336

22.3.2 U-tube Sampling System 341

22.3.3 Monitoring Technologies in China’s CCUS Projects 341

22.4 Monitoring Technology of China’s Typical CCUS Projects 343

22.4.1 Shenhua CCS Demonstration Project 343

22.4.2 Shengli CO2-EOR Project 345

22.5 Environmental Governance and Monitoring Trends in China 345

22.6 Conclusion 351

22.7 Acknowledgements 352

References 352

23 Separation of Methane from Biogas by Absorption-Adsorption Hybrid Method 359
Yong Pan, Zhe Zhang, Xiong-Shi Tong, Hai Li, Xiao-Hui Wang, Bei Liu,Chang-Yu Sun, Lan-Ying Yang, and Guang-Jin Chen

23.1 Introduction 359

23.2 Experiments 361

23.2.1 Experimental Apparatus 361

23.2.2 Materials 362

23.2.3 Synthesis and Activation of ZIF-67 363

23.2.4 Gas-Slurry Equilibrium Experiments 363

23.2.5 Data Processing 364

23.2.6 Breakthrough Experiment 366

23.3 Results and Discussions 367

23.3.1 Adsorbent Characterization 367

23.3.2 Ab-Adsorption Isothermal 368

23.3.3 Breakthrough Experiment 370

23.4 Conclusions 374

23.5 Acknowledgements 374

References 374

Index 377

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