Biodesulfurization in Petroleum Refining

From basic tenets to the latest advances, this is the most comprehensive and up-to-date coverage of the process of biodesulfurization in the petroleum refining industry.

Petroleum refining and process engineering is constantly changing. No new refineries are being built, but companies all over the world are still expanding or re-purposing huge percentages of their refineries every year, year after year. Rather than building entirely new plants, companies are spending billions of dollars in the research and development of new processes that can save time and money by being more efficient and environmentally safer. Biodesulfurization is one of those processes, and nowhere else it is covered more thoroughly or with more up-to-date research of the new advances than in this new volume from Wiley-Scrivener.

Besides the obvious benefits to biodesulfurization, there are new regulations in place within the industry with which companies will, over the next decade or longer, spend literally tens, if not hundreds, of billions of dollars to comply. Whether for the veteran engineer needing to update his or her library, the beginning engineer just learning about biodesulfurization, or even the student in a chemical engineering class, this outstanding new volume is a must-have. Especially it covers also the bioupgrading of crude oil and its fractions, biodenitrogenation technology and application of nanotechnology on both biodesulfurization and biodenitrogenation technologies.

Nour Shafik El-Gendy, PhD, is a Professor of Petroleum and Environmental Biotechnology, vice head for the Department of Process Design & Development and former head manager of the Petroleum Biotechnology Lab at the Egyptian Petroleum Research Institute (EPRI). She is an editor, reviewer, and contributor to many scientific journals, including the Journal of Sustainable Energy Engineering, from Scrivener Publishing. She has numerous awards, papers, and presentations to her credit, including being the author or co-author of several books. She is vice coordinator of the Scientific Research Committee, National Council for Women (NCW) of Egypt and member in the Egyptian Young Academy of Sciences (EYAS). El-Gendy is an expert in the field of environmental pollution, wastewater treatment, biofuel, petroleum upgrading, green chemistry, nanobiotechnology, recycling of wastes and biocorrosion. She has extensive research, teaching, and lecturing experience.

Hussein Mohamed Nabil Nassar, PhD, is a researcher at the Petroleum Biotechnology Laboratory at the Egyptian Petroleum Research Institute (EPRI). He has been the author or co-author of many scholarly papers and has extensive research experience in the field of bioremediation, biofuels, green chemistry, wastewater treatment, petroleum bioupgrading and nanobiotechnology.

Preface xiii

1 Background 1

List of Abbreviations and Nomenclature 1

1.1 Petroleum 2

1.2 Petroleum Composition 7

1.2.1 Petroleum Hydrocarbons 8

1.2.2 Petroleum Non-Hydrocarbons 12

1.2.2.1 Problems Generated by Asphaltenes 14

1.3 Sulfur Compounds 15

1.4 Sulfur in Petroleum Major Refinery Products 20

1.4.1 Gasoline 20

1.4.2 Kerosene 23

1.4.3 Jet Fuel 23

1.4.4 Diesel Fuel 23

1.4.5 Heating/Fuel Oils 24

1.4.6 Bunker Oil 24

1.5 Sulfur Problem 25

1.6 Legislative Regulations of Sulfur Levels in Fuels 29

References 32

2 Desulfurization Technologies 39

List of Abbreviations and Nomenclature 39

2.1 Introduction 43

2.2 Hydrodesulfurization 47

2.3 Oxidative Desulfurization 71

2.4 Selective Adsorption 108

2.5 Biocatalytic Desulfurization 127

2.5.1 Anaerobic Process 127

2.5.2 Aerobic Process 128

References 130

3 Biodesulfurization of Natural Gas 159

List of Abbreviations and Nomenclature 159

3.1 Introduction 161

3.2 Natural Gas Processing 169

3.3 Desulfurization Processes 183

3.3.1 Scavengers 183

3.3.2 Adsorption 187

3.3.3 Liquid Redox Processes 193

3.3.4 Claus Plants 195

3.3.4.1 Classic Claus Plant 196

3.3.4.2 Split-Flow Claus Plant 198

3.3.4.3 Oxygen Enrichment Claus Plant 199

3.3.4.4 Claus Plant Tail Gas 199

3.3.5 Absorption/Desorption Process 201

3.3.6 Biodesulfurization 203

3.3.6.1 Photoautotrophic Bacteria 206

3.3.6.2 Heterotrophic Bacteria 211

3.3.6.3 Chemotrophic Bacteria 212

3.3.7 Other Approaches Concerning the Biodesulfurization of Natural Gas 231

References 242

4 Microbial Denitrogenation of Petroleum and its Fractions 263

List of Abbreviations and Nomenclature 263

4.1 Introduction 265

4.2 Denitrogenation of Petroleum and its Fractions 269

4.2.1 Hydrodenitrogenation 269

4.2.2 Adsorptive Denitrogenation 272

4.2.3 Extractive and Catalytic Oxidative Denitrogenation 278

4.3 Microbial Attack of Nitrogen Polyaromatic Heterocyclic Compounds (NPAHs) 279

4.4 Enhancing Biodegradation of NPAHs by Magnetic Nanoparticles 295

4.5 Challenges and Opportunities for BDN in Petroleum Industries 300

References 307

5 Bioadsorptive Desulfurization of Liquid Fuels 327

List of Abbreviations and Nomenclature 327

5.1 Introduction 329

5.2 ADS by Agroindustrial-Wastes Activated Carbon 332

5.3 ADS on Modified Activated Carbon 342

5.4 ADS on Carbon Aerogels 352

5.5 ADS on Activated Carbon Fibers 353

5.6 ADS on Natural Clay and Zeolites 355

5.7 ADS on New Adsorbents Prepared from Different Biowastes 360

References 365

6 Microbial Attack of Organosulfur Compounds 375

List of Abbreviations and Nomenclature 375

6.1 Introduction 377

6.2 Biodegradation of Sulfur Compounds in the Environment 380

6.3 Microbial Attack on Non–Heterocyclic Sulfur–Containing Hydrocarbons 383

6.3.1 Alkyl and Aryl Sulfides 383

6.3.2 Non – Aromatic Cyclic Sulfur – Containing Hydrocarbons 386

6.4 Microbial Attack of Heterocyclic Sulfur – Hydrocarbons 388

6.4.1 Thiophenes 389

6.4.2 Benzothiophenes and Alkyl-Substituted Benzothiophenes 390

6.4.3 Naphthothiophenes 402

6.4.4 Dibenzothiophene and Alkyl-Substituted Dibenzothiophenes 406

6.4.4.1 Aerobic Biodesulfurization of DBT 406

6.4.4.2 Aerobic Biodesulfurization of Alkylated DBT 419

6.4.4.3 Anaerobic Biodesulfurization of DBT 421

6.5 Recent Elucidated DBT-BDS Pathways 422

References 439

7 Enzymology and Genetics of Biodesulfurization Process 459

List of Abbreviations and Nomenclature 459

7.1 Introduction 461

7.2 Genetics of PASHs BDS Pathway 462

7.2.1 Anaerobic BDS Pathway 462

7.2.2 Aerobic BDS Pathway 463

7.2.2.1 Kodama Pathway 463

7.2.2.2 Complete Degradation Pathway 464

7.2.2.3 4S-Pathway 466

7.3 The Desulfurization dsz Genes 468

7.4 Enzymes Involved in Specific Desulfurization of Thiophenic Compounds 472

7.4.1 The Dsz Enzymes 472

7.4.1.1 DszC Enzyme (DBT-Monooxygenase) 474

7.4.1.2 DszA Enzyme (DBTO₂-Monooxygenase) 476

7.4.1.3 DszB Enzyme (HBPS- Desulfinase) 477

7.4.1.4 DszD Enzyme (Flavin-Oxidoreductase Enzyme) 478

7.5 Repression of dsz Genes 480

7.6 Recombinant Biocatalysts for BDS 484

References 506

8 Factors Affecting the Biodesulfurization Process 521

List of Abbreviations and Nomenclature 521

8.1 Introduction 524

8.2 Effect of Incubation Period 525

8.3 Effect of Temperature and pH 527

8.4 Effect of Dissolved Oxygen Concentration 530

8.5 Effect of Agitation Speed 532

8.6 Effect of Initial Biomass Concentration 536

8.7 Effect of Biocatalyst Age 538

8.8 Effect of Mass Transfer 541

8.9 Effect of Surfactant 541

8.10 Effect of Initial Sulfur Concentration 544

8.11 Effect of Type of S-Compounds 546

8.12 Effect of Organic Solvent and Oil to Water Phase Ratio 553

8.13 Effect of Medium Composition 560

8.14 Effect of Growing and Resting Cells 579

8.15 Inhibitory Effect of Byproducts 580

8.16 Statistical Optimization 590

References 616

9 Kinetics of Batch Biodesulfurization Process 639

List of Abbreviations and Nomenclature 639

9.1 Introduction 642

9.2 General Background 643

9.2.1 Phases of Microbial Growth 643

9.2.1.1 The Lag Phase 644

9.2.1.2 The Log Phase 644

9.2.1.3 The Stationary Phase 645

9.2.1.4 The Decline Phase 645

9.2.2 Modeling of Population Growth as a Function of Incubation Time 645

9.3 Microbial Growth Kinetics 645

9.3.1 Exponential Growth Model 645

9.3.2 Logistic Growth Model 648

9.4 Some of the Classical Kinetic Models Applied in BDS-Studies 650

9.5 Factors Affecting the Rate of Microbial Growth 651

9.5.1 Effect of Temperature 651

9.5.2 Effect of pH 654

9.5.3 Effect of Oxygen 654

9.6 Enzyme Kinetics 654

9.6.1 Basic Enzyme Reactions 656

9.6.2 Factors Affecting the Enzyme Activity 657

9.6.2.1 Enzyme Concentration 657

9.6.2.2 Substrate Concentration 658

9.6.2.3 Effect of Inhibitors on Enzyme Activity 659

9.6.2.4 Effect of Temperature 660

9.6.2.5 Effect of pH 661

9.7 Michaelis-Menten Equation 662

9.7.1 Direct Integration Procedure 664

9.7.2 Lineweaver-Burk Plot Method 666

9.7.3 Eadie-Hofstee 666

9.8 Kinetics of a Multi-Substrates System 667

9.9 Traditional 4S-Pathway 668

9.9.1 Formulation of a Kinetic Model for DBT Desulfurization According to 4S-Pathway 669

9.10 Different Kinetic Studies on the Parameters Affecting the BDS Process 673

9.11 Evaluation of the Tested Biocatalysts 734

9.11.1 Kinetics of the Overall Biodesulfurization Reaction 735

9.11.2 Maximum Percentage of Desulfurization (X^MAX_BDS %) 735

9.11.3 Time for Maximum Biodesulfurization ^tBDS_max (min) 735

9.11.4 Initial DBT Removal Rate R^O_DBT (μmol/L/min) 736

9.11.5 Maximum Productivity P^MAX_BDS (%/min) 736

9.11.6 Specific Conversion Rate (SE %L/g/min) 736

References 737

10 Enhancement of BDS Efficiency 753

List of Abbreviations and Nomenclature 753

10.1 Introduction 756

10.2 Isolation of Selective Biodesulfurizing Microorganisms with Broad Versatility on Different S-Compounds 757

10.2.1 Anaerobic Biodesulfurizing Microorganisms 758

10.2.2 Bacteria Capable of Aerobic Selective DBT-BDS 759

10.2.3 Microorganisms with Selective BDS of Benzothiophene and Dibenzothiophene 769

10.2.4 Microorganisms with Methoxylation Pathway 770

10.2.5 Microorganisms with High Tolerance for Oil/Water Phase Ratio 771

10.2.6 Thermotolerant Microorganisms with Selective BDS Capability 772

10.2.7 BDS Using Yeast and Fungi 776

10.3 Genetics and its Role in Improvement of BDS Process 778

10.4 Overcoming the Repression Effects of Byproducts 789

10.5 Enzymatic Oxidation of Organosulfur Compounds 793

10.6 Enhancement of Biodesulfurization via Immobilization 795

10.6.1 Types of Immobilization 800

10.6.1.1 Adsorption 800

10.6.1.2 Covalent Binding 809

10.6.1.3 Encapsulation 809

10.6.1.4 Entrapment 810

10.7 Application of Nano-Technology in BDS Process 826

10.8 Role of Analytical Techniques in BDS 849

10.8.1 Gas Chromatography 850

10.8.1.1 Determination of Sulfur Compounds by GC 850

10.8.1.2 Assessment of Biodegradation 851

10.8.2 Presumptive Screening for Desulfurization and Identification of BDS Pathway 852

10.8.2.1 Gibb’s Assay 853

10.8.2.2 Phenol Assay 853

10.8.3 More Advanced Screening for Desulfurization and Identification of BDS Pathway 854

10.8.3.1 High Performance Liquid Chromatography 854

10.8.3.2 X-ray Sulfur Meter and other Techniques for Determining Total Sulfur Content 855 References 857

11 Biodesulfurization of Real Oil Feed 895

List of Abbreviations and Nomenclature 895

11.1 Introduction 897

11.2 Biodesulfurization of Crude Oil 903

11.3 Biodesulfurization of Different Oil Distillates 909

11.4 BDS of Crude Oil and its Distillates by Thermophilic Microorganisms 921

11.5 Application of Yeast and Fungi in BDS of Real Oil Feed 923

11.6 Biocatalytic Oxidation 924

11.7 Anaerobic BDS of Real Oil Feed 926

11.8 Deep Desulfurization of Fuel Streams by Integrating Microbial with Non-Microbial Methods 928

11.8.1 BDS as a Complement to HDS 928

11.8.2 BDS as a Complementary to ADS 939

11.8.3 Coupling Non-Hydrodesulfurization with BDS 945

11.8.4 Three Step BDS-ODS-RADS 945

11.9 BDS of other Petroleum Products 946

References 952

12 Challenges and Opportunities 973

List of Abbreviations and Nomenclature 973

12.1 Introduction 975

12.2 New Strains with Broad Versatility 983

12.3 New Strains with Higher Hydrocarbon Tolerance 990

12.4 Overcoming the Feedback Inhibition of the End-Products 994

12.5 Biodesulfurization under Thermophilic Conditions 995

12.6 Anaerobic Biodesulfurization 997

12.7 Biocatalytic Oxidation 1000

12.8 Perspectives for Enhancing the Rate of BDS 1001

12.8.1 Application of Genetics in BDS 1002

12.8.2 Implementation of Resting Cells 1009

12.8.3 Microbial Consortium and BDS 1011

12.8.4 Surfactants and BDS 1014

12.8.5 Application of Nanotechnology in the BDS Process 1017

12.9 Production of Valuable Products 1028

12.10 Storage of Fuel and Sulfur 1031

12.11 Process Engineering Research 1033

12.12 BDS Process of Real Oil Feed 1053

12.13 BDS as a Complementary Technology 1061

12.14 Future Perspectives 1063

12.15 Techno-Economic Studies 1066

12.16 Economic Feasibility 1068

12.17 Fields of Developments 1077

12.18 BDS Now and Then 1080

12.19 Conclusion 1083

References 1084

Glossary 1119

Index 1155

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