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Efficient Petrochemical Processes
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Table of Contents

Preface Acknowledgement Part 1: Basics 1. Overview of This Book 1.1 Why Petrochemical Products are Important for the Economy? 1.1.1 Polyethylene 1.1.2 Polypropylene 1.1.3 Styrene and Polystyrene 1.1.4 Polyester 1.1.5 Polycarbonate and Phenolic Resins 1.1.6 Economic Significance of Polymers 1.1.7 Petrochemicals and Petroleum Utilization 1.2 Overall Petrochemical Complex Configurations 1.3 Context of Process Design and Operation for Petrochemical Production 1.4 Who is this Book Written for? 2 Market and Technology Overview 2.1 Overview of Aromatic Petrochemicals 2.2 Introduction and Market Information 2.2.1 Benzene 2.2.2 Benzene Production Technologies 2.2.3 Toluene 2.2.4 Toluene Production Technologies 2.2.5 Ethylbenzene/Styrene 2.2.6 Ethylbenzene/Styrene Production Technologies 2.2.7 Para-Xylene 2.2.8 Para-Xylene Production Technologies 2.2.9 Meta-Xylene 2.2.10 Meta-Xylene Production Technologies 2.2.11 Ortho-Xylene 2.2.12 Ortho-Xylene Production Technologies 2.2.13 Cumene/Phenol 2.2.14 Cumene/Phenol Production Technologies 2.3 Technologies in Aromatics Synthesis 2.4 Alternative Feeds for Aromatics 2.5 Technologies in Aromatic Transformation 2.5.1 Transalkylation 2.5.2 Selective Toluene Disproportionation 2.5.3 Thermal Hydro-Dealkylation 2.5.4 Xylene Isomerization 2.6 Technologies in Aromatics Separations 2.6.1 Liquid-Liquid Extraction and Extractive Distillation 2.6.2 Liquid-Liquid Extraction 2.6.3 Extractive Distillation (ED) 2.7 Separations by Molecular Weight 2.8 Separations by Isomer Type - Para-Xylene 2.8.1 Crystallization of Para-Xylene 2.8.2 Adsorptive Separation of Para-Xylene 2.9 Separations by Isomer Type - Meta-Xylene 2.10 Separations by Isomer Type - Ortho-Xylene and Ethylbenzene 2.11 Other Related Aromatics Technologies 2.11.1 Cyclohexane 2.11.2 Ethylbenzene/Styrene 2.11.3 Cumene/Phenol/Bisphenol A 2.11.4 Linear Alkyl Benzene Sulfonate for Detergents 2.11.5 Oxidation of Para- and Meta-Xylene 2.11.6 Melt Phase Polymerization of PTA to PET 2.11.7 Melt Phase Polymerization and Solid State Polymerization of PET Resin 2.11.8 Oxidation of Ortho-Xylene 2.12 Integrated Refining and Petrochemicals 3 Aromatics Process Description 3.1 Overall Aromatics Flowscheme 3.2 Adsorptive Separations for Para-Xylene 3.3 Technologies for Treating Feeds for Aromatics Production 3.4 Para-Xylene Purification and Recovery by Crystallization 3.5 Transalkylation Processes 3.6 Xylene Isomerization 3.7 Adsorptive Separation of Pure Meta-Xylene 3.8 Para-Selective Catalytic Technologies for Para-Xylene 3.8.1 Para-selective Toluene Disproportionaiton 3.8.2 Para-selective Toluene Methylation Part 2: Process Design 4 Aromatic Process Unit Design (Dave; done) 4.1 Introduction 4.2 Aromatics Fractionation 4.2.1 Reformate Splitter 4.2.2 Xylene Fractionation 4.2.3 Heavy Aromatics Fractionation 4.3 Aromatic Extraction 4.3.1 Liquid-Liquid Extraction 4.3.1.1 Operating Variables 4.3.2 Extractive Distillation 4.3.2.1 Operating Variables 4.4 Transalkylation 4.4.1 Process Flow Description 4.5 Xylene Isomerization 4.6 Para-Xylene Separation 4.7 Process Design Considerations - Design Margin Philosophy 4.7.1 Equipment Design Margins 4.8 Process Design Considerations - Operational Flexibility 4.9 Process Design Considerations - Fractionation Optimization 4.10 Safety Considerations 4.10.1 Reducing Exposure to Hazardous Materials 4.10.2 Process Hazard Analysis (PHA) 4.10.3 Hazard and Operability Study (HAZOP) 4.11 References 5 Aromatics Process Revamp Design 5.1 Introduction 5.2 Stages of Revamp Assessment and Types of Revamp Studies 5.3 Revamp Project Approach 5.3.1 Specified Target Capacity 5.3.2 Target Production with Constraints 5.3.3 Maximize Throughput at Minimum Cost 5.3.4 Identify Successive bottlenecks 5.4 Revamp Study Methodology and Strategies 5.5 Setting the Design Basis for Revamp Projects 5.5.1 Agreement 5.5.2 Processing Objectives 5.5.3 Define the Approach of the Study 5.5.4 Feedstock and Make-up Gas 5.5.5 Product Specifications 5.5.6 Getting the Right Equipment Information 5.5.7 Operating Data or Test Run Data 5.5.8 Constraints 5.5.9 Utilities 5.5.10 Replacement Equipment Options 5.5.11 Guarantees 5.5.12 Economic Evaluation Criteria 5.6 Process Design for Revamp Projects 5.6.1 Adjusting Operating Conditions 5.6.2 Design margin 5.7 Revamp Impact on Utilities 5.8 Equipment Evaluation for Revamps 5.8.1 Fired Heaters 5.8.1.1 Data Required 5.8.1.2 Fired Heater Evaluation 5.8.1.3 Heater Design Limitations 5.8.1.4 Radiant Flux Limits 5.8.1.5 Tube Wall Temperature (TWT) Limits 5.8.1.6 Metallurgy 5.8.1.7 Tube Thickness 5.8.1.8 Coil Pressure Drop 5.8.1.9 Burners 5.8.2 Vessels - Separators, Receivers, and Drums 5.8.2.1 Data required 5.8.2.2 Separator, Receiver, and Drum Evaluation 5.8.2.3 Process and Other Modifications 5.8.2.4 Test Run Data 5.8.2.5 Possible Recommendations 5.8.3 Reactors 5.8.3.1 Data Required 5.8.3.2 Reactor Process Evaluation 5.8.3.3 Process and Other Modifications 5.8.3.4 Test Run Data 5.8.3.5 Possible Recommendations 5.8.4 Fractionators 5.8.4.1 Data Required 5.8.4.2 Fractionator Evaluation 5.8.4.3 Retraying and Other Modifications 5.8.4.4 High Capacity Trays 5.8.4.5 Test Run data 5.8.4.6 Possible Recommendations 5.8.5 Heat Exchangers 5.8.5.1 Data Required 5.8.5.2 Overall Exchanger Evaluation 5.8.5.3 Thermal Rating Methods 5.8.5.4 Rating Procedures 5.8.5.5 Pressure Drop Estimation 5.8.5.6 Use of Operating Data 5.8.5.7 Possible Recommendations 5.8.5.8 Special Exchanger Services 5.8.5.9 Overpressure Protection 5.8.6 Pumps 5.8.6.1 Data Required 5.8.6.2 Centrifugal Pump Evaluation 5.8.6.3 Proportioning Pumps 5.8.6.4 Use of Operating Data 5.8.6.5 Possible Recommendations 5.8.6.6 Tools 5.8.6.7 Special Pump Services 5.8.7 Compressors 5.8.7.1 Data Required 5.8.7.2 Centrifugal Compressor Evaluation 5.8.7.3 Reciprocating Compressor Evaluation 5.8.7.4 Driver Power 5.8.7.5 Materials of Construction 5.8.7.6 Use of Operating data 5.8.7.7 Potential Remedies 5.8.8 Hydraulics/Piping 5.8.8.1 New Unit Line Sizing Criteria are Generally Not Applicable 5.8.8.2 Pressure Drop Requires Replacement of Other Equipment 5.8.8.3 Approaching Sonic Velocity 5.8.8.4 Erosion Concerns 5.8.8.5 Pressure Drop Affects Yield 5.8.8.6 Pressure Drop Affects Fractionator Operation or Utilities 5.9 Economic Evaluation 5.9.1 Costs 5.9.2 Benefits 5.9.3 Data Requirements 5.9.4 Types of Economic Analyses 5.10 Example Revamp Cases 5.10.1 Aromatics Complex Revamp with Adsorbent Reload 5.10.2 Aromatics Complex Revamp with Xylene Isomerization Catalyst Change 5.10.3 Transalkylation Unit Revamp 5.11 References Part 3: Process Equipment Assessment 6 Distillation Column Assessment 6.1 Introduction 6.2 Define a Base Case 6.3 Calculations for Missing and Incomplete Data 6.4 Building a Process Simulation 6.5 Heat and Material Balance Assessment 6.6 Tower Efficiency Assessment 6.7 Operating Profile Assessment 6.8 Tower Rating Assessment 6.9 Guidelines 6.10 Nomenclature 6.11 References 7 Heat Exchanger Assessment 7.1 Introduction 7.2 Basic Concepts and Calculations 7.3 Understand Performance Criterion - U Value 7.3.1 Required U Value (UR) 7.3.2 Clean U Value (UC) 7.3.3 Actual U Value (UA) 7.3.4 Overdesign (ODA) 7.3.5 Controlling Resistance 7.4 Understand Fouling 7.4.1 Root Causes of Fouling 7.4.2 Estimate Fouling Factor (Rf) 7.4.3 Determine Additional Pressure Drop Due to Fouling 7.5 Understand Pressure Drop 7.5.1 Tube Side Pressure Drop 7.5.2 Shell Side Pressure Drop 7.6 Effects of Velocity on Heat Transfer, Pressure Drop, and Fouling 7.6.1 Heat Exchanger Rating Assessment 7.6.2 Assess the Suitability of an Existing Exchanger for Changing Conditions 7.6.3 Determine Arrangement of Heat Exchangers in Series or Parallel 7.6.4 Assess Heat Exchanger Fouling 7.7 Improving Heat Exchanger Performance 7.7.1 How to Identify Deteriorating Performance 7.8 Nomenclature 7.9 References 8 Fired Heater Assessment 8.1 Introduction 8.2 Fired Heater Design for High Reliability 8.2.1 Flux Rate 8.2.2 Burner to Tube Clearance 8.2.3 Burner Selection 8.2.4 Fuel conditioning System 8.3 Fired Heater Operation for High Reliability 8.4 Efficient Fired Heater Operation 8.5 Fired Heater Revamp 8.6 Nomenclature 8.7 References 9 Compressor Assessment 9.1 Introduction 9.2 Types of Compressors 9.2.1 Multistage Beam Type Compressor 9.2.2 Multistage Integral Geared Compressor 9.3 Impeller Configurations 9.3.1 Between-Bearing Configuration 9.3.2 Integrally Geared Configuration 9.4 Types of Blades 9.5 How a Compressor Works 9.6 Fundamentals of Centrifugal Compressors 9.7 Performance Curves 9.8 Partial Load Control 9.9 Inlet Throttle Valve 9.10 Process Context for a Centrifugal Compressor 9.11 Compressor Selection 9.12 References 10 Pump Assessment 10.1 Introduction 10.2 Understanding Pump Head 10.3 Define Pump Head - Bernoulli Equation 10.4 Calculate Pump Head 10.5 Total Head Calculation Examples 10.6 Pump System Characteristics - System Curve 10.7 Pump Characteristics - Pump Curve 10.8 Best Efficiency Point (BEP) 10.9 Pump Curves for Different Pump Arrangements 10.10 Net Positive Suction Head (NPSH) 10.10.1 Calculation of NPSHA 10.10.2 NPSH Margin 10.10.3 Measuring NPSHA for Existing Pumps 10.10.4 Low NPSH Potential Causes and Mitigation 10.11 Spillback 10.12 Reliability Operating Envelope (ROE) 10.13 Pump Control 10.14 Pump Selection and Sizing 10.15 Nomenclature 10.16 References Part 4: Energy & Process Optimization 11 Process Integration for Higher Efficiency and Low Cost 11.1 Introduction 11.2 Definition of Process Integration 11.3 Composite Curves and Heat Integration 11.3.1 Composite Curves 11.3.2 Basic Pinch Concepts 11.3.3 Energy Use Targeting 11.3.4 Pinch Design Rules 11.3.5 Cost Targeting: Determine Optimal Tmin 11.4 Grand Composite Curves (GCC) 11.5 Appropriate Placement Principle for Process Changes 11.5.1 General Principle for Appropriate Placement 11.5.2 Appropriate Placement for Utility 11.5.3 Appropriate Placement for Reaction Process 11.5.4 Appropriate Placement for Distillation Column 11.5.4.1 The Column Grand Composite Curve (CGCC) 11.5.4.2 Column Integration Against Background Process 11.5.4.3 Design Procedure for Column Integration 11.6 Systematic Approach for Process Integration 11.7 Applications of the Process Integration Methodology 11.7.1 Column Split for Xylene Column with Thermal Coupling 11.7.2 Column Split for Extract Column with Thermal Coupling 11.7.3 Use of Dividing-Wall columns (DWC) 11.7.4 Use of Light Desorbent 11.7.5 Heat Pump for Para-Xylene Column 11.7.6 Indirect Column Heat Integration 11.7.7 Benefit of Column Integration 11.7.8 Process-Process Stream Heat Integration 11.7.9 Power Recovery 11.7.9.1 Organic Rankine Cycle for Low temperature Heat Recovery 11.7.9.2 Variable Frequency Driver on Adsorbent Chamber Circulation Pumps 11.7.10 Process Integration Summary 11.8 References 12 Energy Benchmarking 12.1 Introduction 12.2 Definition of Energy Intensity for a Process 12.3 The Concept of Fuel Equivalent (FE) for Steam and Power 12.4 Calculate Energy Intensity for a Process 12.5 Fuel Equivalent for Steam and Power 12.5.1 FE Factors for Power (FEpower) 12.5.2 FE Factors for Steam, Condensate, and Water 12.6 Energy Performance Index (EPI) Method for Energy Benchmarking 12.6.1 Benchmarking: Based on the Best-in-Operation Energy Performance (OEP) 12.6.2 Benchmarking: Based on Industrial Peers' Energy Performance (PEP) 12.6.3 Benchmarking: Based on the Best Technology Energy Performance (TEP) 12.7 Concluding Remarks 12.8 References 13 Key Indicator and Targets 13.1 Introduction 13.2 Key Indicators Represent Operation Opportunities 13.2.1 Reaction and Separation Optimization 13.2.2 Heat Exchanger Fouling Mitigation 13.2.3 Furnace Operation Optimization 13.2.4 Rotating Equipment Operation 13.2.5 Minimizing Steam Letdown Flows 13.2.6 Turndown Operation 13.3 Defining Key Indicators 13.3.1 Simplifying the Problem 13.3.2 Developing Key Indicators for the Reaction Section 13.3.3 Developing Key Indicators for the Product Fractionation Section 13.4 Set Up Targets for Key Indicators 13.5 Economic Evaluation for Key Indicators 13.6 Application 1: Implementing Key Indicators into an "Energy Dashboard" 13.7 Application 2: Implementing Key Indicators to Controllers 13.8 It is Worth the Effort 13.9 References 14 Distillation System Optimization 14.1 Introduction 14.2 Tower Optimization Basics 14.2.1 What to Watch: Key Operating Parameters 14.2.2 What Effects to Know: Parameter Relationship 14.2.3 What to Change: Parameter Optimization 14.2.4 Relax Soft Constraints to Improve Margin 14.3 Energy Optimization for Distillation System 14.4 Overall Process Optimization 14.5 Concluding Remarks 14.6 References 15 Fractionation and Separation Theory and Practice 15.1 Introduction 15.2 Separation Technology Overview 15.3 Distillation Basics 15.3.1 Difficulty of Separation 15.3.2 Selection of Operating Pressure 15.3.3 Types of Reboiler Configurations 15.3.4 Optimization of Design 15.3.5 Side Products 15.4 Advanced Distillation Topics 15.4.1 Heavy Oil Distillation 15.4.2 Dividing Wall Column 15.4.2.1 DWC Fundamentals 15.4.2.2 Guidelines for Using DWC Technology 15.4.2.3 Application of Dividing Wall Column 15.4.3 Choice of Column Internals 15.4.4 Limitations with Distillation 15.5 Adsorption 15.6 Simulated Moving Bed 15.6.1 The Concept of Moving Bed 15.6.2 The Concept of Simulated Moving Bed 15.6.3 Rotary Valve 15.7 Crystallization 15.8 Liquid-Liquid Extraction 15.9 Extractive Distillation 15.10 Membranes 15.11 Selecting a Separation Method 15.12 References 16 Reaction Engineering Basics 16.1 Introduction 16.2 Reaction Basics 16.3 Reaction Kinetics Modeling Basics 16.4 Rate Equation Based on Surface Kinetics 16.5 Limitations in Catalytic Reaction 16.5.1 External Diffusion Limitation 16.5.2 Surface Reaction Limitation 16.5.3 Internal Pore Diffusion Limitation 16.5.4 Mitigating Limitations 16.5.5 Important Parameters of Limiting Reaction 16.6 Reactor Types 16.6.1 General Classification 16.7 Reactor Design 16.7.1 Objective 16.7.2 Temperature and Equilibrium Constant 16.7.3 Pressure, Reaction Conversion, and Selectivity 16.7.4 Reaction Time and Reactor Size 16.7.5 Determine the Rate-Limiting Step 16.7.6 Reactor Design Considerations 16.7.7 General Guidelines 16.8 Hybrid Reaction and Separation 16.9 Catalyst Deactivation: Root Causes and Modeling 16.10 References Part 5: Operational Guidelines and Troubleshooting 17 Common Operating Issues 17.1 Introduction 17.2 Startup Considerations 17.2.1 Catalyst Reduction 17.2.2 Catalyst Sulfiding 17.2.3 Catalyst Attenuation 17.3 Methyl Group and Phenyl Ring Losses 17.4 Limiting Aromatics Losses 17.4.1 Olefin Removal in an Aromatics Complex 17.4.2 Fractionation and Separation Losses 17.4.2.1 Vent Losses 17.4.2.2 Losses to Distillate Liquid Product 17.4.2.3 Losses to Bottoms Liquid Product 17.4.3 Extraction Losses 17.4.3.1 Common Variables Affecting Aromatic Recovery 17.4.3.2 Feed Composition 17.4.3.3 Foaming 17.4.4 Reaction Losses 17.4.4.1 Xylene Isomerization Unit Losses 17.4.4.2 Transalkylation Unit Losses 17.4.5 Methyl Group Losses 17.4.5.1 Fractionation and Separation Losses 17.4.5.2 Reaction Losses 17.5 Fouling 17.5.1 Combine Feed Exchanger Fouling 17.5.1.1 Chemical Foulants 17.5.1.2 Particulate Foulants 17.5.2 Process Heat Exchanger Fouling 17.5.3 Heater Fouling 17.5.4 Specialty Reboiler Tube Fouling 17.5.5 Line Fouling 17.5.6 Extraction Unit Column Fouling 17.6 Aromatics Extraction Unit Solvent Degradation 17.6.1 Oxygen and Oxygenates 17.6.2 Temperature 17.6.3 Chloride 17.6.4 Other Measurements 17.7 Selective Adsorption of Para-Xylene by Simulated Moving Bed 17.7.1 Purity and Recovery Relationship 17.7.2 Meta-Xylene Contamination 17.7.3 Common Poisons 17.7.3.1 Olefins 17.7.3.2 Oxygenates 17.7.3.3 Heavy Aromatics 17.7.3.4 Water 17.7.4 Rotary Valve (TM) Monitoring 17.7.4.1 Dome Pressure 17.7.4.2 Alignment 17.7.4.3 Maintenance 17.7.5 Flow Meter Monitoring 17.7.6 Hydration Monitoring 17.7.7 Shutdown and Restart Consideration 17.7.7.1 Severe Startup or Shutdown Conditions 17.7.7.2 Oxygenate Ingress 17.7.7.3 Leaking of Adsorption Section Isolation Valves 17.8 Common Issues with Sampling and Laboratory Analysis 17.8.1 Bromine Index Analysis for Olefin Measurement 17.8.2 Atmospheric Contamination of Samples 17.8.3 Analysis of Unstabilized Liquid Samples 17.8.4 Gas Chromatography 17.8.4.1 Nitrogen vs Hydrogen or Helium Carrier Gas 17.8.4.2 Resolution of Meta-Xylene and Para-Xylene Peaks 17.8.4.3 Wash Solvent Interference 17.8.4.4 Over-Reliance on a Particular Analytical Method 17.8.4.5 Impact of Unidentified Components 17.9 Measures of Operating Efficiency in Aromatics Complex Process Units 17.9.1 Selective Adsorption Para-Xylene Separation Unit 17.9.2 Xylene Isomerization Unit 17.9.3 Transalkylation Unit 17.9.4 Aromatics Extraction Unit 17.10 The Future of Plant Troubleshooting and Optimization 17.11 References 18 Troubleshooting Case Studies 18.1 Introduction 18.2 Transalkylation Unit - Low Catalyst Activity During Normal Operation 18.2.1 Summary of Symptoms 18.2.2 Root Cause and Solution 18.2.3 Lesson Learned 18.3 Xylene Isomerization Unit - Low Catalyst Activity Following Startup 18.3.1 Summary of Symptoms 18.3.2 Root Cause and Solution 18.3.3 Lesson Learned 18.4 Para-Xylene Selective Adsorption Unit - Low Recovery After Turnaround 18.4.1 Summary of Symptoms 18.4.2 Root Cause and Solution 18.4.3 Lesson Learned 18.5 Aromatics Extraction Unit - Low Extract Purity/Recovery 18.5.1 Summary of Symptoms 18.5.2 Root Cause and Solution 18.5.3 Lesson Learned 18.6 Aromatics Complex - Low Para-Xylene Production 18.6.1 Summary of Symptoms 18.6.2 Root Cause and Solution 18.6.3 Lesson Learned 18.7 Closing Remarks 18.8 References

About the Author

FRANK (XIN X.) ZHU, PHD, is Senior Fellow at Honeywell UOP, Des Plaines, Illionis. He is a leading expert in industrial process design, modeling, and energy efficiency. He holds 60 US patents; is the co-founder for ECI International Conference: CO2 Summit and the recipient of AIChE Energy Sustainability Award. JAMES A. JOHNSON is the Director of Petrochemical Development in the R&D Department of Honeywell UOP. He has authored several publications and holds 36 US patents. DAVID W. ABLIN was a Fellow at the Aromatics Technology Center of Honeywell UOP before retiring in 2016. He holds 14 U.S. patents and earned several UOP Engineering awards. GREGORY A. ERNST is a Technology Specialist at Honeywell UOP, focusing on aromatics technologies with experience in commissioning, field services, and on-site troubleshooting of operating plants.

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