Chemical Process Design

Computer-Aided Case Studies

Alexandre C. Dimian and Costin Sorin Bildea

InnodataFile Attachment9783527621590.jpg

Alexandre C. Dimian and

Costin Sorin Bildea

Chemical Process Design

S. Engell (Ed.)

Logistic Optimization of Chemical Production Processes

2008

ISBN 978-3-527-30830-9

L. Puigjaner, G. Heyen (Eds.)

Computer Aided Process and Product Engineering

2006

ISBN 978-3-527-30804-0

K. Sundmacher, A. Kienle, A. Seidel-Morgenstern (Eds.)

Integrated Chemical ProcessesSynthesis, Operation, Analysis, and Control

2005

ISBN 978-3-527-30831-6

Related Titles

Chemical Process Design

Computer-Aided Case Studies

Alexandre C. Dimian and Costin Sorin Bildea

The Authors

Prof. Alexandre C. DimianUniversity of AmsterdamFNWI/HIMSNieuwe Achtergracht 1661018 WW AmsterdamThe Netherlands

Prof. Costin Sorin BildeaUniversity “Politehnica” BucharestDepartment of Chemical EngineeringStr. Polizu 1011061 BucharestRomania

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ISBN: 978-3-527-31403-4

Preface XV

1 Integrated Process Design 11.1 Motivation and Objectives 11.1.1 Innovation Through a Systematic Approach 11.1.2 Learning by Case Studies 21.1.3 Design Project 31.2 Sustainable Process Design 51.2.1 Sustainable Development 51.2.2 Concepts of Environmental Protection 51.2.2.1 Production-Integrated Environmental Protection 61.2.2.2 End-of-pipe Antipollution Measures 71.2.3 Effi ciency of Raw Materials 71.2.4 Metrics for Sustainability 91.3 Integrated Process Design 131.3.1 Economic Incentives 131.3.2 Process Synthesis and Process Integration 141.3.3 Systematic Methods 151.3.3.1 Hierarchical Approach 161.3.3.2 Pinch-Point Analysis 161.3.3.3 Residue Curve Maps 161.3.3.4 Superstructure Optimization 171.3.3.5 Controllability Analysis 171.3.4 Life Cycle of a Design Project 171.4 Summary 19 References 20

2 Process Synthesis by Hierarchical Approach 212.1 Hierarchical Approach of Process Design 222.2 Basis of Design 272.2.1 Economic Data 272.2.2 Plant and Site Data 272.2.3 Safety and Health Considerations 28

Contents

V

VI Contents

2.2.4 Patents 282.3 Chemistry and Thermodynamics 282.3.1 Chemical-Reaction Network 282.3.2 Chemical Equilibrium 312.3.3 Reaction Engineering Data 312.3.4 Thermodynamic Analysis 322.4 Input/Output Analysis 322.4.1 Input/Output Structure 332.4.1.1 Number of Outlet Streams 342.4.1.2 Design Variables 352.4.2 Overall Material Balance 352.4.3 Economic Potential 362.5 Reactor/Separation/Recycle Structure 412.5.1 Material-Balance Envelope 412.5.1.1 Excess of Reactant 432.5.2 Nonlinear Behavior of Recycle Systems 432.5.2.1 Inventory of Reactants and Make-up Strategies 432.5.2.2 Snowball Effects 442.5.2.3 Multiple Steady States 452.5.2.4 Minimum Reactor Volume 452.5.2.5 Control of Selectivity 452.5.3 Reactor Selection 452.5.3.1 Reactors for Homogeneous Systems 462.5.3.2 Reactors for Heterogeneous Systems 462.5.4 Reactor-Design Issues 472.5.4.1 Heat Effects 472.5.4.2 Equilibrium Limitations 482.5.4.3 Heat-Integrated Reactors 482.5.4.4 Economic Aspects 492.6 Separation System Design 492.6.1 First Separation Step 502.6.1.1 Gas/Liquid Systems 502.6.1.2 Gas/Liquid/Solid Systems 512.6.2 Superstructure of the Separation System 512.7 Optimization of Material Balance 542.8 Process Integration 552.8.1 Pinch-Point Analysis 552.8.1.1 The Overall Approach 562.8.2 Optimal Use of Resources 582.9 Integration of Design and Control 582.10 Summary 58 References 60

Contents VII

3 Synthesis of Separation System 613.1 Methodology 613.2 Vapor Recovery and Gas-Separation System 643.2.1 Separation Methods 643.2.2 Split Sequencing 643.3 Liquid-Separation System 713.3.1 Separation Methods 723.3.2 Split Sequencing 733.4 Separation of Zeotropic Mixtures by Distillation 753.4.1 Alternative Separation Sequences 753.4.2 Heuristics for Sequencing 763.4.3 Complex Columns 773.4.4 Sequence Optimization 783.5 Enhanced Distillation 793.5.1 Extractive Distillation 793.5.2 Chemically Enhanced Distillation 793.5.3 Pressure-Swing Distillation 793.6 Hybrid Separations 793.7 Azeotropic Distillation 843.7.1 Residue Curve Maps 843.7.2 Separation by Homogeneous Azeotropic Distillation 883.7.2.1 One Distillation Field 883.7.2.2 Separation in Two Distillation Fields 893.7.3 Separation by Heterogeneous Azeotropic Distillation 953.7.4 Design Methods 983.8 Reactive Separations 993.8.1 Conceptual Design of Reactive Distillation Columns 1003.9 Summary 101 References 101

4 Reactor/Separation/Recycle Systems 1034.1 Introduction 1034.2 Plantwide Control Structures 1064.3 Processes Involving One Reactant 1084.3.1 Conventional Control Structure 1084.3.2 Feasibility Condition for the Conventional Control Structure 1114.3.3 Control Structures Fixing Reactor-Inlet Stream 1124.3.4 Plug-Flow Reactor 1144.4 Processes Involving Two Reactants 1154.4.1 Two Recycles 1154.4.2 One Recycle 1174.5 The Effect of the Heat of Reaction 1184.5.1 One-Reactant, First-Order Reaction in PFR/Separation/Recycle

Systems 118

VIII Contents

4.6 Example – Toluene Hydrodealkylation Process 1224.7 Conclusions 126 References 127

5 Phenol Hydrogenation to Cyclohexanone 1295.1 Basis of Design 1295.1.1 Project Defi nition 1295.1.2 Chemical Routes 1305.1.3 Physical Properties 1315.2 Chemical Reaction Analysis 1325.2.1 Chemical Reaction Network 1325.2.2 Chemical Equilibrium 1335.2.2.1 Hydrogenation of Phenol 1335.2.2.2 Dehydrogenation of Cyclohexanol 1355.2.3 Kinetics 1375.2.3.1 Phenol Hydrogenation to Cyclohexanone 1375.2.3.2 Cyclohexanol Dehydrogenation 1395.3 Thermodynamic Analysis 1405.4 Input/Output Structure 1415.5 Reactor/Separation/Recycle Structure 1445.5.1 Phenol Hydrogenation 1445.5.1.1 Reactor-Design Issues 1455.5.2 Dehydrogenation of Cyclohexanol 1515.5.2.1 Reactor Design 1515.6 Separation System 1525.7 Material-Balance Flowsheet 1535.7.1 Simulation 1535.7.2 Sizing and Optimization 1555.8 Energy Integration 1565.9 One-Reactor Process 1585.10 Process Dynamics and Control 1615.10.1 Control Objectives 1615.10.2 Plantwide Control 1625.11 Environmental Impact 1665.12 Conclusions 170 References 172

6 Alkylation of Benzene by Propylene to Cumene 1736.1 Basis of Design 1736.1.1 Project Defi nition 1736.1.2 Manufacturing Routes 1736.1.3 Physical Properties 1756.2 Reaction-Engineering Analysis 1766.2.1 Chemical-Reaction Network 1766.2.2 Catalysts for the Alkylation of Aromatics 178

Contents IX

6.2.3 Thermal Effects 1806.2.4 Chemical Equilibrium 1816.2.5 Kinetics 1816.3 Reactor/Separator/Recycle Structure 1836.4 Mass Balance and Simulation 1856.5 Energy Integration 1876.6 Complete Process Flowsheet 1926.7 Reactive Distillation Process 1956.8 Conclusions 199 References 200

7 Vinyl Chloride Monomer Process 2017.1 Basis of Design 2017.1.1 Problem Statement 2017.1.2 Health and Safety 2027.1.3 Economic Indices 2027.2 Reactions and Thermodynamics 2027.2.1 Process Steps 2027.2.2 Physical Properties 2057.3 Chemical-Reaction Analysis 2057.3.1 Direct Chlorination 2067.3.2 Oxychlorination 2087.3.3 Thermal Cracking 2107.4 Reactor Simulation 2127.4.1 Ethylene Chlorination 2127.4.2 Pyrolysis of EDC 2127.5 Separation System 2137.5.1 First Separation Step 2137.5.2 Liquid-Separation System 2157.6 Material-Balance Simulation 2167.7 Energy Integration 2197.8 Dynamic Simulation and Plantwide Control 2227.9 Plantwide Control of Impurities 2247.10 Conclusions 229 References 229

8 Fatty-Ester Synthesis by Catalytic Distillation 2318.1 Introduction 2318.2 Methodology 2328.3 Esterifi cation of Lauric Acid with 2-Ethylhexanol 2358.3.1 Problem Defi nition and Data Generation 2358.3.2 Preliminary Chemical and Phase Equilibrium 2368.3.3 Equilibrium-based Design 2388.3.4 Thermodynamic Experiments 2398.3.5 Revised Conceptual Design 240

X Contents

8.3.6 Chemical Kinetics Analysis 2418.3.6.1 Kinetic Experiments 2418.3.6.2 Selectivity Issues 2428.3.6.3 Catalyst Effectiveness 2438.3.7 Kinetic Design 2448.3.7.1 Selection of Internals 2458.3.7.2 Preliminary Hydraulic Design 2468.3.7.3 Simulation 2488.3.8 Optimization 2508.3.9 Detailed Design 2518.4 Esterifi cation of Lauric Acid with Methanol 2518.5 Esterifi cation of Lauric Acid with Propanols 2548.5.1 Entrainer Selection 2558.5.2 Entrainer Ratio 2578.6 Conclusions 258 References 259

9 Isobutane Alkylation 2619.1 Introduction 2619.2 Basis of Design 2639.2.1 Industrial Processes for Isobutane Alkylation 2639.2.2 Specifi cations and Safety 2639.2.3 Chemistry 2649.2.4 Physical Properties 2659.2.5 Reaction Kinetics 2659.3 Input–Output Structure 2679.4 Reactor/Separation/Recycle 2689.4.1 Mass-Balance Equations 2689.4.2 Selection of a Robust Operating Point 2729.4.3 Normal-Space Approach 2749.4.3.1 Critical Manifolds 2749.4.3.2 Distance to the Critical Manifold 2759.4.3.3 Optimization 2779.4.4 Thermal Design of the Chemical Reactor 2789.5 Separation Section 2809.6 Plantwide Control and Dynamic Simulation 2819.7 Discussion 2849.8 Conclusions 285 References 285

10 Vinyl Acetate Monomer Process 28710.1 Basis of Design 28710.1.1 Manufacturing Routes 28710.1.2 Problem Statement 28810.1.3 Health and Safety 289

Contents XI

10.2 Reactions and Thermodynamics 28910.2.1 Reaction Kinetics 28910.2.2 Physical Properties 29310.2.3 VLE of Key Mixtures 29410.3 Input–Output Analysis 29410.3.1 Preliminary Material Balance 29410.4 Reactor/Separation/Recycles 29610.5 Separation System 29810.5.1 First Separation Step 29910.5.2 Gas-Separation System 30010.5.3 Liquid-Separation System 30010.6 Material-Balance Simulation 30210.7 Energy Integration 30410.8 Plantwide Control 30510.9 Conclusions 310 References 311

11 Acrylonitrile by Propene Ammoxidation 31311.1 Problem Description 31311.2 Reactions and Thermodynamics 31411.2.1 Chemistry Issues 31411.2.2 Physical Properties 31711.2.3 VLE of Key Mixtures 31811.3 Chemical-Reactor Analysis 31911.4 The First Separation Step 32111.5 Liquid-Separation System 32411.5.1 Development of the Separation Sequence 32411.5.2 Simulation 32411.6 Heat Integration 32811.7 Water Minimization 33211.8 Emissions and Waste 33411.8.1 Air Emissions 33411.8.2 Water Emissions 33411.8.3 Catalyst Waste 33511.9 Final Flowsheet 33511.10 Further Developments 33711.11 Conclusions 337 References 338

12 Biochemcial Process for NOx Removal 33912.1 Introduction 33912.2 Basis of Design 34112.3 Process Selection 34112.4 The Mathematical Model 34312.4.1 Diffusion-Reaction in the Film Region 343

XII Contents

12.4.1.1 Model Parameters 34612.4.2 Simplifi ed Film Model 34812.4.3 Convection-Mass-Transfer Reaction in the Bulk 35112.4.3.1 Bulk Gas 35112.4.3.2 Bulk Liquid 35212.4.4 The Bioreactor 35412.5 Sizing of the Absorber and Bioreactor 35512.6 Flowsheet and Process Control 35712.7 Conclusions 358 References 360

13 PVC Manufacturing by Suspension Polymerization 36313.1 Introduction 36313.1.1 Scope 36313.1.2 Economic Issues 36313.1.3 Technology 36513.2 Large-Scale Reactor Technology 36513.2.1 Effi cient Heat Transfer 36713.2.2 The Mixing Systems 36913.2.3 Fast Initiation Systems 37013.3 Kinetics of Polymerization 37113.3.1 Simplifi ed Analysis 37413.4 Molecular-Weight Distribution 37613.4.1 Simplifi ed Analysis 37713.5 Kinetic Constants 37813.6 Reactor Design 37813.6.1 Mass Balance 37913.6.2 Molecular-Weight Distribution 38213.6.3 Heat Balance 38313.6.4 Heat-Transfer Coeffi cients 38413.6.5 Physical Properties 38513.6.6 Geometry of the Reactor 38513.6.7 The Control System 38513.7 Design of the Reactor 38813.7.1 Additional Cooling Capacity by Means of an External Heat

Exchanger 38913.7.2 Additional Cooling Capacity by Means of Higher Heat-Transfer

Coeffi cient 39013.7.3 Design of the Jacket 39013.7.4 Dynamic Simulation Results 39013.7.5 Additional Cooling Capacity by Means of Water Addition 39213.7.6 Improving the Controllability of the Reactor by Recipe Change 39313.8 Conclusions 396 References 396

Contents XIII

14 Biodiesel Manufacturing 39914.1 Introduction to Biofuels 39914.1.1 Types of Alternative Fuels 39914.1.2 Economic Aspects 40114.2 Fundamentals of Biodiesel Manufacturing 40214.2.1 Chemistry 40214.2.2 Raw Materials 40414.2.3 Biodiesel Specifi cations 40514.2.4 Physical Properties 40614.3 Manufacturing Processes 40914.3.1 Batch Processes 40914.3.2 Catalytic Continuous Processes 41114.3.3 Supercritical Processes 41314.3.4 Hydrolysis and Esterifi cation 41414.3.5 Enzymatic Processes 41514.3.6 Hydropyrolysis of Triglycerides 41514.3.7 Valorization of Glycerol 41614.4 Kinetics and Catalysis 41614.4.1 Homogeneous Catalysis 41614.4.2 Heterogeneous Catalysis 41914.5 Reaction-Engineering Issues 42014.6 Phase-Separation Issues 42214.7 Application 42314.8 Conclusions 426 References 427

15 Bioethanol Manufacturing 42915.1 Introduction 42915.2 Bioethanol as Fuel 42915.3 Economic Aspects 43115.4 Ecological Aspects 43315.5 Raw Materials 43515.6 Biorefi nery Concept 43715.6.1 Technology Platforms 43715.6.2 Building Blocks 43915.7 Fermentation 44015.7.1 Fermentation by Yeasts 44015.7.2 Fermentation by Bacteria 44115.7.3 Simultaneous Saccharifi cation and Fermentation 44115.7.4 Kinetics of Saccharifi cation Processes 44215.7.5 Fermentation Reactors 44415.8 Manufacturing Technologies 44515.8.1 Bioethanol from Sugar Cane and Sugar Beets 44515.8.2 Bioethanol from Starch 44615.8.3 Bioethanol from Lignocellulosic Biomass 447

XIV Contents

15.9 Process Design: Ethanol from Lignocellulosic Biomass 44915.9.1 Problem Defi nition 44915.9.2 Defi nition of the Chemical Components 45015.9.3 Biomass Pretreatment 45015.9.4 Fermentation 45215.9.5 Ethanol Purifi cation and Water Recovery 45615.10 Conclusions 458 References 459

Appendix A Residue Curve Maps for Reactive Mixtures 461Appendix B Heat-Exchanger Design 474Appendix C Materials of Construction 483Appendix D Saturated Steam Properties 487Appendix E Vapor Pressure of Some Hydrocarbons 489Appendix F Vapor Pressure of Some Organic Components 490Appendix G Conversion Factors to SI Units 491

Index 493

Preface

XV

“ I hear and I forget. I see and I remember. I do and I understand. ”Confucius

Chemical process design today faces the challenge of sustainable technologies for manufacturing fuels, chemicals and various products by extended use of renew-able raw materials. This implies a profound change in the education of designers in the sense that their creativity can be boosted by adopting a systems approach supported by powerful systematic methods and computer simulation tools. Instead of developing a single presumably good fl owsheet, modern process design gener-ates and evaluates several alternatives corresponding to various design decisions and constraints. Then, the most suitable alternative is refi ned and optimized with respect to high effi ciency of materials and energy, ecologic performance and operability.

This book deals with the conceptual design of chemical processes illustrated by case studies worked out by computer simulation. Typically, more than 80% of the total investment costs of chemical plants are determined at the conceptual design stage, although this activity involves only 2 – 3% of the engineering costs and a reduced number of engineers. In addition, a preliminary design allows critical aspects in research and development and/or in searching subcontractors to be highlighted, well ahead of starting the actual plant design project.

The book is aimed at a wide audience interested in the design of innovative chemical processes, especially chemical engineering undergraduate students com-pleting a process and/or plant design project. Postgraduate and PhD students will fi nd advanced and thought - provoking process - design methods. The information presented in the book is also useful for the continuous education of professional designers and R & D engineers.

This book uses ample case studies to teach a generic design methodology and systematic design methods, as explained in the fi rst four chapters. Each project starts by analysing the fundamental knowledge about chemistry, thermodynamics and reaction kinetics. Environmental problems are highlighted by analysing the detailed chemistry. On this basis the process synthesis is performed. The result is the generation of several alternatives from which the most suitable is selected for refi nement, energy integration, optimization and plantwide control. Computer

XVI Preface

simulation is intensively used for data analysis, supporting design decisions, investigating the feasibility, sizing the equipment, and fi nally for studying process dynamics and control issues. The results are compared with fl owsheets and per-formance indices of industrial licensed processes. Complete information is given such that the case studies can be reproduced with any simulator having adequate capabilities.

The distinctive feature of this book is the emphasis on integrating process dynamics and plant wide control, starting with the early stages of conceptual design. Considering the reaction/separation/recycle structure as the architectural framework and employing kinetic modelling of chemical reactors render this approach suited for developing fl exible and adaptive processes. Although the progress in software technology makes possible the use of dynamic simulation directly in the conceptual design phase, the capabilities of dynamic simulators are largely underestimated, because little experience has been disseminated. From this perspective the book can be seen as a practical guide for the effi cient use of dynamic simulation in process design and control.

The book extends over fi fteen chapters. The fi rst four chapters deal with the fundamentals of a modern process design, while their application is developed in the next eleven case studies.

Chapter 1 Introduction presents the concepts and metrics of sustainable develop-ment, as well as the framework of an integrated process design by means of two interlinked activities, process synthesis and process integration.

The conceptual design framework is developed in Chapter 2 Process Synthesis by Hierarchical Approach . An effi cient methodology is proposed aiming to minimize the interactions between the synthesis and integration steps. The core activity concentrates on the reactor/separation/recycle structure as defi ning the process architecture, by which the reactor design and the structure of separations are examined simultaneously by considering the effect of recycles on fl exibility and stability. By placing the reactor in the core of the process, the separators receive clearly defi ned tasks of plantwide perspective, which should be fulfi lled later by the design of the respective subsystems. The heat and material balances built upon this structure supply the key elements for sizing the units and assessing capital and operation costs, and on this basis establish the process profi tability.

Chapter 3 deals with the Synthesis of the Separation System . A task - oriented approach is proposed for generating close - to - optimum separation sequences for which both feasibility and performance of splits are guaranteed. Emphasis is placed on the synthesis of distillation systems by residue curve map methods.

Chapter 4 deals in more detail with the analysis of the Reactor/Separation/Recycle Systems . Undesired nonlinear phenomena can be detected at early conceptual stages through steady - state sensitivity and dynamic stability analysis. This approach, developed by the authors, allows better integration between process design and plantwide control. Two different approaches to plantwide control are discussed, namely controlling the material balance of the plant by using the self - regulation property or by applying feedback control.

Preface XVII

The fi rst case study of Chapter 5 Cyclohexanone by Phenol Hydrogenation devel-oped in a tutorial manner, allows the reader to navigate through the key steps of the methodology, from thermodynamic analysis to reactor design, fl owsheet syn-thesis and simulation. The key issue is designing a plant that complies with fl exi-bility and selectivity targets. The initial design of the plant contains two reaction sections, but selective catalyst and adequate recycle policy allow an effi cient and versatile single reactor process to be developed. In addition, the case study deals with waste reduction by design, with both economical and ecological benefi ts.

Chapter 6 on Alkylation of Benzene by Propene to Cumene illustrates the design of a modern process for a petrochemical commodity. The process employs a zeolite catalyst and an adiabatic reactor operated at higher pressure. Large benzene recycle limits the formation of byproducts, but implies considerable energy consumption. Signifi cant energy saving can be achieved by heat integration by using double - effect distillation and recovering the reaction heat as medium - pressure steam. The performance indices of the designed process are in agreement with the best tech-nologies. A modern alternative is catalytic reactive distillation. While appealing at fi rst sight, this method raises a number of problems. Reactive distillation can bring benefi ts only if a superior catalyst is available, exhibiting much higher activity and better selectivity than the liquid - phase processes.

Chapter 7 Vinyl Chloride Monomer Process emphasizes the complexity of design-ing a large chemical plant with multireactors and an intricate structure of recycles. The raw materials effi ciency is close to reaction stoichiometry such that only the VCM product leaves the plant. Because a large spectrum of chloro - hydrocarbon impurities is formed, the purifi cation of the intermediate ethylene di - chloride becomes a complex design and plantwide control problem. The solution implies not only the removal of impurities accumulating in recycle by more effi cient sepa-rators, but also their minimization at source by improving the reaction conditions. In particular, the yield of pyrolysis can be enhanced by making use of initiators, some being produced and recycled in the process itself. In addition, the chemical conversion of impurities accumulating in recycle prevents the occurrence of snow-ball effects that otherwise affect the operation of reactors and separators. Steady - state and dynamic simulation models can greatly help to solve properly this integrated design and control problem.

Chapter 8 deals with the manufacturing of Fatty Esters by Reactive Distillation using superacid solid catalyst. The key constraint is selective water removal to shift the chemical equilibrium and to ensure a water - free organic phase. Because the catalyst manifests similar activities for several alcohols, the study investigates the possibility of designing a multiproduct reactive distillation column by slightly adjusting the operation conditions. The residue curve map analysis brings useful insights. The esterifi cation with propanols raises the problem of breaking the alcohol/water azeotrope . The solution passes by the use of an entrainer. The equip-ment is simple and effi cient. The availability of an active and selective catalyst remains the key element in technology.

Chapter 9 Isobutane/Butene Alkylation illustrates in detail the integration of design and plantwide control. Special attention is paid to the reaction/separation/

XVIII Preface

recycle structure, showing how plantwide control considerations are introduced during the early stages of conceptual design. Thus, a simplifi ed plant mass balance based on a kinetic model for the reactor and black - box separation models is used to generate plantwide control alternatives. Nonlinear analysis reveals unfavourable steady state behavior, such as high sensitivity and state multiplicity. An important part is devoted to robustness study in order to ensure feasible operation when operation variables change or the design parameters are uncertain.

The case study on Vinyl Acetate Process , developed in Chapter 10 , demonstrates the benefi t of solving a process design and plantwide control problem based on the analysis of the reactor/separation/recycles structure. In particular, it is dem-onstrated that the dynamic behavior of the chemical reactor and the recycle policy depend on the mechanism of the catalytic process, as well as on the safety con-straints. Because low per pass conversion of both ethylene and acetic acid is needed, the temperature profi le in the chemical reactor becomes the most impor-tant means for manipulating the reaction rate and hence ensuring the plant fl exi-bility. The inventory of reactants is adapted accordingly by fresh reactant make - up directly in recycles.

Chapter 11 Acrylonitrile by Ammoxidation of Propene illustrates the synthesis of a fl owsheet in which a diffi cult separation problem dominates. In addition, large energy consumption of both low - and high - temperature utilities is required. Various separation methods are involved from simple fl ash and gas absorption to extractive distillation for splitting azeotropic mixtures. The problem is tackled by an accurate thermodynamic analysis. Important energy saving can be detected.

Chapter 12 handles the design of a Biochemical Process for NO x Removal from fl ue gases. The process involves absorption and reaction steps. The analysis of the process kinetics shows that both large G/L interfacial area and small liquid fraction favor the absorption selectivity. Consequently, a spray tower is employed as the main process unit for which a detailed model is built. Model analysis reveals rea-sonable assumptions, which are the starting point of an analytical model. Then, the values of the critical parameters of the coupled absorber – bioreactor system are found. Sensitivity studies allow providing suffi cient overdesign that ensures the purity of the outlet gas stream when faced with uncertain design parameters or with variability of the input stream.

Chapter 13 PVC Manufacturing by Suspension Polymerization illustrates the area of batch processes and product engineering. The central problem is the optimiza-tion of a polymerization recipe ensuring the highest productivity (shortest batch time) of a large - scale reactor with desired product - quality specifi cations defi ned by molecular weight distribution. A comprehensive dynamic model is built by com-bining detailed reaction kinetics, heat transfer and process - control system. The model can be used for the optimization of the polymerization recipe and the opera-tion procedure in view of producing different polymer grades.

The last two chapters are devoted to problems of actual interest, manufacturing biofuels from renewable raw materials. Chapter 14 deals with Biodiesel Manufac-turing . This renewable fuel is a mixture of fatty acid esters that can be obtained from vegetable or animal fats by reaction with light alcohols. A major aspect in

Preface XIX

technology is getting a composition of the mixture leaving the reactor system that matches the fuel specifi cations. This is diffi cult to achieve in view of the large variety of raw materials. On the basis of kinetic data, the design of a standard biodiesel process based on homogeneous catalysis is performed. The study dem-onstrates that employing heterogeneous catalysis can lead to a much simpler and more effi cient design. The availability of superactive and robust catalysts is still an open problem.

Bioethanol Manufacturing is handled in Chapter 15 . The case study examines different aspects of today ’ s technologies, such as raw materials basis, fermentation processes and bioreactors. The application deals with the design of a bioethanol plant of the second generation based on lignocellulosic biomass. Emphasis is placed on getting realistic and consistent material and energy balances over the whole plant by means of computer simulation in order to point out the impact of the key technical elements on the investment and operation costs. To achieve this goal the complicated biochemistry is expressed in term of stoichiometric reac-tions and user - defi ned components. The systemic analysis emphasizes the key role of the biomass conversion stage based on simultaneous saccharifi cation and fermentation.

The book is completed with Annexes on the analysis of reactive mixtures by residue curve maps, design of heat exchangers, selection of construction materials, steam tables, vapor pressure of typical chemical components and conversion table for the common physical units.

The authors acknowledge the contribution to this book of many colleagues and students from the University of Amsterdam and Delft University of Technology, The Netherlands. Special thanks go to the Dutch Postgraduate School for Process Technology (OSPT) for supporting our postgraduate course in Advanced Process Integration and Plantwide Control, where the integration of design and control is the main feature. The authors express their appreciation to the software companies AspenTech and MathWorks for making available for education purposes an out-standing simulation technology.

And last but not the least we express our gratitude and love to our families, for continuous support and understanding.

January 2008 Alexandre C. Dimian Costin Sorin Bildea

Integrated Process Design

1

1

1.1 Motivation and Objectives

1.1.1 Innovation Through a Systematic Approach

Innovation is the key issue in chemical process industries in today ’ s globalization environment, as the best means to achieve high effi ciency and competitiveness with sustainable development. The job of a designer is becoming increasingly challenging. He/she has to take into account a large number of constraints of technical, economical and social nature, often contradictory. For example, the discovery of a new catalyst could make profi table cheaper raw materials, but needs much higher operating temperatures and pressures. To avoid the formation of byproducts lower conversion should be maintained, implying more energy and equipment costs. Although attractive, the process seems more expensive. However, higher temperature can give better opportunities for energy saving by process integration. In addition, more compact and effi cient equipment can be designed by applying the principles of process synthesis and intensifi cation. In the end, the integrated conceptual design may reveal a simpler fl owsheet with lower energy consumption and equipment costs.

The above example is typical. Modern process design consists of the optimal combination of technical, economic, ecological and social aspects in highly inte-grated processes . The conceptual approach implies the availability of effective cost - optimization design methods aided by powerful computer - simulation tools.

Creativity is a major issue in process design. This is not a matter only of engi-neering experience, but above all of adopting the approach of process systems. This consists of a systemic viewpoint in problem analysis supported by systematic methods in process design.

A systematic and systems approach has at least two merits:

1. Provides guidance in assessing fi rstly the feasibility of the process design as a whole, as well as its fl exibility in operation, before more detailed design of components.

2 1 Integrated Process Design

2. Generates not only one supposed optimal solution, but several good alternatives corresponding to different design decisions . A remarkable feature of the systemic design is that quasioptimal targets may be set well ahead detailed sizing of equipment. In this way, the effi ciency of the whole engineering work may improve dramatically by avoiding costly structural modifi cations in later stages.

The motivation of this book consists of using a wide range of case studies to teach generic creative issues, but incorporated in the framework of a technology of industrial signifi cance. Computer simulation is used intensively to investigate the feasibility and support design decisions, as well as for sizing and optimization. Particular emphasis is placed on thermodynamic modeling as a fundamental tool for analysis of reactions and separations. Most of the case studies make use of chemical reactor design by kinetic modeling.

A distinctive feature of this book is the integration of design and control as the current challenge in process design. This is required by higher fl exibility and responsiveness of large - scale continuous processes, as well as by the optimal operation of batchwise and cyclic processes for high - value products.

The case studies cover key applications in chemical process industries, from petrochemistry to polymers and biofuels. The selection of processes was con-fronted with the problem of availability of suffi cient design and technology data. The development of the fl owsheet and its integration is based on employing a systems viewpoint and systematic process synthesis techniques, amply explained over three chapters. In consequence, the solution contains elements of originality, but in each case this is compared to schemes and economic indices reported in the literature.

1.1.2 Learning by Case Studies

Practising is the best way to learn. “ I see, I hear and I forget ” , says an old adage, which is particularly true for passive slide - show lectures. On the contrary, “ I see, I do and I understand ” enables effective education and gives enjoyment.

There are two types of active learning: problem - based and project - based. The former addresses specifi c questions, exercises and problems, which aim to illustrate and consolidate the theory by varying data, assumptions and methods. On the contrary, the project - based learning, in which we include case studies, addresses complex and open - ended problems. These are more appro-priate for solving real - life problems, for which there is no unique solution, but at least a good one, sometime “ optimal ” , depending on constraints and decisions. In more challenging cases a degree of uncertainty should be assumed and justifi ed.

The principal merits of learning by case studies are that they:

1. bridge the gap between theory and practice, by challenging the students, 2. make possible better integration of knowledge from different disciplines,

1.1 Motivation and Objectives 3

3. encourage personal involvement and develop problem - solving attitude, 4. develop communication, teamwork skills and respect of schedule, 5. enable one to learn to write professional reports and making quality

presentations, 6. provide fun while trying to solve diffi cult matters.

There are also some disadvantages that should be kept in mind, such as:

1. frustration if the workload is uneven, 2. diffi culties for some students to maintain the pace, 3. complications in the case of failure of project management or leadership, 4. possibility of unfair evaluation.

The above drawbacks, merely questions of project organization, can be reduced to a minimum by taking into account the following measures:

1. provide clear defi nition of content, deliverables, scheduling and evaluation, 2. provide adequate support, regular evaluation of the team and of each member.

If possible, separate support end evaluation, as customer/contractor relation, 3. evaluate the project by public presentation, but with individual marks, 4. propose challenging subjects issued from industry or from own research, 5. attract specialists from industry for support and evaluation.

1.1.3 Design Project

Teaching modern chemical process design can be organized at two levels:

• Teach a systems approach and systematic methods in the framework of a process design and integration introductory course. A period of 4 – 6 weeks fulltime (160 to 240 h) should be suffi cient. Here, a fi rst process - integration project is proposed, which can be performed individually or in small groups.

• Consolidate the engineering skills in the framework of a larger plant design project . A typical duration is 10 – 12 weeks full time with groups of 3 – 5 students.

Although dissimilar in extension and purpose, these projects largely share the content, as illustrated by Fig. 1.1 . The main points of the approach are as follows:

1. Provide clear defi nition of the design problem. Collect suffi cient engineering data. Get a comprehensive picture of chemistry and reaction conditions, thermal effects and chemical equilibrium, as well as about safety, toxicity and environ-mental problems. Examine the availability of physical properties for compo-nents and mixtures of signifi cance. Identify azeotropes and key binaries. Defi ne the key constraints.

2. The basic fl owsheet structure is given by the reactor and separation systems. Alternatives can be developed by applying process - synthesis meth ods. Use com-puter simulation to get physical insights into different conceptual issues and to evaluate the performance of different alternatives.

4 1 Integrated Process Design

3. Select a good base case. Determine a consistent material balance. Improve the design by using process - integration techniques. Determine targets for utilities, water and mass - separation agents. Set performance targets for the main equip-ment. Optimize the fi nal fl owsheet.

4. Perform equipment design . Collect the key equipment characteristics as specifi ca-tion sheets .

5. Examine plantwide control aspects, including safety, environment protection, fl exibility with respect to production rate, and quality control.

6. Examine measures for environment protection . Minimize waste and emissions. Characterize process sustainability.

7. Perform the economic evaluation . This should be focused on profi tability rather than on an accurate evaluation of costs.

8. Elaborate the design report . Defend it by public presentation.

In the process - integration project the goal is to encourage the students to produce original processes rather than imitate proven technologies. The emphasis is on learning a systemic methodology for fl owsheet development, as well as suitable systematic methods for the design of subsystems. The emphasis is on generating fl owsheet alternatives. The student should understand why several competing

Figure 1.1 Outline of a design project.

technologies can coexist for the same process, and be able to identify the key design decisions in each case. Thus, stimulating the creativity is the key issue at this level.

A more rigorous approach will be taught during the plant - design project. Here, the objective is to develop professional engineering skills, by completing a design project at a level of quality close to an engineering bureau. The subject may be selected from existing and proven technologies, but the rationale of the fl owsheet development has to be retraced by a rigorous revision of the conceptual levels and of design decisions at each step. This time the effi ciency in using materials and energy, equipment performance and the robustness of the engineering solution are central features. The quality of report and of the public presentation plays a key role in fi nal mark. More information about this approach may be found elsewhere [1] .

1.2 Sustainable Process Design

1.2.1 Sustainable Development

Sustainable development designates a production model in which fulfi lling the needs of the present society preserves the rights of future generations to meet their own needs. Sustainable development is the result of an equilibrium state between economic success, social acceptance and environmental protection. Eco-logical sustainability demands safeguarding the natural life and aiming at zero pollution of the environment. Economic sustainability aspires to maximize the use of renewable raw materials and of green energies, and saving in this way valuable fossil resources. Social sustainability has to account of a decent life and respect of human rights in the context of the global free - market economy.

An effi cient use of scarce resources by nonpolluting technologies is possible only by a large innovation effort in research, development and design. Sustain-ability aims at high material yield by the minimization of byproducts and waste. The same is valid for energy, for which considerable saving may be achieved by the heat integration of units and plants.

A systemic approach of the whole supply chain allows the designer to identify the critical stages where ineffi cient use of raw materials and energy takes place, as well as the sources of toxic materials and pollution. Developing sustainable processes implies the availability of consistent and general accepted sustainability measures. A comprehensive analysis should examine the evolution of sustain-ability over the whole life cycle, namely that raised by the dismantling the plant.

1.2.2 Concepts of Environmental Protection

In general, a manufacturing process can be described by the following relation [2] :

1.2 Sustainable Process Design 5

6 1 Integrated Process Design

( ) ( )A B I M C H P S R W FE+ + + + + ⎯ →⎯ + + + +

The inputs – main reactants A, coreactants B and impurities I – shape the generic category of raw materials . In addition, auxiliary materials are needed for technologi-cal reasons, as reaction medium M, catalyst C, and helping chemicals H. The process requires, naturally, an amount of energy E. The outputs are: main products P, secondary products S, residues R and waste W. The term residue signifi es all byproducts and impurities produced by reaction, including those generated from the impurities entered with the raw materials. Impurities have no selling value and are harmful to the environment. On the contrary, the secondary products may be sold. The term waste means materials that cannot be recycled in the process. Waste can originate from undesired reactions involving the raw materials, as well as from the degradation of the reaction medium, of the catalyst, or of other helping chemicals. The term F accounts for gas emissions, as CO 2 , SO 2 or NO x , produced in the process or by the generation of steam and electricity.

There are two approaches for achieving minimum waste in industry, as illus-trated by Fig. 1.2 [2] , briefl y explained below.

1.2.2.1 Production - Integrated Environmental Protection By this approach, the solution of the ecological problems results fundamentally from the conceptual process design. Two directions can be envisaged:

• Intrinsically protection, by eliminating at source the risk of pollution. • Full recycling of byproducts and waste in the manufacturing process itself.

In an ecologically integrated process only saleable products should be found in outputs. Inevitably a limited amount of waste will be produced, but the overall yield of raw materials should be close to the stoichiometric requirements. By applying heat - integration techniques the energy consumption can be optimized. The economic analysis has to consider penalties incurred by greenhouse gases (GHG), as well as for the disposal of waste and toxic materials.

Figure 1.2 Approaches in environmental protection [2] .

1.2.2.2 End - of - pipe Antipollution Measures When a production - integrated approach cannot be applied and the amount of waste is relatively small, then end - of - pipe solutions may be employed. Examples are:

• Transformation of residues in environmental benign compounds, as by incineration or solidifi cation.

• Cleaning of sour gases and toxic components by chemical adsorption. • Treatment of volatile organic components (VOC) from purges. • Wastewater treatment.

Obviously, the end - of - pipe measures can fi x the problem temporarily, but not remove the cause. Sometimes the problem is shifted or masked into another one. For this reason, an end - of - pipe solution should be examined from a plantwide viewpoint and beyond. For example, sour - gas scrubbing by chemical absorption may cut air pollution locally, but involves the pollution created by the manufacture of chemicals elsewhere. In this case, physical processes or using green (recyclable) solvents are more suitable. The best way is the reduction of acid components by changing the chemistry, such as for example using a more selective catalyst.

End - of - pipe measures are implemented in the short term and need modest investment. In contrast, production - integrated environmental protection necessi-tates longer - term policy committed towards sustainable development.

Summing up, the following measures can be recommended for improving the environmental performances of a process:

• If possible, modify the chemical route.

• Improve the selectivity of the reaction step leading to the desired product by using a more selective catalyst. Make use primarily of heterogeneous solid cata-lysts, but consider pollution incurred by regeneration. If homogeneous catalysis is more effi cient then developing a recycle method is necessary.

• Optimize the conversion that gives the best product distribution. Low conver-sion gives typically better selectivity, but implies higher recycle costs. Recycle costs can be greatly reduced by employing energy - integration and process - inten-sifi cation techniques.

• Change the reaction medium that generates pollution problem. For example, replace water by organic solvents that can be recovered and recycled.

• Purify the feeds to chemical reactors to prevent the formation of secondary impurities, which are more diffi cult to remove.

• Replace toxic or harmful solvents and chemicals with environmentally benign materials.

1.2.3 Effi ciency of Raw Materials

Measures can be used to characterize a chemical process in term of environmental effi ciency of raw materials, as described below [2] . Consider the reaction:

1.2 Sustainable Process Design 7

8 1 Integrated Process Design

ν ν ν ν νA B P R SA B P R S+ + → + +....

A is the reference reactant, B the coreactant, P the product, R the byproduct (valu-able) and S the waste product.

Stoichiometric yield RY is defi ned as the ratio of the actual product to the theoreti-cal amount that may be obtained from the reference reactant:

RY A

p

A

P

p

A

=νν

M

M

m

m (1.1)

This measure is useful, but gives only a partial image of productivity, since it ignores the contribution of other reactants and auxiliary materials, as well as the formation of secondary valuable products.

The next measures are more adequate for analyzing the effi ciency of a process by material - fl ow analysis (MFA). Two types of materials can be distinguished:

1. Main reaction materials, which are involved in the main reaction leading to the target product. All or a part of these can be found in secondary products and byproducts in the case of more complex reaction schemes, or in residues if some are in excess and nonrecycled.

2. Secondary materials, as those needed for performing the reactions and other physical operations, as catalysts, solvents, washing water, although not partici-pating in the stoichiometric reaction network.

The following defi nitions are taken from Christ [2] based on studies conducted in Germany by Steinbach ( www.btc - steinbach.de ).

Theoretical balance yield BA t is given by the ratio between the moles of the target product and the total moles of the primary raw materials (PRM), including all reactants involved in the stoichiometry of the synthesis route.

BAmoles target product

moles of primary raw materialst

P= =n MPP

A A B B PRM( . . . )n M n M+ +∑

(1.2)

This measure considers always an ideal process, but in contrast with the stoichio-metric yield, takes into account the quantitative contribution of other molecules. For this reason it is equivalent to an “ atomic utilization ” . This parameter is con-stant over a synthesis route and as a result a measure of material utilization. Thus, it is the maximum productivity to be expected. A lower BA t value means more waste in intermediate synthesis steps and a signal to improve the chemistry, by fewer intermediate steps or better selectivity.

Real balance yield BA is the ratio of the target product to the total amount of materials, including secondary raw materials ( SRM ) as solvents and catalysts, and given by:

BAamount target product

amount primary and secondary mater=

iialsP

PRM SRM

=+ ∑∑

m

m m (1.3)

BA is a measure of productivity, which should be maximized by design.