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BOOK OF ABSTRACTS OF THE
10TH INTERNATIONAL CHEMICAL AND
BIOLOGICAL ENGINEERING CONFERENCE
CHEMPOR 2008
BOOK OF ABSTRACTS OF THE
10TH INTERNATIONAL CHEMICAL AND BIOLOGICAL
ENGINEERING CONFERENCE - CHEMPOR 2008
4-6 SEPTEMBER 2008, BRAGA, PORTUGAL
ORGANIZED BY
UNIVERSIDADE DO MINHO
ORDEM DOS ENGENHEIROS
INSTITUTE FOR BIOTECHNOLOGY AND BIOENGINEERING
SUPPORT
SOCIEDADE PORTUGUESA DE QUÍMICA
SOCIEDADE PORTUGUESA DE BIOTECNOLOGIA
EDITED BY
EUGÉNIO C. FERREIRA
MANUEL MOTA
UNIVERSIDADE DO MINHO, DEPARTAMENT OF BIOLOGICAL ENGINEERING
BRAGA, PORTUGAL
iii
This volume contains abstracts presented at the 10th International Chemical and Biological
Engineering Conference - CHEMPOR 2008, held in Braga, Portugal, between September 4th and
6th, 2008.
Title: Book of Abstracts of the 10th International Chemical and Biological Engineering
Conference - CHEMPOR 2008
Edited by Eugénio C. Ferreira and Manuel Mota
First edition August 2008
ISBN: 978-972-97810-4-9
Depósito legal: #####/2008
Tiragem: 500 exemplares
Cover design: Helena Martins www. helenamartinsdesign.com
Publisher:
Universidade do Minho, Departamento de Engenharia Biológica
Campus de Gualtar, 4700 Braga, Portugal
Printed by:
Candeias Artes Gráficas, Lda.
Rua Conselheiro Lobato, 179, 4700-338 Braga
© Universidade do Minho
This publication was sponsored by:
iv
Foreword
This book contains the extended abstracts presented at the 10th International Chemical and Biological
Engineering Conference - CHEMPOR 2008, held in Braga, Portugal, over 3 days, from the 4th to the 6th of
September, 2008. Previous editions took place in Lisboa (1975, 1889, 1998), Braga (1978), Póvoa de
Varzim (1981), Coimbra (1985, 2005), Porto (1993), and Aveiro (2001).
The conference was jointly organized by the University of Minho, “Ordem dos Engenheiros”, and the IBB Institute for Biotechnology and Bioengineering with the usual support of the “Sociedade Portuguesa de
Química” and, by the first time, of the “Sociedade Portuguesa de Biotecnologia”.
Thirty years elapsed since CHEMPOR was held at the University of Minho, organized by T.R. Bott, D. Allen,
A. Bridgwater, J.J.B. Romero, L.J.S. Soares and J.D.R.S. Pinheiro. We are fortunate to have Profs. Bott, Soares
and Pinheiro in the Honor Committee of this 10th edition, under the high Patronage of his Excellency the
President of the Portuguese Republic, Prof. Aníbal Cavaco Silva. The opening ceremony will confer Prof.
Bott with a “Long Term Achievement” award acknowledging the important contribution Prof. Bott brought
along more than 30 years to the development of the Chemical Engineering science, to the launch of
CHEMPOR series and specially to the University of Minho. Prof. Bott’s inaugural lecture will address the
importance of effective energy management in processing operations, particularly in the effectiveness of
heat recovery and the associated reduction in greenhouse gas emission from combustion processes.
The CHEMPOR series traditionally brings together both young and established researchers and end users
to discuss recent developments in different areas of Chemical Engineering. The scope of this edition is
broadening out by including the Biological Engineering research. One of the major core areas of the
conference program is life quality, due to the importance that Chemical and Biological Engineering plays in
this area. “Integration of Life Sciences & Engineering” and “Sustainable Process-Product Development
through Green Chemistry” are two of the leading themes with papers addressing such important issues.
This is complemented with additional leading themes including “Advancing the Chemical and Biological
Engineering Fundamentals”, “Multi-Scale and/or Multi-Disciplinary Approach to Process-Product
Innovation”, “Systematic Methods and Tools for Managing the Complexity”, and “Educating Chemical and
Biological Engineers for Coming Challenges” which define the extended abstracts arrangements along this
book.
A total of 516 extended abstracts are included in the book, consisting of 7 invited lecturers, 15 keynote,
105 short oral presentations given in 5 parallel sessions, along with 6 slots for viewing 389 poster
presentations. Full papers are jointly included in the companion Proceedings in CD-ROM. All papers have
been reviewed and we are grateful to the members of scientific and organizing committees for their
evaluations. It was an intensive task since 610 submitted abstracts from 45 countries were received.
It has been an honor for us to contribute to setting up CHEMPOR 2008 during almost two years. We wish
to thank the authors who have contributed to yield a high scientific standard to the program. We are
thankful to the sponsors who have contributed decisively to this event. We also extend our gratefulness to
all those who, through their dedicated efforts, have assisted us in this task.
On behalf of the Scientific and Organizing Committees we wish you that together with an interesting
reading, the scientific program and the social moments organized will be memorable for all.
Braga, September 2008
Eugénio C. Ferreira
Manuel Mota
v
Committee Members
Honor Committee:
Under the high Patronage of his Excellency the President of the Portuguese Republic, Prof. Aníbal Cavaco Silva.
Members:
Ministro da Ciência, Tecnologia e Ensino Superior, Prof. Doutor José Mariano Gago
Secretário de Estado Adjunto, da Indústria e da Inovação, Prof. Doutor António Castro Guerra
Bastonário da Ordem dos Engenheiros, Engº Fernando Santo
Reitor da Universidade do Minho, Prof. Doutor António Guimarães Rodrigues
Presidente da Câmara Municipal de Braga, Engº Francisco Mesquita Machado
Governador Civil do Distrito de Braga, Dr. Fernando Moniz
Presidente da Fundação para a Ciência e a Tecnologia, Prof. Doutor João Sentieiro
Presidente da Sociedade Portuguesa de Química, Prof. Doutor José Luís Figueiredo
Presidente da Sociedade Portuguesa de Biotecnologia, Prof. Doutor F. Xavier Malcata
Presidente da Escola de Engenharia da Universidade do Minho, Prof. Doutor António Cunha
Prof. Doutor T. Reg. Bott (Univ. Birmingham)
Prof. Doutor João de Deus Pinheiro (Univ. Minho)
Prof. Doutor Luís J. Soares (Univ. Minho)
Scientific Committee:
President: Manuel Mota (Univ. Minho)
Members:
C. Bernardo (Univ. Minho)
J.C. Bordado (IST-UTL)
M. Carrondo (UNL)
C. Costa (Univ. Porto)
J. Coutinho (Univ. Aveiro)
J. P. G. Crespo (UNL)
J. J. C. Cruz Pinto (Univ. Aveiro)
E. C. Ferreira (Univ. Minho)
S. Feyo de Azevedo (Univ. Porto)
M. M. Figueiredo (Univ. Coimbra)
M. H. Gil (Univ. Coimbra)
J. Lafuente (Univ. Aut. Barcelona)
J. Lema (Univ. Santiago de Compostela)
F. Lemos (IST-UTL)
L. Q. Lobo (Univ. Coimbra)
F.X. Malcata (Univ. Católica)
L. Melo (Univ. Porto)
A. Q. Novais (INETI)
M. Nunes da Ponte (UNL)
R. Oliveira (Univ. Minho)
C. Pedro Nunes (IST-UTL)
F. Ramôa Ribeiro (IST-UTL)
A. E. Rodrigues (Univ. Porto)
R. Salcedo (Univ. Porto)
J. Sampaio Cabral (IST-UTL)
P. Saraiva (Univ. Coimbra)
R. Simões (UBI)
L. Sousa Lobo (UNL)
J. A. Teixeira (Univ. Minho)
Organizing Committee:
President: Eugénio C. Ferreira (Univ. Minho & Ordem dos Engenheiros)
Members:
M. Alves (Univ. Minho)
J. Azeredo (Univ. Minho)
I. Belo (Univ. Minho)
J. C. Bordado (Ordem dos Engenheiros)
J. M. Costa Reis (Soc. Portuguesa Química)
L. Domingues (Univ. Minho)
C. Gaudêncio (Ordem dos Engenheiros)
M. Henriques (Univ. Minho)
A. S. Pinheiro (Ordem dos Engenheiros)
I. Rocha (Univ. Minho)
L. Rodrigues (Univ. Minho)
T. Tavares (Univ. Minho)
A. Venâncio (Univ. Minho)
A. Vicente (Univ. Minho)
vi
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TableofContents
Contents
PLENARY LECTURES
Meetingthechallenge
T.REG.BOTT
Greenchemistryandthebiorefinery
JAMESCLARK
Addingvaluetochemicalproducts
E.L.CUSSLER
Innovationatinterfaces
CHARLESCOONEY
Aprocesssystemsengineeringapproachformanagingthecomplexity
RAFIQULGANI
Developmentofcrystallizationprocessesforseparatingmulticomponentmixtures
KAMINGNG
Educatingchemicalengineersforcomingchallenges
S.FEYODEAZEVEDO
ORAL PRESENTATIONS: ADVANCING THE CHEMICAL AND BIOLOGICAL ENGINEERING FUNDAMENTALS
1
2
3
4
5
6
7
GasͲliquidmasstransferingasͲliquidͲliquiddispersionsinastirredtank:effectofspreadingcoefficient
9
HENRIQUEJ.O.PINHO,RUISANTANA,SEBASTIÃOS.ALVES
OxygentransfercharacterizationinthreeͲphasereactorsusingsiliconeoilasvector
11
GUILLERMOQUIJANO,FRÉDÉRICTHALASSO
Fluidizationbehaviourofdifferentshapedlargeparticulatefoodmaterials:effectofmoistureandshape
13
WIJITHASENADEERA
Modelingofanovelphotoreactorformultiphaseapplications
15
JOANAT.CARNEIRO,ROBBERGER,JACOBA.MOULIJN,GUIDOMUL
Evaluation of parameters and process conditions of the ethylbenzene dehydrogenation in a fixed bed reactor
wrappedwithpermselectivemembrane
17
PAULOJARDELP.ARAÚJO,TERESAM.K.RAVAGNANI
Solubilityofmultifunctionalassociatingmolecules:measurementsandthermodynamicmodeling
19
A.J.QUEIMADA,F.L.MOTA,S.P.PINHO,E.A.MACEDO
Diffusioncoefficientsandconductivitiesof1ͲbutylͲ3ͲmethylimidazoliumͲbasedionicliquids
21
CHUNͲLIWONG,MENGͲHUILI
Inhibitoreffectofselectedanionicsurfactantsonthedissolutionofcalciumsulfateinaqueousbrines
23
CRISTIANALOUREIRO,FÁTIMAFARELO,LURDESSERRANO,MANUELPEREIRA
CrosslinkedanaloguesofionicͲliquids–aversatilemediumandcatalystsfororganicreactions
25
ANDRZEJW.TROCHIMCZUK,SYLWIARONKA
Particleagglomerationincyclones
26
JÚLIOPAIVA,ROMUALDOSALCEDO,PAULOARAÚJO
ExtendingKozenyͲCarmanpermeabilitymodeltohighlyporousmedia
28
MANUELMOTA,ALEXANDERYELSHIN
Optimaloperatingconditionsfortheseparationoflactobionicacid,sorbitol,fructoseandlactoseusinga5Ͳsection
pseudoͲSMB
30
ISRAELPEDRUZZI,PEDROSÁGOMES,EDUARDOA.B.DASILVA,ALÍRIOE.RODRIGUES
Observationofinertialparticlemotioninlaminarflowinastirredvessel
32
NAOTOOHMURA,NAMINISHIOKA,ALATENGTUYA,MOHAMEDN.NOUIͲMEHIDI,JIEWU,NORIHISAKUMAGAI,TEIJITAKIGAWA
Assessmentofthetartaricstabilityofwinesdeionisedbyelectrodialysis
34
PATRÍCIAA.M.H.SOARES,VÍTORGERALDES,CRISTINAFERNANDES,PAULOCAMEIRADOSSANTOS,MARIANORBERTADEPINHO
CharacterizationofamicroporoustitanosilicateAMͲ3membrane–puregaspermeation
36
PATRÍCIAF.LITO,SARAB.BARROS,JOÃOROCHA,ZHILIN,CARLOSM.SILVA
PureSolventSolubilityofSomePharmaceuticalMolecules
38
FÁTIMAL.MOTA,ANTÓNIOJ.QUEIMADA,SIMÃOP.PINHO,EUGÉNIAA.MACEDO
BasicitypromotionandmechanismaspectofliquidselectiveoxidationofalcoholsonAu/ActivedͲCarboncatalyst 40
JUNJIANGZHU,JOSÉL.FIGUEIREDO,JOAQUIML.FARIA
ComputerͲaidedphaseequilibriapredictionfororganicsystems:UNIFACͲCI.Analysis,revisionandextension
42
HUGOE.GONZÁLEZ,JENSABILDSKOV,RAFIQULGANI

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TableofContents
Molecular weight distribution in freeͲradical polymerisation – model development, experimental validation and
processoptimisation
43
BRUNO AMARO, CHARLES D. IMMANUEL, E.N. PISTIKOPOULOS, ANDREAS DAIß, FLORIAN BECKER, KLAUSͲDIETER HUNGENBERG, P.A.
SARAIVA
PVCPasteRheology:PolymerPropertiesandViscoelasticBehaviour
45
A.TOMÁS,A.,M.G.RASTEIRO,L.FERREIRA,S.FIGUEIREDO
OptimizationoffluidizedbedPVCdrying
47
MELANIEBECU,LAURENTBERKOVIC,FREDERICDEBASTE
SEC/MALLS Measurement of the Branched Structure of Methyl Methacrylate + Ethylene Glycol Dimethacrylate
CopolymersSynthesizedbyAtomTransferRadicalPolymerization
49
IVONEM.R.TRIGO,MIGUELA.D.GONÇALVES,ROLANDOC.S.DIAS,MÁRIORUIP.F.N.COSTA
ThermaldegradationkineticsofpolyethyleneindynamicconditionsusingsimultaneousDSC/TGanalysis
51
ANABELACOELHO,LUÍSCOSTA,MARIADASMERCÊSMARQUES,ISABELFONSECA,MARIAAMÉLIALEMOS,FRANCISCOLEMOS
DecylacetatesynthesisbyenzymecatalysisinscCO2
53
S.F.REBOCHO,A.S.RIBEIRO,O.FERREIRA,M.V.OLIVEIRA,P.VIDINHA,S.BARREIROS,E.A.MACEDO,J.M.LOUREIRO
Improvingpropylenestreamspurityusingcatalyticmembranereactors
55
MIGUELTEIXEIRA,MIGUELMADEIRA,JOSÉSOUSA,ADÉLIOMENDES
ImprovementbyalkalinetreatmentofHZSMͲ5zeoliteperformanceinDMEsteamreforming
57
JORGEVICENTE,JAVIEREREÑA,ALAITZATUTXA,ANAG.GAYUBO,JAVIERBILBAO
ApplicationofagroupcontributionCPAEoStothemodelingofbiodieselproduction
59
MARIANA B. OLIVEIRA, FÁTIMA R. VARANDA, MARIA JORGE MELO, ISABEL M. MARRUCHO, ANTÓNIO JOSÉ QUEIMADA, JOÃO A.P.
COUTINHO
Sequential batch reactor and plug flow reactor network comparison under dynamic conditions for wastewater
treatment
61
ADRIÁNFERRARI,EVARISTOC.BISCAIAJR.,PRIAMOA.MELO
ORAL PRESENTATIONS: MULTI-SCALE
INNOVATION
AND/OR
MULTI-DISCIPLINARY APPROACH
TO
PROCESS-PRODUCT
DesignandEngineeringofStructuredMolecularMatter
64
A.A.BROEKHUIS
SystematicmodellingframeworkinproductͲprocessdesignanddevelopment
66
RICARDOMORALESͲRODRÍGUEZ,RAFIQULGANI
Combiningpredictionsatmultiplescalesforprocessmodelling
68
MARCOS.REIS
Integrationoftraditionalandsupercriticalfluidtechniquestodesigndrugdeliverysystems
70
MARIANASOUSACOSTA,A.R.SAMPAIODESOUSA,ANARITAC.DUARTE,M.MARGARIDACARDOSO,CATARINAM.M.DUARTE
ThermoresponsiveHydrogelsforDrugDeliverySystems
71
J.F.ALMEIDA,P.FERREIRA,ARMANDOALCOBIA,A.LOPES,M.H.GIL
CFDsimulationofanoxidationditch
73
ANNAKARPINSKA,JOANAP.PEREIRA,MADALENAM.DIAS,RICARDOJ.SANTOS
CFDmodellingoftrickleͲbedreactorinthecatalyticwetairoxidationofsyringicacid
75
RODRIGOJ.G.LOPES,ROSAQUINTAͲFERREIRA
CharacterizationofwaterspeciesrevealedinthedryingoperationofsquidbyusingwaterprotonNMRanalysis 77
YASUYUKIKONISHI,MASAYOSHIKOBAYASHIANDKOUͲICHIMIURA
MixedconvectiveheattransferaugmentationinabackwardͲfacingsteputilizingnanofluids
78
S.DHINAKARAN
ElectricSwingAdsorptionProcessforGasPurification
79
CARLOSA.GRANDE,RUIP.L.RIBEIRO,ALÍRIOE.RODRIGUES
Cholesterolremovalbynanofiltrationinorganicsolution
81
C.ALLEGRE,E.CARRETIER,P.MOULIN
Beeraromarecoverybypervaporation
83
MARGARIDACATARINO,LUÍSM.MADEIRA,ANTÓNIOFERREIRA,ADÉLIOMENDES
Determinationofthewallshearstressbynumericalsimulation:membraneprocessapplications
85
FANNYSPRINGER,REMYGHIDOSSI,EMILIECARRETIER,DAMIENVEYRET,DIDIERDHALERANDPHILIPPEMOULIN
ActivemixingstrategiesforConfinedImpingingJets
87
M.ASHARSULTAN,ERTUGRULERKOÇ,RICARDOJ.SANTOS,MADALENAM.DIAS,JOSÉCARLOSB.LOPES
Ultrasound–assistedextractionofactiveprinciplesfromArctiumlappaL.(Burdock)roots,SteviarebaudianaBert.
leavesandCynarascolymusL.(Artichoke)leaves
89
ANIALUPULUI,V.LAVRIC

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TableofContents
MonitoringmultiͲcomponentliquidreactionsystemscontaininghighlydispersibleheterogeneouscatalystsusingin
situdiodearrayspectrophotometryandbandͲfittingtechniques
90
LUÍSCOSTA,VÂNIABRISSOS,FRANCISCOLEMOS,FERNANDORAMÔARIBEIRO,JOAQUIMM.S.CABRAL
HighͲthroughputpharmaceuticalprocessmonitoring:integratingthehardwareandsoftwarecomponents
92
M.C.SARRAGUÇA,L.P.BRÁS,J.A.LOPES
PharmaceuticalEngineering
93
JOÃOMOURABORDADO,JOSÉGUIMARÃESMORAIS,ROGÉRIOSÁGASPAR,JOSÉCARDOSOMENEZES
ORAL PRESENTATIONS: SUSTAINABLE PROCESS-PRODUCT DEVELOPMENT THROUGH GREEN CHEMISTRY
ProductionofoligoͲgalacturonicacidsbypectinhydrolysisusingsubͲandsupercriticalwater
94
STEFANTOEPFL,ULFSTRIJOWSKIANDVOLKERHEINZ
SynthesisoftriproprioninfromcrudeglycerolthebyͲproductofbiodieselproduction
95
ZSANETTHERSECZKI,GYULAMARTON
Thefuturesustainabilityofbiodiesel
97
RENATOH.CARVALHO,LUÍSR.VILELADEMATOS
Constructionandbioproductionofa“green”syntheticproteinͲbasedpolymerexhibitingasmartbehaviour
99
RAUL MACHADO, JORGE PADRÃO, ALEXANDRA NOBRE, FRANCISCO JAVIER ARIAS, JOSÉ A. TEIXEIRA, ANTÓNIO CUNHA, JOSÉ CARLOS
RODRÍGUEZͲCABELLO,MARGARIDACASAL
LigninͲbasedpolyurethanematerials
101
CAROLINACATETO,FILOMENABARREIRO,ALÍRIOE.RODRIGUES,NACEURBELGACEM
CatalyticwetairoxidationplusbiologicaltreatmenttodealwithahighͲstrengthoͲcresolwastewater
103
M.E.SUÁREZͲOJEDA,J.LAFUENTE,J.FONTANDJ.CARRERA
TwoͲaqueousphaseextractionfortheremovaloforganicpollutantsandmetalions
105
L.J.NOGUEIRADUARTE,J.P.CANSELIER
BiosorptionofCrVIsupportedonmordenitezeolite
107
FIGUEIREDO,H.,SILVA,B.,QUINTELAS,C.,NEVES,I.C.,TAVARES,T.
Phosphorusremovalfromanindustrialwastewaterbystruvitecrystallizationintoanairliftreactor
109
A.SÁNCHEZSÁNCHEZ,SONIABARROS,RAMÓNMÉNDEZ,J.M.GARRIDO
EcoDesignthroughamultiͲcriteriaenvironmentaldecisiontoolbasedonfuzzylogic
111
MARTAHERVA,AMAYAFRANCO,EUGENIOF.CARRASCO,ENRIQUEROCA
Designofsustainableprocesses:Systematicgenerationandevaluationofalternatives
113
ANACARVALHO,RAFIQULGANI,HENRIQUEMATOS
ModelingofOrangeIIadvancedbiodecolourisationinupflowstirredpackedͲbedreactor
115
GERGOMEZOHEGYI,CHRISTOPHEBENGOA,FRANKSTUBER,JOSEPFONT,AGUSTÍFORTUNY,AZAELFABREGAT
PhotocatalyticPaintProductionfortheAbatementofNitrogenOxides
117
C.ÁGUIA,FRANCESCX.LLABRÉSIXAMENA,ESTHERDOMINGUEZ,HERMENEGILDOGARCÍA,L.M.MADEIRA,A.MENDES
StarchfilterͲcakeenzymaticdegradation
119
ETELKAMEDA,RAFAELF.DEMESQUITA,MARTAA.P.LANGONE,JOÃOC.DEQUEIROZNETO,MARIAALICEZARURCOELHO
RobustmultiͲobjectivecascadecontrollerforananaerobicdigester
121
CARLOSGARCIA,FRANCISCOMOLINA,EUGENIOCARRASCO,ENRIQUEROCA,JUANM.LEMA
Fenton’streatmentofaqueousphenoleffluentsinpresenceofanionicsurfactants
123
XAVIERBERNAT,AGUSTÍFORTUNY,CHRISTOPHEBENGOA,FRANKSTÜBER,AZAELFABREGAT,JOSEPFONT
Electrochemicalozoneproductionforinsituatrazinedegradationinaquifer
125
YSRAELM.VERA,ROBERTOJ.CARVALHO,MAURICIOL.TOREM
Catalyticozonationappliedtothetreatmentofcolouredeffluents
127
PATRÍCIAC.C.FARIA,JOSÉJ.M.ÓRFÃO,MANUELF.R.PEREIRA
Ionexchangemembranebioreactormodellingforremovalofanionicmicropollutantsfromdrinkingwatersupplies
129
A.R.RICARDO,R.OLIVEIRA,S.VELIZAROV,M.A.M.REIS,J.G.CRESPO
PerformancecomparisonofbiologicalandFentonprocessesfortreatmentofurbanlandfillleachates
131
CÁTIAM.AUGUSTO,MARGARIDAJ.QUINA,LICÍNIOM.GANDOͲFERREIRA
DesignandConstructionofaLabͲScaleSimulatedMovingBedUnit.TheFlexSMBͲLSRE–fromTheorytoPractice133
PEDROSÁGOMES,MICHALZABKA,MIRJANAMINCEVAANDALÍRIOE.RODRIGUES
InhibitoryeffectofphenoliccompoundsontheactivityofAngiotensinIconvertingenzyme
135
JOANAAFONSO,CLÁUDIAP.PASSOS,CARLOSM.SILVA,MANUELA.COIMBRA,PATRÍCIOSOARESͲDAͲSILVA
AnovelviewofthemanufactureofpolyurethaneͲpolyureaaqueousdispersions
137
ISABELFERNANDES,FILOMENABARREIRO,MÁRIORUICOSTA

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TableofContents
ORAL PRESENTATIONS: SYSTEMATIC METHODS AND TOOLS FOR MANAGING THE COMPLEXITY
Constructingchemicalreactionnetworksthroughdecoupling,regressionandrationalisation
139
SAMANTHAC.BURNHAMANDMARKJ.WILLIS
AmultiͲobjectiveoptimizationforthedesignandperiodicschedulingofmultipurposefacilities
141
TÂNIARUTEPINTOANAPAULABARBÓSAͲPÓVOAANDAUGUSTOQ.NOVAIS
Theinfluenceofproducts’portfoliodemandontheoptimalsupplychainplanning
143
ANAC.S.AMARO,ANAP.BARBOSAͲPÓVOA
Nonlineardynamicmodelingofarealpilotscalecontinuousdistillationcolumnforfaulttolerantcontrolpurposes
145
NUNOM.R.BATALHA,PEDROM.C.OLIVEIRA,JOÃOM.A.SILVA,CARLAI.C.PINHEIRO
Applicationsofmodelbaseddesignofpolymerproducts
147
DULCEC.M.SILVA,RUIM.BASTOS,NUNOM.C.OLIVEIRA
GlobaldynamicoptimizationofchemicalandbioͲprocessesusingtheScatterSearchmetaheuristic
149
JOSEA.EGEA,MARÍAͲSONIAG.GARCÍA,EVABALSAͲCANTO,JULIOR.BANGA
IntegratingrealͲtimeoptimizationandcontrolforoptimaloperation:ApplicationtothebioͲethanolprocess
151
SILVIAOCHOA,JENSͲUWEREPKE,GÜNTERWOZNY
OnͲLineadaptivemetabolicfluxanalysis:ApplicationtoPHBproductionbymixedmicrobialcultures
153
JOÃODIAS,FILIPAPARDELHA,MÁRIOEUSÉBIO,MARIAA.M.REIS,RUIOLIVEIRA
Modellingofmembranebioreactorsforwastewatertreatmentincorporating2DͲfluorescencemonitoringdata 155
CLAUDIA F. GALINHA, CARLA PORTUGAL, GILDA CARVALHO, GIUSEPPE GUGLIELMI, DANIELE CHIARANI, GIANNI ANDREOTTOLA, RUI
OLIVEIRA,MARIAA.M.REIS,JOÃOG.CRESPO
Modeling,Identificationand,ControlofComplexSystems
157
SRINIVASKARRAANDM.NAZMULKARIM
Performanceindicatorsforreactivedistillationdesign
160
RUIM.FILIPE,HENRIQUEA.MATOS,AUGUSTOQ.NOVAIS
TheImportanceofModelsandPracticalIntegrationinProcessDevelopment.CasesfromtheSimulatedMovingBed
technology
162
PEDROSÁGOMES,MIRJANAMINCEVAANDALÍRIOE.RODRIGUES
AchemometrictooltomonitorhighͲrateanaerobicgranularsludgereactorsduringloadandtoxicdisturbances 164
JOSÉCARLOSCOSTA,M.MADALENAALVES,EUGÉNIOC.FERREIRA
InͲlinemonitoringofparticlesizeduringvinylacetateandbutylacrylateemulsioncopolymerizationinacontinuous
pulsedsieveplatereactorusingNIRspectroscopy
166
CHICOMA,D.;SAYER,C.;GIUDICI,R.
Controlofbromelainrecoveryprocessthroughconventionalandfuzzycontrollers
168
MANUELAS.LEITE,FLÁVIOV.SILVA,TATIANAL.FUJIKI,ANAM.F.FILETI
Optimalcleaningscheduleforheatexchangersinaheatexchangernetworkbasedoncontinuoustimeapproach170
KANYALUKAOͲEKKASIT,SLITANUSONG,SOORATHEPKHEAWHOM
Optimaldesignofwaterusingnetworks
172
JOÃOTELES,PEDROM.CASTRO,HENRIQUEA.MATOS
AShortcutDesignMethodforHybridSeparationProcesses
174
M.SORIN,E.AYOTTEͲSAUVÉANDF.RHEAULT
ORAL PRESENTATIONS: INTEGRATION OF LIFE SCIENCES & ENGINEERING
Methodsandtoolsforglobalsensitivityanalysisofdynamicmodelsofbiologicalsystems
176
MARÍARODRÍGUEZͲFERNÁNDEZ,JULIOR.BANGA
StochasticModellingoftheBaculovirus/InsectCellsSystem:PredictionofRecombinantProteinExpression
178
ANTÓNIOROLDÃO,MANUELJ.T.CARRONDO,PAULAM.ALVESANDR.OLIVEIRA
ScalingͲupcontrolofyeastfedͲbatchcultures
180
L.DEWASME,X.HULHOVEN,A.VANDEWOUWER
AdaptiveextremumͲseekingcontrolofyeastfedͲbatchcultures
182
L.DEWASME,A.VANDEWOUWER,M.PERRIER
Improvement of baculovirus vectors production based on the metabolic characterization and modelling of SfͲ9
cultures
184
NUNO CARINHAS; VICENTE BERNAL; ADRIANA Y. YOKOMIZO; TIAGO VICENTE; MANUEL J. T. CARRONDO; RUI OLIVEIRA; PAULA M.
ALVES
LactosefermentationbyrecombinantSaccharomycescerevisiaestrains
186
PEDROM.R.GUIMARÃES,JOSÉA.TEIXEIRA,LUCÍLIADOMINGUES
StudiesonfedͲbatchoperationmodeonbiosynthesisofshortchainethylesterscatalyzedbycutinase
188
DRAGANAP.C.DEBARROS,SUSANAM.S.A.BERNARDINO,PEDROFERNANDES,JOAQUIMM.S.CABRAL,LUÍSP.FONSECA

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TableofContents
Newenzymaticalprocessforglycerolutilization
190
ANDREABALASSY,ARONNEMETH,BELASEVELLA
BiosorptionofhexavalentchromiumbyArthrobacterviscosus
192
BRUNASILVA,HUGOFIGUEIREDO,CRISTINAQUINTELAS,ISABELC.NEVES,TERESATAVARES
MicroͲscaleandbioreactorsystemsfortheexpansionofmouseembryonicstem(mES)cells
194
ANAM.FERNANDES,TIAGOG.FERNANDES,MARIAMARGARIDADIOGO,CLÁUDIALOBATODASILVA,DOMINGOSHENRIQUE,JONATHAN
S.DORDICK,JOAQUIMM.S.CABRAL
PurificationofhumanantibodiesusingaffinityaqueousͲtwophasesystems
196
PAULAA.J.ROSA,ANAM.AZEVEDO,I.FILIPAFERREIRA,M.RAQUELAIRESͲBARROS
NanoandmicroͲbiocatalystsmanufactureandtheirimpactonthesynthesisofɴͲlactamicantibiotics
197
SUSANAM.S.A.BERNARDINO,JUANF.M.GALLEGOS,FILIPAMADURO,PEDROFERNANDES,JOAQUIMM.S.CABRAL,LUÍSP.FONSECA
BiopolymersproductionbymicrobialfermentationonglycerolͲrichproduct
199
FILOMENAFREITAS,VITORD.ALVES,JOANAPAIS,NUNOCOSTA,MÓNICACARVALHEIRA,RUIOLIVEIRA,M.A.M.REIS
AntibodyconjugatedPLGAnanoparticlescontainingantiͲcancerdrugsforsiteͲspecificdrugdelivery
201
INÊSPEÇA,MARIANASOUSACOSTA, A.C.A.ROQUE,A. BICHO,M.MARGARIDACARDOSO
Bacterial Community Structure in a Biotrickling Filter Treating H2S by Terminal Restriction Fragment Length
Polymorphism(TͲRFLP)
203
JUANP.MAESTRE,ROGERROVIRA,XAVIERGAMISANS,KERRYA.KINNEY,MARYJ.KIRISITS,JAVIERLAFUENTE,DAVIDGABRIEL
Biohydrogen production with an EGSB reactor using chloroform and 2Ͳbromoethanesulfonate as inhibitors of
hydrogenconsumingbacteria
205
ÂNGELAA.ABREU,ANTHONY,S.DANKO,M.MADALENAALVES
Biofilmtechnology:fromsupportdesigntoreactoroperation
207
MARIAF.MATOS,CLÁUDIAF.ALVES,ANTÓNIOG.BRITO,REGINAB.NOGUEIRA
LignocellulosicMaterialsasaFeedstockforPolymerSynthesis
209
MATJAŽKUNAVER,EDITAJASIUKAITYTE,VESNATIŠLER,SERGEJMEDVED
Bioethanolproductionfromsugarsbyyeasthavingsugaruptakeabilitybyexpressionofsugartransporter
210
TAKANORITANINO,CHIAKIOGINO,NORIHISAKUMAGAI,NAOTOOHMURA
Treatmentofwoodhydrolysatesforbioethanolproductionbyfermentation
212
CÁTIAV.T.MENDES,JORGEM.S.ROCHA,CRISTINAM.S.G.BAPTISTA,M.GRAÇAV.S.CARVALHO
Integrationofbioprocessesinpolyestersmicrobialsynthesis
214
ANABELAS.ANTUNES,JORGEM.S.ROCHA
OneͲstepcellulosicethanolproduction
216
M.NAZMULKARIMANDSEUNGHYUNRYU
OptGene–aframeworkforinsilicometabolicengineering
218
ISABELROCHA,PAULOMAIA,MIGUELROCHA,EUGÉNIOC.FERREIRA
ThePotentialandtheChallengesinIntegratingThermodynamicsintoSystemsBiology
220
URSVONSTOCKARANDVOJISLAVVOJINOVIC
Macroscopiccontrolofintracellularregulation:applicationtomammaliancellcultures
222
ANAP.TEIXEIRA,PAULAALVES,MJTCARRONDOANDRUIOLIVEIRA
TowardsPATbioprocessmonitoringandcontrol:nearinfraredandsoftwaresensor
224
ZITAI.T.A.SOONS,MATHIEUSTREEFLAND,ANTONJ.B.VANBOXTEL
NearͲinfraredreflectancespectroscopyasaprocessanalyticaltechnologytoolinpharmaceuticalindustry
226
SÍLVIAS.ROSA;PEDROA.BARATA;JOSÉM.MARTINS,JOSÉCARDOSOMENEZES
ORAL PRESENTATIONS: EDUCATING CHEMICAL AND BIOLOGICAL ENGINEERS FOR COMING CHALLENGES
Enhancingengineeringeducationintheareaofchemicalprocessesthroughavirtualplatform(LABVIRTUAL)
227
M.G. RASTEIRO, L.M. GANDOͲFERREIRA, J.C.TEIXEIRA, F.P. BERNARDO, M.G. CARVALHO, A.G. FERREIRA, R.M. QUINTAͲFERREIRA,
F.P.GARCIA,C.G.BAPTISTA,N.C.OLIVEIRA,M.J.QUINA,L.O.SANTOS,P.A.SARAIVA,A.M.MENDES,F.M.MAGALHÃES,J.GRANJO,
R.BASTOS,M.ASCENSO,R.BORGES,A.S.ALMEIDA,A.MACEDO
AddͲinsforShortcutDesignandSizingofDistillationColumns
229
FERNANDOG.MARTINS,M.I.M.S.CRUZ,DOMINGOSBARBOSA
ContinuousandBatchDistillationinanOldershawTrayColumn
231
CARLOSM.SILVA,RAQUELV.VAZ,TIAGOM.F.CANHOTO,PATRÍCIAF.LITO,ANAS.SANTIAGO
Introductionofdesigntoolsintheexperimentalorganicprocesses
232
ERIKAC.A.N.CHRISMAN;VIVIANEDES.LIMA;ANACLÁUDIAALMEIDA
VirtualLaboratoriesin(Bio)ChemicalEngineeringEducation
234
LUCÍLIADOMINGUES,ISABELROCHA,FERNANDODOURADO,M.MADALENAALVESANDEUGÉNIOC.FERREIRA
POSTER PRESENTATIONS: ADVANCING THE CHEMICAL AND BIOLOGICAL ENGINEERING FUNDAMENTALS
Theresearchoftheheterogeneouscatalyticcombustionofthecombustiblegases
TATJANADOVBYSHEVA,ANNEYASKO

239
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TableofContents
RegenerationofsulfurpoisonednickelbasedcatalystsforsteamreformingcatalystsinRazipetrochemicalcomplex
241
S.MEYSAMHASHEMNEJAD,MATINPARVARI
TotaloxidationofethylacetateoverTiO2supportednoblemetalscatalysts
243
V.P.SANTOS,M.F.R.PEREIRA,J.J.M.ÓRFÃO,J.L.FIGUEIREDO
Incidence of the preparation method of the support on the behavior in the nͲbutane dehydrogenation of
Pt/MgAl2O4,PtSn/MgAl2O4yPtPb/MgAl2O4catalysts
245
SONIABOCANEGRA,ALBERTOCASTRO,OSVALDOSCELZA,SERGIODEMIGUEL
Hydrogenproductionfrommethanereforming:thermodynamicassessment
247
TATIANAV.FRANCO,CÍCERON.ÁVILAͲNETO,LUCIENNEL.ROMANIELO,CARLAE.HORI,ADILSONJ.ASSIS
Hydrogenproductionfrommethaneautothermalreforming:mathematicalmodelingandparametricoptimization
249
SANDRAC.DANTAS,FABIANODEA.SILVA,CARLAE.HORI,ADILSONJ.DEASSIS
FluidͲdynamicsoffluidizedbedsoperatingwithflatparticles
251
RENATADEAQUINOB.LIMAANDMARIAC.FERREIRA
HeterogeneousmodelformasstransferofdissolvedligninduringkraftpulpingofEucalyptusglobulus
253
JOÃOP.F.SIMÃO,CRISTINAM.S.G.BAPTISTA,M.GRAÇACARVALHO
LongitudinalmixinginapeforatedͲplatesextractioncolumn
255
BRANDÃO,M.M.ANDGÓIS,L.M.N.
ThreeͲdimensionalsimulationofbubblyflow:influenceofbreakupandcoalescencemodels
256
MARCELAK.SILVA,RENATODIONÍSIO,MARCOSA.D’ÁVILA,MILTONMORI
Comparisonofhydrodynamicparametersbetweenaninternalandanexternalairliftcolumn
258
M.TERESAM.SENAESTEVES,ISABELM.B.PEREIRA,MARIAN.COELHOPINHEIRO,ALEXANDRAM.F.R.PINTO
MasstransfercoefficientinthreeairliftreactorswithinternalloopusingNewtonianfluid
260
LUCASM.POLICARPO,MARCELO.CERRI,ANTONIOJ.G.CRUZ,CARLOSO.HOKKA,ALBERTOC.BADINO
Predictionofmeanbubblesizeinthreescalesofinternalloopairliftreactor
262
MARCELO.CERRI,JULIANAC.BALDACIN,ANTONIOJ.G.CRUZ,CARLOSO.HOKKA,ALBERTOC.BADINO
EulerͲEulersimulationofgasͲliquidandgasͲliquidͲsolidairliftreactors:casestudy
264
M.SIMCIK,J.HAVLICA,M.C.RUZICKA,J.DRAHOŠ,J.A.TEIXEIRA,T.BRÁNYIK
Interfacialinstabilityofbubbleduringchemosorption
266
S.P.KARLOV, D.A.KAZENIN,A.V.VYAZMIN
Effectofkindsofgasongasholdupinbubblecolumns
268
FUKUJIYAMASHITAANDMEGUMINAKAJIMA
SimulationofdynamicperformanceofozonationtreatmentofsurfactantsinasemiͲbatchbubblecolumnreactorby
CFX
270
FUKUJIYAMASHITA,TOMOYUKISUZUKI,HARUKI,KOBAYASHI
ParticleinteractionwithcoherentstructuresinaconfinedtwoͲphasejet
272
J.C.S.C.BASTOS,R.K.DECKER,M.MORI,U.FRITSCHING
Numericalinvestigationofunsteadyflowandheattransferfromaporoussquarecylinder
274
S.DHINAKARAN,ANTÓNIOVICENTEANDJOSETEIXEIRA
Heattransferinthefreeboardofabubblingfluidizedbed
275
P.NETO,A.M.RIBEIRO,C.PINHO
Dispersioninpackedbeds
277
ULRICHM.SCHEVEN,ROBHARRIS,MIKEL.JOHNS
Operatingthesegregatedflowsofparticulatematerialsasaprincipleoftechnologicalprocessorganization
278
DOLGINUNV.N.,IVANOVO.O.,KLIMOVA.M.ANDUKOLOVALͲDR.A.
Hinderedmotioninhighlyporousmedia:stericandfractalapproaches
280
MANUELMOTA,ALEXANDERYELSHIN
Anotherbasicsegregationmechanisminaeratedgravityflowsofparticulatesolids
282
DOLGINUNV.N.,KUDYA.N.,KLIMOVA.M.ANDIVANOVO.O.
MaxwellͲStefanbasedmodelforionexchangeinmicroporousmaterials
284
PATRÍCIAF.LITO,CARLOSM.SILVA
Competitiveadsorptionofheavymetalsbytwodifferenttypesofsoils
285
BRUNAFONSECA,ALINES.TEIXEIRA,TERESATAVARES
Asequencingmethodappliedtothesolutionofalinearmodelofanadsorptioncolumn
286
R.L.WU,M.F.CUEL,C.O.HOKKA,M.BARBOZA,W.H.KWONG
IndustrialAirSeparationusingPressureSwingAdsorption:AFluidizationStudy
288
D.A.FERREIRA,P.TAVEIRA,A.MENDES

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TableofContents
StudyoftheadsorptionprocessofmethanolandwateroveraSAPOͲ18catalystbymeansofpulsetechniques 290
IRENESIERRA,ANDRÉST.AGUAYO,JAVIEREREÑA,ANAG.GAYUBO,JAVIERBILBAO
Optimization of mobile phase composition for preparative separation of profens enantiomers by chiral liquid
chromatography
292
ANTÓNIOE.RIBEIRO,NUNOS.GRAÇA,LUÍSS.PAIS,ALÍRIOE.RODRIGUES
Uncertaintyassessmentonchromatographicseparationoflapachol
294
AMAROG.BARRETOJR.,EVARISTOC.BISCAIAJR.
Gasfiltrationathighpressure
296
ANAB.N.BRITO,SANDRAG.R.AZEVEDO,EDISONRICCOJR,JOSÉR.COURY,MÔNICAL.AGUIAR
Pervaporationseparationcharacteristicsforthequaternarymixturewater+ethanol+ethyllactate+lacticacid 298
P.DELGADO,M.T.SANZ,S.BELTRÁN,M.GARCÍA
Kineticsofcarbondioxideabsorptionwithchemicalreactioninpiperidineaqueoussolutions
300
ALICIAG.ABUÍN,DIEGOGÓMEZͲDÍAZ,JOSÉM.NAVAZA,ISABELVIDAL
AbsorptionofcarbondioxidebyMDEAaqueoussolutionsinabubblecolumnreactor
302
ESTRELLAÁLVAREZ,DIEGOGÓMEZͲDÍAZ,M.DOLORESLARUBIA,JOSÉM.NAVAZA,LOURDESC.QUINTÁNSͲRIVEIRO
SimulationofmembraneseparationsusingamodifiedMaxwellͲStefanmodel
303
PAULOBRITO,LICÍNIOM.GANDOͲFERREIRA,ANTÓNIOPORTUGAL
InfluenceofpyrolysisparametersontheperformanceofCMSM
305
MARTAC.CAMPO,TYMENVISSER,KITTYNYMEIJER,MATTHIASWESSLING,FERNÃOD.MAGALHÃES,ADÉLIOM.MENDES
LowͲtemperaturewaterͲgasshiftreactioninaPdͲAg“fingerͲlike”configurationmembranereactor
307
DIOGOMENDES,SILVANOTOSTI,FABIOBORGOGNONI,ADÉLIOM.MENDES,LUISM.MADEIRA
Influence of pressure on the yield of supercritical CO2 extraction of linseed (Linum usitatissimum l.) oil and
investigationofitsantioxidantpotential
309
E.L.GALVÃO,J.A.C.BARROS,A.V.B.MOREIRA,H.N.M.OLIVEIRA,E.M.B.D.SOUSA
SupercriticalfluidextractionofgrapeseedoilusinganenzymaticpreͲtreatment
311
C.P.PASSOS,R.M.SILVA,F.A.DASILVA,M.A.COIMBRA,C.M.SILVA
MeasurementandCorrelationofSolubilityofQuinizarinand1Ͳ(Methylamine)anthraquinoneinSupercriticalCarbon
Dioxide
313
JOSÉP.COELHOANDANDREIAF.MENDONÇA
Supercriticalantisolventprocessappliedtothepharmaceuticalindustry
315
A.TENORIO,M.D.GORDILLO,C.M.PEREYRAANDE.J.MARTÍNEZDELAOSSA
Solventeffectsonionicassociationof2,6Ͳlutidiniumchloridesaltat60.00ºC:AQSPRstudy
317
M.REIS,L.MOREIRA,R.E.LEITÃO,F.MARTINS
Modellingofthesolventextractionequilibriumofcadmium(II)inneutralchloridemediumusingCyanex923 319
A.A.LEOPOLD,A.FORTUNY,M.T.COLL,N.S.RATHOREANDA.M.SASTRE
Modelstocorrelatethesurfacetensionofsolventmixtures
321
ALICIAG.ABUÍN,DIEGOGÓMEZͲDÍAZ,JOSÉM.NAVAZA,ISABELVIDAL
Thermodynamicanalysisofsurfacetensioninwater/pyrrolidonesystem
322
ALICIAG.ABUÍN,ANTONIOBLANCO,DIEGOGÓMEZͲDÍAZ,JOSÉM.NAVAZA,ISABELVIDAL
VolumetricpropertiesfortheternarymixtureMethanolͲFormamideͲAcetonitrile
323
NELSONNUNES,FILOMENAMARTINS,LÍDIAPINHEIRO,RUBENE.LEITÃO
Aneffectivemethodforcalculationofhomogeneousazeotropesinreactiveandnonreactivemixtures
325
ADRIANBONILLAͲPETRICIOLET,GUSTAVOA.IGLESIASͲSILVA,JOSEENRIQUEJAIMEͲLEAL
A Portable Library for Equilibrium and Thermodynamics Properties Calculations based on Object Oriented
Paradigms
327
JOANAC.VIEIRA,MIGUELA.MESQUITA,FRANCISCOA.DASILVA
ThermophysicalpropertiesofaqueoussolutionsofCNTsinthetemperaturerange(298.15Ͳ343.15)K
329
FILIPA A.M.M. GONÇALVES, ABEL G.M. FERREIRA, ISABEL M.A. FONSECA J. PONMOZHI, MÓNICA S.A.O. CORREIA, SUBRAMANI
KANAGARAJ
ModellingSolubilityofAminoAcidsinAqueousSolutions
330
CARLOSM.SILVA,SIMÃOA.ALVES,FRANCISCOA.DASILVA
LiquidͲLiquidEquilibria,SurfaceandInterfacialTensionforWater+NͲButylAcetate+1ͲPropanolat323.15K
331
H.F.COSTA,I.JOHNSON,F.M.GONÇALVES,ABELG.M.FERREIRA,ISABELM.A.FONSECA
Thermodinamicanalysisofleathertannedwithdifferenttanningagents
333
MÓNICAROSAS,VALENTINADOMINGUES,TERESAOLIVAͲTELES,PAULOSILVA,ANTÓNIOCRISPIM
EffectofIsooctaneonVaporͲLiquidEquilibriaofWaterandTEGSolution
334
KHOSRAVANIPOURMOSTAFAZADEH,M.R.RAHIMPOUR,A.SHARIATI

Proceedings of the 10th International Chemical and
Biological Engineering Conference - CHEMPOR 2008
Braga, Portugal, September 4-6, 2008
E.C. Ferreira and M. Mota (Eds.)
Optimization of Mobile Phase Composition
for Preparative Separation of Profens Enantiomers by
Chiral Liquid Chromatography
António E. Ribeiro1, Nuno S. Graça1, Luís S. Pais1∗∗, Alírio E. Rodrigues2
Laboratory of Separation and Reaction Engineering
School of Technology and Management, Bragança Polytechnic Institute,
Campus de Santa Apolónia, Apartado 1134, 5301-857 Bragança, Portugal
2
Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias,
4200-465 Porto, Portugal
1
Keywords: Mobile phase composition, Preparative liquid chromatography, Chiral separation,
Non-Steroidal Anti-Inflammatory Drugs, Profens.
Topic: Advancing the chemical engineering fundamentals.
Abstract
In this paper it will be presented and discussed the experimental and simulation results
obtained for the preparative separation of ketoprofen and flurbiprofen enantiomers by chiral
liquid chromatography. Experimental results include solubility studies, elution and frontal
chromatographic experiments and the measurement of competitive adsorption isotherms,
using different mobile phase compositions. Modeling and simulation tools are used to predict
the behavior and the performance of fixed bed and simulated moving bed processes. These
prediction tools are used to select the proper mobile phase composition for the enantiomers
separation in a preparative and production-scale point of view.
1 Introduction
Ketoprofen (R,S)-2-(3-benzoylphenylpropionic acid) and Flurbiprofen (R,S)-2-(2-fluoro-4biphenylpropionic acid) are both examples of profens, the actual most relevant subclass of
the Non-Steroidal Anti-Inflammatory Drugs (NSAIDs). These drugs are frequently prescribed
worldwide in relieve of pain and in the treatment of several forms of inflammation and in the
treatment of main articular diseases such as rheumatoid arthritis, osteoarthritis, ankylosing
spondylitis (Burian and Geisslinger, 2005). The recent literature presents several studies
concluding for different pharmacological proprieties for R and S profen enantiomers.
Following these findings, chiral resolution of profen enantiomers can contribute to the
development of new drugs with distinct therapeutic applications and/or safer pharmacological
actions (Panico et al., 2006).
The optimization of preparative chiral liquid chromatography and Simulated Moving Bed
(SMB) processes is a complex task that requires a careful selection of mobile phase
composition. In this selection, high resolution (or high selectivity) is not the only aspect, since
other parameters, such as high solubility and low retention times, are crucial aspects that
must also be considered (Ribeiro et al., 2008).
In this work, experimental results obtained for the ketoprofen and flurbiprofen enantiomers
will be shown, including solubility and adsorption measurements, and pulse and
breakthrough experiments. Additionally, simulation results, based on the experimental
adsorption isotherms measured, will be presented to compare the performance of fixed-bed
and SMB processes.
∗
Corresponding author. Tel + 351-273-303087. E-mail: [email protected]
2 Experimental tools, modeling and simulation
The experimental tools, modeling and simulation procedures for the optimization of mobile
phase composition are described in a recent published work (Ribeiro et al., 2008). This
includes experimental methods for solubility and adsorption isotherms measurements, and
simulation tools to predict the operation of fixed-bed and simulated moving bed processes.
3 Results and Discussion
3.1 Solubility of profen racemic mixtures
Firstly, the solubility of ketoprofen and flurbiprofen enantiomers was measured in three pure
solvents, all with a composition of 0.01%TFA: 100%n-hexane, 100%ethanol and
100%methanol. These solubility measurements were performed in duplicate and at a
temperature of 23ºC (room temperature). Obtained results (not shown) indicate that profens
solubility increases when the solvent is changed from 100%n-hexane to 100% ethanol and
from this to 100% methanol. On a second stage, the dependency of solubility with the
alcoholic composition in an ethanol/n-hexane mixture was investigated. Results were
consistent with the previous ones. Ketoprofen and flurbiprofen enantiomers have high
solubility values in solvents with a high polar composition. On the other hand, a mobile phase
with an increased polar content is referred as an advantage in preparative chromatography
due, not only because it allows higher racemate solubility, but also because presents lower
retention times (Lynam and Stringham, 2006).
3.2 Elution chromatography
Several experiments of elution chromatography (pulses) were performed on different solvent
mixtures of ethanol/n-hexane and methanol/n-hexane, in order to characterize the system
selectivity at preparative conditions. A preparative column (Chiralpak AD, Daicel, Japan),
with a particle size of 20 µm, was used on these experiments. Six level concentrations were
prepared in the range between 0.05 and 4.0 g/L, and injected using two different loops: 100
µL and 1 mL. Obtained results are presented in Figure 1, for ketoprofen, and in Figure 2, for
flurbiprofen.
For ketoprofen enantiomers, results show that the 20%ethanol/80%n-hexane mobile phase
presents considerable higher retention times than the pure mobile phases (ethanol and
methanol). The hydrocarbon mobile phase also leads to important chromatographic tails,
which is an indication of strong non-linear behavior and not welcome for preparative
separations. Comparing the results obtained for the two pure alcohol mobile phases it can be
clearly concluded that, despite higher ketoprofen solubility, pure methanol does not allows
acceptable selectivity values and, consequently, ketoprofen enantioseparation.
For the flurbiprofen enantiomers, high selectivity values can be obtained for mobile phase
compositions lower than 10%ethanol/90%h-hexane (results not shown). However, this
mobile phase composition exhibits retention times substantially higher and very low solubility
values, which means a clear disadvantage for high productivities. For an ethanol/n-hexanebased mobile phase, a 10/90 composition represents a reasonable compromise between
selectivity, retention time and solubility. For methanol/n-hexane-based mobile phase, due to
the immiscibility range between 6% and 60% methanol, its use is not possible. Taking into
account the very low solubility values, experiments with less than 6% of methanol in nhexane were also not carried out, since they are not attractive under preparative point of
view. On the other side, and despite high solubility, the use of a mobile phase with higher
methanol content (more than 60%) does not allow selectivity values as the ones obtained
with ethanol/n-hexane mixtures.
Figure 1. Experimental elution profiles of ketoprofen enantiomers in different mobile phase compositions:
20%ethanol/80%n-hexane, 100%ethanol and 100%methanol. Racemic ketoprofen concentrations in six different
levels: 0.05, 0.2, 0.5, 1.0, 2.0 and 4.0 g/L; preparative column (particle diameter of 20 µm); UV detection at 260
nm; flow rate of 1 mL/min; temperature of 23ºC; injection volumes of 100 µL and 1 mL.
Figure 2. Experimental elution profiles of flurbiprofen enantiomers in different mobile phase compositions:
10%ethanol/90%n-hexane, 100%ethanol and 100%methanol. Racemic flurbiprofen concentrations in six different
levels: 0.05, 0.2, 0.5, 1.0, 2.0 and 4.0 g/L; preparative column (particle diameter of 20 µm); UV detection at 260
nm; flow rate of 1 mL/min; temperature of 23ºC; injection volumes of 100 µL and 1 mL.
3.3 Multicomponent adsorption isotherm experiments and modeling
Figure 3 (for ketoprofen) and Figure 4 (for flurbiprofen enantiomers) present the experimental
results obtained for the adsorption isotherms measurements in different mobile phase
compositions, showing a good agreement with model predictions. In these figures, the
prediction of the selectivity factor and its concentration dependency is also represented.
Ketoprofen results clearly show three different situations: for 100%methanol, selectivity is low
and constant, which means that the separation of ketoprofen enantiomers hardly can be
achieved using pure methanol as mobile phase. Despite its high selectivity for low
concentrations, the common 20%ethanol/80%n-hexane mobile phase presents a strong
decrease in selectivity with the increase of enantiomers concentrations. The better situation
is obtained for 100%ethanol, where selectivity maintains high values even for high
enantiomer concentrations.
Results obtained for flurbiprofen enantiomers confirm a decrease in selectivity with the
increase of the alcoholic content. High selectivity values can be observed for high
hydrocarbon content. However, this mobile phase composition exhibits retention times
substantially higher and very low solubility values. As stated before, for the separation of the
flurbiprofen enantiomers, a 10%ethanol/90%n-hexane mobile phase composition is a
reasonable compromise between selectivity, retention time and solubility.
Figure 3. Comparison between model and experimental results for the equilibrium adsorption isotherms of
ketoprofen enantiomers using the bi-Langmuir model (BLG6) in 20%ethanol/80%n-hexane and 100%ethanol and
using the Langmuir model (LG3) in 100%methanol. Open and closed circles for the experimental concentration of
the less and the more retained enantiomer, respectively; solid lines for the adsorption isotherm model.
Temperature: 23ºC. The second line presents the prediction of the selectivity factor as a function of both
enantiomers concentration.
Figure 4. Comparison between model and experimental results for the equilibrium adsorption isotherms of
flurbiprofen enantiomers using the modified linear+Langmuir model (LLG5) in 10%ethanol/90%n-hexane,
100%ethanol and 100%methanol. Open and closed circles for the experimental concentration of the less and the
more retained enantiomer, respectively; solid lines for the adsorption isotherm model. Temperature: 23ºC. The
second line presents the prediction of the selectivity factor as a function of both enantiomers concentration.
3.4 Frontal chromatography experiments and simulation
Breakthroughs experiments were carried out with the purpose of testing the selected
adsorption isotherm models. In the present work it is shown experiments using a racemic
feed solution of 40 g/L and the selected mobile phase composition: 100%ethanol for the
ketoprofen and 10%ethanol/90%n-hexane for flurbiprofen enantiomers. It can be clearly
observed from Figure 5 that both the selected models describe very well the experimental
data behaviour in the whole concentration range.
Figure 5. Saturation (adsorption) and regeneration (desorption) curves for a racemic feed concentration of 40 g/L.
Comparison between experimental (points) and simulation (lines) results. Closed and open circles for the less and
the more retained enantiomer, respectively. Temperature: 23ºC. Flow rate: 0.5 mL/min. Ketoprofen: 100%ethanol
and bi-Langmuir model (BLG6); Flurbiprofen: 10%ethanol/90%n-hexane and modified linear+Langmuir model
(LLG5). Model parameters: ε=0.4, Pe=3500, St=kτ=1000 (see Ribeiro et al., 2008).
3.5 Performance of SMB operation
The performance of the ketoprofen enantiomers separation by SMB technology is compared
in Figure 6 for different mobile phase compositions using the Equilibrium Theory model. The
separation region (see plot γ3xγ2) for 20%ethanol/80%n-hexane has operating conditions
considerable different from the ones obtained for the pure alcohol mobile phases (pure
ethanol and pure methanol) due to the higher retention times. Comparing the separation
regions for the three mobile phases, it can be concluded that, for the 20/80 composition, the
separation region becomes quickly smaller with the increase of feed concentration. This is a
sign of stronger non-linear behavior of the adsorption process and a reason for lower
productivities.
The comparison of the SMB performance for the two pure alcohol mobile phases is clear:
both have similar operating conditions due to similar retention times, but pure ethanol
presents considerable better performances due to higher selectivity. Figure 6 also presents
the productivity and the solvent consumption obtained for the different mobile phase
compositions, as a function of feed concentration. These simulation results also clearly show
that pure ethanol is the better choice for the separation of ketoprofen enantiomers through
SMB operation: at high feed concentrations, the productivity using pure ethanol is three times
the ones obtained with the other two solvents, and solvent consumption is only 75% and
25% of the one needed with pure methanol and 20%ethanol/80%n-hexane, respectively.
Figure 6. SMB separation regions and prediction of the performance of SMB operation for ketoprofen
enantiomers: productivity and solvent consumption as a function of feed concentration for the different mobile
phase compositions.
For flurbiprofen enantiomers (see Figure 7) it can be observed high retention time values in
mobile phases with high hydrocarbon contents (the separation regions are progressively
located at higher values of γ2 and γ3 with an increase of the n-hexane content). On the other
side, these results are very different from the ones obtained for the separation of the
ketoprofen enantiomers. The dimension of the separation regions progressively decrease
with the decrease of the n-hexane content (increase of the ethanol content). Therefore, the
best performance (bigger separation region) is obtained with a 10%ethanol/90%n-hexane
composition through all feed concentration range. The performance parameters predictions
also support the previous conclusions. Under preparative conditions, maximum productivity
is achieved with the 10/90 composition, while solvent consumption does not significantly
differ for all mobile phase compositions.
Figure 7. SMB separation regions and prediction of the performance of SMB operation for flurbiprofen
enantiomers: productivity and solvent consumption as a function of feed concentration for the different mobile
phase compositions.
4 Conclusions
For the separation of ketoprofen enantiomers, best situation is achieved using pure ethanol
as mobile phase. For flurbiprofen enantiomers, the experimental results obtained lead to
different conclusions: a 10%ethanol/90%n-hexane composition is the better choice since it
represents a good compromise between selectivity, retention time and solubility. The present
work shows that the choice of the proper mobile phase composition is a topic of utmost
importance for the optimization of preparative liquid chromatographic separations. This
choice will affect the throughput of the separation process since solubility, retention time, and
selectivity are all parameters very sensitive to changes in mobile phase composition.
Acknowledgements
Financial support by the Portuguese R&D foundation FCT (Fundação para a Ciência e a
Tecnologia) and the European Community through FEDER (project POCI/EQU/59738/2004)
is gratefully acknowledged. The authors wish to thank Simão P. Pinho (Bragança Polytechnic
Institute) for the support on the solubility measurements.
References
Burian, M., Geisslinger, G. (2005). COX-dependent mechanisms involved in the
antinociceptive action of NSAIDs at central and peripherical sites. Pharmacol. Ther.
107, 139-154.
Lynam, K., Stringham, R. (2006) Chiral Separations on Polysaccharide Stationary Phases
Using Polar Organic Mobile Phases. Chirality 18, 1-9.
Panico, A., Cardile, V., Gentile, B., Garuti, F., Avondo, S., Rosisvalle, S. (2006). “In vitro”
differences among (R) and (S) enantiomers of Profens in their activities related to
articular pathophysiology. Inflammation 29, 119-128.
Ribeiro, A., Graça, N., Pais, L., Rodrigues, A. (2008). Preparative separation of ketoprofen
enantiomers: Choice of mobile phase composition and measurement of competitive
adsorption isotherms. Sep. Pur. Technol. 61, 375-383.