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Modelling and Optimization of Conventional and Unconventional Batch Reactive Distillation Processes. Investigation of Different Types Batch Reactive Distillation Columns for the Production of a Number of Esters such as Methyl Lactate, Methyl Decanoate, Ethyl Benzoate, and Benzyl Acetate using gPROMS Item Type Thesis Authors Aqar, Dhia Y. Rights <a rel="license" href="http://creativecommons.org/licenses/ by-nc-nd/3.0/"><img alt="Creative Commons License" style="border-width:0" src="http://i.creativecommons.org/l/by- nc-nd/3.0/88x31.png" /></a><br />The University of Bradford theses are licenced under a <a rel="license" href="http:// creativecommons.org/licenses/by-nc-nd/3.0/">Creative Commons Licence</a>. Download date 07/10/2021 06:38:54 Link to Item http://hdl.handle.net/10454/17139 Modelling and Optimization of Conventional and Unconventional Batch Reactive Distillation Processes Investigation of Different Types Batch Reactive Distillation Columns for the Production of a Number of Esters such as Methyl Lactate, Methyl Decanoate, Ethyl Benzoate, and Benzyl Acetate using gPROMS Dhia Yasser AQAR Submitted for the Degree of Doctor of Philosophy Faculty of Engineering and Informatics University of Bradford 2018 Abstract Dhia Yasser Aqar Modelling and Optimization of Conventional and Unconventional Batch Reactive Distillation Processes Investigation of Different Types Batch Reactive Distillation Columns for the Production of a Number of Esters such as Methyl Lactate, Methyl Decanoate, Ethyl Benzoate, and Benzyl Acetate using gPROMS Keywords: CBD, i-CBD, SBD, i-SBD, i-DWCBD, IBD, MVD, Modelling, Optimization, Esterification The synthesis of a number of alkyl esters such as methyl lactate, methyl decanoate, and ethyl benzoate via esterification in a reactive distillation is quite challenging. It is due to the complexity in the thermodynamic behaviour of the chemical species in the reaction mixture in addition to the difficulty of keeping the reactants together in the reaction section. One of the reactants (in these esterification reactions) having the lowest boiling point can separate from the other reactant as the distillation continues. This can result in a significant drop in the reaction conversion in a conventional reactive distillation whether it is a batch or a continuous column. To overcome this challenge, new different types of batch reactive distillation column configurations: (1) integrated conventional (2) semi-batch (3) integrated semi-batch (4) integrated dividing-wall batch distillation columns have been proposed here. Four esterification reaction schemes such as (a) esterification of lactic acid (b) esterification of decanoic acid (c) esterification of benzoic acid (d) esterification of acetic acid are investigated here. A detailed dynamic model based on mass, energy balances, chemical reaction, and rigorous thermodynamic (chemical and physical) properties is considered and incorporated in the optimisation framework within gPROMS (general PROcess Modelling System) software. It is found that for the methyl lactate system, the i-SBD operation outperforms the classical batch operations (CBD or SBD columns) to satisfy the product constraints. While, for the methyl decanoate system, the i-DWCBD operation outperforms all CBD, DWBD and sr-DWBD configurations by achieving the higher reaction conversion and the maximum product purity. For the ethyl benzoate system, the performance of i-CBD column is superior to the CBD process in terms of product quality, and conversion rate of acid. The CBD process is found to be a more attractive in terms of operating time saving, and annual profit improvement compared to the IBD, and MVD processes for the benzyl acetate system. i Acknowledgements First and foremost, I thank Almighty Allah (God) for blessing me with success and prosperity. I would like to thank all the people who have supported me in various ways throughout the period of this work. I would like to express my sincere gratitude to Professor I.M. Mujtaba for his invaluable guidance and advice, continuous co-operation, valuable comments, suggestions, unlimited help and support throughout this work. I would also want to extend my sincere gratitude to Dr. N. Rahmanian for his wonderful guidance, encouragement and support from the beginning of my study. I am grateful to all the staff members of The Higher Committee for Education Development in Iraq (HCED) for giving me financial support and help during my course. I would like to express my gratitude and appreciation to my parents for their enormous love, brothers and sisters for their unconditional support and encouragement. My warmest thanks go to my wife, my daughters for their love, understanding and patience, during my study. ii Tables of Contents Abstract…………………...………………………..…………….…………..……………… i Acknowledgements………………….…………......………………......…………………. ii Table of Contents………………………………..…………………………....…………... iii List of Figures…………..……….……………..…….………………….……...…..……. viii List of Tables……………………….……………....…………………………….……....... x Nomenclature and Abbreviation……………………………..................…..…….…..... xii Chapter One ........................................................................................................... 1 Introduction .............................................................................................................. 1 1.1 Continuous Distillation Column ....................................................................... 2 1.2 Batch Distillation Column ................................................................................ 4 1.2.1 Conventional Batch Distillation .................................................................... 5 1.2.2 Divided-Wall Batch Distillation Column ........................................................ 6 1.2.3 Semi-Batch Distillation Column ................................................................... 9 1.2.4 Inverted Batch Distillation ...........................................................................11 1.2.5 Middle Vessel Batch Distillation ..................................................................12 1.3 Traditional Batch Reactor-Batch Distillation Approach ...................................14 1.4 Scope of This Research ................................................................................16 1.5 The Aim and the Objectives of the Work .......................................................20 1.6 The Thesis Outline ........................................................................................22 Chapter Two ..........................................................................................................25 Literature Survey ....................................................................................................25 2.1 Introduction ...................................................................................................25 2.2 Continuous Reactive Distillation Process ......................................................25 2.3 Batch Reactive Distillation in Conventional Column .......................................28 2.3.1 Esterification of Lactic Acid and Methanol ..................................................28 2.3.2 Esterification of Decanoic Acid and Methanol .............................................28 2.3.3 Esterification of Benzoic Acid and Ethanol..................................................30 2.3.4 Esterification of Acetic Acid and Benzyl Alcohol .........................................31 2.3.5 Dynamic Modelling and Optimization ..........................................................33 2.3.6 Other Reaction Systems in Batch Column ..................................................33 2.4 Batch Reactive Distillation in Semi-Batch Column .........................................38 2.4.1 Esterification of Lactic Acid and Methanol ..................................................38 2.4.2 Other Reaction Systems in Semi-Batch Column .........................................39 iii 2.5 Batch Reactive Distillation in Divided-Wall Column .......................................41 2.6 Batch Reactive Distillation in Inverted Column ..............................................43 2.7 Batch Reactive Distillation in Middle-Vessel Column .....................................44 2.8 Conclusions ...................................................................................................45 Chapter Three .......................................................................................................47 New Reactive Distillation Configurations and Their Applications .............................47 3.1 Introduction ...................................................................................................47 3.2 New Batch Distillation Configurations for Synthesis of Alkyl Esters ...............47 3.2.1 Integrated Conventional Batch Distillation Operation ..................................47 3.2.2 Integrated Semi-Batch Distillation Operation ..............................................48 3.2.3 Split Reflux Divided-Wall Distillation Operation ...........................................50 3.2.4 Integrated Divided-Wall Distillation Operation .............................................50 3.3 Applications of New Configurations for Different Reaction Schemes .............51 3.4 Conclusions ...................................................................................................53 Chapter Four .........................................................................................................55 Process
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