Corrosion Inhibitors in the Oil and Gas Industry

Viswanathan S. Saji, PhD, is an Assistant Professor/Research Scientist at the Center of Research Excellence in Corrosion, King Fahd University of Petroleum and Minerals, Saudi Arabia. Prior to that, he was a Research Scholar at the University of Kerala (PhD, 2003), Research Associate at Indian Institute of Technology (2004–2005) & Indian Institute of Science (2005–2007), Postdoctoral Researcher at Yonsei University (2007–2008) & Sunchon National University (2009), Senior Research Scientist at Ulsan National Institute of Science and Technology (2009–2010), Research Professor at Chosun University (2008–2009) & Korea University (2010–2013), and Endeavour Research Fellow at University of Adelaide (2014).

Saviour A. Umoren, PhD, is an Associate Professor/Research Scientist with Centre of Research Excellence in Corrosion (CoRE-C) of the Research Institute, King Fahd University of Petroleum & Minerals, Dhahran, Kingdom of Saudi Arabia. He was also a lecturer and researcher at the Department of Chemistry, University of Uyo, Nigeria and the Head of Department of Chemistry, University of Uyo.

Preface xv

Acknowledgments xix

Part I Fundamentals and Approaches 1

1 An Overview of Corrosion in Oil and Gas Industry: Upstream, Midstream, and Downstream Sectors 3
Yahya T. Al-Janabi

1.1 Introduction 3

1.2 Corrosion in Upstream Production Operations 4

1.2.1 Causes of Corrosion in Upstream Environments 7

1.2.1.1 Oxygen 8

1.2.1.2 Hydrogen Sulfide, Polysulfides, and Sulfur 9

1.2.1.3 Carbon Dioxide 10

1.2.1.4 Strong Acids 11

1.2.1.5 Concentrated Brines 11

1.2.2 Corrosion Types in Petroleum Production Operations 11

1.2.3 Corrosion Inhibitors for Oil and Gas Production 12

1.2.3.1 Oil and Gas Wells 12

1.2.3.2 Inhibitor Selection 13

1.2.3.3 Practical Challenges with Inhibition 14

1.2.3.4 Inhibitor Application Methods 14

1.2.3.5 Oxygen Removal 16

1.2.4 Problems Encountered and Protective Measures 17

1.2.4.1 Drilling Fluid Corrosion 17

1.2.4.2 Primary Production 18

1.2.4.3 Corrosion in Secondary Recovery Operations 20

1.2.5 CO₂ Injection 23

1.2.6 Corrosion of Oil and Gas Offshore Production Platforms 23

1.2.7 Corrosion of Gathering Systems and Tanks 23

1.2.7.1 Sweet Gas Corrosion 24

1.2.7.2 Sour Gas Corrosion 24

1.2.7.3 Oil Wells Corrosion 24

1.3 Corrosion in Midstream Sector 25

1.3.1 Control of Internal Corrosion in Carbon Steel Oil Pipeline Systems 27

1.3.2 Control of Internal Corrosion in Carbon Steel Gas Pipeline Systems 28

1.3.3 Control of Internal Corrosion in Carbon Steel Water Pipeline Systems 28

1.3.4 Chemical Inhibition of Internal Corrosion in Carbon Steel Pipeline Systems 29

1.4 Corrosion in Downstream Sector 30

1.4.1 Materials of Construction 31

1.4.2 Corrosion in Refineries and Petrochemical Plants 32

1.4.3 Corrosion Inhibitors in Refinery and Petrochemical Plants 33

1.4.4 Corrosion Control of Water-Recirculating Systems 33

1.4.4.1 Typical Corrosion Reactions in Water-Recirculating Systems 34

1.4.4.2 Water Corrosivity 35

1.4.4.3 Corrosion Control 36

1.5 Conclusions and Outlook 37

References 38

2 Fundamentals of Corrosion and Corrosion Control in Oil and Gas Sectors 41
Anil Bhardwaj

2.1 Introduction 41

2.2 Material Degradation and Corrosion 41

2.3 Electromotive Force (EMF) Series and Galvanic Series 49

2.4 Forms of Corrosion 51

2.4.1 Uniform Corrosion 51

2.4.2 Galvanic or Two-Metal Corrosion 52

2.4.2.1 Factors Affecting Galvanic Corrosion 53

2.4.2.2 How to Reduce Galvanic Corrosion 54

2.4.2.3 Benefits of Galvanic Effect 54

2.4.3 Crevice Corrosion 54

2.4.4 Pitting 55

2.4.5 Intergranular Corrosion 57

2.4.6 Erosion–Corrosion 58

2.4.7 Stress-Corrosion Cracking (SCC) 60

2.4.8 Under-Deposit Corrosion (UDC) 61

2.4.9 Acid Corrosion 63

2.4.10 Microbiologically Influenced Corrosion 63

2.5 Factors Influencing Oilfield Corrosion 66

2.5.1 Free Water and Water Composition 66

2.5.2 Type of Oil 68

2.5.3 Gas Composition 69

2.5.4 Pressure Effect 70

2.5.5 Temperature Effect 71

2.5.6 Velocity Effect 71

2.6 Corrosion Control 72

2.6.1 Material Selection 72

2.6.2 Environment Control 73

2.6.3 Proper Design 73

2.6.4 Chemical Treatment 73

2.7 Conclusions and Outlook 74

References 74

3 Environmental Factors Affecting Corrosion Inhibition in Oil and Gas Industry 77
Mohamed A. Migahed

3.1 Introduction 77

3.2 Environmental Factors Affecting Corrosion Inhibition 78

3.2.1 Influence of Temperature and Pressure 78

3.2.2 Influence of Flow Parameters 81

3.2.3 Effect of Natural Gases 83

3.2.3.1 Effect of Sulfur Dioxide 83

3.2.3.2 Effect of Hydrogen Sulfide 86

3.2.3.3 Effect of Carbon Dioxide 88

3.2.4 Effect of Cationic Species 91

3.2.5 Effect of Anionic Species 91

3.2.6 Effect of Microorganisms 96

3.2.7 Effect of pH 98

3.2.8 Effect of the Pre-corrosion 100

3.3 Conclusions and Outlook 101

References 102

4 Key Materials in Oil and Gas Production and the Choice of Inhibitors 111
Thiago J. Mesquita and Hervé Marchebois

4.1 Introduction 111

4.2 Materials in Oil and Gas Industry 112

4.2.1 Carbon Steel or CRA? 112

4.2.2 Non-metallic Materials 116

4.3 The Choice of Corrosion Inhibitor for Oil and Gas Production 116

4.3.1 Factors Affecting the Efficiency of Corrosion Inhibitor 117

4.3.2 Laboratory Corrosion Inhibitor Selection 119

4.4 Principles of CI Qualification Tests 120

4.4.1 Bubble Test 121

4.4.2 Partitioning Test 122

4.4.2.1 Corrosivity of the Water Phase After Partitioning 122

4.4.2.2 Titrability and Partitioning Coefficient 123

4.4.3 Impact on the Process Test 124

4.4.3.1 Emulsion Tendency 124

4.4.3.2 Foaming Tendency 125

4.4.4 Wheel Test 125

4.4.5 HP Corrosion Test Loop 127

4.4.6 HP Jet Impingement Test 128

4.5 Conclusions and Outlook 129

References 130

5 Corrosion Inhibition in Oil and Gas Industry: Economic Considerations 135
Anupama R. Prasad, Anupama Kunyankandy, and Abraham Joseph

5.1 Introduction 135

5.2 Corrosion: Global Economic Loss 136

5.2.1 Historical Summary of Corrosion Cost Studies 137

5.2.2 NACE–IMPACT: Global Corrosion Cost 138

5.2.3 Global Corrosion Management–IMPACT Estimate 139

5.3 Depreciation in Oil and Gas Industries 140

5.3.1 Corrosion Attacks 140

5.3.2 Failures and Risk Factors 141

5.4 Fiscal Impacts 142

5.4.1 Corrosion Costs a Lot 143

5.5 Inhibition: Monetary Measures 144

5.5.1 Worthy Monitoring 145

5.5.2 Protection in Proper Way 146

5.6 Conclusions and Outlook 147

References 148

Part II Choice of Inhibitors 151

6 Corrosion Inhibitors for Acidizing Process in Oil and Gas Sectors 153
Kashif R. Ansari, Dheeraj Singh Chauhan, Ambrish Singh, Viswanathan S. Saji, and Mumtaz A. Quraishi

6.1 Introduction 153

6.2 Acidizing Process 154

6.2.1 Type of Oil Well Reservoirs 154

6.2.2 Types of Acid Used 155

6.2.3 Methods Used to Control Acidizing Process 157

6.2.3.1 Retarded Acid Systems 157

6.2.3.2 Gelled Acids 157

6.2.3.3 Chemically Retarded Acids 157

6.2.3.4 Emulsified Acids 157

6.2.4 Acid Selection 157

6.2.4.1 Rock-Dissolving Capacity of Acid 158

6.2.4.2 Spending Time of Acid 158

6.2.4.3 Solubility of Reaction Products 158

6.2.4.4 Density and Viscosity 158

6.2.4.5 Etching Pattern After Acidizing 158

6.2.5 Types of Acidizing Process 159

6.3 Application of Corrosion Inhibitors in Acidizing Processes 160

6.4 Selected Acidizing Inhibitors 169

6.5 Conclusions and Outlook 170

References 171

7 Corrosion Inhibitors for Sweet Oilfield Environment (CO₂ Corrosion) 177
Ubong Eduok and Jerzy Szpunar

7.1 Introduction 177

7.2 Mechanism of CO₂ Corrosion 178

7.3 Factors Affecting Sweet Corrosion 179

7.3.1 Effects of Hydrogen Concentration (pH) and Temperature 179

7.3.2 Effects of Flow Rate and Partial Pressure 180

7.3.3 Effects of Molecular Oxygen and Iron Ions (Fe²⁺) Concentration 181

7.4 Toward Inhibition and Control of Sweet Corrosion 181

7.5 Altering Corrosion Kinetics with Corrosion Inhibitors 182

7.6 Corrosion Inhibitors for Sweet Oilfield Environments 183

7.6.1 Corrosion Inhibitors Based on Smaller Molecules 183

7.6.1.1 Imidazoline Derivatives 183

7.6.1.2 Cyclic Non-imidazoline Compounds 195

7.6.1.3 Acyclic Non-imidazoline Compounds 197

7.6.2 Corrosion Inhibitors Based on Macromolecules 210

7.6.2.1 Polymers 210

7.6.2.2 Plant Biomass Extracts 211

7.6.2.3 Others 218

7.7 Biocorrosion in Saturated CO₂ Media 218

7.8 Conclusions and Outlook 219

References 220

8 Corrosion Inhibitors for Sour Oilfield Environment (H₂S Corrosion) 229
Saviour A. Umoren, MosesM. Solomon, and Viswanathan S. Saji

8.1 Introduction 229

8.1.1 Impact of Corrosion on Economy and Life 229

8.1.2 Background on Sour Corrosion 230

8.1.3 Factors Influencing Sour Corrosion 232

8.1.3.1 Effect of H₂S Concentration 232

8.1.3.2 Effect of Temperature and Exposure Duration 233

8.1.3.3 Effect of Flow Rate 233

8.1.3.4 Effect of H₂S Partial Pressure 233

8.1.3.5 Effect of Fluid Chemistry 233

8.2 Corrosion Inhibitors for Sour Oilfield Environment 233

8.2.1 Amine-Based Inhibitors 234

8.2.2 Imidazoline-Based Inhibitors 237

8.2.3 Gemini Surfactant-Based Inhibitors 238

8.2.4 Polymer-Based Inhibitors 244

8.3 Conclusions and Outlook 247

References 247

9 Corrosion Inhibitors for Refinery Operations 255
Yahya T. Al-Janabi

9.1 Introduction 255

9.2 Areas/Units Where Inhibitors are in Demand in Refineries 257

9.2.1 Atmospheric and Vacuum Crude Oil Distillation Units 257

9.2.2 Fluid Catalytic Cracking: Coker 259

9.2.3 Hydroprocessing 260

9.2.4 Catalytic Reforming 260

9.2.5 Amine (Acid Gas Treatment) Plants 262

9.2.6 Support Units 262

9.3 Types of Aggressive Species Encountered in Refineries 262

9.3.1 Air 263

9.3.2 Water 263

9.3.3 Hydrogen Sulfide 263

9.3.4 Hydrogen Chloride 263

9.3.5 Nitrogen Compounds 264

9.3.6 Sour Water 264

9.4 Common Types of Inhibitors Employed/Reported in Refinery Units 264

9.4.1 Neutralizers 264

9.4.2 Filming Inhibitors 265

9.5 Conclusions and Outlook 268

References 268

10 Inhibitors for High-Temperature Corrosion in Oil and Gas Fields 271
Vitalis I. Chukwuike and Rakesh C. Barik

10.1 Introduction 271

10.2 High-Temperature Corrosion in Oil and Gas Fields 272

10.3 Mechanism of High-Temperature Corrosion in Oil and Gas Field 273

10.3.1 High-Temperature Oxidation 274

10.3.2 High-Temperature Sulfidation 276

10.3.3 High-Temperature Carburization 276

10.3.4 High-Temperature Chlorination 277

10.3.5 High-Temperature Nitridation 277

10.3.6 Sulfidation–Oxidation 278

10.3.7 Corrosion Due to Formation of Ash, Deposits, and Molten Salts 278

10.4 Categories and Choice of Inhibitors for Oil and Gas High-Temperature Corrosion 278

10.4.1 Calcium Carbonate Scale and Ash Deposit Inhibitors 278

10.4.2 High-Temperature Acidization Corrosion Inhibitors 279

10.4.3 High-Temperature Naphthenic Acid Corrosion Inhibitors 283

10.4.4 Other Inhibitors of High-Temperature Corrosion 285

10.5 Conclusions and Outlook 286

References 287

11 Experience in Using Chemicals to Mitigate Corrosion in Difficult Corrosive Environments in the Oil and Gas Industry 289
Sunder Ramachandran

11.1 Introduction 289

11.2 Corrosion Inhibition for Systems with High Amounts of H₂S 290

11.3 Corrosion Inhibition for CO₂ Tertiary Flood Systems and CO₂ Sequestration 292

11.4 Corrosion Inhibition in Deepwater Systems 295

11.5 Corrosion Inhibition at High Temperatures 296

11.6 Conclusions and Outlook 297

References 298

12 Polymeric Corrosion Inhibitors for Oil and Gas Industry 303
Saviour A. Umoren and Moses M. Solomon

12.1 Introduction 303

12.2 Polymeric Corrosion Inhibitors 304

12.2.1 Polymeric Inhibitors for Chemical Cleaning 304

12.2.2 Inhibitors for Acidization Process 308

12.2.3 Inhibitors for Sweet and Sour Environments 311

12.2.4 Inhibitors for High-Temperature Applications 315

12.3 Conclusions and Outlook 315

References 317

13 Microbiologically Influenced Corrosion Inhibition in Oil and Gas Industry 321
Bhawna Chugh, Sanjeeve Thakur, and Ashish Kumar Singh

13.1 Introduction 321

13.2 Biofilm Formation 322

13.3 Microbial Communities Related to Corrosion 323

13.3.1 Sulfate-Reducing Bacteria 323

13.3.2 Iron-Oxidizing Bacteria 324

13.3.3 Acid-Producing Bacteria 324

13.3.4 Sulfur-Oxidizing Bacteria 325

13.3.5 Slime-Forming Bacteria 325

13.4 Potential Prevention Strategies 325

13.4.1 Periodic Pigging 325

13.4.2 Cleanliness 326

13.4.3 Cathodic Protection and Coatings 326

13.4.4 Biocides/Inhibitors 327

13.4.5 Biological Treatment 328

13.5 Recent Developments of Chemical Inhibitors to Mitigate MIC 329

13.6 Biological Inhibition of MIC 329

13.6.1 Corrosion Inhibition by Nitrate-Reducing Bacteria 329

13.6.2 Corrosion Inhibition by Regenerative Biofilms 331

13.6.2.1 Corrosion Inhibition by Eviction of Corrosive Agents 331

13.6.2.2 Corrosion Inhibition by Formation of Protective Barrier Layer 332

13.6.2.3 Corrosion Inhibition via Antimicrobial Producing Biofilm 332

13.6.2.4 Corrosion Possessing Biofilm Secreted Corrosion Inhibitor 333

13.6.2.5 Corrosion Inhibition with Biofilm Secreted Bio Surfactant 333

13.7 Conclusions and Outlook 333

References 334

14 Vapor Phase Corrosion Inhibitors for Oil and Gas Field Applications 339
Benjamín Valdez-Salas, Michael Schorr-Wiener, and Nelson Cheng

14.1 Introduction 339

14.2 Magna International VPCIs 340

14.3 Corrosion and Its Control in OGI 341

14.3.1 Fundamentals of Corrosion 341

14.3.2 Oil and Gas Industries 342

14.3.3 OGI Sectors 343

14.3.4 Corrosiveness of Oil and Gas Products 345

14.3.5 Metals and Alloys in OGI 346

14.4 Vapor Phase Corrosion Inhibitors 346

14.4.1 Fundamentals 346

14.4.2 VPCI Application in OGI 348

14.4.3 Testing and Monitoring of VPCI 349

14.4.4 Research and Development 350

14.5 Conclusions and Outlook 353

Acknowledgments 353

References 353

15 Mechanisms of Inhibitor Action: Passivation and Self-Healing 359
Ivana Jevremović, Ying-Hsuan Chen, Abdulrahman Altin, and Andreas Erbe

15.1 Introduction 359

15.2 Systematics and Phenomenology 360

15.3 Surface Active Inhibitors 364

15.4 Case Study (1): Imidazoline-Based Surfactant for Mitigation of Mild Steel Corrosion in the Presence of CO₂ 367

15.5 Case Study (2): The Interaction of 2-Mercaptobenzothiazole (MBT) with Copper 369

15.6 Case Study (3): β-Cyclodextrin Facilitates Release of Inhibitors 372

15.7 Conclusions and Outlook 375

References 376

Part III Interaction with Co-additives 383

16 Antiscalants and Their Compatibility with Corrosion Inhibitors 385
Qiwei Wang and Tao Chen

16.1 Introduction 385

16.2 Scale Formation 385

16.3 Scale Mitigation Strategy 388

16.3.1 Flow Control 388

16.3.2 Fluid Alteration 388

16.3.3 Deposit Removal 388

16.3.4 Chemical Inhibition 388

16.4 Antiscalant Chemistry 389

16.5 Antiscalant Function Mechanisms 393

16.5.1 Nucleation Inhibition 393

16.5.2 Crystal Growth Retardation 394

16.5.3 Crystal Shape Modification 395

16.5.4 Dispersion 395

16.6 Antiscalant Treatment 396

16.7 Compatibility with Corrosion Inhibitors 397

16.7.1 Impact of Corrosion Inhibitor on Antiscalant Performance 398

16.7.2 Impact of Antiscalant on Corrosion Inhibitor Performance 399

16.8 Conclusions and Outlook 399

References 400

17 Hydrate Inhibitors and Their Interferences in Corrosion Inhibition 407
Yutaek Seo

17.1 Introduction 407

17.2 Gas Hydrate Blockage Formation Process 407

17.3 Hydrates Inhibition Strategies with Alcohols or Glycols 409

17.4 Kinetic Hydrate Inhibitors 412

17.5 Interaction Between Hydrate and Corrosion Inhibitors 414

17.6 Conclusions and Outlook 416

References 416

18 Sulfide Scavengers and Their Interference in Corrosion Inhibition 421
Viswanathan S. Saji

18.1 Introduction 421

18.2 Sulfide Scavengers: Types and Properties 422

18.3 Corrosion and Fouling Inhibiting/Inducing Properties of Scavengers and Their Compatibility with Co-additives 424

18.4 Conclusions and Outlook 427

References 428

Index 433

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