Practical Advances in Petroleum Processing Volume 2 Practical Advances in Petroleum Processing Volume 2 Edited by Chang S. Hsu ExxonMobil Research and Engineering Company Baton Rouge, Louisiana, USA and Paul R. Robinson PQ Optimization Services Katy, Texas, USA Chang S. Hsu ExxonMobil Research and Engineering Co. 10822 N. Shoreline Avenue Baton Rouge, Louisiana 70809 USA chang.samuel.hsu@exxonmobil.com Paul R. Robinson PQ Optimization Services 3418 Clear Water Park Drive Katy, Texas 77450 USA paul-robinson@houston.rr.com Cover design by Suzanne Van Duyne (Trade Design Group) Front cover photo and back cover photo insert: Two views of the OMV plant in Schwechat, Austria, one of the most environmentally friendly refineries in the world, courtesy of OMV. Front cover insert photo: The Neste Oil plant in Porvoo, Finland includes process units for fluid catalytic cracking, hydrocracking, and oxygenate production. The plant focuses on producing high-quality, low-emission transportation fuels. Courtesy of Neste Oil. Library of Congress Control Number: 2005925505 ISBN-10: 0-387-25811-6 ISBN-13: 978-0387-25811-9 ᭧2006 Springer ScienceϩBusiness Media, Inc. All rights reserved. This work may not be translated or copied in whole or in part without the written permission of the publisher (Springer ScienceϩBusiness Media, Inc., 233 Spring Street, New York, NY 10013, USA), except for brief excerpts in connection with reviews or scholarly analysis. Use in connection with any form of information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed is forbidden. The use in this publication of trade names, trademarks, service marks and similar terms, even if they are not identified as such, is not to be taken as an expression of opinion as to whether or not they are subject to proprietary rights. Printed in the United States of America 987654321 springeronline.com v CONTENTS 15. Conventional Lube Basestock Manufacturing B. E. Beasley 1. Lube Basestock Manufacturing 1 2. Key Base Stock Properties 3 2.1 Lube Oil Feedstocks 4 3. Base Stock Composition 5 4. Typical Conventional Solvent Lube Processes 5 4.1 Lube Vacuum Distillation Unit (VDU) or Vacuum Pipestill (VPS) - Viscosity and Volatility Control 6 4.2 Solvent Extraction - Viscosity Index Control 6 4.3 Solvent Dewaxing - Pour Point Control 6 4.5 Solvent Deasphalting 7 4.6 Refined Wax Production 7 5. Key Points in Typical Conventional Solvent Lube Plants 8 6. Base Stock End Uses 8 7. Lube Business Outlook 9 8. Feedstock Selection 9 8.1 Lube Crude Selection 9 9. Lube Crude Assays 11 10. Vacuum Distillation 12 10.1 Feed Preheat Exchangers 15 10.2 Pipestill Furnace 15 10.3 Tower Flash Zone 15 10.4 Tower Wash Section 15 10.5 Wash Oil 16 10.6 Purpose of Pumparounds 16 10.7 Tower Fractionation 16 10.8 Fractionation Packing 16 10.9 Bottom Stripping Section 18 10.10 Side Stream Strippers 18 10.11 Overhead Pressure 18 4.4 Hydrofinishing - Stabilization 6 s vi Contents 10.14 Factors Affecting Lube Distillate Feed 20 11. Pipestill Troubleshooting 20 11.1 Material Balance and Viscosity Measurements 20 11.2 Tower Pressure Survey 21 12. Solvent Extraction 22 12.1 Characteristics of a Good Extraction Solvent 24 12.2 Extraction Process 25 12.3 Extraction Process Variables 28 12.4 Solvent Contaminants 28 12.5 Solvent Recovery 28 12.5.1 Raffinate Recovery 29 12.5.2 Extract Recovery 29 12.6 Minimizing Solvent Losses 29 12.6.1 Recovery Section 29 12.6.2 Other Contributors to olvent Losses 29 13. Corrosion in NMP Plants 30 14. Extraction Analytical Tests 30 15. Dewaxing 31 16. The Role of Solvent in Dewaxing 32 17. Ketone Dewaxing Processes 34 17.1 Incremental Ketone Dewaxing Plant 34 17.2 DILCHILL Dewaxing 35 17.3 Dewaxing Process Variables 37 18. Process Variable Effects 37 18.1 Crude Source Affects Dewaxed Oil Yield 37 19. Solvent Composition 38 19.1 Miscible and Immiscible Operations 38 19.2 Effect of Viscosity on Filtration Rate 40 19.3 Effect of Chilling Rate n Filtration Rate and Dewaxed Oil Yield 40 19.4 Effect of Temperature Profile 41 19.5 Effect of Solvent Dilution Ratio 41 19.5.1 Filtration Rate 41 19.5.2 DWO Yield 42 19.6 Effect of Water 42 19.7 Effect of Increased Raffinate V I 43 19.8 Effect of Pour Point Giveaway on Product Quality and Dewaxed Oil Yield 43 20. Scraped Surface Equipment 43 21. Filters 45 10.12 Tower Overhead Pressure with Precondensers 19 10.12a Tower Overhead Pressure without Precondensers 19 10.13 Tower Pressure - Ejectors 19 The S . o Contents vii 23. Wash Acceptance 52 24. Wash Efficiency 54 25. Filter Hot Washing 55 26. Dewaxed Oil/Wax-Solvent Recovery 57 27. Solvent Dehydration 58 28. Solvent Splitter 58 29. 2-Stage Dewaxing 59 30. Deoiling 59 31. Propane Dewaxing 63 31.1 Effect of Water 66 32. 2-Stage Propane Dewaxing 66 32.1 Propane Deoiling 66 32.3 Propane Filter Washing with Hot Kerosene 66 33. Dewaxing Aids 67 34. DWA Mechanism 68 35. Asphalene Contamination 69 36. Regulatory Requirements 69 37. Glossary 70 38. Acknowledgements 77 39. References and Additional Readings 77 16. Selective Hydroprocessing for New Lubricant Standards I. A. Cody 1. Introduction 79 2. Hydroprocessing Approaches 83 3. Chemical Transformations 85 3.1 Ring Conversion 85 3.2 Paraffin Conversion 88 3.3 Saturation 91 4.1 Ring Conversion-Hydroisomerization-Hydrofinishing 96 4.2 Extraction-Hydroconversion 99 5. Next Generation Technology 101 6. References 103 17. Synthetic Lubricant Base Stock Processes and Products Margaret M. Wu, Suzzy C. Ho and T. Rig Forbus 1. Introduction 105 1.1 Why Use Synthetic Lubricants? 106 1.2 What is a Synthetic Base Stock? 106 21.1 Filter Operation/Description 45 21.2 Filter Media 47 22. Cold Wash Distribution 50 4. Process Combinations 96 , viii Contents and Use 109 3.1 PAO 109 3.1.1 Chemistry for PAO Synthesis 110 3.1.2 Manufacturing Process for PAO 112 3.1.3 Product Properties 112 3.1.4 Comparison of PAO with Petroleum-based Mineral Base Stocks 113 3.1.5 Recent Developments - SpectraSyn Ultra as Next Generation PAO 116 3.1.6 Applications 116 3.2 Dibasic, Phthalate and Polyol Esters - Preparation, Properties and Applications 118 3.2.1 General Chemistry and Process 118 3.2.2 Dibasic Esters 119 3.2.3 Polyol Esters 120 3.2.4 Aromatic Esters 121 3.2.5 General Properties and Applications of Ester Fluids 121 3.3 Polyaklylene Glycols (PAG) 123 3.3.1 Chemistry and Process 123 3.3.2 Product Properties 124 3.3.3 Application 125 3.4 Other Synthetic Base Stocks 125 4. Conclusion 126 5. Acknowledgement 127 6. References 127 18. Challenges in Detergents and Dispersants for Engine Oils James D. Burrington, John K. Pudelski, and James P. Roski 1. Introduction 131 2. Engine Oil Additive and Formulation 131 2.1 Detergents 132 2.2 Dispersants 134 3. Performance Chemistry 137 4. Current Dispersant and Detergent Polymer Backbones 138 5. Future Polymer Backbones 140 6. Future Trends 142 6.1 Advanced Fluids Technology 143 6.2 Technologies for New Product Introduction 144 6.3 Performance Systems 146 7. Summary and Conclusions 146 1.3 A Brief Overview of Synthetic Lubricant History 107 2. Overview of Synthetic Base Stocks 108 3. Synthetic Base Stock - Chemistry, Production Proce ss, Properties Contents ix 19. The Chemistry of Bitumen and Heavy Oil Processing Parviz M. Rahimi and Thomas Gentzis 1. Introduction 149 2. Fractional Composition of Bitumen/Heavy Oil 150 3. Heteroatom-Containing Compounds 154 4. Properties of Asphaltenes (Solubility, Molecular Weight, Aggregation) 157 4.1 Chemical Structure of Asphaltenes 159 4.2 Thermal Chemistry of Asphaltenes 160 5. Chemistry of Upgrading 163 5.1 Reaction of Feedstock Components - Simplification of Upgrading Chemistry 168 6. Application of Hot Stage Microscopy in the Investigation of the Thermal Chemistry of Heavy Oil and Bitumen 171 6.1 Effect of Feedstock Composition 171 6.2 Effect of Boiling Point 172 6.3 Effect of Additives 174 6.4 Effect of Deasphaltening 174 7. Stability and Compatibility 175 7.1 Physical Treatment 175 7.1.1 Effect of Distillation 175 7.1.2 Effect of Addition of Diluent 177 7.1.3 Thermal/Chemical Treatment 177 8. References 179 20. Mechanistic Kinetic Modeling of Heavy Paraffin Hydrocracking Michael T. Klein and Gang Hou 1. Introduction 187 2. Approach and Overview 188 3. Model Development 191 3.1 Reaction Mechanism 191 3.2 Reaction Families 192 3.2.1 Dehydrogenation/Hydrogenation 192 3.2.2 Protonation/Deprotonation 192 3.2.3 Hydride and Methyl Shift 194 3.2.4 PCP Isomerization 194 3.2.5 β-Scission 194 3.2.6 Inhibition Reaction 195 3.3 Automated Model Building 196 3.4 Kinetics: Quantitative Structure Reactivity Correlations 198 8. Acknowledgements 147 9. References 147 x Contents 6. Summary and Conclusion 202 7. References 203 21. Modeling of Reaction Kinetics for Petroleum Fractions Teh C. Ho 1. Introduction 205 2. Overview 206 2.1 Partition-Based Lumping 206 2.2 Total Lumping 207 2.3 Reaction Network/Mechanism Reduction 207 2.4 Mathematical Approaches to Dimension Reduction 208 3. Partition Based Lumping 209 3.1 Top-down Approach 209 3.2 Bottom-up Approach 211 3.2.1 Mechanistic Modeling 212 3.2.2 Pathways Modeling 215 3.2.3 Quantitative Correlations 217 3.2.4 Carbon Center Approach 218 3.2.5 Lumping via Stochastic Assembly 218 4. Mathematical Reduction of System Dimension 220 4.1 Sensitivity Analysis 220 4.2 Time Scale Separation 221 4.3 Projective Transformation 221 4.3.1 First Order Reactions 221 4.3.2 Non-Linear Systems 223 4.3.3 Chemometrics 224 4.4 Other Methods 224 5. Total Lumping: Overall Kinetics 224 5.1 Continuum Approximation 225 5.1.1 Fully Characterized First Order Reaction Mixtures 226 5.1.2 Practical Implications 227 5.1.3 Partially Characterized First Order Reaction Mixtures 228 5.1.3.1 Plug Flow Reactor 229 5.1.3.2 CSTR 230 5.1.3.3 Diffusional Falsification of Overall Kinetics 231 5.1.3.4 Validity and Limitations of Continuum Approach 232 5.1.3.5 First Order Reversible Reactions 232 5.1.3.6 Independent nth Order Kinetics 233 3.5 The C 16 Paraffin Hydrocracking Model Dignostics 198 4. Model Results and Validation 199 5. Extension to C 80 Model 201 Contents xi 5.1.5 One Parameter Model 235 5.1.6 Intraparticle Diffusion 236 5.1.7 Temperature Effects 237 5.1.8 Selectivity of Cracking Reactions 237 5.1.9 Reaction Networks 238 5.2 Discrete Approach: Nonuniformly Coupled Kinetics 238 5.2.1 Homologous Systems 239 5.2.2 Long- ime Behavior 239 6. Concluding Remarks 241 7. References 242 22. Advanced Process Control Paul R. Robinson and Dennis Cima 1. Introduction 247 2. Useful Definitions 247 3. Overview of Economics 249 4. Source of Benefits 250 5. Implementation 253 6. Costs 254 7. References 255 23. Refinery-Wide Optimization with Rigorous Models Dale R. Mudt, Clifford C. Pedersen, Maurice D. Jett, Sriganesh Karur, Blaine McIntyre, and Paul R. Robinson 1. Introduction 257 2. Overview of Sunco 257 3. Refinery-Wide Optimization (RWO) 259 4. Rigorous Models for Clean Fuels 261 4.1 Feedstock and Product Characterization 262 4.2 Aspen FCC Overview 262 4.3 Aspen Hydrocracker 266 4.3.1 Reaction Pathways 269 4.3.2 Catalyst Deactivation Model 271 4.3.3 AHYC Model Fidelity 272 4.4 Clean Fuels Planning 272 4.4.1 Hydrogen Requirements for Deep Desulfurization .272 4.4.2 Effects of Hydrotreating on FCC Performance 274 5. Conclusions 278 6. Acknowledgements 278 7. References 278 5.1.4 Upper and Lower Bounds 234 5.1.3.7 Uniformly Coupled Kinetics 233 T r [...]... Contents 24 Modeling Hydrogen Synthesis with Rigorous Kinetics as Part of Plant-Wide Optimization Milo D Meixell, Jr 1 Introduction 28 1 2 Steam Reforming Kinetics 28 3 2. 1 Methane Steam Reforming Kinetic Relationships 28 3 2. 2 Naphtha Steam Reforming Kinetic Relationships 28 6 2. 3 Coking 29 2 2. 4 Catalyst Poisoning 29 4 3 Heat Transfer Rates and Heat Balances 29 5 3.1... 328 3.1.4 Minimum Export Steam 329 3 .2 Oxygen Based Technologies 330 3 .2. 1 SMR/O2R 330 3 .2. 2 ATR 331 3 .2. 3 POX 3 32 3 .2. 4 Products 3 32 3 .2. 5 H2/CO Ratio 3 32 3 .2. 6 Natural Ratio Range 333 3 .2. 7 CO2 Recycle 333 3 .2. 8 Import CO2 335 3 .2. 9 Membrane 335 3 .2. 10 Cold Box 335 3 .2. 11 Steam 335 3 .2. 12 Shift... Activity in a Primary Reformer 318 25 Hydrogen Production and Supply: Meeting Refiners' Growing Needs M Andrew Crews and B Gregory Shumake 1 Introduction 323 2 Thermodynamics of Hydrogen 324 3 Technologies for Producing Hydrogen 326 3.1 Steam Methane Reforming (SMR) Technologies 326 3.1.1 Maximum Steam Export 326 Contents xiii 3.1 .2 Limited Steam Export 327 3.1.3... crystallization, and filtering the solid paraffins from the slurry This may be done in “ketone” units which use MEK, MEK/MIBK, MEK/Toluene solvents or in propane units which use liquefied propane as the solvent Secondary effects include viscosity increase, density increase, sulfur increase, and reduction in VI 4.4 Hydrofinishing - Stabilization Hydrofinishing follows extraction or dewaxing The primary goal... condensing rising hot vapor with falling colder liquid At each stage in the fractionation section the highest boiling components are condensed, releasing heat that boils the lowest boiling point components, putting them into the vapor phase Contacting between the phases is needed for the heat and mass transfer Contacting equipment may include bubble cap trays, sieve trays, Glitsch grid, structured packing... undesirable coking and loss of lube oil yield Crude oil was first distilled in batch distillation, like a lab technique, beginning in the 1850s Advancements were made by increasing the size of the batch vessel A continuous process was developed by using a series of batch stills - called a battery The first continuous pipestill appeared in the 1 920 s and the “modern” pipestill came on the scene in the 1930s... non-asphaltenes in a solvent and precipitation of asphaltenes using e.g propane as a solvent Secondary effects include Conradson Carbon reduced, metals reduced, saturates increased, viscosity index increased, and color improved 4.6 Refined Wax Production Wax deoiling and hydrofinishing follows the dewaxing unit The primary goal is to reduce the oil content of the wax and to meet melting point and needle... hydroprocessing-based, making Group II or Group III base stocks The lubricant market is roughly equally split between transportation lubricants (engine crankcase oils, transmission fluids, greases, etc.) and industrial process oils Demand is growing at an average rate of only 1% / year, as robust growth in the developing economies (e.g China, India) is being partially offset by declining demand in the mature markets... unit processes 1 LUBE BASE STOCK MANUFACTURING Lubes and specialties include a number of products that have a variety of end uses Some end uses include: − Automotive: engine oils, automatic transmission fluids (ATF’s), gear oils − Industrial: machine oils, greases, electrical oils, gas turbine oils − Medicinal: food grade oils for ingestion, lining of food containers, baby oils − Specialty: food grade... (350 to 425 oC) vacuum 2, or second, sidestream (390 to 600 oC) vacuum 3, or third, sidestream (450 to 620 oC) vacuum resid stream (500 to >900 oC) Cut points are used to describe the pipestill product Volume cut points are the cumulative yield on the crude and are expressed as a liquid volume percent of product Temperature cut points are the boiling points that correspond to the volume cut point A key . Solvent 24 12. 2 Extraction Process 25 12. 3 Extraction Process Variables 28 12. 4 Solvent Contaminants 28 12. 5 Solvent Recovery 28 12. 5.1 Raffinate Recovery 29 12. 5 .2 Extract Recovery 29 . Conclusion 20 2 7. References 20 3 21 . Modeling of Reaction Kinetics for Petroleum Fractions Teh C. Ho 1. Introduction 20 5 2. Overview 20 6 2. 1 Partition-Based Lumping 20 6 2. 2 Total. 21 1 3 .2. 1 Mechanistic Modeling 21 2 3 .2. 2 Pathways Modeling 21 5 3 .2. 3 Quantitative Correlations 21 7 3 .2. 4 Carbon Center Approach 21 8 3 .2. 5 Lumping via Stochastic Assembly 21 8