Biodesulfurization in Petroleum Refining

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 xiii1 Background 1List of Abbreviations and Nomenclature 11.1 Petroleum 21.2 Petroleum Composition 71.2.1 Petroleum Hydrocarbons 81.2.2 Petroleum Non-Hydrocarbons 121.2.2.1 Problems Generated by Asphaltenes 141.3 Sulfur Compounds 151.4 Sulfur in Petroleum Major Refinery Products 201.4.1 Gasoline 201.4.2 Kerosene 231.4.3 Jet Fuel 231.4.4 Diesel Fuel 231.4.5 Heating/Fuel Oils 241.4.6 Bunker Oil 241.5 Sulfur Problem 251.6 Legislative Regulations of Sulfur Levels in Fuels 29References 322 Desulfurization Technologies 39List of Abbreviations and Nomenclature 392.1 Introduction 432.2 Hydrodesulfurization 472.3 Oxidative Desulfurization 712.4 Selective Adsorption 1082.5 Biocatalytic Desulfurization 1272.5.1 Anaerobic Process 1272.5.2 Aerobic Process 128References 1303 Biodesulfurization of Natural Gas 159List of Abbreviations and Nomenclature 1593.1 Introduction 1613.2 Natural Gas Processing 1693.3 Desulfurization Processes 1833.3.1 Scavengers 1833.3.2 Adsorption 1873.3.3 Liquid Redox Processes 1933.3.4 Claus Plants 1953.3.4.1 Classic Claus Plant 1963.3.4.2 Split-Flow Claus Plant 1983.3.4.3 Oxygen Enrichment Claus Plant 1993.3.4.4 Claus Plant Tail Gas 1993.3.5 Absorption/Desorption Process 2013.3.6 Biodesulfurization 2033.3.6.1 Photoautotrophic Bacteria 2063.3.6.2 Heterotrophic Bacteria 2113.3.6.3 Chemotrophic Bacteria 2123.3.7 Other Approaches Concerning the Biodesulfurization of Natural Gas 231References 2424 Microbial Denitrogenation of Petroleum and its Fractions 263List of Abbreviations and Nomenclature 2634.1 Introduction 2654.2 Denitrogenation of Petroleum and its Fractions 2694.2.1 Hydrodenitrogenation 2694.2.2 Adsorptive Denitrogenation 2724.2.3 Extractive and Catalytic Oxidative Denitrogenation 2784.3 Microbial Attack of Nitrogen Polyaromatic Heterocyclic Compounds (NPAHs) 2794.4 Enhancing Biodegradation of NPAHs by Magnetic Nanoparticles 2954.5 Challenges and Opportunities for BDN in Petroleum Industries 300References 3075 Bioadsorptive Desulfurization of Liquid Fuels 327List of Abbreviations and Nomenclature 3275.1 Introduction 3295.2 ADS by Agroindustrial-Wastes Activated Carbon 3325.3 ADS on Modified Activated Carbon 3425.4 ADS on Carbon Aerogels 3525.5 ADS on Activated Carbon Fibers 3535.6 ADS on Natural Clay and Zeolites 3555.7 ADS on New Adsorbents Prepared from Different Biowastes 360References 3656 Microbial Attack of Organosulfur Compounds 375List of Abbreviations and Nomenclature 3756.1 Introduction 3776.2 Biodegradation of Sulfur Compounds in the Environment 3806.3 Microbial Attack on Non–Heterocyclic Sulfur–Containing Hydrocarbons 3836.3.1 Alkyl and Aryl Sulfides 3836.3.2 Non – Aromatic Cyclic Sulfur – Containing Hydrocarbons 3866.4 Microbial Attack of Heterocyclic Sulfur – Hydrocarbons 3886.4.1 Thiophenes 3896.4.2 Benzothiophenes and Alkyl-Substituted Benzothiophenes 3906.4.3 Naphthothiophenes 4026.4.4 Dibenzothiophene and Alkyl-Substituted Dibenzothiophenes 4066.4.4.1 Aerobic Biodesulfurization of DBT 4066.4.4.2 Aerobic Biodesulfurization of Alkylated DBT 4196.4.4.3 Anaerobic Biodesulfurization of DBT 4216.5 Recent Elucidated DBT-BDS Pathways 422References 4397 Enzymology and Genetics of Biodesulfurization Process 459List of Abbreviations and Nomenclature 4597.1 Introduction 4617.2 Genetics of PASHs BDS Pathway 4627.2.1 Anaerobic BDS Pathway 4627.2.2 Aerobic BDS Pathway 4637.2.2.1 Kodama Pathway 4637.2.2.2 Complete Degradation Pathway 4647.2.2.3 4S-Pathway 4667.3 The Desulfurization dsz Genes 4687.4 Enzymes Involved in Specific Desulfurization of Thiophenic Compounds 4727.4.1 The Dsz Enzymes 4727.4.1.1 DszC Enzyme (DBT-Monooxygenase) 4747.4.1.2 DszA Enzyme (DBTO2-Monooxygenase) 4767.4.1.3 DszB Enzyme (HBPS- Desulfinase) 4777.4.1.4 DszD Enzyme (Flavin-Oxidoreductase Enzyme) 4787.5 Repression of dsz Genes 4807.6 Recombinant Biocatalysts for BDS 484References 5068 Factors Affecting the Biodesulfurization Process 521List of Abbreviations and Nomenclature 5218.1 Introduction 5248.2 Effect of Incubation Period 5258.3 Effect of Temperature and pH 5278.4 Effect of Dissolved Oxygen Concentration 5308.5 Effect of Agitation Speed 5328.6 Effect of Initial Biomass Concentration 5368.7 Effect of Biocatalyst Age 5388.8 Effect of Mass Transfer 5418.9 Effect of Surfactant 5418.10 Effect of Initial Sulfur Concentration 5448.11 Effect of Type of S-Compounds 5468.12 Effect of Organic Solvent and Oil to Water Phase Ratio 5538.13 Effect of Medium Composition 5608.14 Effect of Growing and Resting Cells 5798.15 Inhibitory Effect of Byproducts 5808.16 Statistical Optimization 590References 6169 Kinetics of Batch Biodesulfurization Process 639List of Abbreviations and Nomenclature 6399.1 Introduction 6429.2 General Background 6439.2.1 Phases of Microbial Growth 6439.2.1.1 The Lag Phase 6449.2.1.2 The Log Phase 6449.2.1.3 The Stationary Phase 6459.2.1.4 The Decline Phase 6459.2.2 Modeling of Population Growth as a Function of Incubation Time 6459.3 Microbial Growth Kinetics 6459.3.1 Exponential Growth Model 6459.3.2 Logistic Growth Model 6489.4 Some of the Classical Kinetic Models Applied in BDS-Studies 6509.5 Factors Affecting the Rate of Microbial Growth 6519.5.1 Effect of Temperature 6519.5.2 Effect of pH 6549.5.3 Effect of Oxygen 6549.6 Enzyme Kinetics 6549.6.1 Basic Enzyme Reactions 6569.6.2 Factors Affecting the Enzyme Activity 6579.6.2.1 Enzyme Concentration 6579.6.2.2 Substrate Concentration 6589.6.2.3 Effect of Inhibitors on Enzyme Activity 6599.6.2.4 Effect of Temperature 6609.6.2.5 Effect of pH 6619.7 Michaelis-Menten Equation 6629.7.1 Direct Integration Procedure 6649.7.2 Lineweaver-Burk Plot Method 6669.7.3 Eadie-Hofstee 6669.8 Kinetics of a Multi-Substrates System 6679.9 Traditional 4S-Pathway 6689.9.1 Formulation of a Kinetic Model for DBT Desulfurization According to 4S-Pathway 6699.10 Different Kinetic Studies on the Parameters Affecting the BDS Process 6739.11 Evaluation of the Tested Biocatalysts 7349.11.1 Kinetics of the Overall Biodesulfurization Reaction 7359.11.2 Maximum Percentage of Desulfurization (XMAXBDS %) 7359.11.3 Time for Maximum Biodesulfurization tBDSmax (min) 7359.11.4 Initial DBT Removal Rate RODBT (μmol/L/min) 7369.11.5 Maximum Productivity PMAXBDS (%/min) 7369.11.6 Specific Conversion Rate (SE %L/g/min) 736References 73710 Enhancement of BDS Efficiency 753List of Abbreviations and Nomenclature 75310.1 Introduction 75610.2 Isolation of Selective Biodesulfurizing Microorganisms with Broad Versatility on Different S-Compounds 75710.2.1 Anaerobic Biodesulfurizing Microorganisms 75810.2.2 Bacteria Capable of Aerobic Selective DBT-BDS 75910.2.3 Microorganisms with Selective BDS of Benzothiophene and Dibenzothiophene 76910.2.4 Microorganisms with Methoxylation Pathway 77010.2.5 Microorganisms with High Tolerance for Oil/Water Phase Ratio 77110.2.6 Thermotolerant Microorganisms with Selective BDS Capability 77210.2.7 BDS Using Yeast and Fungi 77610.3 Genetics and its Role in Improvement of BDS Process 77810.4 Overcoming the Repression Effects of Byproducts 78910.5 Enzymatic Oxidation of Organosulfur Compounds 79310.6 Enhancement of Biodesulfurization via Immobilization 79510.6.1 Types of Immobilization 80010.6.1.1 Adsorption 80010.6.1.2 Covalent Binding 80910.6.1.3 Encapsulation 80910.6.1.4 Entrapment 81010.7 Application of Nano-Technology in BDS Process 82610.8 Role of Analytical Techniques in BDS 84910.8.1 Gas Chromatography 85010.8.1.1 Determination of Sulfur Compounds by GC 85010.8.1.2 Assessment of Biodegradation 85110.8.2 Presumptive Screening for Desulfurization and Identification of BDS Pathway 85210.8.2.1 Gibb’s Assay 85310.8.2.2 Phenol Assay 85310.8.3 More Advanced Screening for Desulfurization and Identification of BDS Pathway 85410.8.3.1 High Performance Liquid Chromatography 85410.8.3.2 X-ray Sulfur Meter and other Techniques for Determining Total Sulfur Content 855 References 85711 Biodesulfurization of Real Oil Feed 895List of Abbreviations and Nomenclature 89511.1 Introduction 89711.2 Biodesulfurization of Crude Oil 90311.3 Biodesulfurization of Different Oil Distillates 90911.4 BDS of Crude Oil and its Distillates by Thermophilic Microorganisms 92111.5 Application of Yeast and Fungi in BDS of Real Oil Feed 92311.6 Biocatalytic Oxidation 92411.7 Anaerobic BDS of Real Oil Feed 92611.8 Deep Desulfurization of Fuel Streams by Integrating Microbial with Non-Microbial Methods 92811.8.1 BDS as a Complement to HDS 92811.8.2 BDS as a Complementary to ADS 93911.8.3 Coupling Non-Hydrodesulfurization with BDS 94511.8.4 Three Step BDS-ODS-RADS 94511.9 BDS of other Petroleum Products 946References 95212 Challenges and Opportunities 973List of Abbreviations and Nomenclature 97312.1 Introduction 97512.2 New Strains with Broad Versatility 98312.3 New Strains with Higher Hydrocarbon Tolerance 99012.4 Overcoming the Feedback Inhibition of the End-Products 99412.5 Biodesulfurization under Thermophilic Conditions 99512.6 Anaerobic Biodesulfurization 99712.7 Biocatalytic Oxidation 100012.8 Perspectives for Enhancing the Rate of BDS 100112.8.1 Application of Genetics in BDS 100212.8.2 Implementation of Resting Cells 100912.8.3 Microbial Consortium and BDS 101112.8.4 Surfactants and BDS 101412.8.5 Application of Nanotechnology in the BDS Process 101712.9 Production of Valuable Products 102812.10 Storage of Fuel and Sulfur 103112.11 Process Engineering Research 103312.12 BDS Process of Real Oil Feed 105312.13 BDS as a Complementary Technology 106112.14 Future Perspectives 106312.15 Techno-Economic Studies 106612.16 Economic Feasibility 106812.17 Fields of Developments 107712.18 BDS Now and Then 108012.19 Conclusion 1083References 1084Glossary 1119Index 1155