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 ..........................................