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.

Table of Contents:
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 (XMAXBDS %) 735 9.11.3 Time for Maximum Biodesulfurization tBDSmax (min) 735 9.11.4 Initial DBT Removal Rate RODBT (μmol/L/min) 736 9.11.5 Maximum Productivity PMAXBDS (%/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

About the Author :
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.