Synthesis of Bisphenol A with Heterogeneous Catalysts
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
1 * m
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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@15.
There are many people 1 want to thank in this section. people who offered me their support and their fnendship. Steve Hodgson. Donna. for the endess
conversations about food. 1 would also like to thank Dr. Tom Harris and Barrie Jackson for their support. Lori.
Many thanks to the Queen's Day Care Centre staff.
I would like to thank my supervisors Dr.
As vrea sa multumesc parintilor mei Voica si Aurel Monea pentru ca mi'au dat puterea sa visez si aripi sa zbor. Thankç to everybody in the department for creating such a pleasant work place. 1 thank Gregg Logan for his Eendship. Halina.
1 am grateful to my office mate Shannon Quinn for her sincere fiiendship and her computïng knowledge. Karen. Lisa Prior and Martin York for the& technical assistance with my research equipment. for sleeping overnight and for not
crying as much as she could have. and for introducing me to graduate student life in the department. Sandra. encouragement and understanding throughout the completion of this project.
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 taking such a good care of my daughter and for spoiling her more than I did. Pada. for which 1 am grateful. Sean.
. Brian Hunter for the meaningfid conversations. Whitney and Dr.
2 Simulation of the Bisphenol A Reaction .....3...... ... 1 Catalyst Enhancers... ....................................................3 Reaction Order .............2 Alternatives to Acetone as Feedstock......................1.. 3.1. .6 Bisphenol Stabilizers.......................1.......... 4........1 Apparatus-OveMew ...Table of Contents
1 Introduction.................... ................................2 Hydrogen Chloride-Catalyzed Process ........2....... 2..................... 2..............................................................2 Purification................................................3.......................................... ............................8 Reaction Mechanism ...6 S u m m q ........ 2....................... .1.... 2.......1.2.. 2.......1......................... 2....2....................... 2.......................2.......1..1.1......................2................ 3 Gibbs Reactor Simulations........1............2 By-Products Isomerization to BPA .. 2................................. 3 -4 Conclusions......... 3.......................................................5 ...........1 Catalyst Separation..........1 Acetone Process .................. 3 -3 Surnmary of the Sunulation.......1.5 Chernicd Properties.........................3.........7 Solvents.....1...........2 By-Products Formation ..... 2.1 Effect of Temperature and Acetone:Phenol Molar Ratio on BPA Formation............. 2 Basic Chemistry and Production of BPA .........9 Reactor Configuration........1 Methods of Separating BPA fiom the 1:1 BPAPhenol Aduct ................1..1............................ 4 Experïmental Investigation..........................................1 ............... 2.1............. 2......1 Resin-Catdyzed Process........................ 2............................................1 Preparation of Bisphenol A .1............... 2.................................................................. 2........................................................ 2..................... 3........................3 Resin-Catalyzed Process II ....... 2.....................1 Primary Reaction ......... ................................................4 Physical Properties ...........1........................ 2..1. 2......1......1............... 2............2................. 2................................................... 2.................. 2. 3.......1 The PRO II@ Gibbs Reactor ...1...4 Equilibrium Data..... 3............3 Manufacturing ....1 Analysis of the Simulation Results ..........5 Catalysts... 2...............1.........2...
..........................2......................2 %PASeparation from Cnide ..........................1.......2 By-Products Formation ......2.............. 2........ 2.............................
.......1 General Introduction to the N M R Procedure Used i this Study ..... and 5-4 Experimental Design...4.................................2 Evaluation of Results corn Experimental Design..................3.......... 4.................1 NMR Tube Reaction.... 4....................3 Flow Reactor ..1 Prelimioary Investigation.....5 Summary . 5..3 -3... a 4.............2................... 4............. 5...... 5.............................3 Flow Reactor ............3 Reactor Shut-Down and Clean-Up Procedure ...3....4.........................3 Procedures .......................1...........1................................4......................2................. 5................ 4.......... 4....... 4................. 4.......4................................ 5............3....3......1. 4..... 5.............3 Flow Reactor..............4 Sample Analysis.....3............................1.............4 Experimental Reproducibility... 5.....2 Materials ............. 4......2.......................... 4......... 5....... ............1 -3 Scheme of Reaction ......... 4........ 4..................2 Batch Reactor ...4.....................................2.....................2 High Surface ~ r e NafionBResin..
4..... 5...2 Investigation of Suitability of New Catalysts................4...3......1 ~afion@-~erfiuorosulfonated Ionomer .....1.5 Validity of Simulation Prediction for Depletion of Acetone........................... 4......3 -2 Reactor Sarnpling Procedure and Sample Preparation...... I Gas Chromatography/ Mass Spectrometry Analysis ...2..3 Batch Reactor ..............................2 Batch Reactor............3 Procedure for Caiculating the Yield in BPA ..........2 NMR Analysis . 4.......................3.........................3 Precision of Caiculated Effects..............1 Selectivity of BPA Formation ...4 Effects Analysis.1.......... 4.....................1 Evaluation of System Reactivity and Blank Reactions.............1. 5...........4..............2..............1 Solid Catalysts.......................4.................................4..3................1 Factors Chosen and Responses.3 Performance Comparison of ~ a f i o n @ Amberlysta 15.4... 4....
5 Experimental Results and Discussion ....... 4...1 Reactor Loading Procedures .................2 Cdculation of the Error Associated with the NMR Analysis .........4.............2 Selectivity of O-pIsomer Formation ... 5......3...1-2 Evaluation of Experimental Region .................................... 5.........................4.....................................................3..............1 NMR Tube Reaction ... ...1 NMR Tube Reaction............4............4...2.....1...................... 4....4..............2...........................3 Selectivity of Chromanes Formation...2.................................3 -3... 5................. 4................. 5...4............................ 5.........
........................ 4............... n 4................
.........................1 Mode1 for Selectivity of BPA Formation ......................... 5.....3 Model for Yield in BPA ......1 Reactions with Acidic Activated Alumina...................7..................... 5 4 .................... Reactions in the Plug Flow Reactor....... Conciusions and Recommendations.................3 Reaction with ~ a f i o n @ SAC-13 ................5 Regression Analysis .....................
......6 z4 Experimental Design ............ Summary of Simulation Resuits................................................. 5.................4........................................................................................7... 5...............................4.....................5 3 Model for the Selectivity of Chromanes Formation............. ................ 7................ .2 Recommendations................................................. 6.. 5...............4................ 5......4 Mode1 for the Yield in BPA ............................................4............2 Model for the Selectivity of O-pIsomer Formation.........................4.......5..........5...5...............................................4 Yield in BPA ......................4.......... -.................................................2 Reactions with ~ a f i o n NR-50 ........................................... . Health and Safety Regdations ...........1 Conclusions......................1 Mode1 for Selectiviw of BPA Formation...7 Regression Analysis for the z4 Experimental Design.................. 5................... The NMR Phenornenon............6 Summary of z3Experimentai Design ...... ..............7............. 5-5 Additional Runs .............................4...... 5....... 6... @ 6............2 Mode1 for Selectiviv of Chromanes Formation . 5.... 5.. 6............ PRORI@ Input File .................................................................................. 5...................................... 5......4 S u m m q ..................8 Summary ...6
..19 Sigmficant effectS.... Results of performance cornparison between ~ a f ï o n @ ~mberlyst@-.................... 5.....................12 Resdts of the regression analysis for the selectivity of chromanes formation.... 5............................................20 Results of the regression analysis for the selectivity of BPA formation..................
....... .................... .................................. Equilibrium constant for the BPA o.....................................................................................................4 Variation of vapor pressure with temperature... temperature (T) and molar ratio of acetone and phenol (R) ...3 Solubilities of bisphenol A in various solvents (g/100g solvent) ................... .................................List of Tables
-1 Quality characteristics for BPA as raw matenal for polycarbonates .............. Precision of calculated effects............................................................. 5............ 5.............................p-isomer transformation.......... Calculated effects. ......................................................................16 Cornparison between the calculated effects in the fkst set and the second set of experiments...........13 Results of the regression analysis for the yield in BPA ................................................................. 5..................................p4somer transformation based on simulated data.................15 Calculated effects for the additional runs .. Responses for the experiments perfomed in the 23experimental design ................. 5.............................. Data acqursrtion parameters..18 Calculated effects for the 24 design.................................................... 2.......................... .................................................. Experimental runs used to investigate the efTect of catalyst concentration (C)........................................... Acquisition method on the mass spectrometer........... 2................... Peak table with retention times and boiling points of the products ......... Materials used in experiments....................................... .............. and 15 High value.....................1 Equilibrium constant for the BPA f o.1 1 Results of the regression analysis for the selectivity of O-p isomer formation.................................................... range and half range for each factor. ......... Results of the experiments performed with AmberlystB-15 in the batch reactor ..... .. midpoint............................... 5...... .......................... 5..................................................... 5.............. low value..................2 Results of the reaction of acetone with phenol in the presence of zeolites and cation-exchange resin........... 5..... ................................... Gibbs reaction simulation with reaction parameters.... Summary of the experiments .............10 Results of the regression analysis for the selectivity of BPA formation.14 Additional runs .......17 Data for the z4experimental design. Results of the second set of experirnents...... 5..
......................... 6................. o.... and triphenol formation with the acetone:phenol molar ratio at 323.... . The results are presented in mol
%......15 K.............21 Results of the regression analysis for the selectiviv of chromanes formation..... 5............
............................................................................................................. 07p-isomer (II)......... The results are presented in mol
%.......... and triphend (III) with the temperature at various acetone:phenol molar ratios.................2Variation of bisphenol A........ and triphenol formation with the acetone:phenol molar ratio at 333..15 K...
C. ........ ...................... The results are presented in mol
C.....15 K.......... 07p-isomer......... 6.................................... C.......... ...... The results are presented in mol
%.............. ..... 1PRO/LI@ keyword input file............................ 6........... The results are presented in mol
CAVariation of bisphenol A............ ...22 Results of the regession analysis for the yield in BPA............. 6..................................3Variation of bisphenol A........ ..............l Variation of bisphenol A...... B.....15 K.... .......... CSVariation of bisphenol A.... and triphenol formation with the acetone:phenol molar ratio at 343......4 Results of the experiment with Nafion@SAC-13............................. ...... A............... and triphenol formation with the
acetone:phenol molar ratio at 363......... og-isomer.......5......................... og-isomer.3 Results of the experiments with Nafion@NR-50.. and triphenol formation with the acetone:phenol molar ratio at 353.....................................15 K...2 Results of the experiments with AM001 HCl................ op-isomer.........6Variation of selectivity of bisphenol A 0........................1 Summary of the experiments................ 1 Chernicals used in experiments! associated hazards and safety requirements .........
....... 3..................... 4.............................. 3-7 Variation of triphenol formation with molar ratio acetone...... 2.....15 ..............1 Plug flow reactor ..........5 Mechanism of condensation of acetone with phenol s a hydrogen bonds ...........................................pheno1...........6 Variation of selectivity of og-isomer with temperature at various molar ratios acetone:phenol ..... 2......... 2................ 2...3 Electron withdrawing effect............ 3....2 Nanon@structure...6 Reactor configuration.............................................. x = 1.................... 4................... .....................14Variation of BPA...................................... 2........................ ................................................... 4.....p... 3....p&orner formation with temperature at various rnolar ratios acetone. 2.. 3. ...12 Variation of triphenol formation with temperature and acetone:phenol molar ratio .15 K ..........................p 4somer formation with temperature and molar ratio .....................................................4 Variation of og-isomer formation with acetone:phenoI molar ratio ...........................9 Variation of selectivity of triphenol with temperature at various molar ratios acetone............... or 3 ......... 2.........9 Production of bisphenol A with resin catalyst II ........ 3.......... 3................ 3.............pheno1.......................................................... acetone...................... 3............List of Figures
2.....4 Styiized view of polar/ nonpolar microphase separation in a hydrated ionomer...............................1 Conversion of phenol versus time for various catalysts................................. 2.......5 The Yeager 3 phase mode1 of Nafion@ clusters................ 3 -8 Variation of triphen01 formation with temperature at various molar ratios acetone....3 Product selectivity versus time for the reaction catalyzed by Hmordenite ........1 1 Variation of 0.......................................7 Production of bisphenol A with resin catalyst................. 3.........isomer.....2 Product selectivity versus time for the reaction catalyzed by Re-Y .........................5 Variation of o...........................10 Variation of BPA formation with temperature and acetone:phenol molar ratio ..................pheno1....... n 1000....13 Variation of BPA..2 Variation of BPA formation with temperature and acetone:phenoI molar ratio ........ 2......................
.. o.................... 3....pheno1.... opisomer.................3 Variation of selectivity of BPA with temperature and acetone:phenol molar ratio ......... m = 6 or 7...........................8 Production of bisphenol A with hydrogen chlonde catalyst....... 4... and triphenol formation with temperature...... 4.................................................pheno1.................... 3................4 Product selectivity versus time for the reaction cataiyzed by Amberlyst.......1 Variation of BPA formation with molar ratio acetone.........................................pheno1.... and triphenol formation with molar ratio acetone:phenol at 353......................................... .... 3..........
...................14 Variation of BPA yield with temperature ........ .6 Analysis of the reaction with heterogeneous catalyst (after nine days) ...2 1 Effects present in the molecule of phenol and the nucleophilic attack................4 pprn to 3 ..............0 ppm) ...............................................12 NMR spectnun of the initial mixture of reaction (fiom 1........13 Variation of chromanes selectivity with temperature............. 5....... ppm) 4................................. ........ ) ......................... 4...........................4... 5-5 Crystals of BPA ........ 5-9 Variation of selectivity of O-pisomer in tirne...............................0 ppm) 5............. pprn to 3..............15 Disappearance of acetone...2 Analysis of the reaction with homogeneous catalyst (after six days) ....... [6 h] ....13 NMR spectrum of the final mi>aure of reaction (firom 0.......................................20 Effects of considered factors on selectivity of O-pisomer formation and their significance .................................................................0 0 ........... 5 -7 Analysis of the reaction with no catalyst (after three days) . 5.......19 Effects of considered factors on selectivity of BPA formation and their significance.. 5....................... 5......................................... Chromatogram of the products for the process catalyzed by AA 300/ HCL S [6 hl ........................
.............................. 4........ 5.7 Chromatogram of the products obtained in the condensation process ...15 ...................................... 5............. 5........................22 Effects of considered factors on selectivity of chromanes formation and their significance ..............9 NMR spectrum of phenol (CDCI........ 5.......................................... -4.... 5................11 NMR s p e c t m of the initial mixture of reaction (fiom 0..................... 5.................................. 5......................10 NMR spectrum of bisphenol A (CDCl........... 5.......................... 4......4 Analysis of the reaction with homogeneous catalyst (after twelve days) ............ ) ............4 pprn to 3.............................................12 Variation of +p isomer selectivity with temperature. ) ........................................ 5.10 Variation of chromanes selectivity in time .................17 Chromatogram of the products for the process catalyzed by Nafion@ NR50 [3 hl ........ .......................................... 4........................................ 5....................8 NMR spectrurn of acetone (CDCl.....16 Chrornatogram of the products for the process catalyzed by Amberlyst................. 5................... 5..................................8 Variation of BPA selectivity in tirne.1 Analysis of the reaction with hornogeneous catalyst (after three days) ..........................................23 Effects of considered factors on yield in BPA and their significance ..........6 Temperature profile of method used on GC .....3 Analysis of the reaction with homogeneous catalyst (afier nine days) ....................... 5.1 1 Variation of BPA selectivity with temperature ............ 4.... 5................................... 5.......
P. initial in Ionization ioniz. fmal fin gram G s Chromatography/ Mass Spectroscopy a hour hydrochloric acid mercury Hertz ist est 1.A.C.g . 1.1 -tnchloro-2.e.U. cubic centimetre centimetre cm carbon number c m Company Co. International Union of Pure and Applied Chemistry I. Infia red IR Kelvin K
. concentration conc.1. experiment exp.2-bis-(p-chloropheny1)-ethane DDT diglycidyl ether bisphenol A DGEBA dimethyl sulfoxide DMSO exempli gratia e. Free Induction Decay FID Figure Fig.List of Abbreviations
US dollars micro litre Angstrom activated alumina activated with hydrochloric acid acetone atomic mass unit amu Analyticd Solution of Groups ASOG atmosphere atm bisphenol A BPA BSPHNOLA bisphenol A Celsius C calibration Cal calorie cal catalyst cat.
System International Simulation Sciences SIMSCI SOLUPARA solubility parameter SSE Surn of Squared Errors SSR Sum of Squared Residuals STDPRES standard pressure STDTEMP standard temperature T Tesla Temp.kcai
km01 1 b
mega Hertz minimum minute millilitre mi llimetre milli mass unit m u MSDS Matenal Safety Data Sheet NIA not applicable normal boiling point NBP nanometre nnl normal melting point NMP NMR Nuclear Magnetic Resonance non-library NONLIB NRTL non-random two liquid ortho O Para P PFR plug flow reactor Ph phenol PID proportional integral denvative parts per million psi pound per square inch poïyvinyl chloride PVC radians rad rf radio fiequency seconds s/n signal to noise SANS small angle neutron scattering SAXS small angle X-ray scattering SI. temperature TFE tetrafluoroethylene
min niin ml
LIBID h4AF'P max MHz
kilocalorie kilojoul kilomol pound library methylacetylene and propadiene
tetramethylsif ane Time Proportional Phase increments Total Sum of Squares United Kingdom universai functionai activity coefficient United States micro seconds weight hydrogen deficiency nurnber
.TMS TPPI TSS U.
to be used a s intermediate for producing coating
resins (McKetta and Cunningham.
Dianin prepared bisphenol A for the first time in 1891 via condensation of acetone and
phenol catalyzed by hydrochloric acid.U. The molecule of BPA c m be described as two phenolic
rings joined together by a bridging isopropylidene group (ChernicalAbstract now calls
the radical 1-methylethylidene) (McKetta and Cunningham.
The method was not patented until 1917. 1976). 1976).
Bisphenol A was manufactured on an industrial scale for the first time in 1923 by a
German f-.4'isopropylidenediphenol. In Europe I.Chapter 1
Bisphenol A (BPA) is the commercial name used in the United States for 4. nomenclature and other unsystematic names are still used. Its commercial name indicates the preparation fkom two molecules of phenol and one of acetone.
T i four fold hs
.K. phenoxy resins. and alkylated foms are used as stabilizen and antioxidants for rubber and other plastics. as a fungicide and as a component of dental filling compositions. Esquirn in Mexico. Ketjen and Shell in the Netherlands. Raghanandan Chemical Indumies in India and others (McKetta and Cunningham.org/listproc/dioxin-l/msgO0464. like PVC for example
(essential. compared with 1. epoxy resins.h) It is also used as a component of foodpackaging adhesives. (since 1967) in the United States. polysdfone resins.
BPA production i the US in 1974 was only 4 5 million lb (McKetta and Cunningham.vanderbiIt. Bisphenol A is generally used as a reagent for producing polycarbonates. Mitsui Toatsu Chemicals. 1997). Some of the first large-scale producers were Firma Resins & Vernis Artificiels in France. n 1
Aniline and Film (fiom 1941 to 1954). that contains BPA.Graesser and Co. and R. acrylic resins.65 billion Ib of BPA in 1996 (Hileman. and other polyesters and as an intermediate for semi-synthetic wax (mc. Recently a toner for developing electrostatic images. Shawinigan Chemicals in Canada.
(fiom 1956 to 1971): Union Carbide (from 1960 to 1982) and General Electric Co. Farbenfabriken Bayer in Germany. (since 1954). Honshu Chemical Industries and Nippon Steel Chemical Co. Halogenated foms are used as flame retardants. in England. was developed
l. Shell Chernicals U. 1997). in Japan. Dow Chemical Company (since I941).edu/vumcdept/derm/contact1008). (Unno et a . Shell Chemical Co. 1976). the production of BPA as an intermediate for epoxy resins continued to grow.Since then. Monsanto Co.
20 to 30 Percent in Real Terrns Each Time Accumdated Experience Doubles" (Jackson. Considering the inflation (Consumer Pnce Index).
the BPA pnce in 1998 should have been 1. The price for BPA in 1974 was by average 0.
It is well known that for obtaining light-coloured hi&
rnolecular weight poIymers via
linear condensation. This "decrease" c m be related to the increase in production and interpreted with "The Boston Leamhg Curve" which States that: "Average Unit Selling Pnces. 1998).86 $Ab. Considering that the production in 1998 is the same as the production in 1996.45$/lb
(McKetta and Cunningham.8% purity has been mentioned as a minimum requirement (McKetta and Cunningham.94$/lb (Chemical Market Reporter. in Constant Dollars. and each t h e it doubled the average unit selling price in constant dollars declined 25% by average. 1976)).52$/lb. Ordinary BPA is adequate
for making most epoxy resins.
that it doubled twice since 1974. while BPA of very high puity is needed for polycarbonates (99. This is slightly lower than the actuai price for BPA in 1998..1 (Catana et al. the calculated price of BPA is 0. the PLU@ of the monomers m u t be high.
The characteristics of BPA used as a raw material for producing polycarbonates are
presented in Table 1. 1993):
. The actual price for BPA in 1998 was
by average 0.increase of the production over the period of 20 years proves a high demand on the
market for the product in question.
Table 1. 1993) l.
The technique that is most used for estimating the pur@ of BPA is the melting point (McKetta and Cunningham.1976). 1997). max ~ron. "Hz Light transmission. 1971). 1976) or 420 MI (Shinohara. Cnide products have wide-range melting points starting at about 140°C.1: Quality characteristics for BPA as raw materiai fer polycarbonates (Catana et a. wtY0.
Specification Aspect. The rnelting point of the pure compound is 157OC. OC Colour of melt. 1960). 1 0. Another
. due to the coloured complexes that are formed (Wasilewska. and it was found that iron is one of the agents that changes the colour of BPA. The colour can be estimated by analyMg the percentage transmission of a 50% solution of BPA in methanol or acetone and comparing it to a blank at 350 nm (McKetta and Cunningham. The cryoscopic constant has been reported as
10°C (McKetta and Cunningham. D ~ max D . min Water.005
There are several methods of evaluating the quality o f BPA.
The most important
parameter that characterizes the quality of BPA is its colour. max Ash. Good commercial grades melt at 154 to 155°C. pallets or crystals Melting rioint. 1976). wt%. %. and 17°C (Challa and Hermans.
Vaiue white 156
50 98 O.
. since not only one operational unit is eliminated. Prior to the final goal of producing BPA by catalytic distillation. cyclohexane for example (McKetta and Cunningham. homogeneous and heterogeneous. Either the yield or the selectivity of the process.
The purpose of this investigation is to outline the b a i s of a search for new solid catalysts
that could be used in a catdytic distillation unit for produchg bisphenol A to improve
yields and selectivities. were considered for improvement and several modification of the original method were studied: different catalysts. and alternatives to acetone and phenol as feedstock. alternatives to acetone as feedstock.
Catalytic distillation is a process that has the potential of producing bisphenol A at lower production costs. 1997).simple test is to measure the percent of impurities that easily dissolve in a paraffinic solvent. Catalytic distillation is a process where a reaction takes place simultaneously with a separation process in the same unit (Podrebarac et al. or both. the investigation of more suitable catalysts for the process is of great interest. but also the
nt associated piping and instrumentation that are required to connect the reaction u i with
the separation unit are eliminated.
Since obtaining high purity BPA is of great importance.. improvement of the manufacniring process \vas continuously investigated by researchers. With this purpose in mind. 1976). The major advantage of this type of system over traditional systems are the potential savings
in production costs. prelirninary investigations m u t be performed to eventually identie new.
Also included are some physical and
chernical properties of bisphenol A.
In Chapter 4 the experimental apparatus and the instrumentation employed to analyze the
products. using these catalysts. Safety procedures are detailed as well. The results of these simulations are used to determine the levels.
In Chapter 2 a criticai literature review is conducted. The purpose of this thesis is to examine the curent technologies available to produce BPA. and to £ïnd appropriate reaction conditions.
In Chapter 3 the Gibbs reactor simulations are investigated and the results are compared to the results in the literature. to invetigate the fesib-ity of new cataiysts. the alternatives that have been evaluated
with the purpose of improving the process.
This simulation provides insight about the reaction
mechanism which leads to BPA formation. A two factorial design is used to examine the effects of the chosen factors on the selected respcnses.
.more suitable catalysts. the factors and the responses chosen for the subsequent expenmentd designs. also the methods used for data processing are described. which details the existing processes
used in the BPA manufacniring and purification. and to perform experiments to investigate the effects of selected reaction parameters.
In Chapter 5 the results obtained in the preliminary runs and the results obtained from the
experiments performed in the batch reactor are presented.
important conclusions and lines of fùture work emerged. n Recommendations for future investigations are given. Although the nurnber of reactions in the plug flow reactor
was kept to a minimum.
Finally. i Chapter 7 the concIusions derived fiom the experimental work are presented. which was investigzted
in the batch reactor as well. and also for one of the new identified catalysts.In Chapter 6 the results obtained in the expenments performed in the plug flow reactor are presented.
. This setting was used for the systerns which could not be investigated in
the batch reactor.
General purification issues will be presented.
Basic Chemistry and Production Process for BPA
The intent of this chapter is to give an overview of the existing rnethods and reaction schemes for producing crude BPA and to ernphasize the ones that are used industrially.1 Preparation of Bisphenol A
T i subsection describes the chemistry of BPA formation including mechanisms. hs
possible reactions. 1976. The physicd and chernical properties of bisphenol A will be summarized. by-products. and order of reaction. Most of the information presented in this chapter is £tom McKetta
and Cunningham. This background material is necessary to expiain process alternatives.
dehydration by various water-binding agents (such as calcium
. in the presence of concentrated
hydrochloric acid or sulfuric acid 70% at room temperature deposits a mass of crude BPA crystals (McKetta and Cunningham. since water is a product of the desired reaction.1. is calcdated fiom heats of formation as +18-4 kcdmol. 1974).1. On the other hand. 1980). To
counterbaiance this effect. 1994).
a 1:2 molar ratio mixture of acetone and phenol. 1976).1. Severe conditions are not required.1 Primary Reaction
The acid catalyzed condensation of acetone with 2 moles of phenol is the oldest process for producing BPA.
The reaction conditions predominantly
favour the formation of the products (Nenitescu.
The heat of reaction. its presence decreases the yield of BPA. for reactants and products in their natural physical state at 25OC.
Some sources claim that the presence of 10% water in the reaction mixture greatly increases the rate of the reaction catalyzed by hydrochloric acid (Scheibel.1 Acetone Process 2. Other sources claim that processes catalyzed by suIfonic acid ion exchange resins rnodified with -1-SH groups are also improved by the presence of 0.6 to 5% by weight water in the
initial reaction mixture @erg and Buysch.2.
This first step of the mechanism is very similar to the one in
the production of phenolphthalein and DDT and in the akylation of phenol with olefins
(McKetta and Cunningham.chlonde or phenyl acetate) or by azeotropic distillation have been suggested (McKetta
The reaction proceeds with an electrophilic attack of the proton fYom the acidic catalyst on the molecuie of acetone.Products Formation
For reactions involving the substitution of a proton in an aromatic ring. 1980). both the rate of reaction and the equilibrium distribution of products are influenced by the density of electrons at the centre of reaction (Nenitescu.1.
2. 1976). This only applies if there are no
.2 By .1.
The p-isopropenyl phenol fonned can dimerize and the dimer c m add phenol to yield another triphenol ("triphenol II" or 4.4'.stenc effects. 1976) is the so called "triphenol 1" (4.1 -propanyl-3-ylidene) triphenol) (McKetta and Cunningham.4" -(1.1.
It was observed that the o.3-Trimethyl.4'-(4-Hydroxy-m-phenyIenediisopropylidene)diphenol):
TnphenolI P-isopropenyl phenol can be obtained when the p-phenyl isopropylidene ion loses a proton.o-isomer are observed. Thus the pp-isorner (BPA) is the most likely to f o m since the density of electrons in the para position of the phenol is higher than in the ortho position. Still. the p. 1976). opisomer and some o. Aiso. 1976):
.p-isomer formation is favoured fiom the thermodynarnic point of view (McKetta and
Cunningham.o-isorner is produced in negligible amounts. Another possible product that can result fiom the reaction of the already formed BPA with the tertiary carbonium ion @-phenyl isopropylidene) (McKetta and Cunningham.
An irreversible cyclization of the dùner to 4'-hydroxy-2. 1 7 ) 96:
.4.4-trimethylflavan (flavan) can
occur if the hydroxyl group in the dimer is in the ortho position relative to the carbon
bearing the methylene group (McKetta and Cunningham. 1976):
If both hydroxyl groups in the dimer are in the ortho position relative to the aliphatic
chain. the 2'-hydroxy isomer is formed (McKetta and Cunningham.
The mesityl oxide formed
can M e r react with two molecules of phenol to give a product isomeric with flavan. many other components can be produced and are
present in the reaction mixture.The acetone can dimerize with itself and form mesityl oxide. rnelting point
158°C were al1 isolated fiom cmde BPA (McKetta and Cunningham.
No unsaturated products were observed in the cmde product. 1962). leading to the idea that al1 of the unsaturated products formed M e r react to give other by-products. are the same as the conditions that favor the BPA formation. The phorone is
chroman (McKena and Cunningham. 1976):
H~C' ' H C.
Due to the high reactivity of the system. The o. which c m be obtained fkom two molecules of phenol and one molecule of phorone.p-isomer. A likely one is the spirobiindan (Curtis. triphenol 1 melting point 191O and chromane. 1976).
chroman 1 chroman il
The dimer resulted from the dimerkation of p-hydroxy-a-methyl styrene. C melting point 11l O C . The reaction conditions that favor the formation of al1 the by-products presented so
far. triphenol II and
flavan can be obtained as a result of the reaction between mesityl oxide and phenol as well.
In another study (Kato. 1965) the activation energy for the overail process is 15 kcdmol.the resdt of the condensation of three molecules of acetone.3 Reaction Order
The BPA formation is a condensation in two steps. First a molecule of acetone reacts
with a molecule of phenol. the o. the HC1-catalyzed reaction was second order in phenol. an equilibrium c m be established between BPA and the main by-product. which c m occur in the acidic medium provided for the process of BPA formation:
H C' .
. The reaction was reported first order in both acetone and phenol.p-isomer. which indicates that the first step is slower than the second step. 1976). 1963). 1.
2. In the presence of an acid. reacts with the
second molecule of phenol. These processes are reversible fike most other electrophific substitutions. then the product. According to Kato (Kato. According to de Jong and Dethmers (Dethmers and de Jong. therefore it is rate determining (McKetta and Cunningham. or the corresponding ion.
HG. 1963) the activation energy is19 kcal/mol.1.
0.. the reaction of BPA formation is reported to be first order in catalyst.
2.08 at 60°C.
40 0. E s is the reason why it was recommended to
the process at several atmospheres (Takenaka et al. sulfuric acid 70% to 75% concentration
can be used as catalyst.1 1 at 80°C.p-isomer transformation.067 at 40°C. the data presented in Table 2.16 at 100°C (Dethmers and de Jong.1 were generated for the equilibrium constant for the BPA+o. 1965).
In this case the concentration of the acid m u t not exceed the
.4 Equilibrium Data
Using phenol as a solvent for the process. and 0.1.
The first catalyst used to produce BPA was concentrated hydrochloric acid. 0.1. 1968).2.1.1: Equilibrium constant for the BPA
Table 2. 0. Aithough the process is slower and the product more difficult to puri@
than in the hydrochlonc acid catalyzed process.08
The ortho-para ratio increases by increasing the temperature therefore temperatures as low as possible are preferred in order to maximize the BPA formation (McKetta and Cunningham.5 Catalysts
For the process catalyzed by gaseous hydrochloric acid. Processes that use gaseous hydrochloric acid or acid ion-exchange resins are also operated in the United States.
hydrogen fluoride. 1976).
other catalysts. phosphorus chlorides. polyphosphoric acid.
In principle. 1976). phosphorus pentoxide. With such catalysts longer reaction times and/or higher temperatures (70 to 90°C). silicon tetrachloride. The acidic zeolites for the production of BPA were tested
(Singh. considering the reaction products
present in large quantities. boron trifluoride. zeolites should be more shape selective than
The reaction scheme proposed by Singh (Singh.
The use of strong acid ion-exchange resins as catalysts for making BPA is widespread. boric acid. When
using ion-exchange resin as cataiyst the corrosion is minimal and no recycling or disposal
of the catalyst is required. It is mentioned that any acid with an ionization constant y greater than 1O5 is suitable to catalyze the process (McKeîta and Cunningham. 1992). 1976). phosgene. are required to attain high conversions compared to soluble catalysts.both undesirable.
Other homogeneous catalysts that can be used but do not seem to have practicai
importance are: hydrogen bromide. and benzenesulfonic acid (McKetta and Cunningham. femc chlonde. 1992) in the atternpt of a comparative study of preparation of BPA over zeolites
and cation-exchange resins. There are some advantages
in using sulfunc acid as catalyst for the process: the apparatus is simpler and the
corrosion is less severe (McKetta and Cunningham.above mentioned b i t s in order to minimize the sulfonation. is:
00 57-91 38.59 29.88 8.28 23.83
5 17 27 4 16 27 5 17 27
I is bisphenol A.2. II is 2.13 37.10 9.54 20.56 3.12 2. III is 4 -hydroxyphenyl2.14
Product distributiona (wt %) 1 II III+-IV Others
59. Others are lan compounds found o d y in trace quantities (Singh.41 4.2):
Table 2.80 85.72 89.49 15.83 8.37 88.35 4.62 11.08 19-10 28.4'-isopropylidenediphenol (ogisorner).66 3.25 3.2.50 20.4-trirnethyl chroman 1.4 'isopropy lidenediphenoi
4'hydroxyphenyl-2.54 3.O8 4.4.
.00 9.19 8.30 1.4-trimethy1 chro~ II.Phenol
2.57 16.42 36.12 2.56 3 1.6 1 1.2: Results of the reaction of acetone with phenol in the presence of zeolites and cation-exchange resin
Conversion of phenol
(wt %) 1.44 5.52 2.26 60.02 19.4-trimethy l chroman II
The results show a strong influence of different catalysts on the total conversion of
phenol (see Table 2.4.43 7.67 20.35 11. N is 4'-hydroxyphenyl-2.80 25.06 4.4-trimethyl chroman 1
4chydroxyphenyl-2. 1992).74 19.
2.2. H-mordenite and H-ZSM-5).1 Conversion of Phenol versus Time for Various Catalysts
Reaction Time [hl
. They show that in the case of zeolites.1). 2.
This rnight be due to its highest concentration of acid sites compared to the other zeolites
used (H-Y.2.4.3. Re-Y gives the highest activity (Fig.The data in Table 2.
The relative activities of various catalysts decrease in the order: ~ r n b e r l y f 15 > Re-Y > H-mordenite > H-Y > H-ZSM-5
The concentration of the undesired products increase in the order:
Amberlyst" 15 c Re-Y c H-mordenite
2.2 are plotted and the graphs are illustrated in Figures 2.2.1.
2 3 Rodud Seleaivity versuç T
i for the Readon C t l z d by H-mordenite aaye
+ BPA m
+amxrian 1 and Chroman II [m+W
.2 Product Selectiviry versus Time for the Reaction CataIytcd by Re-Y
Reactian Timc [hl
op-isomer [II] 1 and Chroman II [III+IV]
the activity of the tested zeolites for the formation of BPA is lower than that of the cation-exchange resins.3.
.Fig. The data also show that the more acidic the catalyst is. However. 2. 2. and 2. the selectivity of the BPA formation is higher (Fig.4 Product Selcctivity venus Time for the Reaction Catalyzed by Amberlyst-15
Rcaction Timc [hl
+ BPA [q
o p i s o m e r [lu Chroman 1 and Chroman II [III+IV]
The conversion of phenol increases monotonie with time and the higher the concentration of acid sites in the catalyst the higher the conversion (Fig. However. the method is of no use because both yield and quality of product are
The conversion of acetone and phenol to BPA is catalyzed by bases as well as acids.2.
sodium phenoxyde (C.ONa) is particularly specified (McKetta and C m g h a m .
1981.laminoorgano mercaptan groups (Faler and Loucks. 1982.2. hydrogen sulfide. 1976).1.
In 1994 Rudolph developed a catalyst modified with mercapto amines to be used for BPA
. iron suifide. alkanethiois. 1976). selectivity and stability of these sulfonated aromatic organic resins.
mercaptoalkanesdfonic acids. it can
exist in higher concentration in the reaction rnixtare and consequently dkylate faster the phenol ring (McKetta and Cunningham. havîng organic mercaptan groups .
Sulfonated aromatic organic polymers. thioglicolic acids. 2 976). Some of the compounds containing mercapto groups are su1fur dichloride. 2-mercaptobenzothiazote and others (McKetta and Cunningham. Being more stable. sodium thiosul fate.1. aminoorgano mercaptan groups (Faler and Loucks.5.
This improvement in rate and yield is possible due to the fact that the carbonium ion containing sdfûr (CHJIC+SR is more stable than (CH&2+OH. These polymers have been developed with the intention of improving
the degree of activity. arenethiols.1 Catalyst Enhancers
Both rate of formation and yield in BPA c m be improved by using 1% or less by weight compounds that contain mercapto groups (McKetta and Cunningham. such as sulfonated polysiyrene. Also a sulfonated polystyrene ion-exchange resin
having ionically bound N-allcylaminoorgano mercaptan groups was developed (Pressman
and Willey. 1986). alkali alkyl xanthates. 1984). N-alS. 1983) attached to backbone sulfonyl radicals by covalent nitrogen-sulfur Iinkages have been used as ionexchange resins for making BPA.
acetic acid.and other bisphenols formation (Rudolph et al. to avoid the formation of even more by-products. Feeding acetone at successive stages in multistage or cascade reactors rnawnizes the advantages of excess phenol (McKetta and Cunningham. 1976). involves a melting stage (Dachs et al. These hydroxy carboxylic acids or their ammonium or alkali metal salts
c m be added to the feed reactants used to make the bisphenols or to the reaction mixture after the reaction is complete or at any time in between.. Thus it is preferable to perfonn the reaction in a solvent.
.. This continuous search for new and enhanced catalysts demonstrates the serious need for improved yields and selectivities in the process of BPA formation. 1982). Suggested solvents are
chlorinated aliphatic hydrocarbons.1. Excess phenol i preferred since it suppresses the condensation of s
acetone with itself and it is easy to recover and recycle.
2.1. They are particularly useful when the bisphenol is exposed to high temperatures. in most cases. glyceric and lactic acids have been found to be highly efficient for the stabilization
of bisphenols.6 Bisphenols Stabilizers
Malic. which h to be inert in the given reaction a condition.7 Solvents
The viscosity of the reaction mixture may increase as the process advances. which.1. 1994). such as during the separation of the bisphenol £tom the reaction mixture .1. or aromatic hydrocarbons (McKetta and
1993) suggested a mechanism for the condensation process. which transforms rapidly into a carbonium ion (III).2.1. These bonds were observed experirnentally by IR spectroscopy. This mechanism involves the formation of hydrogen bonds between the ketone and the sulfonic resin. This intermediate is expected to react with the phenol in the nonpolar surrounding medium. This type of mechanism also explains the formation
of some of the by-products which can appear during the synthesis or during subsequent
processing of the BPA. the formation of the BPA molecule.5). which c m be a carbonium ion.8 Reaction Mechanism
Reinicker and Gates (Catana et al. In the fus1 step the hydrogen bonds are formed between the carbonyl group of the ketone and the sulfonic group of the resin (1). for the reactions catalyzed by sulfonic resins.1..
The proposed mechanism consists of the electrophilic attack of a polar reactive intermediate.2. forming a tertiary alcohol (II). on the aromatic ring. takes place through hydrogen bonds (Fig.
. The final step.
1995) (Fig. which comprises 15 to 25% of the bed volume as a whole. and comprises 75 to 85% of the bed volume as a whole. the volume/time yield c m be improved by providing the resin as a two-layer bed (Berg et al.1.6):
the lower layer of the bed comprises an unrnodified resin having a low degree of crosslinking.. 2.. and the upper layer of the bed. less than or equal to 2%.5 Mechanism of Condensation of Acetone with Phenol via Hydrogen Bonds
(Catana et ai.1.9 Reactor Configuration
If the reaction for producing BPA fiom phenol and acetone is conducted in a fixed bed
reactor containing gel-form or macroporous sulfonic acid ion exchanger resins. 1993)
2.Fig. comprises either:
* a resin having a low degree of crosstirking. in which 1 to
35 mol % of the sulfonic acid groups are optionally covered with
species containing alkyl-SH groups by ionic fixing. One of the processes semicommercially applied in Russia used propyne (methylacetylene). less than or equal to 2%.*
a resin having a higher degree of crosslinking than the lower bed. Other processes clairn the use of isopropenyl acetate or 2-chloropropene instead of acetone (McKetta and Cunningham. or a commercial mixture of propyne and propadiene (MAPP).2 Alternatives to Acetone as Feedstock
Compounds that react with acid to generate the isopropylic carbonium ion can be generally used instead of acetone. 1976):
in which 1 to 25 mol % of the sulfonic acid groups are covered with
species containhg alkyl-SH groups by ionic fixing.2. 1976).1.6 Reactor Configuration
2. fiom equal to or greater thm 2% to less than or equal to 4%.
. as an alternative to acetone as feedstock (McKetta and Cunningham.
. 1993). 1976). like that of (CH3)2C(SR)I types (from acetone and thiols) (McKetta and
Cunningham. avoids the formation of water as a by-product.C(CH3)200H). The
p-isopropenyl phenol necessary for the process is obtained together with phenol fiorn the by-products of BPA manufacture via alkaline cracking at 220°C and 55 mm Hg.. This way by-products of the BPA formation process c m be transformed in the desired product. the phenol and the acetone are obtained together in the acid cataiyzed
decomposition of cumyn hydroperoxide (C.
BPA can be produced with good yields by adding phenol to p-isopropenyl phenol. The simplification achieved in this manner is compensated by inferior yields and selectivities. were used to make BPA (Kiedik et al. It is thus namal that cmde reaction mixtures.Use of these. either enriched in phenol by addition or depleted in acetone by distillation thereof (to produce a more suitable ratio of reactants).
14.oisorner. The ratio of BPA to 07p-isomer to chromane in another crude product meam w 90:7:3 (McKetta and Cunningham.. for an overall improvement of the yield and the selectivity of the process (McKetta and Cunningham.2% phenol. 0.
. 36. 1976). It is still expected to contain phenol.05% flavan. 3% triphenol1.2% 07p-isomer. a thiol promoter.
It was reported that BPA is formed in a reaction between phenol and a urea-acetone condensation product (McKetta and Cunningham. acid cataiyst (unless an acid ion-exchange resin was used). by-products.1% o. 1. 3..2 Purification
The process used to produce BPA influences the composition of the mixture fiom the reactor. and sorne acetone (if the reaction was not carried out to depletion of acetone) (McKetta and Cunningham. s
composition of the BPA usually available on the market is 94% BPA. 1976). a cmde product Stream consisted of 4 1% BPA.
For exampie.5% chromane. 1973). and 12% of unidentified compounds (Verkhovskaya et al. 4% og-isomer. The urea-acetone condensation product is presented below:
2.BPA. BPA. al. 1959). 1976). water. and 1% chromanes (Anderson et. 1976).
The addition of benzene facilitates the water removal
without the use of vacuum equiprnent (McKetta and Cunningham.Small differences in the operating conditions may have considerable effect on the process
of BPA formation. 1976).1 Catalyst Separation
No catalyst separation is required for the resin catalyzed processes. In the first step 25 to 90% of the water is removed by vaporization. because it can be recycled and the waste disposal problems are
thus reduced. It can be removed by stripping with inert gas such as carbon dioxide
or nitrogen. 1976). or distilled out in the case of hydrochloric acid.
In the second step the dehydration is completed by
saturating the catalyst with pllenol. or with benzene. its removal and recycling is a step found in most purification processes (McKetta
and Cunningham. and different purification processes may be necessary. This results in purification procedures that are numerous and diverse.2. The process involves two steps. In 1992 Cipullo announced a more effective way of removing the water fiom the cataiyst bed (Cipullo.
2. The hydrochloric acid is the most preferred one among the homogeneous catalysts. If a homogeneous
catalyst was used than this has to be neutralized. or washed with water.
The water has to be removed fiom the system whether homogeneous or heterogeneous catalyst was used. Since excess phenol is generally used.
This adduct c m be separated by filtration. These acids can decrease the yield and the selectivity of the overall process by cataiyzing the cracking of BPA during purification and finishing steps. 1991). heating in vacuum to distill out the phenol or heating with excess water (McKetta
1988). or tartric acid) (McKeîta and Cunningham.2 BPA Separation from Crude
The crude is the mixture of products and unreacted reagents that corne out of the reactor. Most of the BPA produced separates as a 1:1 adduct with phenol afier partially stripping
and cooling the crude.Sometimes the resin catalyzed processes
to 50% conversion of acetone and in such
cases dong with water the h p p i n g removes acetone and some phenol as well.
These processes may be remelting.
recrystallization. citric. melting and passing over an ion exchange resin (Faler and CipiifIo. The product may be M e r refined by soIvent treatment or vacuum distillation.
Strong acids can leach fiom the acidic ion exchange resin catalyst into the reaction mixture during the reaction. centrifugation or both.
The phenol adduct can be M e r subjected to a series of processes with the purpose of
separating the BPA fiom the phenol. and this can be done effectively by an inorganic oxide (Powell and Uzelmeier.2. Therefore it is important to remove them before starting the purification of the product. 1976).
2. 1976). The
acetone and phenol removal c m be minimized by adding a trace of a metal complexing acid before stripping (oxalic.
Formation of the 1:1 BPA-phenol adduct c m be prevented by: operating the process with very little excess phenol. Such solvents are berizene. 1976). 1994 and 1995).2.
2.1 Methods of Separating BPA from the 1: 1 BPA-Phenol
Since most of the modem processes for obtaining BPA operate with a high excess of phenol.2. vacuum-stripping phenol fiom the crude. cold ethylene dichlonde. and
steaming to remove remaining thiol promoter (McKetta and Cunningham.
. heptane. operating the process with acetone and phenol in a molar ratio close' to stoichiometry in inert solvent or to a less than 100% conversion of acetone. Such a method
has been reported and consists of fusing the adduct in an atmosphere having a maximum
oxygen content of 0. the formation of the 1:1 BPA-phenol adduct is inevitable. 1976). partiy crystallized or not.005% by volume. W O H ) and organic solvent-water emulsions (McKetta and
Cunningham. weak aqueous alkalies (NaCo. with excess water. a mixture of an aromatic and an aliphatic solvent.
Selective solvents that dissolve the maximum of by-products and a minimum of BPA are used to separate the BPA fYom the 1:1 8PA:phenol adduct. and so new ways of obtaining high quality BPA fiom the said adduct have been investigated. followed by evaporation of liberated phenol (Asaoka et al... or treating the acid-stripped crude.
a mixture of a aromatic solvent with a polar n solvent. 1993) in spite of the
special equipment required.. 1976). The solvents usually used are aromatic solvents like toluene and chlorobenzene. A system that uses the combined efTect of a filter and a centrifuge was considered in order to minimize the liquid impurities that rernain on the
crystal cake. acetic acid. and isopropyl alcohol (McKetta and Cunningham. Another disadvantage of this procedure is the tendency of
BPA to decompose at pot temperatures above 200°C. as a result of oxidation by
air (McKetta and Cunningham.. 1993).Recrystallization is another effective procedure. 1976). 1. In order to avoid
. filtration and precipitation with a strong
acid or carbon dioxide (Flippen et al. also a reducing agent (sulfite or hydrosulfite) is advisabIe to add to prevent the BPA f?om becoming coloured. The crystals are also washed to reduce the surface adherent impurities on
the final crystals. especially if acidic or basic
irnpurities are present (McKetta and Cunningham. Anhydrous ammonia can be used to precipitate
adduct "salts" that can be isolated and dissociated to yield pure BPA (McKetta and
Cunningham.2tetrachloroethane.1. 1976).. Decoiorizing carbon and inorganic salts c m be added.
Vacuum distillation has already been mentioned (Kiedik et al.2.
The dissolution of cmde BPA in caustic alkali. 1976). methanol or a mixture of methanol and ethylene dichloride.
A newly developed process purifies the BPA by a two stage crystallization procedure
(Sakashita et al. 1970) is another possibility.
The most industrially used processes for making BPA in the 'Jnited States and Western Europe are the acetone-phenol ones.decomposition. The BPA can also be regenerated with good yields fiom scrap resins (McKetta and Cunningham. a secondary or tertiary aikaline earth phosphate.
This high temperature is necessary
because the chromanes are relatively refractory and tend to build up in recycle strearns (McKetta and Cunningham. The chroman can also be isolated and purified as a crystalline ciathrate.
the resin-catalyzed process is preferred and it has been improved continuously. Considering the costs involved and the net advantages the heterogeneous catalysis offers. 1976).2 By-Products Isomerization to BPA
BPA by-products can be isomerized to BPA in the presence of an acid catalyst (which
can Se an ion-exchange resin or hydrogen chloride) and a fiee mercaptan CO-catalyst (Li. The alkaline cracking at 220°C and 55 mm Hg of the by-products to yield phenol
andp-hydroxy-isopropenynil phenol that c m be recycled to the process has aiready been
mentioned (McKetta and Cunningham. 1976). or diethyl malonate before distillation (McKetta and Cunningham. in homogenous as weIl as heterogeneous catalysis..2. 1976). The decornposition can also be reduced by distilling under a nitrogen
atmosphere and dding polypropylene glycol. thin-film distillation can be performed instead of vacuum distillation
(Pahl et al.
In the second stage the
reaction mixture fiom the first step is
reacted in the presence of hydrochloric acid as catalyst.
2. In the f s stage the
acetone is reacted with very little excess phenol in the presence of a sulfonated cation exchange resin catalyst modified with a rnercapto goup-containing compound to convert
20 to 60% of acetone.
Although the literature shows that processes using alternative feeds.Catalyzed Process
A process catalyzed by a sulfonated cation exchange resin modified with 2-
mercaptoethmol is presented in Fig. A mixture
. et al. three flow sheets are presented in this chapter:
a) the resin-catalyzed process using acetone and phenol.
ut 1990). 1976). such a process has been developed and it is now industrially used in the United States. such as a postreaction mixture resulting fiom the synthesis of phenol and acetone. The reaction stage of this process comprises of two steps.
b) the hydrogen chloride-catalyzed process .A process which considers reacting acetone with very Iittle excess phenol (1:4 to 1:12 molar ratio acetone:phenol in the initial reaction mixture) was reported (Iimun. and
c) the resin-catalyzed process using a post-reaction mixture of the cumylhydroperoxide decomposition.1 Resin . are not convenient because of the great variety of by-products and the infenor yields.3. 2.7 (McKetta and Cunningham..
The overhead passes through a series of
. BPA and by-products.
The overhead at the
concentrator is a mixture of acetone. BPA and by-products go to the
concentrator. 1976). 1976) 1-Feed tank. The process runs to a 50% conversion of acetone (McKetta and Cunningham. which is undesirable since it would favour the adduct formation. Aithough not stated in the reference. 5.. +
BPA PHENOL ADUCT
PHENOL. 3-Concentrator.9-Distillation columns. The residence time is set at one hour. 6-Melter. 10-Phenol stripper. 2-Reactor. the nt
molar ratio of acetone to phenol would be about 1:16. the
u i s for product distribution are most likely to be wt'X0.consisting of 83.
The concentrator is operated at 200mm Hg. BPA RECYCLE
Fig.4% recycled BPA and 8. If the units were mol%. 5-Solid-Liquid separator. 2.
.4% phenol.0% recycled by-products are preheated and fed to the reactor.
ACETONE ACETONE WATER
. The boîton Stream consists of phenol. water and phenol (18 to 20%).1% acetone. The reactor effluent. 4-Crystallizer.
. The reactor is operated at about 75°C. 3.1% water. 8. 0.7 Production of Bisphenol A with Resin Catalyst (McKetta and Cunningham. together with some recycled phenol. BYPRODUCT. 7-Flaker.
2. acetone. which are recycled to the reactor.. A version of this is used by Mitsui Chemical in Japan and by General Electric in the United States (McKetta and Cunningham. The mixture is reacted for several hours under continuous stimng. The bonom Stream from the concenmtor goes to a crystdlizer where it is cooled d o m to separate the BPA as phenol adduct. 1976). This overhead goes to a decanter where the two layers separate. and fieed of phenol by melting at 130°C. The effluent fiom the reactor undergoes a preliminary stripping that removes a two-phase mixture of hydrochloric acid.
1965). The phenol and by-products separated in this stage are
A process that uses hydrogen chloride as cataiyst is presented in Fig.distillation columns to remove the water fiom the acetone and the phenol.8 (Pahl et A. The phenol recovered in the sûipper is recycled to the centrifuge and the centrifuge liquor is recycled to the reactor (McKetta and
Cunningham. then stripping in a column at 200°C and lmrn Hg. The purity of the product obtained with this process is over 90%.p-isomer in the isomer still. The water goes to the drain. A mixture of excess phenol. water and some phenol. The reactor is operated at about 50°C. BPA and by-products fiom the recycle strearns are saturated with gaseous hydrochlonc acid and fed to the reactor. The hydrochloric acid is recovered fiom the aqueous phase and recycled. The stripped crude is fed to a senes of separation columns and successively freed of phenol in the phenol still (at about 10 mm Hg) and of o. washed with phenol.3.2 Hydrogen Chloride . Afier crystallization the mixture is separated in a centrifûge. 1976).
1976). 8-Isomer still.recycled to the reactor (McKetta and Cunningham. 7-Phenol still. The liquor fiom the centrifuge goes to a solvent d l . 4-HC1 recovery column. The impurities with higher boiling points are separated fiom BPA by vacuum distillation in the BPA still at 1 to 5 mm Hg. 1976). 10-Crystallizer. The by-products separated at this stage are recycled to the reactor and the solvent is stored for subsequent uses (McKetta and Cunningham. 1965) 1-Reactor. 3-Decanter. 12-Dryer
. then cooIed in the crystallizer to cause crystallization. 6-Solvent storage. 2-HC1 still. The BPA overhead is mixed with some solvent (e. .
.8 Production of Bisphenol A with Hydrogen Chloride Catalyst (Pahl et al. The purified crystals are separated in a centrifuge and then dried for a high quality product. benzene) under pressure while molten.
H a RECYCLE
Fig. 5-Solvent still.. 2. 9-BPA still. 11-Centrifuge.g.
6. The precipitate is separated by centrifugation into crystalline BPNphenol adduct and
phenolic mother liquor 1.9. l.4 wt% phenol.Catalyzed Process II
The resin catalyzed process for obtaining bisphenol A fkom a post-reaction mixture resulting fiom the step of synthesis of phenol and acetone (Kiedik et a. reaction of phenol with p-isopropenylphenol resulting from thermal decomposition of process by-products and recycled to the reaction systern.
The reactor feed at steady-state operation consists of 55.
The process consists of the following steps: 1. including 4.6 wt% water.8 wt% acetone. uses a vertical drurn reactor filled up to 70% with a mixture composed of 70% microporous Wofatit-KPS cation-exchange resin and 30%
2.3.2. 1993). The post-reaction mixture together with water (1-4% by weight) and acetone (2-65% by weight) is cooled down to 40°C to obtain a precipitate of BPNphenol in phenolic solution. 2.3 wt% by-products. Reaction of phenol with acetone.pisorners.
3. and isomerizational rearrangement of process by-products to obtain
BPA.9 WWO BPA and 18.4 wi% o. represented by Fig.3 Resin . 18.11 O cation exchanger. operated at 85°C. The crystalline BPNphenol adduct is washed with mother
Fig. A high-purity BPA is separated fiom the BPNphenol adduct by distillation at 160°C
and 10 mm Hg of a substantial volume of phenol and the phenolic residue is removed
by steam stripping. obtained in step 5.
6 . 5.Iiquor II.9 Production of Bisphenol A with Resin Catalyst II (Kiec
4. The BPNphenol adduct is dissolved using the mother liquor II obtained in step 5
andor phenolic solution obtained in step 7.2-2.0 parts by weight of the liquor per
1 part by weight of the crystailine adduct. The precipitate obtained in step 4 is separated into t e crystalline BPNphenol adduct h
and mother liquor II to be tumed back to step 3 of the process. The BPNphenol
crystalline adduct is washed with fiesh and regenerated phenol obtained in step 6 and used in a ratio of 1-3 parts by weight of fiesh phenol per 1 part by weight of regenerated phenol. in an amount of 0.
2%by-products including 4.8%
og-isomers. The phenolic mother liquor 1obtained in step 3 is distilled to remove the acetone. the
water. is conducted in the presence of oxaiic acid used in an amount of 0..2% water.3 parts by weight per 1 part by weight of mother liquor 1
8. and process by-products. and part of phenol.96% by weight.05-0.p-isomer in trace amounts. resuiting a distillate comprising phenol.
principal product 99. codirner in trace amounts. o.7. while leaving the p-isopropenylphenol contained therein substantially intact.1-0. 5. n i e catalytic
decomposition is conducted in the temperature range of 200"-300°C. The cataiytic rearrangement of the reactive components of the distillate obtained in
step 8. The volume of phenol distilled off the rnother liquor I is
.95% phenol. The bisphenol A product shows the following properties: crystallization point 156. trisphenol 15ppm.
The composition of the product obtained is: 24% BPA. NaOH.
The rearranged distillate is recycled to step 1 of the process. NaHCO. The mother liquor I obtained in step 3 a d o r 7 is exposed to a themal catalytïc
decomposition in an amount of 0..65% acetone and 1.2 parts by weight.5% by weight.
9. coloration of 50% solution
4 APHA. and in the absolute pressure range of 1-50 mm Hg in the presence of catdyst selected fiom the group of: Na&IPO.8"C. 16. 0. 52.
7 c d g (McKetta and Cunningham. As it might be suspected. BPA is volatilized only i traces by s t e m n at 1 atm. and alcohols and esters are the best (Korenman and Goronkhov.
and 230°C at 5 mm Hg.2f O S kcaUmol (McKetta and Cunningham. 195 to 200°C at 6mm Hg.4 contains data regarding the variation of the BPA vapor pressure with the temperature. The value found in the Material Safety Data Sheets for the
boiling point is 220°C. 181 to 195OC at 4 mm Hg. !ts specific gravity is given as 1. Other sources (NTP Chernical Repository. appearing like small white to light brown flakes or powder.2. The flash point is 2 13OC (McKetta and Cunningham..195g/ml (McKetta and Cunningham.
Based on the partition coefficients for BPA between water and some organic solvents. There i no data regarding its vapor density.no highly precise and reliable value has been published..=88. it
can be concluded that the alkanes are the poorest extractants.3 (McKetta and Cunningham. 210 to 220°C at 4 mm Hg. which sinks in water. The heat of combustion is 1869
kcdmol and AH. although many are on record.195 at 25/2S0C. 1976). 1973). The heat of fusion is 30. Pure %PAmelts at about 157OC. 230°C at 7. with mild phendic odor. 1991) suggest 250252OC at 13 mm Hg. 1976). For the boiling point s records show discordant temperature ranges and imprecise pressures. e.. 1976). Table 2..
.Some values of the solubilities are given in Table 2. The density of the monoclinic pnsmatic crystals is given as 1. aromatic solvents are much better. 1W6).6mm Hg. 1976).g.13
g/ml or 1.4 Physical Properties
Bisphenol A is a white crystalline solid.
94 0. CCI.2 1. ClCH.0
.4: Variation of vapor pressure with te~perature(McKetta and Cunningham. 1973) Temperature "Room Temperature" 18°C (except as specified)
200.CHOH (CHJzCO C6E cyclo-C6H.2
Solvent Hz0 CH.1 0.0
0.CI.Table 2.gb 0.86 0. CHCI.0
50 . lb
1 1 1 1 1 1 1 1 1 1 1 1
0.8-1 .).03 7 0.61. 109 0.9
10.5 1.3: Solubilities of Bisphenol A in Various Solvents (g/100g solvent) (Korenman
150 2 1.08
08 . O.0
40.035' 1. a cbCold"
Boiling Point (except as specified)
<O.COOH (CH.OH CZKOH CH.CH.05 3 -6 0.0
25 Chemical Properties .
1976). such as allyl chloride.
Bisphenol A reacts as a typical para-substituted phenol. 1976):
These s d t s are easily alkylated with alkyl halides. One or both hydroxyl groups. to f o m diethers
(McKetta and Cunningham.
BPA is convexted by caustic alkalis into its soluble alkali salts (McKetta and
Cunningham. with basic catalyst. 1976):
BPA cm undergo cyanoethylation. one or both rings can experience modifications. to f o m dinitriles that c m be hydrogenated to diamines (McKetta and Cunningham. Transformations involving the aliphatic methyl groups of the bndging group can also take place (McKeîta and Cunningham. 1976):
so that the monomer units altemate in a linear polyrner ('McKetta and
Cunningham. In this reaction the phenolic groups are
BPA reacts with epichlorohydrin to form a bis(chlorohydroxypropyl) ether which yields
the diglycidyl ether (DGEBA). 1976):
c H. 1976).Dow and ICI Amenca produced ethers for use as components of unsaturated polyesters. the monomer for most epoxy resins. (polyesters of fumaric acid for example). in a caustic medium (McKetta and Cunningham.
Phenoxy resin pattern
. and for coatuigs applications by reacting BPA
with epoxides (McKetîa and Cunningham. 1976):
The phenoxy resins are produced when BPA is condensed in a 1:l ratio with epichlorohydrin.
Polymers with terminal phenolic groups are obtained when reacting BPA with Iess dian
one molar equivalent of a dihalide such as bis(2-chloroethyl ether) or 1.4-
bis(chloromethy1)benzene.. 1976).. 1995).
Commercial polysulfone resins are manufactured when
reacting stoichiometrïc amounts of BPA and bis(4-chloropheny1)sulfone (McKetta and Cunningham. Other diacid chlorides have been also reacted
with BPA to obtain polycarbonates (Shaikh and Sivaram. 1994):
Polycarbonate resin pattern Poly(ary1enecarbonate)s oligomers cm be obtained by carbonate interchange reaction of dimethyl carbonate with BPA (Shaikh et al. Hill et al. 1992):
Polysulfone resin pattern Polycarbonates are obtained by esterification of BPA with phosgene or its dibenzoate ester (McKetîa and Cunningham. 1976.
.. one of the processes used for manufacturing polycarbonate resins. is generated by the instability caused by the hydroxyl groups. Ln the first step the aromatic
polyester prepolymer is formed (Mahajan et al.
Base. The process has two steps. temperatures exceeding 150°C: Highly reactive isopropenylphenol is produced at
Aromatic polyesters cari be obtained by transesterification of BPA with dimethyl
terephthalate/isophthalate.BPA can be converted to a bis(alky1 carbonate) and fiom there to similar poiyrners by
reacting it with aliphatic esters of the carbonic acid (McKetta and Cunningham. R-O-C-
One of the side reactions that can occur in the melt polycondensation. 1976):
+ O=C. 1996):
In the second step the prepolymer eliminates methanol and yields a high molecular weight aromatic polyester (Mahajan et al..
Polyphosphate esters can be also used as flarne retardants. in the presence of an
.. bisphenol A was reacted with
tetranuoroethylene (TFE) and carbon dioxide in dimethyl sulfoxide. prepared from alcohol and POCI. 1988):
In order to create new useful monomers. Catalyst
The aromatic protons adjacent to the hydroxyl groups in BPA are easily substituted. (&shore et al. 1976):
The typical catalyst for chlorination is aluminium chloride and the process is performed in chlorinated aliphatic solvents.
BPA is reacted with
phosphorodichloridates.300-330°C O. The solvent used for bromination is acetic acid or a lower alcohol with chlorine added concurrently (McKetta and Cunningham. The
halogenation of the aromatic rings in the ortho positions relative to the hydroxyl groups is usehl for rnaking flame retardants (McKetta and Cunningham. 1976).5 Torr.
aqueous solution of sodium hydroxide to give the salt of a carboxylic acid. using dioxane as solvent. which is conveniently isolated as its methyl ester after reaction with dimethyl sulfate (ArnoldStanton and Lemal. diamine. 1976). 1991).
By reacting BPA with formaldehyde and methylarnine. nitrosation. This ester can be M e r tramformed in the correspondhg diol.
. The condensation of BPA with formaldehyde was used in the past to obtain phenolic resins (McKetta and Cunningham. and diazo coupling (McKetta and Cunningham. t 994):
BPA can participate in other reactions as nitration. diisocyanate and bis(methy1 carbarnate) which can be valuable monorners for tailored polyurethanes.
Base DMSO (cH~~)~so:
Usefid stabilizers and antioxidants for rubbers and other plastics can be obtained by acidcatalyzed allcylation of BPA with reactive olefins such as isobutylene and styrene. sulfonation. aminomethylation. for example. Kolbe
reaction. 1976). a benzoxazine is formed (Ning and Ishida.
H O ~ F ~ O H
it produces phenol and some isopropylphenol as well. the decomposition of BPA
can go as far as obtaining acetone and water (McKetta and Cunningham. If the process is performed at low hydrogen pressure. The isopropylidenedicyclohexanol is used as a di01 to improve the chernical resistance of polyester resins. Pisopropylphenol c m be oxidized with hydrogen peroxide in acid solution to yield hydroquuione. BPA is rapidly hydrogenated at 75aC and 365 psi in 2-propanol with 5% rhodiurn/carbon as catalyst. p-isopropylphenol. By autoclaving the aqueous alkaline solution.
If the process is performed at high
hydrogen pressure. p-isopropenylphenol is best obtained by cracking BPA in the presence of bases. 1976). (McKetta and Cunningham. it produces only phenol.The hydrogenation of BPA to the isopropylidenedicyclohexanol is described by several
BPA is decomposed by heating in hydrogen. whereupon this alkenylphenol and phenol are obtained in yields of over 90%. 1976): The acetates of BPA also decompose
. Pyrolysis of BPA yields phenol. and residual tars.
They are used in the process of BPA purification (McKetta and
Cunningham.The electrolysis of a concentrated aqueous solution of BPA conducted on a platinum mesh occurs with total degradation of the aromatic rings. purification issues. leading in the end to simple short chain aliphatic acids. It is clear that the number of synthesis routes available to produce BPA is quite impressive.
Another important finding is that acetone and phenol are preferred as reagents for this reaction over some alternative feeds. The formation of these products is not
well understood. physical and chemical properties of the bisphenol A have been reviewed in this chapter. This study also revealed that the purification process is very cornplex.
BPA forms solid adducts with phenol and cresols. since a higher purity crude BPA is obtained. 1976). The
. reaction rnechanism. This procedure is used for BPA removal fiom wastewaters.
The synthesis routes available to produce BPA. which are more selective to the production of BPA. Consequently it was decided that the synthesis of BPA in this investigation will be pursued via condensation of acetone and phenol with acidic heterogeneous catalyst. al1 the compounds involved in the process are very reactive. This is the reason why there is a need for new catalysts. This is due to the fact that in the given conditions. and they c m interact with themselves or with each other to form a varieîy of compounds whch are also very reactive. catalysts.
hydrations and dehydrations.
and disproportionations. acylations. which have been tried successfully for various reactions. such as alkylations. isomerizations.reason for considering heterogeneous catalyst is the fact that the final purpose of this
research is to develop a process based on cataiytic distillation. etherifications.
the better the yield and the selectiviv of the process of BPA formation.
Another fact the literanire review has revealed is that the higher the acidity of the catalyst. This finding
suggested the idea of investigating the suitability of solid superacid catalysts. esterifications.
The purpose of Gibbs reactor simulations is simulation is to better understand the reaction which leads to BPA formation. One of the interests is to narrow down the experimental
region with respect to the molar ratio acetone:phenol. Consequently it is not possible to detemine how long it will take to reach equilibrium for a given systern. compositions and phases of a reaction mixture. The results would be useful in determinhg the levels for the experimental design as well.e. 1991).
. It is also intended to evaluate the behavior of the process in the range of temperature mentioned by the 1itera-e
Smith and Missen.Chapter 3
Gibbs Reactor Simulations
Gibbs reactor simulations are used to calculate equilibrium yields. Kinetic factors are not considered in the Gibbs reactor simulation. The general theory is discussed in many references (i.
. Interactions between two molecules are assurned to be a function of group-group interactions. In this study NRTLO l (non-randon two-liquid) thermodynamic method with a UNIFAC fil1 (universal functional activity coefficient). Jones.
This method estimates activity coefficients based on the group contribution concept
following the Analytical Salution of Groups (ASOG) mode1 proposed by Derr and Deal in 1969. 1991) to make use of the local composition concept. The NRTL equation was developed by Renon and Prausnitz (Smith
and Missen. 1991). This requires selection of an appropriate thermodynamic method for the specified mixture. The
thermodynamic method needs to account for the interactions among species. Gibbs Reactor
In this study the Pro II" implementation of the Gibbs reactor is used.
In the PRO II@ implementation it is possible to:
a) use library data for components. The particular PRO
II" implementation is discussed in the users manual (Reference Manual. was selected. Group-group interaction data are obtained fiom reduction of experimental data for binary component pairs. 1982). and Prausnitz (Smith and Missen. 1982). The UNIFAC rnethod was developed in 1975 by Fredenslund. Whereas there are thousands of chemical compounds of interest in chemical processing.3 1 The PRO II@ . 8 1994 . the number of functional groups is much smaller.
In order to calculate the Gibbs fiee energy of the cornponents it is necessary to estimate or specia activity coefficients for the components (Van Ness.1997). as being the most appropriate
were considered: 2. isophorone. also sorne thennodynarnic data were supplied for
the nonlibrary isomer (opisomer). group contribution methods do not allow
distinction between isomers. These data were found in the literature (Catana et al.b) estimate activity coefficients.
If Iiterature or Iibrary data are not available. For a non-ideai mixture.
1993) (the llbrary value was 633.
1993) and are as follows:
. bisphenol A. chroman and triphenol. are potential by-products. isophorone.. the results of the simulation are expected to be sensitive to the thermodynamic method and the quality of the input data.4'isopropylidenediptienol (o. the normal boiling
point for BPA was cfianged with the value of 493 K. found in the literature (Catana et al. mesityl oxide and mesitylene.2 Simulation of the Bisphenol A Reaction
The following components were present in the Pro II" component library : water. d) al1 of the above. which were not present in the library.
3.65 K). In order to
differentiate between the p-p and the O-p isomers of the bisphenol.. Also
The last three
components. acetone. These nonlibrary
components were individually defined and their thermophysical properties were fiIled f7om structure.p-isomer).
c) input ail data. mesityl oxide and mesitylene. The thermophysical properties of the library components required for the Gibbs calculations were provided by the interna1 database of Pro II".
In a Gibbs reactor the extent of
the reaction is deterniined by minimizing the overail fiee energy of the reacting species. Normal melting point: 383. Carbon number: 15.
isobaric operating conditions were selected.1. After reviewing the data found in the literature about the pressure at
which the reaction is perforrned. no reaction set was input. Hydrogen deficiency number: 14.6928~10~ (kJ/kmoI).67).15 K.6034 (caUcc)"O.
. in order to determine the effect of
temperature and of the molar ratio acetone:phenol on conversion (Table 3. The input file
for these simulations is listed in Appendix B.5 (0. at latm.
at different temperatures and different acetone:phenol rnolar ratios. expected products. the pressure should not influence the results.
Since the investigated reaction is carried out in liquid phase.
The supplied data for the simulations consisted of reactants. The reaction parameters are summaiized in Table 3.05) to 1 :1. Solubility parameter: 9.the molar ratio acetone:phenoI was varied from 1:19 (0. The reactor temperature was varied fiom 50 to 90°C. the simulations were conducted at atmospheric pressure.1). and reaction conditions.S. Since it is not essential for a full solution. and
the pressure was maintained constant.Enthalpy of formation: -3.
Table 3.1: Gibbs reaction simulation with reacuon parameters
1 1 1 1 1 1 1 1
2.3 show the variation of bisphenol A formation with the acetoneqhenol molar ratio and the temperature. the
time dependence of the reaction is not available.2.
3.1.1 Analysis of the Simulation Results
The results provided by these simulations are a steady state final value. The Gibbs reactor does not require any information about catalysts.1. There were also no conmaints imposed on the products. since it does not consider kinetic eEects. 3.1 Effect of Temperature and Acetone:Phenol Molar Ratio on BPA Formation
Figures 3. these simulations do not allow the possibility of investigating the effect of various catalysts on either yield or selectivity
of the process.The extent of the reaction is a measure of how far the reaction goes towards completion and what proportion of the reactants are converted into products. The numencal data for these simulations is tabdated and presented in
. Therefore. The maximum number of iterations was
lefi at the default value of 50.2 and 3. and the variation of the selectivity with the two factors. Hence.
3.2 Variation of BPA Formation with Temperature
and Molar Ratio Acetone:Phenol
.1 Variation of BPA Formation with MoIar Ratio Acetone:Phenol
Acetone:PhtnoI [molar ratio]
the yield of BPA formation
decreases with the temperature (Fig. For acetone:phenol molar ratios between 0.1). 3.5 and temperatures higher than 333. 3 -2). 3. and then it decreases (Fig. 3.2).05 and 0.Fig.
.25 and 0.
For acetone:phenol molar ratios between 0. 3.2).67.15 K boâh the
temperature and the molar ratio have no significant influence on the selectivity (Fig.5.54 and 0. the yield of BPA formation presents an optimum at around 343. the temperature has a negfigible effect on the yield of BPA formation (Fig. For acetone:phenoI molar ratios between 0.
3 -3).15 K (Fig.43.3 Variation of SeIectivity of BPA with Temperature and MoIar Ratio Acetone:Phenol
The results can be summarized as follows:
The yield of BPA formation increases by hcreasing the acetone:phenol molar ratio up to a value of 0.18.
For molar ratios srnaller than 0.
3. mesityl oxide and mesitylene did not appear in the product stream and they were disregarded as well.5 molar ratio the temperature has a negligible effect on the selectivity of the
BPA formation (Fig.2 and Fig. no more BPA is produced. some BPA is formed d l the phenol is consumed. and
the BPA aiready formed is probably reacting with acetone or other products formed in the reaction to give heavier by-products.
7.3).2. Therefore. 3. a list of reactants and expected products was supplied.
The decrease in both yield and selectivity of BPA formation for acetone:phenol molar ratios under 0.9 show the variation of the
The insignificance of the effect of temperature on selectivity for molar ratios greater than
0. the selectivity decreases with both the rnolar ratio
and the temperature (Fig. 3. After this point. therefore it was disregarded. 3 -3). For molar ratios greater than 0. Also isophorone. which lead to by-product formation. By heavier by-products it is understood products with molecular weights higher than the bisphenol A.4 to 3.5 is due to the fact that these rnolar ratios are smaller than the stoichiometric ratio required by the process (Fig.3).2 By-Product Formation
For the simulations.5 can be explained by the fact that the formation of BPA is definitely favored in
comparison with the other cornpetitive reactions.6 . It was observed that the chroman appeared only in traces in the product stream.5. For 0. Figures 3.
Fig.15 K (Fig. 3.4 Variation of 0. The o.
3. 3 -4). 3.
The results can be summarized as follows:
1.8). The formation of triphenol is positively influenced by increases of both the
temperature and the acetone:phenol molar ratio (Fig.
2.5 molar ratio acetone:phenol
for temperatures tower than 343.p-tsomer Formation with Molar Ratio Acetone:Phenol
Acetone:Phenol [moIar ratio]
. 3.p-isomer formation shows a maximum at around 0.
4.yield and the selectivity of the by-product formation with the temperatrue and the molar ratio acetone:phenoI.54 (Fig. For temperatures of 343.7 and Fig. 3 -5). L 5 K and higher the formation of op-isomer is uisignificant
regardless of the molar ratio acetone:phenol (Fig. Some ûiphenol starts to form only for acetone:phenol molar ratios over 0.
Fig, 3.5 Variation o f oq-Isomer Formation with Temperature at Various Molar Ratios Acetone:Phenol
T e m p e n t u r e [KI
Fig. 3.6 Variation of Selectivity o f og-Isomer with Temperature at Various Molar Ratios Acetone:Phenol
Fig. 37 Variation o f Triphenoi Formation with Molar Ratio Acetone:Phenol .
Acetone:Phenol [rnolar ratio]
Fig. 3.8 Variation of Triphenoi Formation with Temperature at Various Molar Ratios ~cetone:~henol
Fig. 3.9 Variation o f Selectivity of Triphenol Formation with Temperature at Various Molar Ratios Acetone:Phenol
5. For acetone:phenol molar ratios of 0.54 and 0.67 the formation of triphenol increases
significantly with the temperature over the whole range (Fig. 3.8).
6 . For acetone:phenol molar ratios smaller than 0.54 some triphenol is formed, but the
amounts are not significant even at high temperatures within the considered range (Fig. 3.8).
7. The molar ratio has negligible effect on the selectivity of o,p-isomer formation (Fig. 3 -6).
8. The selectivity of the op-isomer formation decreases with the temperature (Fig. 3.6).
9. At 353.15 K, regardless of the acetone:phenol molar ratio, the quantity of o,p-isomer
formed is negligible and it continues to decrease with increasing temperature (Fig. 3.5
and Fig. 3 6 . .)
10. For acetone:phenol molar ratios greater than 0.5, the selectivity of triphenol formation increases significantly with the temperature (Fig. 3 -9).
11. For acetone:phenol molar ratios smailer than 0.5, the variation of the selectivity of
triphenol formation with the temperature is significant (Fig. 3.9).
12. For acetone:phenol molar ratios smailer than 0.5, the variation of the selectivity of
triphenol formation with the acetone:phenol molar ratio is significant (Fig. 3.9).
Both yield and selectivity of triphenol formation are significant for acetone:phenoI molar ratios over 0.5, because, as shown in the previous chapter, triphenol 1 is formed via condensation of an aiready formed molecule of BPA and a molecule of hydioxy isopropyiidene phenol (the product of the fnst step of condensation in the process of fonnation of BPA). This is also another explanation for the decrease of the yield and the selectivity of the BPA formation for molar ratios of the initial reagents over 0.5.
The o,p-isomer formation is favored by low temperatures because it is an exothermic process. Therefore, the higher the temperature. the lower the yield and the selectivity of
the o,p-isomer formation. Also, the closer the ratio acetone:phenol to stoichiometry, the
lower the amount of op-isomer formed, because given the same conditions, the fonnation of BPA is thermodynamically favored.
3.3 Summary of the Simulation
Both the formation of bisphenol A and oop-isomershow a maximum at around 0.5 molar
ratio acetone:phenol, while the triphenol seems to just start fomiing at the specified molar
ratio. From the analysis presented it appears that there is an optimum at around 0.5
acetone:phenol molar ratio and temperatures somewhere between 343.15 K and 353.15
K. In order to better visualize the optimum, 3-D graphs are presented in Figures 3.10.
3.1 1, and 3.12.
Fig. 3.10 Variation o f BPA Formation with Temperature and Molar Ratio Acetone:Phenol
Fig. 3.11 Variation of o,p-Isomer Formation with Temperature and MoIar Ratio Acetone:Phenol
Fig. 3.12 Variation o f Triphenol Formation with Temperature and Molar Ratio Acetone:Phenol
Fig. The reason is very likely to be the fact that limited physical property data were available for the o.0
0.p-isomer and that the physical properties were estimated with the group contribution methods.14 represents the formation of the three products at
0.. As previously mentioned.15 K
.We are looking for reaction conditions which maximize the amount of bisphenol A and muiimize the amounts of og-isomer and ûiphenol. .8
Acetone:Phenol [molar ratio]
The equilibrium constant for the BPA
o.15 K and 0.5 molar ratio acetone:phenol.
. 3. These data are not in agreement with the data presented in Table 2.5 acetone:phenol molar ratio over the considered range of temperatures. and Triphenol Formation with MoIar Ratio Acetone:Phenol at 353.5
0.13 represents the formation of the three products at 353. Figure 3.13 Variation of BPA.1 (page 15).7
0. The optimum for the system is
positioned somewhere around 353. op-Isomer.O .2.p-isomer transformation calculated fiom the
simulated data are presented in Table 3.4
0. the group contribution methods are unable to differentiate between isomers.15 K over the considered range of acetone:phenol molar ratios.6
0. Figure 3.
60 O. and Triphenol Formation with Temperature
3.p-Isomer. 3.14 Variation of BPA.
The simulation shows that actually a
stoichiometric ratio of acetone and phenol is a better choice.2 Equilibrium constant for the BPA
opisomer transformation based on
simulated data Temperature ( O C ) K
. the Literature mentions that the process of BPA
formation is favored by excess phenol. o.0039
90 0.Table 3.
The simulation also
concludes that the considered ranges for both the temperature and the molar ratio acetone:phenol are feasible experimental regions.4 Conclusions
As presented in the previous chapter.
The Gibbs reactor simulations has been used to speci@ the experimental region with respect to the molar ratio acetone:phenol. The simulations showed
that the chromanes are produced in negligible quantities. Therefore there is a considerable need for catalytic systems andor reaction
conditions which will produce a cleaner crude. This was one of the conclusions of the previous chapter
Subsequent work involved experimental investigation of the process simulated in this chapter. and catalyst on BPA and by-products formation and selectivity are analyzed and compared with the results of the simulation and the findings in the literature. The effects of temperature.
These simulations have confmed that the species present in the system are remarkably reactive at the given conditions. molar ratio acetone:phenol.
The literature review in the previous chapter indicated that the formation of chromanes as by-products of the BPA production process has been observed.
It has dso contributed to a better
understanding of the reaction behavior and should give some indication of what to expect from the experimental program in terms of yields and selectivities.
%y cleaner crude is understood a mixture of
products and unreacted reagents that corne out of the reactor with as few by-products as possible. and the triphenols are actually
n present in larger quantities i the product stream.
. which is translated is less complex and less expensive separation processes.
Determine the reaction conditions that significantly innuence the process and explain
4. the analytical
methods employed to analyze the samples.Overview
Different setups were used for different stages of the experimental investigation. and
the methods used for data processing are discussed in this chapter. the experimentai procedures employ ed.
The apparatus and the materials used in the experimental investigation. Safety issues are also discussed. The stage of identi@ing new catalysts was carried out in NMR (Nuclear Magnetic Resonance)
. Identiw new suitable catdysts for BPA formation. Find appropriate reaction conditions.1
II. III.Chapter 4
The purposes of the experimental investigation were to:
the plug flow reactor (PFR). was used as batch reactor.tubes. for the reactions
with acidified activated dumina. 1992). The arrangement was sirnilar to that descnbed by Singh (1992)
(Singh. The temperature was monitored by a thennometer inserted via the second neck of the flask. A condenser was placed in
the central opening to reflux the vapors of acetone and other vapors which may be
produced during the reaction.
And fïnally a third setup was considered.
Once this phase was accomplished. The batch reactor was used to perform the experiments with ~a. The third opening remained plugged with a stopper and was used for removuig samples. n Another advantage was the fact that the sampling was automatic.2 was
and ~mberlyst@'15. This
was a batch reactor. A PFR with configuration as shown in Figure 4. Basically at this stage the reaction was studied i a drop of reaction mixture. A 250 ml. a new experimental setup became of interest. A magnetic stirrer was employed for agitation of the catalyst. 3 neck round bottom flask with a central opening. The setting was not suitable for the reaction with acidified activated
dumina because this catalyst was not robust enough to withstand mixing. This setting provided qualitative information about the formation of the product of interest while using very srnall amounts of catalysts and reagents. imrnersed in a thermostated paraffinic oil bath. The result was the identification of
suitable catalysts: ~ a f i o n @ activated alumina acidified with and
hydrochloric acid. A brief overview of the theory underlying the NMR phenornenon and associated references is given in Appendix D.
The volatizing and reaction zone were separated by wire rnesh. that regulated power supply to the heater. attached to a P D (proportionai-integrai-derivative) controller. The nitrogen was fed to the reactor fiom a pressurized gas cylinder with the flow regulated by a
. This type of reactor was selected to sirnulate reactive distillation conditions.Reaction Zone
Fig.1 Plug Flow Reactor
The liquid reagents were fed to the reactor using a 350 ml syringe pump. The reactor consisted of volatizkg zone (an insulated circular pipe with length and radius of approximately 19 cm and 1. 4. and the entire reactor was encased in an insulated heating unit.used. Temperature control was accomplished by means of a thennocouple located in the catalyst bed.
2 .4 cm respectively) filled with Ioosely packed ceramic saddles followed by a reaction zone filled with the cataiyst (a circular pipe with length and radius of approximately 21 cm and 1 cm respectively).
nitrogen. Once through the reactor. deuterated chlorofom. phenol.3% (9%H.O)
DuPont ALCAN CHEMICALS ALCAN CHEMICALS BDH Inc.
CAS 80-05-7 UN 1066 LOT NO.rotameter. the products were collected in a pot. activated alumina. 97018 SAMPLE NO. The pressure of the system was maintained using a back-pressure reguiator.5-38% NIA 99. KGO348-349 . ~ m b e r l y s t15. Supplier information is presented in Table 4.1: Materials used in experiments
Material Acetone Phenol Bisphenol A Nitrogen ~ a f i o n TYR-50 @ Nafion@SAC. LOT NO. 97018
ACS 393-02 393 89-20-3 (H20: 7732-1 8-5)
97% N/A N/A
36.13 Activated dumina 8x14 mesh Activated alumina 14x18 mesh Hydrochloric acid Amberlyst@15 Deuterated chloroform Nitric acid
Supplier Fisher Scientific Fisher Scientific
CHIMICA BOC GASES DuPont
Catalog # CAS 67-64. and nitric ~ acid.1 CAS 108-95-2
(H20: 7732-18-5) CAS
Purity histological grade 9 1.
4. hydrochloric acid. ROHM and HAAS Cambridge Isotope Laboratones BDH Inc. 924 SAMPLE NO.2
The materials used for this study are: acetone.
Table 4.1. Since many of the compounds uivolved in the reaction are liquid under the
operating conditions used. it was decided that a downflow configuration would be more suitable for this application. bisphenol A.8% 69-71%
. The nitrogen and liquid feeds were mixed pnor to addition to the volatizïng zone. N&on@.
mechanical strength.Al1 the materids are hazardous. It is commercially available in
the form of millimeter sized beads known as ~ a f i o n NR-50 resin.I.
Nafion@ is a copolymer of tetrduoroethene and perfluoro-2-(fluorosulfonylethoxy) propyl Wiyl ether that belongs to the class of solid superacid catalysts. and Amberlyh 15.2.
Because of its thermal and chemical resistance. it has widespread application. activated aiumina 8x14 mesh and 14x18 mesh.itlch/DipIFM/fisica/eccc /
. and insolubility in water.aictly followed
when operating and analyzing the experiments. Naf50na SAC-13.Nafion@Research). a
registered trademark of E.ch. ion-exchange
properties. n i e
are structure and the properties of Nafion@ presented below. It exhibits acid 1 strength greater than that of 100% H. fuel cells. selectivity.1. and the chlor-
aikali industries.Perfiuorosulfonated Ionorner
~ a f i o n @ a poly(tetrafluoroethy1ene) based ionomer (Mauritz is
. it has many applications in liquid and gas separations. DuPont de Nemours and Co.SO.1 ~ a f i o n @ . (scienze.unito.2.1 Solid Catalysts
The solid catalysts used in the experimental investigation were Nafion@NR-50. thcrefore safety regulations must be cl.
More detailed health and safety
regulations about the materials mentioned above and about the products obtaùied in the process are presented in Appendix A. Since its development @
such as alkylations. to
hydrations and dehydrations. Although the exact structure is not known. nitrations.2 Nafion@Structure. 1996). 4. The study presented in this thesis will show that ~ a f i o n @ able to catalyze condensation as well. and esterifications has been descnbed in detail (Harmer et al.2. is
5-1 5% Sulfonic Acid Groups
Fig. isomerizations.htd)... several models have been proposed since the early 1970s. disproportionations. Robertson (1994) has summarized many of these such models: The Mau&-Hopfinger Model.
The Eisenberg Model of Hydrocarbon Ionomers and The Gierke Cluster Network Model.--CF. 1996).
Structurally. It has hydrophobic (--CF.
. The use of
~ a f i o n @ catalyze various reactions. and the electron wididrawing effect respectively. H ) regions i n
its polymeric structure.way in which ionic groups aggregate within the Nafion@polyrner. or 3 (Harmer et al.3 show the chernical structure. acy lations.-)
and hydrophilic ( 4 0 . The Yeager Three Phase Model. etherifications. and 4.nafZon. to describe th. Nafion@is cornplex. and its superacidity is attributed to the electron withdrawing effect of the perfluorocarbon chah acting on the sdfonic acid group. x = 1.2. m = 6 or 7. n n 1000. Figures 4.
Although no mode1 has been found to provide a complete explanation of the properties and selectivities found.3 Electron Withdrawing Effect
(scienze. as well as the ionic transport properties of p e r f l u o ~ a t e d ionomer membranes. Figure
. 4.ch.Nafion@ Research).it/~h/DipIFM/fisica/ecccI/nafion.
As a result of electrostatic interactions. 1994)..unito. several models base these properties and selectivities on an extensive micro-phase separated morphology (Mauritz . these ionic groups tend to aggregate to form tightly packed regions referred to as clusters (Butler et al.flectron withdrawing atom
Fig. 1982) and neutron
scattering (SANS) experirnents clearly indicate that ionic clustering is present in ~ a f i o n ? However. details on the arrangement of matter within these clusters have not been fûlly realized.html)
A common objective of these models is to predict the hdamental feature of unique
equilibrium ionic selectivities.
Small angle X-ray scattering (SAXS) (Yeager and Eisenberg. The presence of these electrostatic interactions between the ions and the ion pairs enhances the intermolecular forces and thereby exert a significant effect on the properties of the parent polymer.
4 Stylized View of Polar/Nonpolar Microphase Separation in a Hydrated Ionorner (Mauritz .
Fig.5. and (C) the clustered regions where the
.~ a f i o n @ Research)
The Yeager Three Phase Mode1 is a phenomenological based model. the hydrophilic region contains the ionic groups and their counter ions. This model is based on a three-phase clustered system with intercomecting channels within the polymer.
The hydrophobic region is composed of the polyrner
fluorocarbon backbone.4 shows the sîylized view of polar/nonpoIar microphase separation in a hydrated
This over-simplification shows a phase separated morphology of discrete hydrophobic and hydrophilic regions. and those sulfate ~ O U P S
and counter ions which are not in clusters. (B) an interfacial region of relatively large fiactional void volume containing some pendant side chahs. 4. represented in Figure 4. On the other hand. some of which is microcrystalline. some water. The three regions consist of (A) a fluorocarbon backbone.4.
From experimental means. it has been detemined that the phase-separated morphology is on the order of 30-50A Bragg spacing (Brookrnan and Nicholson. and temperature. 1982). 4.5 The Yeager 3 Phase Mode1 of N&on@ Clusters (Mauritz .~ a f i o n @ Research)
. Upon hydration. counter ion.upon hydration. counter ions. 1986).majority of the ionic exchange sites. Howeve. cm increase its dry weight by as much as 50% or more. cluster diarneter and the nurnber of exchange sites are thought to increase (Brookrnan and Nicholson. and sorbed water exists (Yeager and Eisenberg. depending on equivdent weight. such as small-angle-X-ray scattering (SAXS). 1986).with its ability to sorb relatively large amounts of water. Nafion@.
The Nafion@NR50 resin begins to lose the sulfonate groups at about 280°C (Harmer et
ai., 1996). This temperature stability is much higher than hydrocarbon-based sulfonate
t~ ion-exchange resins, such as ~ m b e r l y s 15, which is stable only up to 130°C.
NR-50 resin is very low, typically 0.02 m' g-' or less, and The surface area of the ~ a f i o n @
most of the active sites are buried within the polymer beads. Under many types of reaction conditions, these sites are inaccessible or poorly accessible, and as a result the observed activity for rnany reactions is very low (Harmer et al., 1996).
126.96.36.199 High Surface Area Piafion@Resin
In order to compensate for the shortcoming outlined in the end of the previous section, a
newly developed matenal (Harmer et al., 1996) was tested. It is a nanocomposite of nanometer shed ~ a f i o n @ particles entrapped withui a highly porous silica network. resin
It is commercially available and it is known as ~afion@' SAC-13 resin (for a content of 13
wt % of ~ a f i o n @ the Nfo @ in ai n '
With the new material, the
accessibility of the acid groups is supposed to significantly improve. The inherent
thermal stability of the Nafion@SAC-13 resin is about the same as Nafion' M - 5 0 resin.
4.3.1 Reactor Loading and Set-up
188.8.131.52 NMR Tube Reaction
1. Weigh a clean, empty NMR tube.
2. Weigh 0.04 g of catalyst in the NMR tube (Note: The desired quantity of catalyst was
measured directiy in the tube to avoid transfer losses.).
3. Prepare a mixture of acetone and phenol with a molar ratio of 1:2 acetone:phenol.
4. Take 40 pl of the mumire w i t h an Eppendorf pipette and put them into the tube.
5. Add 700 pl of deuterated chloroform to the tube. 6. Cover the NMR tube and seal carefully with parafilm.
7. Insert the tube in the appropriate spinner and adjust the depth using the sample depth gauge.
8. T m on the air and position the tube in the magnet.
9. Lower the tube into the magnet by tuming the air off.
10. Start the spinning air.
11. When the spinning rate reaches its set value, adjust lock power and lock gain.
12. Center and then lock the signal.
13. Start heating the magnet by tuming on the heater, setting the temperature at 343 K,
and increase the air flow through the magnet.
14. Once the temperature is reached, shim the field, and start the routine for data
184.108.40.206 Batch Reactor
1. Put on protective clothing, lab coat, goggles, and gloves.
Ail the steps were
perfomed in the fume hood. 2. Weigh the desired quantity of catalyst (10 g or 20 g) in a clean measuring dish.
3. Transfer the catalyst into the flask.
4. Weigh the desired quantities of phenol and acetone (75.55 g or 89 g of phenol and
24.12 g or 11 g of acetone). 5. Add the measured quantities of reagents to the reactor.
6. Turn on cooIing water to condenser.
7. Turn on magnetic stirrer.
8. Turn on the heat and adjust the thermostat for the desired temperature.
220.127.116.11 Flow Reactor
Put on protective clothing, [ab coat, goggles, and gloves. All the steps were perfomed
in a ventilated explosion proof bunker.
Place the desired catalyst in the reaction zone. Assemble cleaned reactor. Set temperature to desired value to dry catalyst. Open nitrogen tank and pressurize the reactor to 50 - 55 psi. Adjust back-pressure valve to maintain this pressure. Check for leaks.
2 Reactor Sampling Procedure and Sample Preparation
4. Set pump control to get desired flow rate and turn the power on to the pump. Let catalyst dry ovemight. was the sample. that is the reactor. Set temperature to desired value for m. Close bunker door. Let the pressure stabilize.
16. because the tube itself.
4.8. At the end of the reaction the
l files with d the FID's were saved on disk and M e r analyzed with appropnate
software. It shodd corne back to where it was set.1 NMR Tube Reaction
The routine was set to sample the reaction every 20 minutes. Set flowmeter (NI 12-02) to maintain nitrogen pressure at 50 . 9.
14. Open valve to reactor.
13. Vent reactor to remove water that came off the catalyst.
.55 psi.3. Load reactants into the pump.
15. The Free
Induction Decay (FID) for each sample was saved in a file.
10.2. No samples were removed fiom the tube. Weigh the desired quantities of phenol and acetone.
2.3 Flow Reactor
After 24 hours of reaction. Dilute the sample with 700 p l of deuterated chloroform.2.
3. Remove the tube fiom the magnet. Dilute the sample with 1ml of acetone. and set the temperature back to the room temperature value.
Tum the magnetic stirrer back on. reduce the air flow through the magnet.1 NC R Tube Reaction lP
1. the liquid in the receiver was collected in a clean flask for
The reaction was sampled every 24 hours.
Collect 40 pl of reaction mixture with the Eppendodpipette and put them in an NMR tube.3 Reactor Shut-Down and Clean-Up Procedure 4.3. Turn off the heater.
4.3. Coliect 200 pl of reaction mixture with the Eppendorf pipette an put them in a 2 ml sample vial.3.
one in the NMR tube and the second in a sampling vial. When the magnet cooled down.2 Batch Reactor
Turn the magnetic stirrer off. Two samples were prepared the same way as described for the batch reactor.3.
Vent the receiver into a clean flask for sampling. goggles.
Wash the catalyst with acetone on the filter.
T m off the magnetic stirrer.3. and gloves.3. and gloves. then with water and
soap. then dispose in a special container. Separate the solid catalyst fiom the reaction mixture on a Büchner funnel. lab coat.
Turn off the heater. 11.2 Batch Reactor
Put on protective clothing. lab coat.3. Put on protective clothing.
3. and allow them to dry.
10.3 Flow Reactor
.3. reaction mixture and wash acetone into the solvent cm.
Tum off the cooling water to the condenser. the stopper.
4. Turnpump off. Set temperature to about 50°C and let the reactor cool down so that it can be handled. Wash the Bask. Dispose of the separated liquid. then with distilled water. Rime thoroughly the sampling syringe with acetone to remove any residual BPA or phenol.4. and the themorneter with acetone. goggles.
When reactor is at roorn temperature.
Allow catalyst to dry on the filter. remove the reactor fkom the c-clamp.
Because the samples were concentrated.When the reactor cooled down. Clean the reaction zone. the sampling and the analysis of the reactor content should have been done on line. acetone was used to dilute the samples for the
10. Place solvents in solvent can for disposal. As a result the analysis on the GCMS was used to monitor the selectivity of the
process. tum off the nitrogen tank and vent the reactor by opening the back-pressure valve. Open the bunker door. and the NMR analysis was used to determine the quantity of BPA produced. then dry them in a clean oven. Disassemble the reactor. Unfominately the necessary equipment to do so was not available. on a High Pressure Liquid Chromatograph (HPLC) equipped with a split injector.
The calibration of the GC/MS was not possible due to the fact that most of the byproducts produced in the reaction were not available as standards. Drain the pump of remaining reactants and rime with acetone to remove any left over
phenol which could solidfi in the pump when it is not operational.
Clean the ceramic saddles with sulfi.uk acid.
4. and an adequate solvent for
the reaction mixture was not determineci. and an NMR Spectrometer. Also a split injector
was not available.4 Sample Analysis
:deally. that is a Gas Chromatography/Mass Spectrometer (GCMS). and alternate options
had to be considered.
.2 outlines the acquisition method of the MS. The apparatus employs a high performance Varian Mode1 3400 Gas
Chromatograph (GC) with a 1093 Septum equipped Programmable Injector (SPI) and a
1077 Splitless Capillary Injector. The Satum uses an ultratrace ion trap
Cornplete separation of the components is necessary in order to get an accurate rneasure
of the quantities of each within the sample.4.32 mm diameter. supplied by Supelco Inc. 0. and they were considered together. Table 4. for improved retention time stability." was
employed.7.6.1 Gas Chrornatography/Mass Spectrometry Analysis
A Varian Satum II Gas Chrornatography/Mass Spectrometer with an ion trap detector
was used for product identification and to determine the seiectivity of the process of BPA
formation under heterogeneous catalysis. A fused silica capillary column SPBTM-20.
and the boiling points and retention times of the products fiom this reaction are presented
in Table 4. A representative chromatogram of the products from the condensation of
acetone with phenol is presented in Figure 4.25 pn film thickness. The temperature profile of the GC
method is displayed in Figure 4.
The GC is also equipped with thermostated
pneumatics.4. Complete separation was not possible for the
71760 Cla 174 323
470 O-pisomer 546 Chromanes (601 .29
17010.14 1 301760 Mesitylene 216 120.3
. mode EI ON Auto ion control Cal gas ON
Table 4.29 228.19 164.25 17010.34 228.6 Temperature Profile of Method Used o n GC
Table 4.3: Peak tabIe with retention times and boiling points of the products Peak Retention Time (min) Molar Weight (ghofe) Boiling Point (°C)lmm Hg Mesityl oxide 152 98.Fig.29 268.3-pentadiene 2-@-hydroxyphenyl)-4-methylpent-3-en-2-oi
228.607) BPA 632 " 4-@-hydroxypheny1)-2-rnethyl-1.2: Acquisitior method on the Mass Spectrometer 1 29 to 350 Mass range ( m u ) Seconddscan (4Scans) 1 .25 165-17010.O00 Acquire time (minutes) 12 ~il/MÜl delav (seconds) 1110 Il Peak threshoid (counts) Mass defect (mmu/lOOamu) 1 85 Backrrround mass (arnu) 1 28 Ioniz. 4.
The GC/MS analysis was used to detelmine the selectivity of the process.7 Chrornatogram of the Products Obtained fiom the Condensation Process
C a m m e n t : EXîERIHENT 4 W I O H FE39 WTER 96 HOURS Scan No: 1 RetentionTima' 8!01 RIC: 8 Range: 1 ta 728 Plotted: 1 to 728
Chramaabgram P l o t
-C:~ATLIRWUILICIP(AWXP1\FEBSs4ts W W 9 8 a s
IB&A = 351694116
The calibration of the G C M S method was not possible because most of the by-products
observed in the reaction were not availabie as standards. 4. The preparation of the sample and the analysis conditions were identical. the sarnpling procedure. Therefore it was decided to consider the area of the peaks proportional with the mass of the corresponding compound.
. NI the sarnples contained
relatively the same components in comparable amounts.Fig.
032 Acquisition Time (sec) 1 104.4.132339 Frequency (MHz) 4032.O Recycle DeIay (sec) 200. acquisition parameters are summarized in Table 4. commercial NMR data processmg 1995).O 2.3 Sweep Width (Hz) Dwell Titne (usec) 248.9 Offset Freauencv 1 8 192 Number of Points Time Domain TPPI Acquisition Type
The procedure for calculating the error associated with the NMR analysis is also
N M R data are anaIyzed using
as NUTS (Acom NMR.2 NMR AnaIysis
A Bruker ACF-200 NMR Spectrometer with a
frequency was used to
deterrnine the amount of BPA produced with heterogeneous catalysis.4.2.4: Data acquisition parameters
Parameter 1 Value 16 Number of Acquisitions 5.4.O Pulse Width (usec) 3 .1 General Introduction to the NMR Procedure Used in
The procedure for calculating the yield in BPA in this study is based on the fact that
acetone and BPA have peaks that do not overlap and can be integrated and compared.
8. 4. respectively.10.)
Fig. phenol. The NMR spectra of acetone. and 4.
Fig.described.9 NMR Spectnim for Phenol
.4.8 NMR Spectmn for Acetone (CDCI.9. and bisphenol A are presented in Fi-ures 4. 4.
1 l). 4.4.10 NMR Specaum for Bisphenol A (CDCI.
.Fig. Since there is no BPA initially present in the system.2. and if it is nof
then the error is attributed to the noise level within the integrated interval of the spectrum. The portion of the spectnim where the two methyl groups of the BPA should appear was also integrated. the integrai of the
acetone peak was attributed the value of 100. the value of this integral should be zero.)
4.2 Calculation of the Error Associated with the NMR
In the NMR spectrum of the initial mixture acetone:phenol (Fig. 4.
11 NMR Spectrum of the Initial Mixture of Reaction (fiom 0.
caiculation presented for signal to noise the fiequency domains were expressed. it was necessary to attribute a value
of 10. The eequency domain can be expressed both in Hertz or in ppm. by choice. 4.000 to the integral of the acetone peak in order to calculate the processing error.0 ppm)
Since the processing error seems to be under 0.01 %. ppm represents the ratio of
the resonant frequency (in Hz) and the fiequency of the magnet (in Hz). The denominator is the area integrated over a region in the spectrum where no peak is supposed to appear divided by the frequency domain over which it was integrated.4 ppm to 3.Fig.
The signal to noise (sh) is calculated as a ratio of two ratios.
Then the integrated noise showed a non zero value (Fig. The ratio signal to noise (sh) is:
. 4. The numerator is the area
of a peak divided by the frequency domain over which the peak was integrated. in Hertz.12).
1994. taken at the end of the reaction.13.
of the sample taken at the
4.4.using the same normalization
constant.O ppm to 3. 4. was analyzed on the NMR. 1993.The error associated with NMR analysis is:
Fig. as the sample shown in Figure 4.1995).1 1. The specend of the reaction is presented in Figure 4.12 NMR Specûum of the Initial Mixture of Reaction (fiom 1.2. and
processed with NUTS (Acom NMR.3 Procedure for Calculating the Yield in BPA
.41 mole of acetone and 0. This means that if the initial composition of the mktwe is known.4 pprn to 3. the number of moles of BPA and of acetone in a subsequent spectnim c m be calculated. It is known that both integrals considered in this application (the acetone peak and the peak of the methyl groups in the BPA) are accounted for six protons each. Therefore the initial rnixhue consists of 0. and it is also known that the integrals are proportional to the number of moles in the mixture corrected with the a m b e r of protons (a correction not necessary since the number of protons is the same).
Fig. 4.12 g of acetone and 75.13 NMR Spectrum of the Final Mixture of Reaction (fiom 0.9 mole % phenol. by setting the value of an integral at 100. in mole percent.1 1 g/mole respectively.08 g/mole and 94.When processing spectra with the same normalization constant.55 g of phenol.0 pprn)
The initial mixture contains: 24.1 mole % acetone and 65. 34.8 mole of phenol. in al1 subsequent spectra the values of the integrals considered are going to be percentages of the set integral. The molecular
weights for acetone and phenol are: 58. or.
The yield in BPA is caiculated with the following formula:
7 is the yieId in BPA;
q p ~ , f i n the number of moles of BPA present in the finai reaction mixture, and it is is
caiculated as the product of the initiai number of moles of acetone and the value of
the BPA methyl peak integrai in the NMR spectnun;
~ is A molecuiar weight of the BPA; the
m i , is the weight of îhc reaction mixture.
This chapter presented the matenals and the analytical methods used for this research, and the apparatus employed by the experimentd part of this study. The NMR tube reaction was used to identifi new catalysts. The batch reactor was used to perform the experiments with ~ a f i o n @ , order to assess the effects of the selected process parameters in on the synthesis of BPA. The plug flow reactor was employed for the reactions with acidified activated alumina, since this catalyst was not mechanically robust enough to undertake the mixing in the batch reactor. A significant amount of time was required to ensure that al1 safety concerns were satisfied.
in the next chapter the experimental results are presented and discussed. Several sets of
experiments were performed to evaluate the reactivity of the system of interes&to veri& the experimental reproducibility, and to narrow down the experimental region which will be investigated usïng an experimental design.
Experimental Results and Discussion
Eight sets of experiments were performed to examine the synthesis of bisphenol A under various reaction conditions. The first set used homogeneous and heterogeneous catalysis
at roorn temperature. The second set used ~afTon@ various temperatures in a batch at
reactor. The third set used AmberlystB 1 5 as heterogeneous catalyst, with the purpose of evaluating the experimental reproducibility. The fourth set consisted of one reaction with heterogeneous catalyst, and had the purpose of validating the simulation prediction that
the reaction goes to depletion of acetone. The nfth set consisted of reactions performed
with heterogeneous catalyst in an NMR tube. The sixth set used heterogeneous catalysis
in a batch reactor with the purpose of cornparhg the performance of ~ a f ï o n @ NR-50
versus ~mberlyst@ Finally, the seventh and the eighth sets employed heterogeneous 15. catalysis at various ternperatures, catalyst concentrations, and molar ratios acetone:phenol in a batch reactor. Ln these experiments a two factorial design was perfomed to examine
the effects of catalyst type, catalyst concentration, temperature, and molar ratio acetone to
phenol. AU the experiments presented in this chapter are summarized in Table 5.1.
1 NMR Tube 1:2 70 6 ~ m b e r l y s 15 t~ 10 V. Temp.8 24
. 1 Batch 1:2 72 10 Nafionam-50 11.7 Nafionam-50 Batch 1:5 82 20 24 ~ @ VII. Acetone:Phenol Reactor Type Catalyst Exp.5 Batch 72 12 10 5 ~rnberlyst~ 15 IL?.2 20 27 ~ a f i o n NR-50 @ Batch 102 1:2 10 24 VII.4 1 6 1 AA 300/HC1 1 10 1 70 1 1 :2 1 NMR Tube NMR Tube 1:2 70 AA 300/HCl 6 10 V.8 .10 NafionBNR-50 Batch 1:2 92 10 VII.1 1:2 Batch 25 ~mberlyst"15 10 2 16 1.2 1:2 Batch 25 72 No Catalyst 1.2 Batch 72 1:2 10 5 ~ m b e r l y s 15 t m.12 Nafion@ NR-50 Batch 15 102 24 10 VIII.4 24 82 Nafion@ NR-50 Batch 1:5 82 24 VIII.2 102 Batch 1:2 20 %iÏT24TizzmmT 1:2 Batch 10 VIII.1 72 1:2 Batch 10 5 ~mberIyst@ 15 111.3 Batch 82 1:2 24 Nafion@ NR-50 30 VI1-4 Batch 82 1:5 24 10 ~~on@NR-50 VIL5 102 1 :2 Batch 20 24 VII.2 96 Batch 1:2 83 10 96 ~ a £ i o nNR-50 @ 11.4 Batch 102 1:2 10 Nafion@ NR-50 96 11. 1 NafionQNR-50 Batch 15 102 24 20 ~afion@NR-50 VIII.5 Batch 1:5 92 20 27 ~ m b e r l y s 15 t~ VI. # 1 Time 1 Molar Ratio (Oc) (wt %) (h) Type Batch 1:2 25 HC1 10 288 1.9 92 Batch 1:s 10 24 VXI.6 Nafiona NR-50 Batch 15 102 20 24 VII.2 NMR Tube 1:2 70 10 3 ~ a f i o n NR-50 @ V.-
Table 5.3 V.3 Batch 1:2 63 10 96 ~afion@NR-50 II.1 Summary of the experiments 1 Catalyst Conc.1 1 24 1 NafionQNR-50 Batch 1:2 92 24 10 Vn.3 Batch 72 1:2 10 240 Amberiyst@15 IV.7 Batch 1:2 82 20 ~afion@NR-50 VIIT. 1 Batch 92 15 VI.5 10 ~afion@NR-50 102 1:2 Batch 24 10 Nafion@NR-50 VIII. I NMR Tube 1:2 70 10 3 Nafion@ NR-50 V.3 Batch 92 1:2 ~ a f i o n NR-50 @ 10 96 11.6 82 Batch 15 24 20 Nafion@ NR-50 VIII.a f i o n NR-50 Batch 1:2 92 10 24 Nafion@NR-50 VII. 1 Nafion@ NR-50 102 Batch 1:5 10 24 VIL2 Nafion@ NR-50 82 Batch 1:2 10 24 NafionaNR-50 VII.
1 Preliminary Investigation
The purpose of the preliminary investigation was to evaluate system reactivity.
The non-catalytic process was analyzed once a day. every three days. Two of the experiments were conducted under catalytic conditions: for the first experiment concentrated hydrochloric acid (HCL) was used. ~
experiments were conducted at room temperature. once a day. a 1:2 mixture acetone:phenol was used in al1 three experiments. once a day. scheme of reaction.5. Based on the results of the simulation. and experimental reproducibility.2 and 1. at various temperatures. discussed in Chapter 3. In the diird experiment no catalyst was used.1 Evaluation of System Reactivity and Blank Reactions
For evaiuating the system reactivity.
5. three days
.3 presented in Table 5. consecutively.
The homogeneous catalysis was sampled and analyzed four times. Homogeneous and heterogeneous catalysts were used at this stage. 1. three experiments were conducted (experiments 1. The reaction
with heterogeneous catalyst was under continuous stirring (the magnetic stirrer was set on
position 5). and for the second experiment ~ r n b e r l y s t15 was used. experimental region.1. every three days.1). The experiments with hornogeneous
catalyst and the reaction with no catalyst were conducted without stirring. The heterogeneous catalysis was sampled and analyzed three times.1. blank reactions.
The high peak at approximately 2. 5.It was reported (McKetta and Cunningham.
Figures 5. 1992):
HC1> ~mberlyst' 15 > Acidic zeolites with large pore openings (> 7.3.4 represent the NMR spectra of the samples taken h m the reaction mixture with homogeneous catalyst (HCI). The split peaks in the region 6. 1976) that a 1:2 mixture of acetone and phenol treated with concentrated hydrochloric acid which is allowed to stand for some hours at room temperature deposits a mass of crude bisphenol A crystals.2. 5. and 5.2 ppm is the acetone (Pouchert and Behnke. The reaction mixtures from the experiment with heterogeneous catalyst and fkom the experiment with no catalyst showed no change i n color and no crystals were observed on the bottom of the flask either. This last verification is needed because some of the samples taken fiom the reaction mixture were to be analyzed several hours afier sampling and it is important to make sure that there is no reaction between sampling and analysis. 1993). decreases as follows
(Singh. Another statement found in the literature is that the activity of the catalysts for the formation of bisphenol A.
The reaction mixture treated with hydrochloric acid started to darken (brown) the next day and it continued to do so until the last day of analysis (the 12' day).1. and to veriQ how fastklow the acetone and the phenol react at room temperature when no catalyst is added.0 A)
The intention was to validate these two statements. No crystals were observed on the bottom of the flask.5 ppm -
. at temperatures appropriate for the said process.
The peak at approximately 1.
. at 7.24 ppm
(Pouchert and Behnke. 1993).1 Analysis of the Reaction with Homogeneous Catalyst (after h e e days)
i " "
i " '
.27 ppm is believed to be given by the methyl protons fiom the hydroxyisopropylidene phenol.5 ppm belong to the aromatic protons fiom phenol.59 ppm is given by the
methyl protons in bisphenol (Pouchert and Behnke. The solvent peak appears in the overlapped region. The peak at approximately
hydroxyisopropylidene phenol (the product of the fust step of condensation) (Pouchert and Behnke.7. 1993). 1993).
. bisphenol A. 5.
. 5 3 Analysis of the Reaction with Homogeneous Catalyst (after nine days) .2 Analysis of rhe Reaction with Homogeneous Catalyst (after six days)
These crystals continued to grow. growing in d l directions.Fig. Three months later crystals of BPA were observed on the bottom of the flask. show that bisphenol A is formed when reacting acetone with phenol in the presence of hydrochloric acid at room temperature. meaning that the process of bisphenol A formation continued. They were needle shaped. about 1 cm in length. 5. Figure 5. The reaction mixture used in this experiment was left in the fume hood.5 illustrates the crystals after several rnonths.4 Analysis of the Reaction with Homogeneous Catalyst (after twelve days)
. although not quantitative.
6 represents the NMR spectrum of the sarnple taken from the reaction mixture
with heterogeneous catdyst (AmberlystB 15).Fig.5 Crystais of BPA
Figure 5. The description of the
peaks is the same as the one given for Figures 5.1 to 5.4. after nine days.
the same range of temperatures. This demonstrates that in 15.
. after three days. at room temperature.Fig. the hydrochloric acid is more active with respect to the formation of bisphenol A than the ~mberlyst@ 15.
Figure 5.1 to 5-4.6 Analysis of the Reaction with Heterogeneous Catalyst (afier nine days)
'I r " "
The spectra of the samples taken fiom the reaction with heterogeneous catdyst show that bisphenol A is not obtained when reacting acetone with phenol in the presence of ~ m b e r l y s t ~ under continuous stin-ing. 5.7 represents the NMR spectrum of the sample taken fiom the reaction mixture
with no cataiyst.
. The description of the peaks is the same as the one
given for Figures 5.
The reactions were sampled every 24 hours ind 15
. five reactions were performed in a batch reactor.7 Analysis of the Reaction with No Catalyst (afler three days)
The spectra of the samples taken fiom the reaction with no catalyst show that bisphenol A is not obtained when reacting acetone with phenol at room temperature.1. I .3. The results of the experiment with heterogeneous catalyst and of the experiment with no cataiyst leads to the conclusion that there is no risk of the reaction advancing during the period between the sarnpling and the NMR analysis.Fig.
using Nafion@catalyst. and a molar ratio acetone:phenol of 1:2 (experiments II. I2 11. for a duration of 96 hours. presented in Table 5.2 Evaluation of Experimental Region
In order to evaluate the temperature range and the duration that should be considered for
the reaction. .
5. Ii.4 and 1 .1). 5. 1. since there was no detectable conversion at âny time.
11.the sarnples were analyzed on the GC
. Others are cornpounds found only in trace quantities.2: Results of the second set of experiments Exp.
.14 present the variation of BPA.
.2. and chromanes selectivity with the temperature. OnIy mesityl oxide was detected.MS.
One sample was prepared and analyzed on
the NMR at the end of each reaction as well. O-p isomer.5
1 is bisphenol
24 48 72 96
11. O-p isomer. and chromanes selectivity in tirne. ("Cl
.4-trimethyi chroma. The mesityl oxide was not detected.
Catalyst Reaction Time Conc. 1
11. variation of BPA. Figures 5.4
11. and variation of yield in BPA with the temperature. trimethyl chroman 1 IV is 4'-hydroxyphenyl-2.
Product distribution (wt%) II II[I+NOthers
II.4.8 to 5. II.
The results are presented in Table 5.
Fig.8 Variation o f BPA Selectivity in Time
Fig. 5.9 Variation of Selectivity of O-p lsomer in Time
1 1 Variation of BPA Selectivity with Temperature
. 5. 5.Fig.10 Variation of Chromanes Selectivity in Time
12 Variation of O-p Isorner Selectivity with Temperature
Fig. 5. 5.Fig.13 Variation of Chromanes Selectivity with Temperature
Temperature [ l C
The negative influence of the temperature on the selectivity of the BPA formation can also be observed in Figure 5.8. and as the reaction advances. At 83OC the rate of BPA formation is lower than at higher temperahires. shows that the data for the selectivity of
BPA formation converge. At higher temperatures the weight percent of BPA in the rnass of reaction stays
fairly constant (a small decrease of the weight percent is observed at 92OC and a small
increase at 1 0 2 O C ) because in this case the rate of formation of BPA is higher and the
. which indicates that different temperatures result in a
difference in the rate of BPA formation. variation of BPA selectivity in time. the weight percent of BPA in the m a s of reaction decreases until it reaches a plateau.14 Variation of BPA Yield with Temperature
Temperature [ l C
Figure 5. 5. which is considered to be the equilibrium composition. most of them have a rnolecular weight greater than
BPA. The explanation for this is that although the number of moles
of by-products formed is smaller.1 1. 92OC and 102"C. but not in a difference in mechanism.Fig.
also for a 48 hour reaction the selectivity of O-p isomer formation is slightly ùicreasing.higher amount of BPA formed compensates for the difference in molecular weight between BPA and the heavier products. the temperature has a different effect on the selectivity of O-p isomer formation. and dramatically decreases in Ume for the reaction performed at 102 OC.10 shows that the formation of the chromanes increases in tirne.12 shows that.1. the selectivity of the O-p isomer decreases with increasing temperature.1 are equilibnum data.
The graph presented in Figure 5. As expected.
It is not appropriate to compare the data obtained in this set of experirnents with the data
in Table 2.14. the yield in BPA increases with the temperature and it tends to level off. is constant for the reaction at 92 OC. This can be seen in Figure 5. There is no evidence
. also the temperature has a positive effect on the formation of chromanes. That is: for a 24 h o u reaction. but the effect of temperature is sri11 negligible. Figure 5. and for a 72 hour reaction the selectivity of O-p isomer formation is slightly decreasing. Recall that the data in Table 2. depending on the tirne. the selectivity remains constant. For a 96 hour reaction the effect of the temperature is significant.9 shows that the selectivity of the O-p isomer formation increases in tirne for the reaction at 83 OC. This can be dso seen in Figure 5-13.
3 Scheme of Reaction
Based on the findings in the previous section.
+ O=C. and the condensation of acetone with itself or the dehydration of acetone and some other by-products formation is actually favored.that equilibrium has been achieved. n
Based on the above mentioned conclusions. a scheme of reaction was proposed. C
5. it was decided to run the subsequent reactions for only 24 hours. The
isomer also forms. but at a much lower rate. Therefore the process starts with the condensation of one molecuie of acetone with a molecule of phenol.
CH. Then the hydroxyisopropylidene phenol (ortho and para isomers) formed reacts very fast with a second molecule of phenol.1. for the data shown in Table 5.2. I =?-OH CH . It was also decided that the temperature region to be investigated will be between 82 O and 102 OC. We know that there is still some acetone present i the mixture. leading to the formation of BPA or its O-p isomer.
. The most favored reaction is by far the formation of BPA.
2-hydroxyPhenol i opropylidenephenol s
HF.+H. H. a OH.
C-HC-C-CH. This product can get dehydrated in the presence of acids and form 4-@-hydroxypheny1)-2-methyl-1.2*-isopropylidenediphenol
O-2-hydroxyPhenoi isopropylidene phenol
The mesityl oxide can react with a rnolecule of phenol and form a product of
condensation named 2-@-hydroxyphenyl)-4-methylpent-3-en-2-01.p .
C=O H~/ C
+ O=C.3pentadiene.H3C. C ' + H.
.O H.C/ 0
O M e e l Oxide
H? CH.4 r-isopropyiidenediphenol
II H.l.C O
OH -ZH. 0-0. and the reason for not being
. product which undergoes dehydration and
forms another by-product observed in the final reaction mixture (4-@-hydroxypheny1)-2methyl.2.!H
H3C.4-tnmethyl chroman II
The triphenol formation indicated by the simulation was not confirmed.3-pentadiene).O @. and O-p isomers.3-p entadiene
The mesityl oxide can react with two molecules of phenol and fomi chromanes. 4-01 2-p entanone
This mechanism was based on the observation of the appearance and disappearance of the
product peaks in the chromatograms of the mass of reaction.C . and the result of the reaction between phenol and mesityl oxide (2-(p-
hydroxypheny1)-4-methylpent-3-en-2-01). Some products which were not indicated in the literature.2-methyi. while chromanes were formed. These two cornpounds are the products of the first step of condensation in the process of formation of BPA.4. were obtained. 4-p-phenyl.4-trimethyl chroman 1 2. as expected based on the data found in the literature. The
isopropylidene phenol were not observed in the chromatograms at any t h e . and therefore not considered in the simulation either.
2 C=HC-C-CH. These were the result of the reaction of acetone with itself (mesityl oxide and mesitylene). They are definitely produced.
In most of the experiments.
bisphenol A and the O-p isomer. Also.seen in the chromatograms is that the second step of condensation is very fast. which was determined to be 4-@-hydroxypheny1)-2-methyl. the amount of the bisphenol A (the p-p isomer) was obviously greater than the amount of the O-p isorner produced at al1 tirnes during the reaction. To summarize then.1. The areas of the corresponding peaks indicate that the amount of chromanes in the reaction mixture increases faster than the amounts of mesitylene and 0-0isomer.
isomer and the chromanes peaks appear in the chromatograms
almost at the same tirne.4 and 11.
In some experirnents (11.
. the product of dehydration of 2-@-hydroxyphenyl)-4-methylpent-3-en-2-o1. after 24 hours the only products observed were mesityl oxide. Almost at the sarne tirne another peak appeared in the chromatogram
of the reaction mixture.3 pentadiene.5) the mesityl oxide was observed afier 24 hours and
after 48 h o u . therefore
they are consumed as soon as they are formed. the experimental data strongly support the scheme of reaction proposed in this section.
This last compound was identified
hydroxypheny1)-4-methylpent-3-en-2-01.the product of condensation between mesivl
oxide and phenol. and their production stays at low quantities. but after 72 hours the corresponding peak disappeared and another product appeared in the chromatogram.
0. at 72OC.
Temp.4 Experimental Reproducibility
The experimentai reproducibility was evaluated both qualitative1y and quantitatively during the preliminary nuis. there was no acetone lefi.15.3. and the average of the yield in BPA was 0. The results are presented in Table 5.
Catalyst Conc.1.1. with ~ m b e r l y f l 15 as heterogeneous catalyst. 1 111. at 7Z°C. while the literature indicates that the reaction is first order in acetone.2
10 ~ m b e r l y s 15 t~ ~mberlyst@ 15 10 ~ r n b e r l ~ s t @ 1 5 10
Table 5. The results are presented in Figure 5. with ~ m b e r l y d15 as heterogeneous catalyst.3: Results of the experiments performed with ~ r n b e r l y ç 15 in the batch reactor t~
Exp.37 wt%. The experiments
' were performed in the batch reactor for five hours. The standard deviation was calculated as a rneasure of reproducibility and it was found to be 0. nie intent of this experiment was to examine whether the reaction depletes acetone as predicted by the simulation's results.5 Validity of Simulation Prediction for Depletion of Acetone
One experiment was performed in the batch reactor.5. The difference is most
. The disappearance of acetone indicates that the reaction is zero order in acetone.44
Reaction Time (h)
Acetone:Phenol Molar Ratio
1:2 1:2 1:2
Yield in %PA
III. It was observed that. A quantitative rneasure of the experimentai reproducibility
was also estimated from the replicate runs in the experimentid design. after 10 days.104 wi??.
this set of reactions was
.2 Investigation of Suitability of New Catalysts
Two new catalysts were tried.
The reaction with Amberlyst@15 served as basis of cornparison for the other two. 5. Since the amount of Nafion@ 15
available was small and there was little chance of getting more. 1992) that with higher acidity catalysts the
yield and the selectivity of the BPA formation are increasing. ~ a f i o n @ . including catalyst type and initial reaction stoichiometry .15 Disappearance of Acetone
~ m b e r l y f is the solid catalyst widely used in industry.likely due to different reaction conditions. one was a solid super acid catalyst. The reproducibility of the processes was also verified.
Fig. other one the
was activated alumina acidified with hydrochlonc acid (AA 3 00/HC1). A third expeninent was
carried out using Amberlyst@' 15.
One experiment was performed with each of the two catalysts. These catalysts were selected since it was reported (Singh.
Fig.16 Chromatogram of the Products for the Process Catalyzed by ~ m b e r l y s 15(6 h) t~
. and 5. and the temperature was 70°C.
The purpose of these nins was only to identie the formation of the desired product.MS. The intent was not to obtain a quantitative result.
The chromatograms are shown in Figures 5. 5.
Therefore the values obtained for the yield and selectivity served only the purpose of cornparison of the processes catalyzed by the new catalysts with the process catalyzed by Amberlystm 15. BPA.27.16.
. The reaction mixtures were also analyzed on the GC 5. The molar ratio acetone:phenol was 1:2.performed in N M R tubes to rninimize the quantities of catalysts and reagents used.18.
18 Chromatogram of the Products for the Process Catalyzed by AA 300/HC1(6h)
Scan Ho: 628 Retention Tine: Plcrttud: 1 to 988
.17 Chromatogram of the Products for the Process Catalyzed by Nafion@(3 h)
Fig. 5. 5.Fig.
2.3 Performance Cornparison of Nafione and ~ m b e r l y s 15 t~
In order to compare the performance of Nafion" with ~ m b e r l y s t ~ two expenments 15.01
Product ratios II/I III+~VA 0. by Singh (Singh. the yields in BPA are
0. The results are presented in Table 5.4: Results of performance cornparison between Nafion@and Amberlystm15
Catalyst Reaction Yield tirne (h) i BPA n (wtY0) Product distribution (wt%)' 1 II m+N v
0.31 71. 1992 t See notation in Table 5.21
5.29 15. one with Nafion@. A mumire of 1 5 acetone:phenol was reacted for 27 hours.18
27 ~ m b e r l y s 15" t~ 27 AmberlystB 15 27 Nafion@ " Singh.15 80.one with ~mberlyst@ in the conditions described 15.87 16. Both the yield in BPA and the selectivity of BPA formation are better for the processes that used new catalysts than for the process that used ~ r n b e r l y s t 15.08 25. 1992) and compared with the results claimed by this author.27 4. under heterogeneous catalysis
(20 % catalyst).05 0.28 0.00
The results published by Singh could not be reproduced.The resdts showed that both the ~ a f i o n @ the AA 300/HCl can be used as catalysts and for the process of BPA formation. The two experiments conducted gives better results under the sarne conditions.4.00 4. ~ Comparing the two new catalysts.23 0. but the selectivity of the process is clearly higher in the process catalyzed by
AA 300/HC1. for cornparison show that Nafion@
It is important to realize that a factor is considered controllable by the experimenter if the values of the factor. the test run. process design. It is
an integral component of quality improvement. the noise variables (covariates). and the effect needs to be defined. The factors are controllable variables thought to have influence on the responses. the expenment is simply used to
distuiguish the significant factors fiom the insignificant factors. c m be determined prior to the beginning of the test program and can be maintained at the values required by the experimental design.5.4 Experimental Design
An experimental design is a disciplined plan for collecting data (McLeIlaq 1998). The responses are rneasurable outcornes of interest.
Continuhg with the terminology. The test run is a set of factor level combinations for one experimental nui. also called factors. In many cases. Once these significant factors have been identified. Designed experiments are fiequentiy used in industry in order to detexmine what factors influence the process of interest. These experiments corne in many different forms since the purposes of the experiment may differ fiom situation to situation. and supports improvement in product design. and process operation. other designs c m be used in order to determine the optimum setting for the process. known as levels. be identified dong with the appropriate response variables. The noise variables are variables affecthg
. the extraneous variation.
Designed experiments require that a set of controlled process variables.
The two levels for catalyst concentration were chosen tu be 10% and 20% by weight of the mass of reaction. The minimum number of runs was calculated with the formula 5.
It is desired to conduct a minimum nurnber of runs at each level. temperature (T). and acetone:phenol molar ratio (R).1. the effect of factors on response is measured by change in average response under two or more factor level combinations. 1998):
.2 and 0.5 the size of the inherent noise standard deviation. And finally. and for acetone:phenol rnoiar ratio.the process or product performance which cannot or are not controlled. and on the selectivity of O-p isomer and chromanes formation.05 and a failure to detect probability of 0.4.
5. The magnitude of the
effects to be detected was arbitrarily chosen as 2. Based on previous experimental expenence and simulation results. the levels for temperature were chosen to be 82°C and 102OC. with a fdse detection probability of 0. al1 correlated with data f?om literature. The extraneous variation is the variation in rneasured response values in an experiment attributable to sources other than deliberate changes in the level of the factors. 0.1 (McLellan.1 Factors Chosen and Responses
The purpose of the factorial design in this snidy is to investigate the effects of three
factors on the yield and selectivity of the production of bisphenol A. The three factors are: catalyst concentration (C).5.
4.95 and 0.3
10 1 -1 8 2 1 -1 0.
Table 5. 15
.9 respectively. Typical values for a and Pare 0.
5. [Tl. the minimum number of required is 8.2 ( -1
15 92 0. The detection of effects was considered A = 2 .is the criticai value of the standard normal random variable with upper tail
probability d 2 . range and half range for each factor
High Level Low Level Midpoint Range % Range
C (Y%$%) 20 T(OC) 1102 R(moVrn01) 1 0.5: High value.35
0. 5 ~ . low value.2 Evaluation of Results from Experimental Design
The values of each of the factors of interest were converted to their corresponding coded values. temperature and molar ratio acetone:phenol respectively. and z. low value.5 and the formulae used for coding were (McLellan. The hi& value. range and half range for each of the factors are summarized in Table 5. midpouit. and CR] are the uncoded catalyst concentration. is the critical value of the standard normal random variable with upper tail probability P. Since the proposed design is a two-Ievel factorial design.-. midpoint. 1998):
Ma W f f e c t =
&PC. Nurnber W1.The nuis that were performed in the experimental design are listed in Table 5. 1998).ktor=-. This is calculated as the difference between the average of responses at high Ievel of the factor and the average of responses at low Ievel of the factor (McLellan. Replicate nuis were also executed in order to
v e a the reproducibility of the results.6: Experimental runs w d to investigate the effect of catalyst concentration (C).I VII.
The main effect of a factor is the average influence of a change in level of the single
factor on the response.
C -1 -1
.6 in the
randomized order they were performed.
temperature (T) and molar ratio of acetone and phenol (R).Or=.
. and seffecfis an estimate of the standard deviation of the calcdated effect.a.
**? Am =-.. 1998). and therefore it is not statistically significant.3 Precision of Calculated Effects
The significance of the calculated effects is assessed by estimating the precision of the calculated effect with respect to the factor of interest.
InteractionEfect = YX. where n is the number of runs in the replicate set. . 1998). and it is taken into consideration. equais +1 and . caiculated as the difference between the average of the are
responses at high level and the average of responses at Iow level (McLeIlan. If the confidence interval contains zero.
considering n factors (x.
-y=.1. . a is the desired confidence level (a = O. The interaction effects. Confidence intervals were
constnicted. v = n ..x. the effect is plausibly zero.
Precision = f ty 4/2 * seffeCt
where v is the number of degrees of fkeedom of the inherent noise variance estimate. Standard t-tables and the standard deviation of the calculated effects are required for estimating the precision of each eEect (McLellan.OS). Otherwise it is significant. *x.
5.The interaction is the extent to whch the influence of one factor on response depends on
the level of another factor..1. The difference in calculating interaction effects versus calcuiating main effects is that the high and low level in calcuiating interaction effects actually mean levels at which the product
x. or combination of other factors.
8. 1998).4. two-factor interaction and three-factor interaction effects were calculated for each of these responses and are summarized in Table 5.
. The variance of the calculated effect is e s h a t e d fiom the number of runs in the designed experiment (2'3 and the inherent noise variance (sih ).9. which can be estirnated fiom replicate nins (McLellan. presents the precision of the calculated effects.1 and Table 5.6 (randomized order).The standard deviation of the calculated effect is calculated as the square root of the variance of the calculated efEect. The main effects.
experiment number (Exp.4 Effects Analysis
Table 5. Table 5. #) corresponds to the same designation numbers outlined in Table 5.7 contains the data for ail four responses for the corresponding run.
Selectivity of chromanes .05 13-54 15.37~ I
(m%) 2.2 VIL3 VIL4 VII.Table 5.41b t 1.00 2.00 0.9 : Precision of calculated effects
Response YI(m%) 14.23 64.35 3 .52 Inherent Noise Variance 7.90 63.O5
Table 5. X
vn.69 8.17 26.00 0.26' 1 f 2.26 Variance 2.58 0.69 1.00 11.33b Precision a 95 % conndence. 11 VIL 12
Selectivity of BPA formation.32 7. y
Yield in BPA.O2 73-95 73-97 80.77 16.83 72.10 VII.8 : Calculated effects
Table 5.28 2 1-27
0.53 0.00 10. (WtYo) 70.9 0.00 0.19' 1 6.07 68.44 2.01 21.29 1. formation.10 1.8 VII.584 3.69 Standard Deviation 8-561 t 6.50 2.95 2.35 2.0 1 0.29 9.89 9.42 7.i
WI.72a 1 + 1. y.68 77.5 1 9.00 11.7: Responses for the experirnents performed in the 2 experimental design '
Selectivity of O-pisomer formation.27 71.O3 0.80~
Y4 (m%) 0.00
2-35 10. Y4 (wtO/o)
19-32 30. 5 VU.8 1 0. yz
Exp. 90 % confidence
16.76 2.9 VII.55 78.74 13-47 22.59 27.6 VIL7 VII.56 2.
3+R.19 Effects o f Considercd Factors on Srlectivity o f BPA Formaticn and their Siynificanct:
1 _ _ _ _ 90%
Note: 1-C. The significance of the effects was also analyzed for 90%
Fig.1 Selectivity of BPA Formation
At the 95% confidence level. According to these results. at the specified level of confidence. the temperature was the single factor to significantly affect the selectivity of the BPA formation. the temperature was the only factor that significantly af3ected the selectivity of BPA formation. for the conditions chosen for these experiments.4.
2-T. The temperature is still the only significant factor for the selectivity of BPA formation. the selectivity of the BPA formation will decrease. 7+CTR
. increasing the temperature. acetone:phenol molar ratio and al1 the associated interaction effects were insignificant. The catalyst concentration. The effects and their significance at the wo levels of confidence are presented in Figure 5. 5+CR.4. 6+TR. 5. 4+CT.
. as the acetone:phenol molar ratio is increased.5. The effects and their significance at the two levels of confidence are presented in Figure 5.2 Selectivity of O-pIsomer Formation
At 95% confidence Level.20 Efïëcrs of Considered Factors on Sclectivity of O-p isomer Formation and their Siçnificance
Note: 1+C. 5+CR. 5.4. The effect of the ratio of the reagents is very close to being significant. none of the factors had a significant effect on the formation of
the O-p isomer. the lower the probability that
the formation of 0. the selectivity
of the O-pisomer formation will decrease. This could be explained by the fact that the
lower the concentration of phenol in the mass of reaction. 6+TR. 3+R.20. 4+CT.
and it actually becornes significant at the 90% confidence level.
Fig. since the formation of the p-p isomer is favored in
comparison with the formation of the O-p isomer. 2+T. 7+CTR
According to these results.4.p-isomer will occur.
According to these results. the selectivity of the chromanes formation will increase by increasing the temperature.4. molecules which did
.4. the temperature was the only factor that significantly afEected the selectivity of chromanes formation.21). The hvo-factor interaction associated
widi the catalyst concentration and the molar ratio (CR) and the three-factor interaction
( C m ) were very close to being significant. acetone:phenol
molar ratio and al1 the other associated interaction effects were insignificant. This is explained by the fact that an increase in temperature will result in an increase of the energy of the molecules.
5.3 Selectivity of Chromanes Formation
At the 95% confidence level. The catalyst concentration. at the specified level of confidence. therefore the molecules of phenol will be more likely to react with the etectrophilic substrate in the para position. 5. fonnuig the p-p isomer (BPA). Therefore.OH
Fig.21 Effects Present in the Molecule of Phenol and the Nucleophiiic Attack
As shown in the above figure (Fig. there is a higher density of electrons in the para position. 5.
and the higher the temperature.
According to these results.
The signiscance of the effects was also analyzed for 90% confidence levei. 4+CT.
Aiso the main effect of the molar ratio (R) and the two-factor interaction effect associated
with the temperature and the molar ratio (TR) became significant. also the cyclization of the dimer formed by
dimerization of isopropenyl phenol.not have the energy to react. This is explained by the fact that the more
. 3 4 2 . The effects and their
significance at the two levels of confidence are presented in Figure 5. both leading to chromanes. have higher activation energies than the formation of BPA or its o-p isomer. In this case.22 Effects o f Considcred Factors on Selcctivity o f Chromanes Formation and their Significance
95% conficience 90% confidence
Note: 1-C. will now be accelerated and will be more likely to react. 6+TR.
the effects which were very close to being significant became significant (CR and CTR). 5+CR. the higher the probability of reaction occurrence. the selectivity of the chromanes formation will increase by decreasing the molar ratio acetone:phenol.22.
The reaction of mesityl oxide with phenol.
and therefore more molecules can participate in the first step of condensation. the two-factor interactions associated with the
catalyst concentration and the temperature (CT). The catalyst concentration and the molar ratio of the reagents have significant effects only in conjunction with the temperature. such as the formation of chromanes. the higher the concentration of active sights.
As well. The yield in BPA increases by decreasing the catalyst concentration. at the specified level of confidence.phenol available. also the three-factor interaction (CTR) were significant. This can be explained by the fact that the process has two steps.4 Yield in BPA
At the 95% confidence level. the observation is valid only for the studied range of catalyst concentration. and the temperature and the molar ratio
Accordhg to these results. The higher the concentration of catalyst. In this marner more phenol is
. the higher the possibility of less thermodynamically favored reactions to occur.4. The three-factor interaction effect is also significant.
The analyses performed for 90% confidence level added the significance of the catalyst concentration. This does not mean that the reaction with no catalyst gives 100% yield. the yield in BPA will increase by increasing the temperature.
acetone:phenol molar ratio and al1 the other associated interaction effects were insignificant. The catalyst concentration. 10 to 20% of the mass of reaction.4. temperature was the oniy main factor that significantly affected the yield in BPA.
3-T. and chromanes formation. O-p isomer. and Iess phenol will be available for the second step of condensation.
3-R.5 Regression Analysis
The regression analysis was performed based on the previous results of the experimental design.23 Effects o f Considcred Factors on Yield in B P A and their Significance
Note: l+C.23. 5+CR.
Fig. The effects and
their sipificance at the two levels of confidence are presented in Figure 5. The adequacy of the models was
assessed using F ratio tests. 5. The least squares estimates
for the parameters were detemiined for each model.
4+CT. like the condensation of acetone with itself and others. 6+TR.consumed in the fint step of condensation. Models linear in parameters are fitted to the data for the selectivity of BPA. 7-iCTR
5.4. and for the yield in BPA. Also the high concentration of active sites encourages other side reactions.
the error vector. the surn of squared errors (SSE). The variance of the random error is constant over the range of data collected. The assumptions for the least squares estimation are
(McLellan. The random fluctuations i each measurement are statistically independent fiom those n
of other measurements.
The least square method h d s the parameter values that rninimize the s u . 1998):
TSS = SSR + SSE
3. of squares of
the residuals over the data set.
1. and the total sum of squares (TSS) were calculated w"iththe formulas (McLellan. The form of the equation provides an adequate representation for the data.
In the assessrnent of mode1 adequacy one most often makes the assumption that the
random fluctuations are normally distnbuted.The sum of squared residuals (SSR). The values of the explanatory variables are known exactly.
Therefore the suggested mode1 is:
The T and the Y.5.5.= (TT)-'~ E .1 Mode1 for Selectivity of BPA Formation
The analysis of the effects of the diEerent factors on the selectivity of BPA formation lead to the conclusion that only the temperature has a significant effect on this response.4. T
. vectors are:
In order to calculate the least squares estimates:
The least squares parameter estirnates are obtained as:
10: Results of the Regression Analysis for the Selectivity of BPA Formation
7 377. and the Residual Variance Ratio.60875 1.5519
Coefficients Standard Emr
72.99375 1. = 8. Residual Variance Ratio is compared against F .The parameters for this model are:
The results of the regression are presented in Table 5.-.9406.9874.98134 -5.
This analysis confims
the statisticd significance of the temperature effect. .
Table 5. .370459 52. The significance of this model
was assessed using the Mean Square Regression Ratio.370459 4.37353
It is also straightforward to calculate individual confidence intervals for the parameters.
The results of the regression analysis are summarized in Table 5.. and the
. The Mean Square Regression Ratio is compared against F.4003 287.4003 6 90.15157 15.
.5. w .2 Mode1 for the Selectivity of O-p Isomer Formation
The analysis of the effects of the different factors on the seIectivïty of O-p isorner
formation shows that only the molar ratio acetone:phenol has a significant effect on this response.9406. = 72.99 T
(*3. and the Residual Variance Ratio.
Residual Variance Ratio is compared against F.5. The significance of this model
was assessed using the Mean Square Regression Ratio.9874.
5. = 8. and the Residual
Variance R t o indicates that the model is adequate.
.To summarize. .4.
. Therefore the suggested model is:
j. = 5. The Mean Square Regression Ratio
ht test shows t a the proposed model accounts for significant trend. ~
The least square parameter estimates for this model are:
The results of the regression are presented in Table 5.35) (+ 3. the proposed model is:
(+ value) represents the 95% confidence intervals for the individual parameters.
This anaiysis confirms
the statistical significance of the temperature effect.
The Mean Square Regression Ratio is compared against FI+ .6 1.. =
a.11.. . .
Table 5.13994 0.51375 1-236929 15.01 1032 -7.03)
(it value) represents the 95% confidence intervals for the individual parameters.48375 1.03) (k 3.498563 Erro r Observations ( 8
F SS MS SignifTcance F 1 160.77597 4. Therefore the suggested mode1 is:
.686519 Adjusted R 0.48709 22.48R (+ 3.62491 0.236929 -3. both two-factor interaction effects associated with the molar ratio acetone:phenol (CR and TR).8321 13.
5.01 1032 6 73. the proposed mode1 is:
= 1931-4.11: Results of the Regression Analysis for the Selectivity
Regession Statistics Multiple R 0. and the three-factor interaction effect (CTR).3 Mode1 for the Selectivity of Chromanes Formation
The analysis of the effects of the different factors on the selectivity of chromanes formation shows that the factors that have a significant effect on this response are the temperature (T).43968 12.54041 -4.1 1E-06 16. the molar ratio acetone:phenol (R).634273 Square Standard 3.4.51041 -1 -45709
Regression Residual Total Parameter lntercept R
To summarize.23995 7 234.828565 R Square 0.5.8321 160.27181 I 1 Coeficients Standard t Stat P-value Lower 95% Upper 95% Error 19.
49) (+ value) represents the 95% confidence intervals for the individual parameters. The Mean Square
Regression Ratio test shows that the proposed model does not account for signîficant trend.12. are on the verge of statistical signincance. al1 the parameters.9406.
8. and the Residual Variance Ratio.. This
.O8T .The least square parameter estimates for this mode1 are:
The results of the regression are presented in Table 5. the calculated model is:
j3 = 4. ody the intercept and the temperature coefficient are statistically significant. The significance of this mode1
was assessed using the Mean Square Regression Ratio.
To summarize.08 + 4..49) (k3.1.126TR + 1. except the intercept and the temperature coefficient. .. and the Residual Variance Ratio indicates that the model is adequate.
At the 95% confidence level. Residual Variance Ratio is compared against F.26R + 1. At the 90% confidence levef. and the
The Mean Square Regression Ratio is compared against F.63CTR (k3-49) ( 3-49) ( 3 k 5-49) (+3 -49) (G.63CR .
641529 Square Standard 3.19625 -1 -0501 1.25625 1 -62625
1.5515 I P-value Coefficients Standard t Sa tf
0.571785 2.076303 0.5857 -4.analysis is in agreement with the calculated effects analysis presented in section 5.9.
The intercept and the parameter associated with the temperature are significant.89623 1 1.076303 0.62625 -1.306988
0.7493 -1 -8668
7.12: Results of the Regression AnaIysis for the Selectivity of Chromanes
Regression ~tatistjcs 0.359457 6 1.5857 0.1 9625 -1 .306988 0. d l the
other parameters are not.3
and Tables 5-8 and 5.236785 5 1i 9285 .07875 -1 .505473 01 2 22.19625 3.383506
Regression Residual Total Parameter Iritercept T R CR TR CTR
5 200.409613 1.19625 1.6553 4 .89758 Adjusted R 0.19625 3.359457
0.25625 1.947407 Multiple R R Square 0.236722
4.571785 7.O501 6 1 -19625 1.409613 1.07875 4.403823 0.7493 -1 -8668 -4. al1 the
two and three factor interaction terrns. 2.
.4481 1 7 223. 3105 3.4.236785 51 19285 . It should be considered dropping the molar ratio term. The new mode1 is:
Table 5.403823 0.4.
5.1c+&. both two-factor interaction effects associated with the temperature
(CT and TR).4 Model for the Yield in BPA
The analysis of the effects of the different factors on the yield in BPA shows that the
factors that have a significant effect on this response are the catalyst concentration (C). Residual Variance Ratio is compared against F.
The Mean Square Regression Ratio is compared against F..2~fh.5. The significance of this model
was assessed using the Mean Square Regression Ratio..9406.9874. .5c~~
The least square parameter estimates for this mode1 are:
The results of the regression are presented in Table 5. and the
. Therefore the suggested
.13. and the three-factor interaction effect (CTR).5. 0
+b4. .4. the temperature (T).4~~+d..3c~+k.
the Residuai Variance Ratio indicates that the model is adequate. and the Residual Variance Ratio..
The Mean Square
Regression Ratio test shows that the proposed model accounts for significant trend.
51.003087 0.109144 -1 -96 0.109144
F [ Significance F MS 0.38461 1
The calculated mode1 is:
j.1 09144 1.47) (k0.13: Results of the Regression Analysis for the Yield in BPA
SS 5 88.09531
P-value 0.37689 -5.137889 6.47)(&0.6525 0.0771 11 -1-122111 -0.109144 -0.47) (?0.65C+ l.4.54556
5.2952 0.6878891 1.
5.000379 0.47) (k0.47)
(k value) represents the 95% confidence intervals for the individual parameters.1906 7 88.915 0.005376 17. This conclusion agrees with the data obtained fiom both the literature and the
simulation.1 09144 1-3275 0. A 10% catalyst concentration is preferred.9579 17.48375 Coeficients Standard Emr 5.1.18289 0.1 575 0.47)
(3.2931 5 2 0. Moderate temperatures are
.Table 5.008774 0.4453891 2.026858 0.006692 0.33T
+ l38CT .6271 11 -2.6 Summary of z3 Experimental Design
The results obtained in this experimental design indicate that a 1:2 molar ratio of acetone:phenol in the initial mixture should be used.6075 0.96TR + 1.65863 185.1 09144 1.60522 -17.42961 -1 -49039 1.16279 10. = 5.8578891 1.92CTR
(20.7971 11 0.97832 12.
00 4.57 83.39
. therefore some changes in the significance of the effects of the investigated parameters might appear. the by-products formation.
Eight additional nuis were conducted at the sarne levels as for the first set of experiments (see Table 5. High temperatures influence positively both the formation of BPA and byproducts. The main effects.
+1 -1 -1
+1 -1 +1 -1 +1
80.75 4.3 VIII.00 0.53 14.1 VIII.49
17. two-factor interaction effects and three-factor interaction effects were calculated and are summarized in Table 5.4 W.
5 5 Additional Runs .
TabIe 5.62 1.8
+1 +l -1 -1 -1
T +1 +1 +1 -1
R -1 -1
y.46 0. and the chromanes are produced in much lower quantities than BPA.1).7 VIII. it is also concluded that more experimental points would be necessary to better estimate the parameters for the models proposed for the selectivity of the chromanes formation and the yield in BPA.67 76.62 0.00 81.5
VLII. in other words.Higher catalyst concentrations favor the production of chromanes and O-p isomer.57 9.67 f 72.25 75.2 VIII.02
1 ( 1
1.00 0. but this factor is not significant for the formation of O-p isomer.14 lists the experiments in the randomized order they were performed. Lower molar ratios favor the by-products
formation.00 15.14: Additional runs Number VILI.98 100.89 3.86 15.27 16. The particle size of the catalyst used i this second set of experiments was n smailer.86 71.70 1.00 0.6
0.53 12.00 9.50
2. Table 5.
04 2.83 -2.11 3. there are sorne changes in the significance of the calculated effects for the second set of experiments.58 -3.39 2.means that the ef5ect is significant and negative.37
7.15: Calcdated effects for the additional nuis
Effect Y1 Y2 Y3
C T -8.64 -0.63 -4.83 -2. . the selectivity of the BPA formation decreases.05
As expected. it means that there are more active sites available to cataiyze the formation of the by-products (b).34
space means that the effect is not significant. compared with the fxst set of experiments.97
Table 5.71 0.09
CTR -4.10 5 .
.89 3. The cornparison
n between the two sets of experiments is presented i tabulated form in Table 5. 6 9 0. due to the fact that the catalyst used had a bigger specific active surface. and + means that the effect is significant and positive).15 -0.27 1.74
1.21 3.46 1 1 .34 -1.78 -5.5 2
-9. and increasing its quantity.Table 5.16: Cornparison between the calculated effects in the first set and the second set
The results require explanation: By increasing the catalyst concentration y).95 3.69 -1.84 2.
The fact that excess phenol favors the BPA
formation was mentioned in the literature. or maybe with already formed products. Another noticeable fact is the significance of the two factor interaction effect associated with the catalyst concentration and the temperature.
The explanation might be in the daerence in acidity
It is important to ernphasize the fact that the only main factor that appeared significant for the yield of BPA formation in both 23 experimental designs was the temperature. and the significance of the three factor interaction effect. the
second set of experiments cannot be adopted as a replicate set. the selectivity of the BPA formation
decreases. to account for the two different batches of catalyst. and the coding for the experiments
which used catalyst with smaller particle size was -1 (second set). and contradicted by the simulations and the
first set of experiments. which is explained by the fact that the more acetone in the system. Therefore . Z4 factorial design was considered.6 z4 Experirnental Design
Due to the changes in significance of the effects of the investigated paraneters. and
5. The coding for the experhnents which used
cataiyst with bigger particle size was +1 (first set). the higher the probability that the acetone will react with itself. to yield by-products. The coding for al1
. a new qualitative factor was introduced.By increasing the molar ratio acetone:phenol (3. between the two catalysts.
they were not. The calculated effects are presented in Table 5. and indeed. and their significance is presented in tabulated form in Table 5.12 1 -1 1 O 1 +1 1 +L 1 72. It was expected that the four-factor interaction effects are not significant.18.17 Data for 2' expenmentai design
VII.17.other factors remains unchanged. three-factor interaction effects. and fourfactor interaction effects were calculated and their statistical significance was assessed.76 * Effect associated with the difference between the twc i batches of catalyst
Main effects.19 @la& space means that the effect is not
Table 5. The data for the z4experimental design are presented in
Table 5. two-factor interaction effects.
increasing the catalyst concentration.19: Significant effects
According to these results.significant. and + means that the effect is significant and positive).
. This is due to the fact that higher catalyst concentrations translate into more active sites capable of catalyzing the process. increasing the probability of already formed products to M e r react. the selectivity of BPA formation will decrease. and. and the selectivity of chromanes formation will increase.18: Calculated effects for the 2' design
Table 5. to form more chromanes. in this case. .
Table 5.means that the effect is significant and negative.
The effect of temperature is significant for the selectivity of BPA and chromanes formation. the higher the selectivity of chromanes formation.7. the lower the selectivity of BPA formation. and the combined effect is an increase in the selectivity of the chromanes formation and in the yield in BPA.
if the temperature and the particle size increase simultaneously.
5.1 Model for Selectivity of BPA Formation
Based on the significance of the calculated effects. but also more by-products are formed. The higher the temperature.
since smdler paaicle size means that the active sites inside of the catalyst bead are not as accessible as in the case of the bigger catalyst beads. This is explained by the fact that a higher temperature increases the reactivity of the system. and the higher the yield in BPA. the result is an increase in the reactivity of the system. and
hs the yield in BPA increases. If the particle size and the molar ratio acetone:phenol are both decreased. the combined effect is an increase in the selectivity of BPA formation and a decrease in the yield in BPA. More BPA is formed.) is:
. the proposed mode1 for the selectivity of BPA formation (y. and for the yield in BPA. T i effect is similar to the catalyçt concentration eEect.
Increasing the particle size of the catalyst the selectivity of BPA formation decreases.7 Regression Analysis for the z4Experimental Design
. particle size-N. .1 122. = 3.46 .97 compared with -1 1.69) (k2..
It can be noticed that the effect of the temperature on the selectivity of BPA formation is slightly smaller in the case of the combined design in cornparison with the 23 design (-
8.0B5 4. and the Residual Variance Ratio. = 76.3.43C . 6 9 ) (52.The parameters for this model are:
The results of the regression are presented in Table 5. and interaction effect associated with the molar ratio of the reagents and the particle size-RN).335N + 329RN
(52.69)( S ..49T .69) (f2.4.
The Mean Square Regression Ratio is compared against F1. In the combined design other factors become significant
(cataiyst concentration-C.99). The significance of this model
was assessed using the Mean Square Regression Ratio.
The calculated model is:
.20.6001 and the Residual Variance Ratio is compared against F.69) (+ value) represents the 95% confidence intervals for the individual parameters.4.
2.651 14 -1 -23886 -2.20: Results of the Regression Analysis for the Selectivity of BPA Formation
) 0.67489 -6.1454 -0.7746 79. the proposed model for the selectivity
of chromanes formation (y.26886 -5.9971 1182.7446 -6.778371
261.81791 t Sfat 62.53665.0% Upper 90.29261 -1 -66011 5.2 Model for Selectivity of Chromanes Formation
Based on the significance of the calcuiated effects.1 6915 -1 -79835 -6.1 154 -7.0091 35 0.22009 1.621 14 -6.47864
5.22009 1.136 Standard Emr 1.042391 1.694473
P-value Lower 95% Upper 95% Lower 90.020862
73.66751 -2.7.) is:
The parameters for this model are:
.67493 -3.1 5653 2.096361
74.22009 122009 1.1 2E-15 0.22009
23.602099) 5.01 693 0.Table 5.81 127 -3. -1-16585 0.003658 0.
6001 and the
.300925 2.49451 6
Upper 95% 4.1 19234 0.639385 2.013125 0.201875 0. .082Ol6 -2.681 559 1-524375 0.365325 -2.040746 O.21313 0.681 559 1 2. The significance of this mode1
was assessed using the Mean Square Regression Ratio.. and the Residual Variance Ratio.000844 0.16).005766 0.030734 2.
The effect of the molar ratio (R) becomes
.32371 7.600625 -1-77993 TR -1.
Table 5.4371 75
0.348475 0.012661 0.13 compared with 8..726238
MS SS 5 234.683266 0.681559 T 2.6815591 2..0 144-43
Lower 95% 1.065625 0.681559 CR 1.547016 O.
Residual Variance Ratio is cornpared against F.966575
Upper 90.1 122.o.0% 4.042984 3.96599 1 O 74. .236599 C 3.953704 TN
F Significance F' 6-349112 0. IO544 0.The resdts of the regression are presented in Table 5.248425
The calculated mode1 is:
It can be noticed that the effect of the temperature on the seIectivity of chromanes formation is two times smaller in the case of the combined design in cornparison with the
î3 design (4.305484 3.830325 0.44843 0.049288 0.777825
90.1536 1 Total tStat Parameter Coefficients Standard Enor I 4.8299 46.697866 lntercept 3..21.584234 3.759675
3.731 73 0.835925 0.
1. = 3.432371 Residual 1 5 309..022175 3.
The Mean Square Regression Ratio is compared against F.006741
0.21: Results of the Regression Analysis for Selectiviq of Chromanes Formation
Adjusted R Square Standard Observations
The significance of the two factor interaction eEects (CR and TR) is almost the same for both 2) and designs..
Based on the significance of the calcdated effects. The three factor
interaction effect (CTR). which appeared in the 2 design. The new model is:
5 7 3 Mode1 for Yield in BPA . the proposed model for the yield in
BPA (y. loses its significance in the Z4 design.insignificant in the combined design.
The parameter for the two factor interaction associated with temperature and molar ratio
acetone:phenoI is not significant and its deletion is considered.) is:
The parameters for this model are:
. In the combined design the two factor interaction effect associated with the temperature and the particle size (TN) becomes significant.
372053 -3..968634 -0.956016 0.372053 -2.024603 -1-94102 -0.747384 -0.372053 2.372053 0.O6125 0.953169 R Square 0.
= 4.2525 0.041484 1.803994 Square 1-488213 Standard
lntercept T R N
CT TR TN RN CTR
F SS MS SignKcance F 8 153.371 366 1.588984 2.54762 1.947687 0.691 023 0.164766 -0.763866
Upper 90.396691 0.337616 -1 .558866 -1.004978 7 15.801016 0.92125 0.1 122.1435161 0.023226 0.41988 0.651484 5.17903 5..989884 1.372053 3.7 96484 1.372053 2.216366 1.2361 34 0.173634
The proposed mode1 is:
.892731 0.50345 2. The significance of this model
was assessed using the Mean Square Regression Ratio..37273 -1-95738 1.781 134 1. = 3.0425 0.026447 0.18148 -1.01 19781 -2.59477 1.01 149410.9895 19.22: Results of the Regression halysis for the Yield in BPA
Regression Stafistk 1 I Multiple R 10.214779 15 169..922266 0.85241 0..476124 0..493 Coeficients Standard t Stat P-value Lower Lower Upper Emr 90.90853 Adjusted R 0.348516 0. The Mean Square Regression Ratio is compared against F..
TabIe 5.36645 0.766019 0.
.531 25 0.O7625 0.24869 8.The resuits of the regression are presented in Table 5.-.76E-06 3.005548 0.802018 0.35637
2.383984 2.468703 -0.6001 and the
Residual Variance Ratio is compared against F.26375 0.372053 2.0% 5.826366 0.372053 3.22.7661 3 1-46875 0..626134 1.41 1016 3..285 0. and the Residual Variance Ratio.04245 0.162734 1.1 3227 -0.372053 12.0% 95% 95% 4.
51 n compared with -3. factor interaction effect associated with the temperature the two
and the particle size (RI).The effect of the catalyst concentration ( C ) becomes insignificant in the combined design. The two factor
interaction eEect associated with the temperature and the molar ratio of the reagents (TR) is smaller in the case of the combined design i comparison with the 2' design (-2. also the variation of BPA and by-
. and experimental reproducibility. catalyst concentration.
This chapter presented the results obtained for the experiments performed in the NMR tube and in the batch reactor. blank reactions. and molar ratio acetone:phenol in the
initiai reaction mixture were examined in depth. A scherne of reaction
was set up.09 compared with 2. the particle size 0. and the two factor interaction effect associated with the molar ratio of the reagents and the particle size (RN).66). The effect of the temperature on the yield in BPA is just slightly srnaller in the case of the combined design in comparison with the 2' design (2.92). These experiments investigated and evaluated the reactivity of the system. In the combined design some factors become significant: the molar ratio
(R). New catalysts were tested and found suitable
for producing BPA. The significance of the two factor interaction effect associated with the catalyst concentration
' and the temperature (CT) is almost the same for both z3 and 2 designs. The three factor interaction effect (CTR) is significant in both z3
and z4 designs. based on the results obtained.
The effects of temperature.
Harmer et al. the
n yield i BPA is higher. This can ih
be explained by the fact that the occurrence of swelling of the smalier particles of catalyst
was insuffkient and the access of the reagents to the acidic sites inside the catalyst
particle w s reduced. a 10 wt% catalyst concentration and a 1:2 molar ratio acetone:phenol.
The examination of the experimental design provides a better understanding of the operating conditions and the effects the chosen factors have on the system under investigation.products formation and the variation of the yieId of BPA with respect to t h e were analyzed. and a stoichiometric ratio is defïnitely preferred. which confirms the simulation results and contradicts the data in the literature.
The particle size of the catalyst beads also influences the production of BPA. but so is the formation of chromanes.. The initial molar ratio of acetone and phenol is significant only for the yield in BPA. 1996 indicate that the accessibility of the active sites a inside the catalyst can be improved by using as catalyst a new rnaterial instead of the
The analysis of the results obtained in the 2" experimental design indicate that a moderate temperature is desirable. The results were compared to data obtained fiom Literature and simulation. Larger
amounts of BPA were obtained with the cataiyst with bigger particle size. At temperatures close to the upper limit of the experimental range.
The purpose is to maximize the amount of BPA produced while
minimizing the number and the amount of by-products produced. and better selectivities of the BPA formation w t the catalyst with smaller particle size. This fact c o b s the
fîndings in the literature and the simulation results.
The intent of these experirnents is to take M e r the investigation of the process
of BPA formation and to identiw Iines of future work.that is Nafion" SAC-13. which is essentially silica irnpregnated with the basic smictural polymer ~ a f i o n ? T i new material seems to hs fomuiately combine the benefits of the porous structure of the silica and the super acid capabifities of ~afion".
The next chapter presents the results of the experiments performed in the plug flow reactor.basic stmctural polyrner Nafion@.
24 24 24 24 24
Flow Rate Temperature Acetone:Pheool Molar Ratio Wh) (Oc)
AA 300/HC1 Nafion@ NR-50 Nafion@ NR-50 NafionmNR-50 Nafion@ SAC-13
92 102 102 102 92
1:2 1:s 15 15 1:2
.1). Al1 the experiments presented in
this chapter are summarized in Table 6.
Table 6. and bJafïonmSAC.1: Summary of the experiments
Exp. 1 X.8 4.2 X.Chapter 6
Reactions in the Plug Flow Reactor
Preliminary results obtained in the experiments performed in the plug flow reactor (PFR)
are presented and discussed in this chapter (see PFR diagram in Figure 4.13.0
catalysts used for these
were: activated alumina acidified with hydrochloric acid
(AA 300/HCl).2 X.8 4.3 XI.0 4.8 4.
.overnight.1 Reaction with Acidic Activated Alumina
Several experiments were tried with AA 300/HC1 in the batch reactor.
The product was cloudy. that regulated the power of the heater. the quantity produced was small. Although a BPA peak was observed. The reaction was stopped after 24 hours. Two reactions were performed using as catalyst activated alumina acidified with hydrochlonc acid (AA 300MC1)-
For the first reaction. at 102OC. The catalyst was dried in the reactor with hot nitrogen (105"C).6. M e r separation. at a rate of 4.8 cch. The temperature was maintained constant during the reaction. The activated
alumina was not robust enough to withstand mixing and it crushed. by means of a thennocouple located in the catalyst bed. No other products were observed. attached to a PID (proportional-integral-derivative) controller. This is the reason
why a plug flow reactor was necessary to Uivestigate this system. The reactor
was fed with a 1:5 initial mixture of acetone and phenol (molar ratio) using a syringe
pump previously calibrated. a 8 1 mesh AA 300 was acidified for two hours with a 2:l x4 solution of hydrochloric acid and water (volurneiric proportion) at room temperature. a sarnple was anaiyzed on the GC-MS. but only after half hour the reaction mixture became cloudy and the reactions were stopped.
that regulated the power of the heater. III is 4'-hydroxyphenyl-2. some modifications were considered. at 92"C. II is 2. The o d y product observed in significant amount was bisphenol A. The results are presented in Table 6.4. at a rate of 4.8 100.0 cch.79 100. a second experiment was performed.
With the intent of increasing the yield in BPA. The reactor was fed with a 1:2 initial mixture of acetone and
phenol (molar ratio) using a syringe pump previously calibrated.2 4. trimethyl chroman 1 IV is 4'-hydroxyphenyl-2.0 1.4. V are other byproducts.00 0. Yield Reaction Molar Flow Time (h) Ratio cc/h O C 1 n III+N V wt% 102 0. A 1:2 molar ratio of
rm the initial reagents was preferred. by means of a thermocouple located in the catalyst bed.5 0.2.2: Results of the experiments with AA 3001 HCl
Exp. The catalyst was dried ovemight in the reactor
with hot nitrogen (105°C). based on the conclusions f o the previous
investigations.00 IX.4'-isopropylidenediphenol.00 0. attached to a P D controller.00 IX. The temperature was maintained constant during the reaction. 1 24 4. The changes in process conditions were intended to increase the activity of the cataiyst and the retention time in the reactor.00 24 1:2 ' I is bisphenol A.2. #
Product Distribution' (wtO/o) Temp.
The yields in BPA obtained in these two experiments are comparable to the yields
obtained for some of the experiments presented in the previous chapter (experiments
.00 92 0.00 0.00 1:5 c 0. 20 grarns of a 14x18 mesh AA 300 were acidified for two hours with concentrated hydrochloric acid at room temperature.Taking into account the resdts of the first reaction.
Table 6. The reaction was stopped after 24 hours. Both variables were changed to increase the contact time between the catalyst and the reagents.4-trimethylchroman II.
The reaction was stopped after 24
catalyst was dned prior to the reaction with Nz at 105OC.
6. attached to a
Two samples fiom the fist reaction were prepared and analyzed. 11.2 Reactions with Piafion@ NR-50
The reactions with Nafion@NR-50 (the basic polymer) were performed at 102OC.
nie reason for the separation is believed to be the fact that the catdyst was not washed
and dried well enough after regeneration. a light one and a dark one. 1. higher than the selectivity obtained in any previous experiment These prelirninary results prove that acidified activated alumina is a suitable catalyst for the production of bisphenol A. VIII. W . 5 . The temperature was maintained constant during the reaction. the other one on the NMR. VIII.6. at a rate of 4. using a syringe purnp previously
calibrated.7). at 50°C.8 cch.WI. which was allowed to flow through the catalyst bed at a rate of 20
cc& for six hours. therefore an aqueous and an organic layer
. one on the GC-MS. The reactor was fed with a 1:5
initial mixture of acetone and phenol (molar ratio). VIII. Both layers were analyzed on the GC-MS. Between the two reactions the catalyst was regenerated with a 15% solution of niûic acid. The product fiom the second reaction separated hto two layers. that regulated the power of the heater. at 102"C. VIII.
The selectivities obtained in the
experiments performed in the PFR using AA 300/HC1 as catalyst are 100%. by means of a thermocouple located in the catalyst bed.
O C 102 102 102
A third experiment was tried with the sarne catalyst.00 X. The reason appeared to be the fact that the polymer particles swelled and expanded to the extent that they almost formed a block inside the reactor.2 31.8 24 1 5 4.53 0.2 " 1O 0 x. and obtained oniy in the reaction performed with regenerated catalyst. 1 4.00 0.17 7. Another possible and interesting experiment to examine is to mix the Nafion@ NR-50 with acidified activated alumina. This situation might be solved by mWng the Nafion@NR-50 particles with g l a s beads.00 60. Besides solving
. The product
Table 63: Results of the experiments with ~ a f i o n NR-50 @
Exp.1 1 82. No BPA or any of its isomers were detected in the light colored bction.37' a Light colored fraction of the product in the second reaction Dark colored fiaction of the product in the second reaction Products unidentified. but it was stopped because the
pressure was building up rapidly.existed in the system.97 0. distribution and yield for both reactions are presented in Table 6. without leaving any space for the reactants or the nitrogen to flow through. Also the presence of the nitric acid made possible the formation of some nitro compounds.3. Some BPA. to ensure the flow space in the reactor.8
Temp.63d 20. which were observed in the light colored fiaction. believed to be nitro derivatives Selectivity of BPA formation.00 0.86 79. if the unidentified products are not taken into
Reaction 1 Molar Flow Time Ratio c c 5 24 4. #
Product Distribution (wt%) wt% I II III+TV V VIc X.8 15 24 i:5 4. if the unidenîified products are not taken into account Selectivity of o-p isomer formation. 0-0 isomer and o-p isorner were observed in the dark colored fraction.47 17.
the flow problem inside the reactor. at 9SaC.
The phenol used in this reaction was not the liquid form as for al1 the other experiments. since the drying process can occur ordy at temperatures above 100aC. was arbitrarily chosen
between 105°C and 160°C. The reactor was fed with a 1:2 initiai mixture of acetone and
phenol (molar ratio). that regulated the power of the heater.
This new materid combines the benefits of the porous structure of the silica with the
super acid properties of ~ a f i o n ? The purpose of this reaction is to evaluate 60m the qualitative point of view the suitability of this new material to catalyze the production of bisphenol A. one couid also snidy the combined effect of the two cataiysts on the process of BPA formation. by means of a
thermocouple located in the catalyst bed.0 cch. at a rate of 4. 155"C. The reason for this was that a1 of the liquid phenol l
.3 Reaction with ~ a f i o n @ SAC-13
~afion@' SAC-13 is essentially silica impregnated with the basic polymer Nafion@ NR-50.
The reaction with Nafion@ SAC-13 was performed at 92OC. using a syringe pump previously calibrated.
The crystals form was used instead. The reaction was stopped after 24 hours. attached to a P D controller.
The temperature was maintained constant during the reaction. The catalyst was dried prior
to the reaction with N. and on the instructions that came with the catalyst drying temperatures under
160°C were indicated. The drying temperature.at
and Fisher Scientific stopped distributhg this product. 1974).4: Results of the experiment with ~ a f i o n @ .
1 Exp. and BPA.
Product Distribution (wtY0)
This reaction proves that bisphenol A can be obtained in a process that uses Nafion@ SAC
13 as catalyst. besides BPA. 1 Reacîion 1
Molar ( Flow
The only products observed were mesityl oxide.4. the other one on the NMR. the water content in this system was lower and a decrease i the yield was expected. Further investigation is
required to see if the reactor configuration and the catalyst are feasible for commercial production. The fact that only mesityl oxide and 0-0 isomer were obtained. but they do not fiunish the phenol in liquid fom. with 9% water as impurity. The yield obtained in this experiment is comparable with the yield
obtained in experiment VIII. Two samples were prepared and analyzed. since it was found in the n Iiterature that about 10% water in the initial reaction mixture increases the rate of the reaction (Scheibel.was consurned. one on the GC-MS.1 and the selectivity obtained is much lower than the selectivities obtained in any of the previous experiments. in very s m d
quantities. The product distribution and the yield for the reaction are presented in Table 6.
Table 6. because they could
not stabilize their b ~ c h e s . As a result. Other suppliers were contacted.
. were found suitable to catalyze the production of bisphenol A in a flow system. Nafion@NR-50.
This chapter presented the results obtained for the experiments performed in the plug flow reactor.indicates that an excess phenol and a lower ternpenture might be more appropriate for
The next chapter presents the final conclusions of the present study and identifies
directions for future investigation. These experiments investigated the siiitability for producing bisphenol A of
~ r new catalyst. the retention tirne. the molar ratio of the initial reagents in the feed. that could not be investigated in the batch reactor. and the type of cataiyst seem to be factors that significantly influence the process of BPA formation.and Nafion@SACU
phenol and acetone as starting materials. Keeping in mind that the motivation for this work is
the production of bisphenol A via catalytic distillation. The temperature. the next step is to optimize the
reaction configuration in the plug flow reactor. also studied the behaviour of the Nafion@
A three new catalysts: acidified activated alumina. These experiments o
NR-50 in the plug flow reactor.
The synthesis of bisphenol A @PA) with heterogeneous catalysts was investigated in a batch system and in a plug flow reactor. The resdts of this investigation are surnmarized below. Experiments were conducted with ~rnberlyst@'
15. ~afïon@' SAC-1 3. but so is the formation of chromanes. This fact confirms the findings in the literature and the simulation results.
Both the simulation and the experirnental work indicated that the species present in the system are remarkably reactive in the provided conditions. and activated alumina acidified with concentrated
hydrochlonc acid (AA300/HCl). A t temperatures close to 100°C the yield in BPA is higher. It was also shown that the stoichiometric ratio acetone to phenol (1:2) represents a better choice for operation instead of excess phenol as mentioned in the literature. Gibbs reactor simulations were also conducted. Nafion@NR-50. The results indicate that a moderate temperature and a 10% catalyst concentration are desirable.Chapter 7
Conclusions and Recommendations
the closer to the stoichiometric ratio. the higher the yield in BPA. the retention t h e . and better selectivities of the BPA formation with the catalyst with smaller particle size. the molar ratio of the initial reagents in the feed.
The particle size of the catalyst beads in the case of Nafion@NR-50 also influences
the production of BPA. Larger amounts of BPA were obtained with the catalyst with bigger particle size. The temperature. The experiments were done in a stirred
batch reactor under continuous reflux.
The results of the Z4 experirnental design are
z4 experimental design was
. Nafiof NR-50. using Nafion@NR-50 as catalyst and acetone
and phenol as starting matenals. using phenol and acetone as starting matenals. 2. and ~ a f i o n @ SAC-13. were
found suitable to catalyze the production of bisphenol A in a flow system. and the type of catalyst are factors that significantly (in a statistical sense) infiuence the process of BPA formation. The selectivity of BPA formation decreases by increasing the catalyst concentration. The selectivity of chromanes formation increases by increasing the catdyst concentration.The initiai molar ratio of acetone and phenol is signifiant o d y for the yield in BPA.
Ml three new catalysts: AA300/HC1.
The significance of the three factor interaction involving the catalyst
5. The selectivity of the BPA formation decreases by increasing the particle size
of the catalyst bead.
4. The selectivity of chromanes formation increases with increasing temperature.
The available results indicate that the operating conditions that rnaximized the
quantities of bisphenol A and muiimized the quantities of by-products are: a
. the combined effect is an increase in the selectivity of BPA formation and a decrease in the yield in BPA. The yield of the process increases with increasing the size of the catalyst bead. the temperature and the initial molar ratio of acetone and phenol indicates the possibility that an optimum might exist in the operation of the system. The yield of the process increases with the temperature.
7. and the combined effect is an increase in the selectivity of the chromanes formation and in the yield in BPA. since smaller
paaicle size means that the active sites inside the catalyst bead are not as accessible as for the larger catalyst beads. If the particle size and the molar ratio acetone:phenol are both decreased. The higher the temperature the lower the selectivity of BPA formation. the result is an
increase in the reactivity of the system.
6 . If the temperature and the particle size increase simultaneously.
This effect is similar with the catalyst conceniration eEect.
No chromanes were obtained in any of these two experiments. The choice of the catalyst type effect wodd be of great
7. and 9. since the demand of high purity bisphenol A on the market is constantly increasing. Also the effect of the water content in the initiai reaction mixture is a factor requirhg investigation. higher
selectivities for this process is critical. Future experirnents should be conducted to investigate the effect on yield and selectivity of compounds containing mercapto groups.
.09g BPA/100g crude.temperature of 82"C.98% for the experiment performed with catalyst
with catdyst with smaller particle size). compared to 76. catalyzed by ~ r n b e r l y s t ~ While the importance of a better yield is obvious.55%.2 Recommendations
Future experiments to investigate the synthesis of BPA should be continued in the plug flow reactor. The experiment performed with catalyst with larger particle size had a higher selectivity of BPA formation (84.
The significance of this work is that the yields and the selectivities obtained for the
processes conducted with the newly identified catalysts are better than for the process
15.79g BPN100g cmde respectively. The quantities of BPA obtained in these two cases were 9. and the separation and purification processes for obtaining higher punty bisphenol A are complicated and costly. a molar ratio of 1 2 acetone:phenol in the initial reaction
mixture. and a 10% catalyst concentration. for both the catalyst w t smaller particle ih
size and the catalyst with bigger particle size.
Shell Ltd.The resdts indicate the possible presence of an optimum within the ùivestigated
experimental region. by getting them invo lved in the research project. Two
reasons contributed to this hstration:
1. Complete separation was not possible for the chromanes. These standards could be obtained fiom a big producer of BPA. the use of high pressure liquid
chromatography is advisable.
. Further experiments should be performed to verie the presence of the optimum and to identiQ the optimum.
One of the most hstrating parts of this work was to find a method of analysis. The search for the o p h u m imply an elaborate experimental
2. for example. Most of the by-products obtained in the process were not available as
standards. as is the use of standards for calibration. in case it exists.
In order to overcome these difficulties.
safety glasses and appropriate gloves whenever handling these materials. and it provided a barrier against toxic vapors. The bunker shielded the experimenter fiom debris in case the pressure would have increased and run out of control. The batch reactor was installed in the fiune hood.l was obtained Erom the MSDS for the respective chemicais. The fume hood
shielded the experimenter fiom splashes and protected against toxic vapors. Table A. The information in table A.Appendix A: Health and Safety Considerations
The ex~erimental aspect of this research entailed several safety concerns which had to be de& with. Standard laboratory procedures required the mandatory use of lab coats.
. Al1 the components used or produced in the reaction could have been hamiful in sufficient quantities. except the solid catalysts.l lists the components used or produced in the reaction. and the PFR was installed
within a c o n t h e n t bunker to reduce the possibility of incidents. hazards associated with these components and the suggested safety requirements.
Nitric acid 1 toxic and corrosive 1 protectiodLab coat
. 1 Neoprene gloves/Eye 1 toxic and corrosive 1 ~rotectiodLab coat * Latex glovesEye protection Skin and severe eye irritant Amberlyst 15 Polyvinyl alcohol gloves/Eye Severe eye and skin irritant. Deuterated chloroform protectiofiab coat toxic and carcinogenic Neoprene gloves/Eye Severe eye and skin irritant.l: Chemicals used in experiments. narcotic. Neoprene gloves1Eye Bisphenol A protectiodLab coat toxic Latex g1ovesEye protection Asphyxiant Nitrogen Latex glovesEye protection Mild eye and skin irritant ~afion@' Latex gloves/Eve * protection Not hazardous Activated alumina Hydrochloric acid 1 Severe eye and skin irritant. flammable Neoprene gloves/Eye Phenol Severe eye and skin irritant. associated hazards and safety requirements
Safety Requirements Hazards Skin and eye irritant.Table A. Latex gloves/Eye protectiodLab coat toxic. toxic. carcinogenic Mild eye and skin irritant. protectiodab coat narcotic.
ratio and temperature were the oniy factors changed at each nui.
The flow sheet for the simuiation is:
. 1 contains the input file used for the simulations.Appendix B: PRO/II@Input File
The simulations were run using a windows based version of PROLI'.
15 CNUM 5. COMPOSITION(M)=2. COMPONENTS=1.111(3).-3. STDTEMP=273.l:
PRODI" Keyword Input File
Generated by PRO/iI Keyword Generation System <version 2. I S O T H E W PARAMETER PHYSPROP=1 ELEMENTS REACTANTS= 1/2/3/4/5/6/7.15/5.75.ACETONE/3 .16.9OO(2). STDPRES= 101. 1ZOO(l l).15 ZNUM 5.6. TVP=3 10.93 COMPONENT DATA LIBID 1. SET-NRTLOI.1.Table B.6/4.9O3(2) NBP 4. ENTROPY(L)=SRK.2. NAMES=H.-14 FORMATION(V. 1200(8). 1.15.16. PHASE=M.18/ & 18.104.22.168.6928E5 T'HERMODYNMC DATA METHOD SYSTEM=NRTL. & RATE(M)=45 -3593.O/2.1225(2).325 SEQUENCE SIMSCE CALCULATION RVPBASIS=APIN. TEMPERATURE=343.02-14-95> E Generated on: Thu Oct 09 15:39:38 1997
rITLE DIMENSION SI.2. SET=DEFAULT UNIT OPERATIONS GIBBS UID=Rl FEED S l PRODUCT M=S2 OPERATION PHASE=M.15/6.900(3).Triphenol.Chroman/7.O.15.BSPHNOLA FILL=SIMSCI NONLIB 5.PHENOL/4.90 1(1).383.71 .6034 N M P 5.M) 5. STRUCTURE 5.20. 1201(2).493 SOLUPARA 5.111 (2).Isopropylidene/6. 1201(4).26.655(1)/ & 7.2.3/ & 3.9.lîOO(8).9OO(4).9O3(1)/ & 6.C END
. & NORMALIZE.H20/2.6.li 1(1).24.25/3. & DEFAULT STREAM DATA PROPERTY STREAM=S 1.
o. The initial reaction mixture consists of acetone and phenol only.p-isomer. ogisomer ( I .
Bisphenol A (
. og-isomer.Appendix C: Summary of Simulation Results
The following 5 tables show the moi percent content of bisphenol A. at 1 atm. and triphenol in the final product Stream as a function of temperature and molar ratio over the considered range of temperature. The final table shows the variation of
selectivity of bisphenol A (I).1: Variation of bisphenol A.
Table C. I and triphenol (III) with the temperature at ) various acetone:phenol molar ratios. The results are presented in mol %. and triphenol formation with the acetone:phenol molar ratio at 323.15 K.
The results are presented in mol %. o. and triphmol formation with the acetone:phenol rnolar ratio at 333.
* The equilibrium was not achieved.15 K. and triphen01 formation with the acetone:phenol molar ratio at 343.2: Variation of bisphenol A.15 K. o.p-isomer.
the 50 iterations.3: Variation of bisphenol A.
The numbers r lect the result obtained at the end of c
.Table C. The resdts are presented in mol %.p-isomer.
o.15 K.0006 0.0 156 0.0305 0.1336 0. and aiphenol formation with the acetone:phenol molar ratio at 3 63.-
0.1 5 K.060 1 0.
.Table C. The results are presented in mol %.0074 0. and triphend formation with the acetone:phenol rnolar ratio at 353.p-isomer.4: Variation of bisphenol A.0028 0.
Table CS: Variation of bisphenoi A.p-isomer. The results are presented in mol %. o.
III 0.p-isomer (I.
Molar Ratio Ac:Ph 0.00
. and triphenol I) (III) with the temperature at various acetone:phenol molar ratios. o.77
Variation of selectivity of bisphenol A ( ) I .15
1993). OR. Protons farther removed fiom such groups. thus requiring a slightly lower value of v.. rad/s). These variations are calied chemical shifts and are commonly expressed in relation to the resonance of the tetramethylsilane (TMS) as the zero of reference. of fiequency vo. OCOR.
Do1 Magnetic Energy Levels and Transitions
When the spin quantum number 1 of a nucleus is nonzero. cailed Zeeman levels. Protons attached to or near electronegative groups such as OH. COOR. which shields the nucleus against the magnetic field. 1993).2 The Chernical Shift
Resonaxce occurs at slightly different fiequencies for each type of proton.Appendix D: The NMR Phenomenon
Nuclear Magnetic Resonance (NMR) spectroscopy is a method of great interest and importance for the study of chemical substances. to achieve resonance than for a bare proton (Sanders and Hunter. Transitions between energy levels occur when the fiequency of the rf field equals the Larmor precession frequency (Sanders and Hunter. The proton ('H) has a spin 1 of X. as in hydrocarbon chains. This variation is caused by the cloud of electrons about each nucleus. = 2nv0. The use of puised Fourier transform methods with spectnim accumulation made it possible to obtain high resolution spectra (Sanders and Hunter. This condition is met if the mass number and atomic number are not even. a nucleus undergoes Larmor precession about the field direction at a rate given by v. A way of picturing the resonance phenornenon e s e s fiom the fact that when placed in a magnetic field. and halogens expenence a lower density of shielding electrons and resonate at higher v. depending on its chemical binding and position in a molecule. nuclei with nonzero 1 occupy quantified magnetic energy levels.
D.. The total range of proton chernical shifts in organic compounds is on
. The relative population of the Zeeman levels are normally given by a Boltzmann distribution. 1993). resonate at lower v. the number of which is equal to 21 + 1 (Sanders and Hunter. the nucleus possesses a magnetic moment. or a. o. 1993). ( a o is the resonant fiequency. Transitions between energy levels can be made to occur by means of a resonant radio r) fiequency (f field B. When placed in a magnetic field of strength Bo.
therefore they do not have a visible effect. the separation of chemically shifted resonmces. and so on. Rapid tumbling of the molecde does not reduce this interaction to zero. The 13c abundance is very small. If Bo can be made very homogeneous over the sample.
D. as common. If the nucleus has n suffIcient1y close. This is indirect or scalar nuclear coupling. The strength of the coupling is denoted by a coupling constant J and is expressed in Hz. For any nucleus. e. the motional averaging produces an isotropie value of the chemical shift. three a 1:3 :3: 1 quartet. expressed in H z .Dipole Coupling
In most substances. the width of the resonance lines may be very small. but their naturai have a marked effect.
D3. In this case. equivalently coupled spin -% neighbors.3. When expressed in ppm.
. the locai magnetic field at each nucleus is essentially equal to Bo. two produce a 1:2: 1 triplet. but also through the intervening covalent bonds.the order of 10 ppm. ca 1 kHz in a magnetic field of 2.2Indirect Nuclear Coupling
Magnetic nuclei may transmit information to each other concerning their spin states not only directly through space.
D. In solution. aiso known as J coupling. the chemical shifts are independent of Bo. The eiectronic screening of nuclei is actually anisotropic so that the chemical shift is a directional quantity and depends on the orientation of the molecule with respect to the direction of the magnetic field. protons contribute to local fields and are sufficiently numerous to atoms also conhbute to the local fields.3 Nuclear Coupling
Nuclei sficiently removed fiom each other do not feel the effects of the magnetic fields of the other nuclei. are proportional to Bo. its resonance will be split into n + 1 spin states of the neighboring group of spins.1Direct Dipole . Thus one neighboring spin splits the observed resonance to a doublet.g.34 T (Sanders and Hunter. 1993).
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