Gas Hydrate in Water Treatment

Bhajan Lal, PhD, is a Senior Lecturer, Chemical Engineering Department, Universiti Teknologi PETRONAS (UTP), Malaysia. He is a core research member of the Carbon Dioxide Research Centre at the UTP Institute of Contaminant Management. After receiving his PhD degree from JMI, Central University, India, he worked as postdoctoral research fellow and Research Scientist in USA, Canada, South Africa, Turkey, and Malaysia. His main areas of research interests are gas hydrates and their applications in CO2 capture and storage, natural gas storage, flow assurance, Desalination. He graduated five MSc, seven PhD, and one postdoc students since 2013. He has published 90 peer-reviewed journal papers, 45 conference papers, and 4 book chapters and two books titled Chemical Additives for Gas Hydrates and Application of ionic liquids in Flow assurance. Dr. Lal has secured consultancy projects and delivered short courses on gas hydrate in flow assurance and machine learning in flow assurance. In addition, as project leader, he has secured eight gas hydrate-related research projects worth RM 2.3 million from oil and gas industries, UTP, and the Malaysian Government.Sirisha Nallakukkala is a Research Fellow and Graduate Assistant at Research Centre for CO2 Capture (RCCO2C), Chemical Engineering Department, Universiti Teknologi PETRONAS (UTP), Malaysia. She holds an ME in Chemical Engineering from McNeese State University, USA and is also a recipient of Graduate Academic Scholarship and B.Tech in Chemical Engineering from Jawaharlal Nehru Technological University, Hyderabad. She has worked as a process engineer and as an academician prior to pursuing her PhD. Her main research areas are desalination, gas hydrates, and separation techniques.

• Preface xiii1 Introduction to Desalination 1Jesa Singh, Vinayagam Sivabalan, and Bhajan Lal1.1 Coping with Water Scarcity 11.2 Origin of Gas Hydrates 41.3 Concept of Hydrate Formation 51.4 Application of Gas Hydrate in Desalination 71.5 Phase Behavior and Thermodynamic Measurement 71.6 Kinetics of Hydrate Formation 81.6.1 Induction Time 101.6.2 Moles of Gas Used Up 101.6.3 Rate of Hydrate Formation 111.6.4 Water to Hydrate Conversion 111.7 Hydrate Decomposition 122 Technologies in Desalination 15Jai Krishna Sahith and Bhajan Lal2.1 Introduction 152.2 Conventional Desalination Methods 152.2.1 Multistage Flash Desalination 152.2.2 Multi-effect Desalination 192.2.3 Reverse Osmosis 212.2.4 Other Desalination Methods 232.3 Gas Hydrate-based Desalination 263 Prospectives on Gas Hydrates-based Desalination 31Jesa Singh and Bhajan Lal3.1 Introduction 313.2 General Proposed Gas Hydrate-based Desalination Design 323.2.1 Design 1 323.2.2 Jacketed Reactor Designs 333.2.2.1 Design 1 333.2.2.2 Design 2 363.2.3 Silica Sand Bed Crystallizer Reactor Design 393.2.3.1 Design 1 393.2.3.2 Design 2 413.2.3.3 Design 3 423.2.4 Stirred Reactor Design 433.2.4.1 Design 1 433.2.4.2 Design 2 453.2.4.3 Design 3 473.2.5 Novel Reactor Design 504 Hydrate Promoters in Gas Hydrate-based Desalination 55Sirisha Nallakukkala and Bhajan Lal4.1 Chemical Additives in Desalination 554.2 Overview of Gas Hydrate Additives in the Desalination Process 574.3 Favorable Conditions Used to Determine Suitable Hydrating Agents 584.4 Formers and Promoters in Hydrate-based Desalination 584.5 Hydrate Formers Investigation 644.5.1 Gaseous Hydrate Formers 644.5.2 Liquid Hydrate Formers 654.5.3 Functional Additives 664.6 Conclusion 685 Modeling of Seawater Desalination by Gas Hydrate Method 77Sirisha Nallakukkala and Bhajan Lal5.1 Introduction 775.2 Gas Hydrate Thermodynamic and Kinetic models 785.3 Statistical Thermodynamic Modeling of Hydrate Equilibrium 795.3.1 Modeling Thermodynamic Equilibrium of Cyclopentane Hydrates in the Presence of Salts 845.3.1.1 Standard Freezing Point Depression Calculation 855.3.1.2 Hu–Lee–Sum Correlation 855.3.1.3 Kihara Approach 865.3.1.4 Activity-Based Occupancy Correlation Approach 865.3.2 Modeling of Thermodynamic Equilibrium of Mixed Cyclopentane/Carbon Dioxide Hydrates 875.4 Kinetic Models for Hydrate Formation 885.4.1 Mathematical Model for Seawater Desalination 885.4.2 Lattice Boltzmann Model for Hydrate Formation 925.5 Machine Learning Models to Predict Desalination Efficiency 955.5.1 Machine Learning Techniques to Model Hydrate-based Desalination 955.5.2 Adaptive Neuro-fuzzy Inference System 955.5.2.1 Layer 1: Input Membership Function Layer 965.5.2.2 Layer 2: Product Layer 975.5.2.3 Layer 3: Normalization Layer 975.5.2.4 Layer 4: Output Membership Function Layer 975.5.2.5 Layer 5: Overall Output Layer 985.5.3 SVM Approach 985.5.4 Genetic Algorithm 995.5.5 Conclusion 1006 Gas Hydrates in Wastewater Treatment 113Adeel Ur Rehman, Dzulkarnain B Zaini, and Bhajan Lal6.1 Ecosystem Approach to Pollution Control 1136.2 Interaction of Wastewater with the Ecosystem 1146.3 Sources of Wastewater 1166.3.1 Agricultural Wastewater 1166.3.2 Municipal Wastewater 1186.3.3 Industrial Wastewater 1186.4 Impact of Wastewater on Ecology 1226.5 Current Technologies for Addressing Wastewater Issues 1236.5.1 Chemical Precipitation 1236.5.2 Adsorption 1246.5.3 Membrane Technologies 1256.5.4 Electrodialysis 1256.6 Gas Hydrates 1266.6.1 Formation Process of Gas Hydrates 1276.6.2 Gas Hydrate Growth Process 1276.6.3 Kinetics of Hydrate Formation 1276.6.3.1 Effects of Salt During Hydrate Formation 1286.6.3.2 Effect of Water to Gas Ratio 1296.6.3.3 Effect of Pressure During Hydrate Formation 1306.6.3.4 Effect of Stirrer during Hydrate Formation 1306.6.4 Hydrate Dissociation 1306.6.4.1 Water Recovery 1306.6.4.2 Removal Efficiency, Enrichment Factor, and Yield 1316.6.5 Kinetic Models of Gas Hydrate Growth 1317 Artificial Intelligence in Water Treatment Process Optimization 139Jai Krishna Sahith and Bhajan Lal7.1 Introduction 1397.2 Background Information 1407.3 Optimization of Water Treatment Plants 1417.4 Application of Artificial Neural Networks for Freshwater Treatment 1447.5 Application of Artificial Neural Networks for Wastewater Treatment 1457.6 Other Artificial Intelligence Techniques for Wastewater Treatment 1477.7 Application on Gas Hydrate Plants 1478 Standard Analytical Techniques for Analysis of Wastewater 155Sirisha Nallakukkala and Bhajan Lal8.1 Methods, Scope, and Their Applications 1558.2 Physical Properties of Water 1558.2.1 Color 1568.2.1.1 Visual Comparison Method 1568.2.1.2 Spectroscopic Single-wavelength Method 1568.2.1.3 Spectrophotometric Multiwavelength Method 1578.2.1.4 Tristimulus Spectrophotometric Method 1578.2.1.5 ADMI Weighted-ordinate Spectrophotometric Method 1588.2.2 Turbidity 1588.2.2.1 Nephelometric Method 1598.2.3 Odor 1598.2.3.1 Threshold Odor Test 1608.2.4 Taste 1608.2.4.1 Flavor Threshold Test 1618.2.4.2 Flavor Rating Assessment 1618.2.4.3 Flavor Profile Analysis 1618.2.5 Acidity 1628.2.5.1 Titration Method (Acidity Measurement) 1628.2.6 Alkalinity 1638.2.6.1 Titration Method (Alkalinity Measurement) 1638.2.7 Calcium Carbonate Saturation 1648.2.7.1 Saturation Index Basis 1658.2.7.2 Saturation Index by Experimental Determination 1658.2.7.3 Calcium Carbonate Precipitation Potential for Alkalinity Measurement 1668.2.8 Hardness 1668.2.8.1 Calcium Carbonate Precipitation Potential for Hardness Measurement 1668.2.8.2 EDTA Titrimetric Method 1678.2.9 Conductivity 1678.2.10 Salinity 1688.2.11 Solids 1698.2.11.1 Total Dissolved Solids 1698.2.11.2 Total Suspended Solids 1698.2.12 Asbestos 1708.2.13 Oxidation–Reduction Potential 1718.2.14 Tests and Methods on Sludges 1718.2.14.1 Oxygen Consumption Rate 1728.2.14.2 Sludge Volume Index 1728.2.14.3 Specific Gravity 1728.2.14.4 Zone Settling Rate 1728.2.14.5 Time for Capillary Suction 1728.2.15 Anaerobic Sludge Digester Gas Analysis 1738.2.15.1 Volumetric Method 1738.2.15.2 Gas Chromatographic Method 1748.3 Analysis of Inorganic Metal Constituents 1748.3.1 Conductivity 1758.3.2 Dissolved and Suspended Metals Filtration 1758.3.3 Digestion of Metals 1758.3.3.1 Selection of Acid 1768.3.3.2 Nitric Acid Digestion 1768.3.3.3 Microwave-assisted Digestion 1778.3.4 Metals by Atomic Absorption Spectrometry 1778.3.4.1 Metals by Flame Atomic Absorption Spectrometry 1788.3.4.2 Direct Air–Acetylene Flame Method 1788.3.4.3 Extraction/Air–Acetylene Flame Method 1788.3.4.4 Direct Nitrous Oxide–Acetylene Flame Method 1798.3.5 Cold Vapor Atomic Absorption Spectrometry 1798.3.6 Electrothermal Atomic Absorption Spectrometry 1798.3.7 Arsenic and Selenium by Hydride Generation 1808.3.8 Inductively Coupled Plasma Optical Emission Spectroscopy 1808.3.9 Inductively Coupled Plasma–Mass Spectrometry 1818.3.10 Anodic Stripping Voltammetry 1818.4 Analysis of Inorganic Anion Constituents 1828.4.1 Ion Chromatography with Chemical Suppression of Eluent Conductivity 1828.4.2 Single-column Ion Chromatography with Direct Conductivity Detection 1828.4.3 Ion Chromatography Determination of Oxyhalides and Bromide 1838.4.4 Capillary Ion Electrophoresis with Indirect Ultraviolet Detection 1838.5 Analysis of Organic Constituents 1848.5.1 Biochemical Oxygen Demand 1848.5.2 Five-Day BOD Test 1848.5.3 Ultimate BOD Test 1858.5.4 Chemical Oxygen Demand 1858.5.5 Total Organic Carbon 1868.5.6 Oil and Grease 1878.5.7 Phenols 1888.5.8 Surfactants 1898.5.9 Tannin and Lignin 1908.5.10 Organic and Volatile Acids 1908.6 Analysis of Radioactive Materials 1918.7 Toxicity Test Systems, Requirements, Evaluation, and Implementation 1928.7.1 Requirements for Toxicity Test 1938.7.2 Categories of Toxicity Test: Uses, Pros, and Cons 1938.7.3 Short-term Toxicity Test 1948.7.3.1 Range-finding Examination 1948.7.3.2 Short-term Definitive Examination 1948.7.3.3 Intermediate Toxicity Examination 1948.7.3.4 Long-term Partial or Complete Toxicity Examination 1958.7.3.5 Short-term Examination for Estimating Chronic Toxicity 1958.7.4 Toxicity Test Systems 1958.7.5 Source Evaluation of Toxicity 1968.7.6 Toxicity Reduction Evaluation 1968.7.6.1 Pretreatment Control Evaluation 1978.7.6.2 In-plant Control Evaluation 1978.7.7 Toxicity Control Implementation 1978.7.8 Calculating, Investigating, and Reporting Toxicity Results 1989 Economic Analysis of Desalination Process 207Vinayagam Sivabalan, Jesa Singh, and Bhajan Lal9.1 Overview 2079.2 Cost of Treated Water 2089.2.1 Fixed Cost 2109.2.2 Variable Cost 2109.3 Factors Affecting the Product Cost 2119.4 Case Studies 2149.4.1 Multistage Flash Distillation 2159.4.2 Multi-Effect Evaporation 2169.4.3 Mechanical Vapor Compression (MVC) 2179.4.4 Reverse Osmosis 2189.4.5 Gas Hydrate-Based Desalination 21910 Renewable Energy in Desalination and Hybrid Technologies 237Jai Krishna Sahith and Bhajan Lal10.1 Introduction 23710.2 Renewable Energy 23810.3 Renewable Energy Usage in Desalination 24210.3.1 Solar Energy 24210.3.2 Wind Energy 24310.3.3 Nuclear Energy 24610.3.4 Geothermal Energy 24710.3.5 Wave Energy 24810.4 Hybrid Technologies 24910.4.1 Forward Osmosis–Nanofiltration Hybrid Systems 25010.4.2 Electrodialysis–Reverse Osmosis Hybrid Systems 25110.4.3 Reverse Osmosis–Membrane Distillation Hybrid Systems 25210.4.4 Forward Osmosis–Membrane Distillation Hybrid Systems 25310.4.5 Forward Osmosis–Electrodialysis 25310.4.6 Freeze Desalination–Membrane Distillation Hybrid Systems 25410.4.7 Gas Hydrates–Reverse Osmosis Hybrid System 25410.4.8 Gas Hydrate–Capacitive Deionization Processes (CDI) 25510.5 Future Prospects 25610.6 Conclusion 25711 Waste Brine Management 269Sirisha Nallakukkala and Bhajan Lal11.1 Introduction 26911.2 Waste Brine Watercourse Constituents 27011.3 Waste Brine Discharge Methods 27011.3.1 Sewer Discharge 27011.3.2 Surface Water Discharge 27011.3.3 Evaporation 27111.3.4 Recycling and Reuse 27111.3.5 Deep Well Injection 27111.3.6 Environmental Impact and Regulatory Compliance 27211.4 Waste Brine Management Methods 27211.4.1 Chemical Precipitation 27311.4.2 Adsorption 27311.4.3 Bipolar Membrane Electrodialysis 27411.4.4 Crystallization and Evaporation 27411.4.5 Acid and Caustic Production 27511.4.6 Regeneration of Wetlands and Agricultural Applications 27511.4.7 Softener Brine Recycling 27611.4.8 De-icing and Dust Control 27611.4.9 Recovery and Trade of Solid Salts 27611.4.10 Cooling 27611.4.11 Brine Incineration 27611.5 Waste Brine Valorization: Opportunities and Challenges 27711.5.1 Waste Brine as a Resource and Its Application in Gas Hydrates 27711.5.2 Membrane-based Process for Valorization of Waste Brine 27811.5.3 Recovery of Calcium and Its Conversion to Calcium Sulfate 28011.5.4 Retrieval of Magnesium Oxide from Waste Brine 28011.5.5 Opportunities and Challenges 28111.6 Evolving Waste Brine Treatment Strategies and Sights for Future Feasibility 28211.7 Conclusion 28212 Post-Treatment of Desalinated Water: Effects and Remedy by Remineralization Methods 289Adeel Ur Rehman, Dzulkarnain B Zaini, and Bhajan Lal12.1 Introduction 28912.2 Safeguarding Human Health 29012.2.1 Desalinated Water Quality 29012.2.2 Remineralization of Desalinated Water for Consumption 29112.3 Impacts on Agriculture 29212.3.1 Effects of Desalinated Water on the Irrigation System 29212.3.2 Remineralization Needed for Irrigation 29412.4 Corrosion of Distribution Network and Scaling 29412.4.1 Corrosion Problems Involving Desalinated Water 29412.4.2 Remineralization Needed for Corrosion Control 29512.5 Remineralization Techniques 29512.5.1 Emerging Techniques 29512.6 Conclusion 297Index 303