Devocht, Brigitte

Rajkhowa, Tapas

Thybaut, Joris

Toch, Kenneth

English

Ghent University Academic Bibliography

Laboratory for Chemical Technology, Ghent Universityhttp://www.lct.UGent.beOpportunities for Automation in theMicrokinetic Assessment of Complex Reactions: from Conventional toRenewable FeedsTapas Rajkhowa, Brigitte R. Devocht, Kenneth Toch,Guy B. Marin Joris W. Thybaut1PETROTECH-2016, New Delhi, India, December 5-7information driven catalyst & reactor designPETROTECH-2016, New Delhi, India, December 5-7catalyst library activity libraryoptimizeddescriptorsnewconceptindustrialapplicationperformance testingdesignsynthesiskinetic and catalystdescriptorsmodelling1234 HHHHHHHHHHHHHHHHHHHHHHH HHHHH******** ****HHHHHHHHHHH*13 62 45789101112 13k(2,2) k(2,2)k(2,2)k(2,2)k(2,2) k(2,2)k(1,2)k(1,2)k(1,2)k(1,2)k(1,2)k(1,2)k(1,2)k(1,2)k(0,2) k(0,2)k(0,2)k(0,2)k(0,2) k(0,2)2J.W. Thybaut et al., Topics Catal. 52 (2009) 1251-1260Single-Event MicroKinetics (SEMK)Sabbe et al. AIChE J. 57 (2011) 482-496Quintana-Solorzano et al. Chem. Eng. Sci. 62 (2007) 5033-5038Kumar et al. Catal. Today 215 (2013) 224-232Kumar et al. Ind. Eng. Chem. Res. 52 (2013) 1491-1507Lozano-Blanco et al. Ind. Eng. Chem. Res. 47 (2008) 5879-5891J. Van Belleghem et al. Appl. Catal. A Gen. 524 (2016) 149-162 Bera et al. ACS Catalysis 2 (2012) 1305-1318Thybaut et al. J. Catal. 202 (2001) 324-339Cochegrue et al. Oil Gas Sci. Technol. 66 (2011) 367-397Toch et al. Appl. Catal. A Gen 489 (2015) 292-3043• thermal cracking• acid catalysis– catalytic cracking– methanol to olefins• metal catalysis– Fischer Tropsch synthesis– hydrogenation• bifunctional catalysis– hydrocracking– catalytic reforming– ethene oligomerizationPETROTECH-2016, New Delhi, India, December 5-7• pour point reduction• slight decrease in viscosity index• objective– enhanceisomerization– avoid product lossesvia cracking4PETROTECH-2016, New Delhi, India, December 5-7lube oil productionJ.A. Martens et al. Angew. Chem. Intl. Ed. 34 (1995) 2528W. Souverijns et al. J. Catal. 174 (1998) 177external surface(Pt clusters)pore mouthsmicroporesPoremouthsiteBridgesite: nearBridgesite: far• pore mouth sites: isomerization• micropore sites: cracking linear alkanes• bridge sites: aselective reactions5PETROTECH-2016, New Delhi, India, December 5-7ZSM-22 as catalystC.S.L. Narasimhan et al. J. Catal. 218 (2003) 135-147C.S.L. Narasimhan et al. J. Catal. 220 (2003) 399-413reaction pathway analysis6PETROTECH-2016, New Delhi, India, December 5-7C.S.L. Narasimhan et al. J. Catal. 220 (2003) 399-413I.R. Choudhury et al. J. Catal 290 (2012) 165-176superior ZSM-22 synthesis020406080100423 473 523 573Isomer Yield / mol%Temperature / K• original ZSM-22– calcination– “stronger” sites– additional microporesites creation• novel ZSM-22– dual ion exchange– “weaker” sites– comparatively lessmicropore sites.7PETROTECH-2016, New Delhi, India, December 5-7H. Kazuaki et al. Chem. Eur. J. 13 (2007) 10070-10077US20100181229 (catalyst synthesis)US20110042267 (lube oil dewaxing process)aromatic hydrogenation8PETROTECH-2016, New Delhi, India, December 5-7020406080400 420 440 460 480 500 520Surface coverage, %Temperature, KHydrocarbonHydrogenFree site010203040506070400 420 440 460 480 500 520Conversion, %Temperature, K1 MPa2 MPa3 MPaT. Bera et al. Ind. Eng. Chem. Res. 50 (2011) 12933-12945 T. Bera et al. ACS Catalysis 2 (2012) 1305-1318metal catalysis, Ptreaction families- # unsatured neighbouring C atoms- carbon atom typeXylene isomerization on a bifunctional Pt/H-ZSM-5 catalystReaction network consists out of:• acid catalyzed reactions:(de-)protonation,alkyl shift (MS),dealkylation, (DA)transalkylation (TA)• metal catalyzed reactions:Hydrogenation (HYD)• physisorptionxylene isomerization: SEMK catalyst design9PETROTECH-2016, New Delhi, India, December 5-7K. Toch et al. Appl. Catal. A-Gen 425 (2012) 130-14410long alkane hydrocracking over BETAPETROTECH-2016, New Delhi, India, December 5-7USY n-octane BETA n-hexadecaneB. Vandegehuchte et al. Appl. Catal. A-Gen 441-442 (2012) 10-20shape selectivitysize entropy effectsrenewable feed conversion11OOHOHOHOHOHOHOHOHOHOHOOOHOHOHOHOHOHOOHOHOHOHcomplex mixtures → model compoundsPETROTECH-2016, New Delhi, India, December 5-7outline• introduction• kinetics assessment automation– opportunities– Fischer Tropsch synthesis– network generation algorithm• renewable feeds– challenges and strategy– glycerol hydrogenolysis• conclusions12PETROTECH-2016, New Delhi, India, December 5-7opportunities for automation13complex mixture reaction families• reaction types(de)protonationpcp-branchingβ-scissionalkylation• intermediate stabilitycarbon atom typenearest neighboureffectsreactant 0,# 0,#global b#globalσ k T S Hk exp expσ h R RT          energy -enthalpyentropyJ.W. Thybaut and G.B. Marin, J. Catal. 308 (2013) 352-362ne k~PETROTECH-2016, New Delhi, India, December 5-7ethene oligomerization on Ni on acid supportopportunities for automation14complex mixturenumber of alkenes 1220number of carbenium ions 972number of elementary stepsmetal-ion oligomerization 5protonation 1985deprotonation 1985pcp-branching 10961,2 alkyl shift 668alkylation 330β-scission 330K. Toch et al. Appl. Catal. A Gen 489 (2015) 292-304PETROTECH-2016, New Delhi, India, December 5-7example: Fischer-Tropsch synthesis15reaction families based on carbeneinsertionmechanism1. initiation: dissociation of hydrogen and CO formation of CHx groups on the surface2. chain growth: CH2 group insertion into adsorbedalkyl species3. termination: hydrogenation or recombination of surface species to paraffins and desorption of olefinssyngasGasificationGasificationGTLnatural gascoalbiomasshigherhydrocarbonsFTCOH2PETROTECH-2016, New Delhi, India, December 5-7reaction familieshydrogen adsorption carbon hydrogenationhydrogen desorption carbene insertionCO adsorption carbene deinsertionCO desorption olefin desorptionCO dissociation olefin adsorptionoxygen hydrogenation β- Hydrogen eliminationexample: Fischer-Tropsch synthesis16reaction families based on carbeneinsertionmechanismsyngasGasificationGasificationGTLnatural gascoalbiomasshigherhydrocarbonsFTCOH21. initiation2. chain growth3. terminationPETROTECH-2016, New Delhi, India, December 5-7Fischer Tropsch reaction network17H2COHCOreaction familieshydrogen adsorptionhydrogen desorptionCO adsorptionCO desorptionCO dissociationoxygen hydrogenationcarbon hydrogenationcarbene insertioncarbene deinsertionolefin desorptionolefin adsorptionβ- Hydrogen eliminationsurface deactivationuser inputiterate over speciescheck each reaction familyexecute reaction family recipeadd products and reactions to networkare termination criteria met?COCHOHH2OCH2…CH3C2H5G. Lozano-Blanco et al. Ind. Eng. Chem. Res. 47 (2008) 5879-5891PETROTECH-2016, New Delhi, India, December 5-7species representation18CH3CH2CH2M1 2 2 11 2 3 3𝑀 0 1 0 0𝐶 1 0 1 0𝐶𝐶001 0 10 1 0Standarized labelBoolean matrixUsed to store the species Used to generate the reactionsAre interconverted at runtimeG. Lozano-Blanco et al. Ind. Eng. Chem. Res. 47 (2008) 5879-5891PETROTECH-2016, New Delhi, India, December 5-7kinetic model parameters19𝑘 =𝜎𝑔𝑙,𝑟𝜎𝑔𝑙,‡𝑘𝐵𝑇ℎ𝑒𝑥𝑝∆ ሚ𝑆0,‡𝑅𝑒𝑥𝑝∆𝐻0,‡𝑅𝑇constant for a reaction family (chain length independent)determined by the reaction network generation code∆ ሚ𝑆0,‡ single-event activation entropyCalculated based on changes in translational degrees of freedom∆𝐻0,‡ activation enthalpyobtained by regression to experimental data𝑛𝑝𝑎𝑟𝑎𝑚𝑒𝑡𝑒𝑟𝑠 = 𝑛𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑓𝑎𝑚𝑖𝑙𝑖𝑒𝑠for each reaction family:G. Lozano-Blanco et al. Ind. Eng. Chem. Res. 47 (2008) 5879-5891PETROTECH-2016, New Delhi, India, December 5-7thermodynamic model parameters20Thermodynamic consistency of the overall Fischer Tropsch reaction is guaranteed by using the principle of microscopic reversibility:𝐸𝑎𝑟𝑒𝑣 = 𝐸𝑎𝑓𝑜𝑟 − ∆𝐻𝑅,𝑠𝑢𝑟𝑓0ሚ𝐴𝑟𝑒𝑣 =ሚ𝐴𝑓𝑜𝑟𝑒𝑥𝑝∆ ሚ𝑆𝑅0𝑅𝑛𝑝𝑎𝑟𝑎𝑚𝑒𝑡𝑒𝑟𝑠 =12𝑛𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑓𝑎𝑚𝑖𝑙𝑖𝑒𝑠 + 3∆𝐻𝑅,𝑠𝑢𝑟𝑓0 = ∆𝐻𝑅,𝑔𝑎𝑠0 + ෍𝑖=1𝑟𝑒𝑎𝑐𝑡𝜈𝑖∆𝐻𝑐ℎ𝑒𝑚,𝑖0 − ෍𝑖=1𝑝𝑟𝑜𝑑𝜈𝑖∆𝐻𝑐ℎ𝑒𝑚,𝑖0∆𝐻𝑅,𝑔𝑎𝑠0 = ෍𝑖=1𝑝𝑟𝑜𝑑𝜈𝑖∆𝑓ℎ𝑖0 − ෍𝑖=1𝑟𝑒𝑎𝑐𝑡𝜈𝑖∆𝑓ℎ𝑖0∆𝐻𝑐ℎ𝑒𝑚,𝑖0 = 𝑓(𝑄𝐶 , 𝑄𝑂, 𝑄𝐻) by UBI-QEP are taken from existing databasesparameters in the model and are determined by regressionG. Lozano-Blanco et al. Ind. Eng. Chem. Res. 47 (2008) 5879-5891PETROTECH-2016, New Delhi, India, December 5-7network generation algorithm21ReNGeP – Reaction Network Generation Programinputnetworkgenerationoutput usespecies, thermodynamics, reactions, rate coefficientsiterate over speciescheck eachreaction familyexecute reactionfamily recipeare terminationcriteria met? yesnoadd products and reactions tonetworksub-molecular patternsspecies uniquenessrule-basedreactionisomorphismreaction family concept, nearest neighbour effectsPETROTECH-2016, New Delhi, India, December 5-7outline• introduction• kinetics assessment automation– opportunities– Fischer Tropsch synthesis– network generation algorithm• renewable feeds– challenges and strategy– glycerol hydrogenolysis• conclusions22PETROTECH-2016, New Delhi, India, December 5-7challenges renewable feedstocks23conventional renewablenew challenges for network generation and kinetic model construction?• accounting for heteroatoms• new functions → new reaction families, next nearest neighbour effects,…• smarter (adaptive) network size controlcorresponding strategy• assessment of simple reaction network: glycerol hydrogenolysis• extension towards more complex ones: hydrodeoxygenationR. Van de Vijver et al. Current Opinion Chem. Eng. 13 (2016) 142-149PETROTECH-2016, New Delhi, India, December 5-7glycerol hydrogenolysis kinetics24p: 7.0 MPa, FH2/Fgly: 5, T: 503 K(■) PG, (▲) acetol acetol is a primary product (from glycerol dehydration) acetol hydrogenation is faster than glycerol dehydrationp:  7.5 MPa, FH2/Fgly: 5,  X ~ 0.35 higher activation energy for dehydration stepT. Rajkhowa et al. revised version submitted to Appl. Catal. B Env.PETROTECH-2016, New Delhi, India, December 5-7reaction network25reaction familiesdehydration hydrogenationC-C bond scission isomerizationPETROTECH-2016, New Delhi, India, December 5-7graph representation26boolean matrix𝐶𝐶𝐶𝑂𝑂𝑂010100101010010001100000010000001000graphABCDEFѵ simplicityx covers small range ofpossible elementspossible structuresgraph theoryobject-oriented programmingѵ more complex, flexible data structuresѵ application graph-theoreticalgorithms chemoinformaticse.g. calculation symmetry numbersPETROTECH-2016, New Delhi, India, December 5-7kinetics assesment and model performance27T. Rajkhowa et al. revised version submitted to Appl. Catal. B Env.PETROTECH-2016, New Delhi, India, December 5-7Rate coefficientA Ea k483k1comp 1015 78.5 ± 2.15 3.2 x 106k2comp 1013 59.8 ± 1.07 3.4 x 106k3 1013 98.9 ± 11.2 2.0 x 102k4 1013 93.8 ± 11.1 7.1 x 102k5 1014 91.6 ± 1.26 1.2 x 104k6 1014 91.6 ± 0.97 1.3 x 104k7 1014 88.8 ± 1.18 2.5 x 104k8 1012 112.4 ± 3.51 0.70Adsorption coefficient∆S0 -∆H0 K483KG -168 71.2 ± 1.09 8.4 x 10-2KA -166 68.0 ± 3.97 4.8 x 10-2KPG -143 53.6 ± 1.45 2.1 x 10-2KH -136 64.8 ± 10.6 8.0 x 10-1KH2O -154 53.3 ± 1.27 5.3 x 10-3Equilibrium coefficient∆S0 -∆H0 K483KAH 0 5.3 ± 1.8 1.00F value 1.7 x 105 (Ftab : 2.79)p:  7.5 MPa, FH2/Fgly: 5,  X ~ 0.35p: 7.0 MPa, FH2/Fgly: 5, T: 503 K(■) PG, (▲) acetolinputnetworkgenerationoutput useiterate over speciescheck eachreaction familyexecute reactionfamily recipeare terminationcriteria met? yesnoadd products and reactions tonetworksub-molecular patternsspecies uniquenessrule-basedreactionisomorphismspecies, thermodynamics, reactions, rate coefficientsnetwork generation algorithm28matrix → graph• accounting for heteroatoms• new functions → new reaction families, next nearest neighbour effects• adaptive network size controlPETROTECH-2016, New Delhi, India, December 5-7conclusions• elementary kinetics based models– detailed insight in reaction mechanism– information driven catalyst and reactor design • complex mixtures → automated assessment– reaction families– kinetic and thermodynamic parameter estimation andcalculation• transition from conventional to renewable feeds– hetero-atoms (oxygen, nitrogen, sulfur)– reaction family definition, (next) nearest neighbour effects– species representation and reaction generation– network size control29PETROTECH-2016, New Delhi, India, December 5-7acknowledgementsdr. Laxmi Narasimhandr. Lozano Blancodr. Indranil Choudharydr. Tapan Beradr. Pravesh Kumardr. Bart Vandegehuchtedr. Kenneth Tochir. Jonas Van Belleghemir. Tapas Rajkhowair. Brigitte Devochtprof. Guy B. Marin 30PETROTECH-2016, New Delhi, India, December 5-7

Opportunities for Automation in the Microkinetic Assessment of Complex Reactions: from Conventional to Renewable Feeds

https://biblio.ugent.be/publication/8523985/file/8525261

Opportunities for Automation in the Microkinetic Assessment of Complex Reactions: from Conventional to Renewable Feeds

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