DOCSLIB.ORG

Synthesis of Bisphenol a with Heterogeneous Catalysts

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Synthesis of Bisphenol a with Heterogeneous Catalysts Synthesis of Bisphenol A with Heterogeneous Catalysts by Liliana Neagu A thesis submitted to the Deparment of Chernical Engineering in conforrnity with the requirements for the degree of Master of Science (Engineering) Queen' s University Kingston, Ontario, Canada August, 1998 Copyright O Liliana Neagu, October 1998 National Lib rary Bibliotheque nationale 1*m of Canada du Canada Acquisitions and Acquisitions et Bibliographie Sewices services bibliographiques 395 Wellington Street 395. rue Wellington Oftawa ON KlA ON4 Ottawa ON KIA ON4 Canada canada The author has granted a non- L'auteur a accordé une licence non exclusive licence dowing the exclusive permettant à la National Library of Canada to Bibliothèque nationale du Canada de reproduce, loan, distn'bute or sell reproduire, prêter, distribuer ou copies of this thesis in microform, vendre des copies de cette thèse sous paper or electronic formats. la forme de microfiche/fïh de reproduction sur papier ou sur format électronique. The author retains ownership of the L'auteur conserve la propriété du copyright in this thesis. Neither the droit d'auteur qui protège cette thèse. thesis nor substantial emcts fiom it Ni la thèse ni des extraits substantiels may be printed or otherwise de celle-ci ne doivent être imprimés reproduced without the author's ou autrement reproduits sans son permission. autorisation. Abstract The synthesis of bisphenol A (BPA) with heterogeneous catalysts was uivestigated in a batch system and in a plug flow reactor. Gibbs reactor simulations contributed to a better understanding of the reaction which leads to BPA formation. Experiments were conducted with ~mberlyst@-15,Nafion@ NR-50, Nafione SAC-13. and activated alumina acidified with concentrated hydrochloric acid (AA300/HCl). An experùnental design was used to investigate the effects of temperature, catalyst concentration, molar ratio of acetone and phenol in the initial reaction mixture, and the size of the catalyst bead. Al1 the factors significandy innuence some or al1 the aspects of the process of BPA formation. Al1 three new catalysts: AA300/HC1,Nafion@ NR-50, and Nafion@SAC-13, were found suitable to catalyze the production of bisphenol A, using phenol and acetone as starting materials. Both yield and selectivity are significantly higher for the processes that use the newly identined catalysts than the yield and selectivity obtained in the process that uses Amberlyst@1 5. Acknowledgments There are many people 1 want to thank in this section, people who offered me their support and their fnendship, for which 1 am grateful. I would like to thank my supervisors Dr. Tom Harris and Barrie Jackson for their support, encouragement and understanding throughout the completion of this project. 1 would also like to thank Dr. Whitney and Dr. Brian Hunter for the meaningfid conversations, Steve Hodgson, Lisa Prior and Martin York for the& technical assistance with my research equipment. 1 am grateful to my office mate Shannon Quinn for her sincere fiiendship and her computïng knowledge. 1 thank Gregg Logan for his Eendship, for the endess conversations about food, and for introducing me to graduate student life in the department. Thankç to everybody in the department for creating such a pleasant work place. 1 would like to thank my husband for being supportive and understanding sometimes and to rny daughter for being a good and happy child, for sleeping overnight and for not crying as much as she could have. Many thanks to the Queen's Day Care Centre staff, Halina, Donna, Pada, Sean, Karen, Lori, Sandra, for taking such a good care of my daughter and for spoiling her more than I did. As vrea sa multumesc parintilor mei Voica si Aurel Monea pentru ca mi'au dat puterea sa visez si aripi sa zbor. Table of Contents 1 Introduction.......................................................................... 2 Basic Chemistry and Production of BPA ...................................... 2.1 Preparation of Bisphenol A ................................................. 2.1.1 Acetone Process .................................................. 2.1.1.1 Primary Reaction ...................................... 2.1.1.2 By-Products Formation ............................... 2.1.1.3 Reaction Order ......................................... 2.1.1.4 Equilibrium Data ...................................... 2.1.1.5 Catalysts..................... .. ...................... 2.1.1 .5. 1 Catalyst Enhancers ......................... 2.1.1.6 Bisphenol Stabilizers .................................. 2.1.1.7 Solvents................................................. 2.1.1.8 Reaction Mechanism .................................. 2.1.1.9 Reactor Configuration ................................ 2.1.2 Alternatives to Acetone as Feedstock ......................... 2.2 Purification................................................................... 2.2.1 Catalyst Separation .................. .. ........................... 2.2.2 %PASeparation from Cnide .................................... 2.2.2.1 Methods of Separating BPA fiom the 1: 1 BPA- Phenol Aduct ............................................... 2.2.2.2 By-Products Isomerization to BPA ................. 2.3 Manufacturing ............................................................... 2.3.1 Resin-Catdyzed Process ........................................ 2.3.2 Hydrogen Chloride-Catalyzed Process ........................ 2.3.3 Resin-Catalyzed Process II ...................................... 2.4 Physical Properties .......................................................... 2.5 Chernicd Properties .............................. .. ......................... 2.6 Summq...................................................................... 3 Gibbs Reactor Simulations........................................................ 3.1 The PRO II@Gibbs Reactor ................................................ 3.2 Simulation of the Bisphenol A Reaction .................................. 3.2.1 Analysis of the Simulation Results ............................. 3.2.1.1 Effect of Temperature and Acetone:Phenol Molar Ratio on BPA Formation .......................... 3.2.1.2 By-Products Formation ............................... 3 -3 Surnmary of the Sunulation ................................................ 3 -4 Conclusions.................................................................. 4 Experïmental Investigation ........................................................ 4.1 Apparatus-OveMew ......................................................... 4.2 Materials ....................................................................... 4.2.1 Solid Catalysts..................................................... 4.2.1.1 ~afion@-~erfiuorosulfonatedIonomer .............. 4.2.1.2 High Surface ~reaNafionB Resin ................... 4.3 Procedures .................................................................... 4.3.1 Reactor Loading Procedures .................................... 4.3.1.1 NMR Tube Reaction. ................................. 4.3.1.2 Batch Reactor .......................................... 4.3.1.3 Flow Reactor ........................................... 4.3 -2 Reactor Sarnpling Procedure and Sample Preparation ....... 4.3.2.1 NMR Tube Reaction .................................. 4.3.2.3 Batch Reactor .......................................... 4.3.2.3 Flow Reactor ........................................... 4.3.3 Reactor Shut-Down and Clean-Up Procedure ................ 4.3 -3.1 NMR Tube Reaction .................................. 4.3.3.2 Batch Reactor .......................................... 4.3 -3.3 Flow Reactor ........................................... 4.4 Sample Analysis .............................................................. 4.4. I Gas Chromatography/ Mass Spectrometry Analysis ........ 4.4.2 NMR Analysis ................................................... 4.4.2- 1 General Introduction to the NMR Procedure Used in this Study ........................................ 4.4.2.2 Cdculation of the Error Associated with the NMR Analysis .............................................. 4.4.2.3 Procedure for Caiculating the Yield in BPA ....... 4.5 Summary ...................................................................... 5 Experimental Results and Discussion ........................................... * 5.1 Prelimioary Investigation ................................................... 5.1.1 Evaluation of System Reactivity and Blank Reactions ...... 5.1 -2 Evaluation of Experimental Region ............................ 5.1 -3 Scheme of Reaction .............................................. 5.1.4 Experimental Reproducibility................................... 5.1.5 Validity of Simulation Prediction for Depletion of Acetone .............................................................. 5.2 Investigation of Suitability of New Catalysts............................ 5.3 Performance Comparison of ~afion@and Amberlysta 15 .............. 5 -4 Experimental Design ........................................................ 5.4.1 Factors Chosen and Responses................................. 5.4.2 Evaluation of Results corn Experimental Design ............ 5.4.3 Precision of Caiculated Effects................................. 5.4.4 Effects Analysis .................................................. 5.4.4.1 Selectivity of BPA Formation ...................... 5.4.4.2 Selectivity of O-pIsomer Formation ............... 5.4.4.3 Selectivity of Chromanes Formation ............... 5.4.4.4 Yield in BPA ..........................................
Load more

Recommended publications
  • Targeted and Non-Targeted Analysis of Plastic-Related Chemicals in Food
    TARGETED AND NON-TARGETED ANALYSIS OF PLASTIC-RELATED CHEMICALS IN FOOD LEI TIAN Department of Food Science and Agricultural Chemistry McGill University, Montreal April 2020 A thesis submitted to McGill University in partial fulfillment of the requirements of the degree of Doctor in Philosophy © Lei Tian, 2020 Abstract Plastic-related chemicals (PRCs) are substances related to plastics including the initial components of the plastics (e.g. monomers, antioxidants, additives) and the degradation products of plastics. The occurrence of PRCs in food and their potential adverse health effects have raised concerns about the health of consumers. To date, the surveillance of PRCs in food has mostly focused on the targeted screening and quantification of specific residues using tools such as high performance liquid chromatography (HPLC) or gas chromatography (GC) coupled with mass spectrometry (MS). For example, bisphenol A (BPA) and several phthalates have been detected in different types of food. To ensure food safety though, it is now acknowledged there is a need for analytical tools able to screen and identify not only “known” PRCs in food, but also the new “unknown” compounds. The main objective of my research is to develop and optimize a non-targeted method to investigate PRCs in food with an emphasis on the investigation of the influence of data processing parameters on the identification of trace residues in food. In Chapter 3, a non-targeted workflow was optimized based on the HPLC hyphenated to quadruple time-of-flight MS (HPLC- QTOF-MS) analysis to investigate leachable residues from reusable bottles. Low method detection limits (MDL) and high mass accuracy were achieved for 11 bisphenol analogues.
    [Show full text]
  • Preparatory Problems
    IChO-2013 Preparatory Problems Preparatory problems 45th International Chemistry Olympiad (IChO-2013) Chemistry Department Moscow State University Russian Federation Edited by: Vadim Eremin, Alexander Gladilin e-mail: [email protected] [email protected] Released January 31, 2013 1 IChO-2013 Preparatory Problems Contributing authors Moscow State University, Chemistry Department A. Bacheva M. Beklemishev A. Belov A. Bendrishev A. Berkovich E. Budynina A. Drozdov V. Eremin A. Garmash A. Gladilin Eu. Karpushkin M. Korobov E. Lukovskaya A. Majuga V. Terenin I. Trushkov S. Vatsadze A. Zhirnov Bashkirian Medical State University B. Garifullin National Polytechnic Institute, Toulouse, France D. Kandaskalov Kazan’ Federal University, A.Butlerov Institute of Chemistry I. Sedov 2 IChO-2013 Preparatory Problems PREFACE Dear friends! We are happy to present you the Booklet of Preparatory problems. Members of the Science Committee really did their best to prepare interesting tasks. The set covers all major parts of modern chemistry. All the tasks can be solved by applying a basic knowledge of chemistry, even in case a problem refers to a topic of advanced difficulty. Still, we expect it will take some time and efforts of yours to find the correct answers. Thus, most probably we know how you will spend some of your time in the coming months. We wish you much pleasure while working with this set of problems. FACE YOUR CHALLENGE, BE SMART! Note to mentors In addition to the problems, you will find in the Booklet: • The list of topics of advanced difficulty • The Safety rules and recommendations set by the IChO International Jury • The hazard warning symbols, their designations and explanations, R-ratings and S- provisions Worked solutions will be posted at the website by the end of May, 2013.
    [Show full text]
  • PREPARATORY PROBLEMS Icho 2013 RR
    tthhth 445545 PREPARATORY PROBLEMS Edited by Anton Sirota 27 theoretical problems 8 practical problems 2013 THE PREPARATORY PROBLEMS FROM THE INTERNATIONAL CHEMISTRY OLYMPIADS, Series 1 The preparatory problems from the 45 th IChO Edited by Anton Sirota IChO International Information Centre, Bratislava, Slovakia ISBN 978-80-8072-167-1 Copyright © 2016 by IUVENTA You are free to copy, distribute, transmit or adapt this publication or its parts for unlimited teaching purposes, however, you are obliged to attribute your copies, transmissions or adaptations with a reference to "The Preparatory Problems from the International Chemistry Olympiads, Series 1" as it is required in the chemical literature. The above conditions can be waived if you get permission from the copyright holder. Issued by IUVENTA in 2016 with the financial support of the Ministry of Education of the Slovak Republic Number of copies: 200 Not for sale. International Chemistry Olympiad International Information Centre IUVENTA Karloveská 64 84258 Bratislava 1, Slovakia Phone: +421-907-473367 E-mail: [email protected] Web:www.icho.sk Original title page: Preparatory problems 45 th International Chemistry Olympiad (IChO-2013) Chemistry Department Moscow State University Russian Federation Edited by: Vadim Eremin, Alexander Gladilin January 31, 2013 Contributing Authors Moscow State University, Chemistry Department A. Bacheva M. Beklemishev A. Belov A. Bendrishev A. Berkovich E. Budynina A. Drozdov V. Eremin A. Garmash A. Gladilin Eu. Karpushkin M. Korobov E. Lukovskaya A. Majuga V. Terenin I. Trushkov S. Vatsadze A. Zhirnov Bashkirian Medical State University B. Garifullin National Polytechnic Institute, Toulouse, France D. Kandaskalov Kazan’ Federal University, A.Butlerov Institute of Chemistry I.
    [Show full text]
  • Synthesis of Novel, Highly Bio-Based Monomeric Materials Derived from Lignocellulosic Biomass and Their Respective Epoxy Resins, Polycarbonates, and Polyesters
    Rowan University Rowan Digital Works Theses and Dissertations 2-15-2017 Synthesis of novel, highly bio-based monomeric materials derived from lignocellulosic biomass and their respective epoxy resins, polycarbonates, and polyesters Joseph Randall Mauck Rowan University Follow this and additional works at: https://rdw.rowan.edu/etd Part of the Chemical Engineering Commons Recommended Citation Mauck, Joseph Randall, "Synthesis of novel, highly bio-based monomeric materials derived from lignocellulosic biomass and their respective epoxy resins, polycarbonates, and polyesters" (2017). Theses and Dissertations. 2362. https://rdw.rowan.edu/etd/2362 This Thesis is brought to you for free and open access by Rowan Digital Works. It has been accepted for inclusion in Theses and Dissertations by an authorized administrator of Rowan Digital Works. For more information, please contact [email protected]. SYNTHESIS OF NOVEL, HIGHLY BIO-BASED MONOMERIC MATERIALS DERIVED FROM LIGNOCELLULOSIC BIOMASS AND THEIR RESPECTIVE EPOXY RESINS, POLYCARBONATES, AND POLYESTERS by Joseph Randall Mauck A Thesis Submitted to the Department of Chemical Engineering Henry M. Rowan College of Engineering In partial fulfillment of the requirements For the degree of Master of Science in Chemical Engineering at Rowan University December 16, 2016 Thesis Chair: Joseph F. Stanzione, III, Ph.D. © 2016 Joseph R. Mauck Dedications For Mom, Dad, and Meagan Acknowledgements First and foremost I wish to express my deepest gratitude to Dr. Joseph F. Stanzione, III; my graduate advisor, teacher, mentor, teammate, hunting partner, and thesis chair. For the past 16 months, Dr. Stanzione has encouraged me through difficult academic times, guided me in research decision-making, and most importantly, given me the opportunity to study and perform this work and become a contributing part of the greater biomaterials research community.
    [Show full text]