A computational approach to solvent selection for biphasic reaction systems [Elektronische Ressource] / vorgelegt von Martina Peters

Description

A Computational Approach to SolventSelection for Biphasic Reaction SystemsVon der Fakult¨at fu¨r Mathematik, Informatik und Naturwissenschaften derRWTH Aachen University zur Erlangung des akademischen Grades einerDoktorin der Ingenieurwissenschaften genehmigte Dissertationvorgelegt vonDiplom-ChemikerinMartina Petersaus BitburgBerichter: Universit¨atsprofessor Dr. rer. nat. Walter LeitnerUniversit¨atsprofessor Dr.-Ing. Andreas PfennigTag der mu¨ndlichen Pru¨fung: 15.12.2008Diese Dissertation ist auf den Internetseiten der Hochschulbibliothek online verfu¨gbar.The present doctoral thesis was carried out at the Institute of Technical and Macro-molecular Chemistry at RWTH Aachen University, Germany, under the supervision ofProf. Dr. Walter Leitner from 12/2005 until 12/2008. It was part of and financially sup-ported by the DFGgraduate school 1166BioNoCo - Biocatalysis using non-conventionalmedia.Parts of this thesis have already been published:• M. Peters, M. Zavrel, J. Kahlen, T. Schmidt, M. Ansorge-Schumacher, W. Leitner,J. Bu¨chs, L. Greiner, A. C. Spiess, Eng. Life Sci. 2008, 8, 546-552.• M. Peters, L. Greiner, K. Leonhard, AICHE J. 2008, 54, 2729-2734.• A. C. Spiess, W. Eberhard, M. Peters, M. F. Eckstein, L. Greiner, J. Bu¨chs, Chem.Eng. Proc. 2008, 47, 1034-1041.• M. Peters, M. F. Eckstein, G. Hartjen, A. C. Spiess, W. Leitner, L. Greiner, Ind.Eng. Chem. Res. 2007, 46, 7073-7078.• M. F. Eckstein, J. Lembrecht, J. Schumacher, W. Eberhard, A. C.

Informations

• Publié par: rheinisch-westfalischen_technischen_hochschule_-rwth-_aachen
• Publié le: 01 janvier 2008
• Nombre de lectures: 11
• Langue: English
• Poids de l'ouvrage: 4 Mo

Extrait

AComputationalApproachtoSolvent
SelectionforBiphasicReactionSystems

VonderFakulta¨tfu¨rMathematik,InformatikundNaturwissenschaftender
RWTHAachenUniversityzurErlangungdesakademischenGradeseiner
DoktorinderIngenieurwissenschaftengenehmigteDissertation

vorgelegtvon

Diplom-Chemikerin
MartinaPeters
ausBitburg

Berichter:Universita¨tsprofessorDr.rer.nat.WalterLeitner
Universita¨tsprofessorDr.-Ing.AndreasPfennig

Tagdermu¨ndlichenPru¨fung:15.12.2008

DieseDissertationistaufdenInternetseitenderHochschulbibliothekonlineverfu¨gbar.

ThepresentdoctoralthesiswascarriedoutattheInstituteofTechnicalandMacro-
molecularChemistryatRWTHAachenUniversity,Germany,underthesupervisionof
Prof.Dr.WalterLeitnerfrom12/2005until12/2008.Itwaspartofandnanciallysup-
portedbytheDFGgraduateschool1166BioNoCo-Biocatalysisusingnon-conventional
media.

Partsofthisthesishavealreadybeenpublished:
•M.Peters,M.Zavrel,J.Kahlen,T.Schmidt,M.Ansorge-Schumacher,W.Leitner,
J.Bu¨chs,L.Greiner,A.C.Spiess,Eng.LifeSci.2008,8,546-552.

•M.Peters,L.Greiner,K.Leonhard,AICHEJ.2008,54,2729-2734.

•A.C.Spiess,W.Eberhard,M.Peters,M.F.Eckstein,L.Greiner,J.Bu¨chs,Chem.
Eng.Proc.2008,47,1034-1041.

•M.Peters,M.F.Eckstein,G.Hartjen,A.C.Spiess,W.Leitner,L.Greiner,Ind.
Eng.Chem.Res.2007,46,7073-7078.

•M.F.Eckstein,J.Lembrecht,J.Schumacher,W.Eberhard,A.C.Spiess,M.Pe-
ters,C.Roosen,L.Greiner,W.Leitner,U.Kragl,Adv.Synth.Catal.2006,348,
1597-1604.

•M.F.Eckstein,M.Peters,J.Lembrecht,A.C.Spiess,L.Greiner,Adv.Synth.
Catal.2006,348,1591-1596.

Abstract

Biphasicreactionsystemswithareactiveandanon-reactivephasearewidespreadin
technicalapplications.Thenon-reactivephaseservesasareservoirofdissolvedsubstrates
athighconcentrationsandallowsfortheextractionoftheproductduringthereaction.
Theproperchoiceofthephasecombinationwillhavemanifoldinuenceoncatalytic
parameterssuchasactivity,selectivity,andstability,butalsoonmaximumconversionor
yield.Tooptimizesuchbiphasicreactions,conversionandyieldconstituteconcisetargets
ofpracticalrelevanceforarationalsolventscreeningwhichrequiresthermodynamic
informationoncoupledreactionsandphaseequilibriaasinput.Usually,theexperimental
determinationofthesedatarequiresconsiderablelaboratoryeort.
Tominimizetheexperimentaleortandtoenlargethedataspaceforoptimization,an
insilicosolventscreeningformaximumconversionandyieldindierentbiphasiccat-
alyzedreactionsisevaluated.Theprimarytargetoftheinvestigationsisinbiocatalytic
applicationsasthesebenetgreatlyfromtheadditionoforganicnon-reactivemediato
thereactiveaqueousphase.Theconductor-likescreeningmodelforrealisticsolvation
(COSMO-RS)isusedforthepredictionofsolutepartitioningbetweenorganicsolvents
andareactionmedium.Althoughthecalculatedresultsshowsignicantabsolutede-
viations,COSMO-RSstillpredictsthecorrecttrendsforthepartitioncoecientsof
solutesindierentsolvents.Furthermore,acombinationofstatisticalthermodynam-
icsandclassicalquantummechanicsisusedforthepredictionofthereactionequilibria.
Thecalculatedoverallreactionequilibriumusingthecalculatedpartitioncoecientsand
thecalculatedequilibriumconstantsagainresultsinthepredictionofthebestsolvent
combinationregardingconversionandyield.Extendingtheapproachwithnumerical
simulationsprovidesamoredetailedinsightintothereactionsystem.

Contents

Nomenclature

Listofgures

Listoftables

Listofschemes

v

xi

ix

iiix

1.Introduction1
1.1.Industrialapplicationsofsolvents......................2
1.2.Molecularmodelsforuidphases......................3
1.2.1.Constraintsforuid-phasemodels..................3
1.2.2.Inter-andintramolecularpotentialenergy.............5
1.2.3.Fundamentalequations........................5
1.2.4.Implicitmodelsforcondensedphases................6
1.2.4.1.Continuumsolvationmodels................7
1.2.4.2.Quantummechanics....................7
1.2.4.3.COSMO...........................9
1.2.5.Excessfunctionmodels........................11
1.2.5.1.Basicsofexcessfunctionmodels..............11
1.2.5.2.Groupinteractionmodels-UNIFAC...........12
1.2.5.3.Surfacechargeinteractionmodels-COSMO-RS.....15
1.3.Applicationsofuid-phasemodels......................20
1.4.Objective...................................21

i

Contents

2.Mathematicalanalysisofbiphasicreactionsystems25
2.1.Introduction..................................25
2.2.Materialsandmethods............................25
2.2.1.Computational............................25
2.2.2.Experimental.............................26
2.3.Resultsanddiscussion............................26
2.3.1.Mathematicaldescription......................27
2.3.2.Equilibriumconstant.........................30
2.3.3.Partitioncoecients.........................31
2.3.4.Co-substrateexcess..........................32
2.3.5.Phasevolumeratio..........................32
2.3.6.Experimentalvalidation.......................34
2.4.Conclusion...................................39

3.CalculatingpartitioncoecientsusingCOSMO-RS41
3.1.Introduction..................................41
3.2.Materialsandmethods............................41
3.2.1.Computational............................41
3.2.2.Experimental.............................43
3.3.Resultsanddiscussion............................44
3.3.1.Alcoholdehydrogenasecatalyzedreductions............44
3.3.2.Calculationofconcentration-dependentpartitioncoecients...44
3.3.3.Calculationofinnitedilutionpartitioncoecients........47
3.3.4.Solventscreening:partitioncoecients...............49
3.3.5.Solventscreening:equilibriumconversion..............49
3.4.Conclusion...................................53

4.Calculatingequilibriumconstants55
4.1.Introduction..................................55
4.2.Materialsandmethods............................55
4.2.1.Computational............................55
4.2.2.Experimental.............................56
4.3.Resultsanddiscussion............................56

ii

Contents

4.3.1.Gibbsfreeenergyofreactioninthegasphase...........58
4.3.2.Gibbsfreeenergyofsolvation....................60
4.3.3.StandardGibbsenergyofreactioninsolution...........61
4.3.4.Experimentalvalidation.......................63
4.4.Conclusion...................................64

5.CombiningCOSMO-RSwithdynamicmodelingforsolventscreening67
5.1.Introduction..................................67
5.2.Materialsandmethods............................68
5.2.1.Computational............................68
5.2.2.Experimental.............................69
5.3.Resultsanddiscussion............................69
5.3.1.Benzaldehydelyasecatalyzedcarbon-carboncoupling.......69
5.3.2.COSMO-RS..............................73
5.3.3.Dynamicmodeling..........................74
5.4.Conclusion...................................78

6.ConclusionandOutlook

Bibliography

Appendix

97

84

59

A.Computationaldetails95
A.1.Hardware...................................95
A.2.Software....................................95
A.2.1.Workowofageometryoptimization................96
A.2.1.1.Buildingofamolecule...................96
A.2.1.2.Denitionofcalculationparameters............96

B.Calculatingequilibriumconstants99
B.1.Gibbsfreeenergyofreactioninthegasphase...............99
B.2.StandardGibbsenergyofreactioninsolution...............102

iii

Contents

.C

.D

vi

Acknowledgements

Curriculum

tivea

501

701

Nomenclature

Symbols
AaA,B,C,D
EciGHJKkimnPi1PPsRSTUVX

Nomenclature

freeenergy,interfacialarea
segmentsurfacearea
compoundsA,B,C,D
energy
concentrationofcompoundi
Gibbsfreeenergy
enthalpy
masstransferux
equilibriumconstant
masstransfercoecientofcompoundi
factoraccountingforpartitioninginbiphasicmedia
molaramount
partitioncoecientofcompoundi
innitedilutionpartitioncoecient
-prole
partitioncoecientratioofproductandsubstrate,generalgasconstant
)B(n0cosubstrate/substrateratioS=n(A)0
temperature
internalenergy
phasevolumeratioV=VVN
Requilibriumconversion

v

Nomenclature

xz,,,
ii

molefraction
numberofelectrons
electrostaticmis