Computational Study on the Effect of Thermal Boundary Conditions and Axial Aspect Ratio on Catalytic Oxidative Coupling of Methane

Wadkar, Chaitanya; Kumar, Aviral; Lee, Hyewon; Rollins, Benjamin; Grosjean, Nicolas; Singh, Satbir; Northrop, William F.

doi:10.1021/acs.iecr.3c02285

Title: Computational Study on the Effect of Thermal Boundary Conditions and Axial Aspect Ratio on Catalytic Oxidative Coupling of Methane

Journal Article · 08 November 2023 · Industrial and Engineering Chemistry Research

DOI: https://doi.org/10.1021/acs.iecr.3c02285 · OSTI ID:2274950

Wadkar, Chaitanya ^[1]; Kumar, Aviral ^[2]; Lee, Hyewon ^[3]; Rollins, Benjamin ^[4]; Grosjean, Nicolas ^[4]; Singh, Satbir ^[2];

^[3]

University of Minnesota, Minneapolis, MN (United States); University of Minnesota: Twin Cities
Carnegie Mellon University, Pittsburgh, PA (United States)
University of Minnesota, Minneapolis, MN (United States)
Johnson Matthey Technology Centre, Reading (United Kingdom)

Packed-bed reactor models with a large reactor-diameter-to-particle-diameter ratio (N > 10) are commonly used in catalysis research. Their use is underpinned by strong simplifying assumptions including unidirectional plug flow, negligible radial gradients, small axial diffusion, and isothermal operation. However, the complex exothermic–endothermic nature of reactions like oxidative coupling of methane (OCM) coupled with heat transfer from the catalyst surface and convective heat losses from the reactor wall provides an interesting case study to evaluate packed-bed assumptions and understand axial and radial temperature variations that may impact conversion and selectivity. This computational study investigates the effect of thermal boundary conditions on catalyst performance in laboratory OCM reactors (N = ~13) through computational fluid dynamics (CFD) simulation. Further, the 1-D model typically used for modeling plug flow reactors assumes negligible radial temperature and species concentration gradients. This assumption is evaluated for OCM reactors over a range of geometric axial aspect ratios, defined as the reactor length divided by the diameter, comparing the 1-D with 3-D CFD results. 1-D model predictions of catalyst performance start to deviate from the 3-D model predictions as the axial aspect ratio decreases, specifically as diameter increases at constant length. In the work, the 1-D model assumption is only found to be valid for axial aspect ratios higher than 1.6, a result considered to be relevant for all exothermic catalytic reactors.

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Research Organization:: University of Minnesota, Twin Cities, MN (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: EE0008333

OSTI ID:: 2274950

Journal Information:: Industrial and Engineering Chemistry Research, Journal Name: Industrial and Engineering Chemistry Research Journal Issue: 46 Vol. 62; ISSN 0888-5885

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (62)

Autothermal oxidative coupling of methane with ambient feed temperature Sarsani, Sagar; West, David; Liang, Wugeng Chemical Engineering Journal, Vol. 328 https://doi.org/10.1016/j.cej.2017.07.002	journal	November 2017
Packed Tubular Reactor Modeling and Catalyst Design using Computational Fluid Dynamics Dixon, Anthony G.; Nijemeisland, Michiel; Stitt, E. Hugh Computational Fluid Dynamics https://doi.org/10.1016/S0065-2377(06)31005-8	book	October 2006
Contact Modifications for CFD Simulations of Fixed-Bed Reactors: Cylindrical Particles Wehinger, Gregor D.; Fütterer, Carsten; Kraume, Matthias Industrial & Engineering Chemistry Research, Vol. 56, Issue 1 https://doi.org/10.1021/acs.iecr.6b03596	journal	December 2016
An artificial structure modeler for 3D CFD simulations of catalytic foams Wehinger, Gregor D.; Heitmann, Helge; Kraume, Matthias Chemical Engineering Journal, Vol. 284 https://doi.org/10.1016/j.cej.2015.09.014	journal	January 2016
Heat-Transfer Studies in Packed-Bed Catalytic Reactors of Low Tube/Particle Diameter Ratio Castillo-Araiza, C. O.; Jiménez-Islas, H.; López-Isunza, F. Industrial & Engineering Chemistry Research, Vol. 46, Issue 23 https://doi.org/10.1021/ie070097z	journal	August 2007
Oxidative coupling of methane with La2O3–CeO2 nanofiber fabrics: A reaction engineering study Noon, Daniel; Zohour, Bahman; Senkan, Selim Journal of Natural Gas Science and Engineering, Vol. 18 https://doi.org/10.1016/j.jngse.2014.04.004	journal	May 2014
Coupling CFD with detailed microkinetic modeling in heterogeneous catalysis Maestri, Matteo; Cuoci, Alberto Chemical Engineering Science, Vol. 96 https://doi.org/10.1016/j.ces.2013.03.048	journal	June 2013
Microkinetics of methane oxidative coupling Sun, J.; Thybaut, J.; Marin, G. Catalysis Today, Vol. 137, Issue 1 https://doi.org/10.1016/j.cattod.2008.02.026	journal	August 2008
Autothermal reforming of methane on rhodium catalysts: Microkinetic analysis for model reduction Dixit, Marm; Baruah, Renika; Parikh, Dhrupad Computers & Chemical Engineering, Vol. 89 https://doi.org/10.1016/j.compchemeng.2016.03.032	journal	June 2016
Quantitative screening of an extended oxidative coupling of methane catalyst library Alexiadis, V. I.; Chaar, M.; van Veen, A. Applied Catalysis B: Environmental, Vol. 199 https://doi.org/10.1016/j.apcatb.2016.06.019	journal	December 2016
Investigating dry reforming of methane with spatial reactor profiles and particle-resolved CFD simulations Wehinger, Gregor D.; Kraume, Matthias; Berg, Viktor AIChE Journal, Vol. 62, Issue 12 https://doi.org/10.1002/aic.15520	journal	October 2016
Synthesis of ethylene via oxidative coupling of methane I. Determination of active catalysts Keller, G. Journal of Catalysis, Vol. 73, Issue 1 https://doi.org/10.1016/0021-9517(82)90075-6	journal	January 1982
Catalyst design based on microkinetic models: Oxidative coupling of methane Thybaut, Joris W.; Sun, Jianjun; Olivier, Louis Catalysis Today, Vol. 159, Issue 1 https://doi.org/10.1016/j.cattod.2010.09.002	journal	January 2011
Estimation of Effective Thermal Conductivity of Two-Phase Materials Using Collocated Parameter Model Reddy, K. S.; Karthikeyan, P. Heat Transfer Engineering, Vol. 30, Issue 12 https://doi.org/10.1080/01457630902837533	journal	October 2009
Detailed numerical simulations of catalytic fixed-bed reactors: Heterogeneous dry reforming of methane Wehinger, Gregor D.; Eppinger, Thomas; Kraume, Matthias Chemical Engineering Science, Vol. 122 https://doi.org/10.1016/j.ces.2014.09.007	journal	January 2015
A High-Fidelity CFD Model of Methane Steam Reforming in a Packed Bed Reactor Kuroki, Mayu; Ookawara, Shinichi; Ogawa, Kohei JOURNAL OF CHEMICAL ENGINEERING OF JAPAN, Vol. 42, Issue Supplement. https://doi.org/10.1252/jcej.08we256	journal	January 2009
Detailed Reaction Mechanisms for the Oxidative Coupling of Methane over La ₂ O ₃ /CeO ₂ Nanofiber Fabric Catalysts Karakaya, Canan; Zhu, Huayang; Zohour, Bahman ChemCatChem, Vol. 9, Issue 24 https://doi.org/10.1002/cctc.201701172	journal	December 2017
Advances in fixed-bed reactor modeling using particle-resolved computational fluid dynamics (CFD) Jurtz, Nico; Kraume, Matthias; Wehinger, Gregor D. Reviews in Chemical Engineering, Vol. 35, Issue 2 https://doi.org/10.1515/revce-2017-0059	journal	February 2019
Effect of pressure on the oxidative coupling of methane in the absence of catalyst Chen, Q.; Couwenberg, P. M.; Marin, G. B. AIChE Journal, Vol. 40, Issue 3 https://doi.org/10.1002/aic.690400313	journal	March 1994
Estimation of Effective Transport Properties in Packed Bed Reactors Kulkarni, B. D.; Doraiswamy, L. K. Catalysis Reviews, Vol. 22, Issue 3 https://doi.org/10.1080/03602458008067540	journal	January 1980
Productivity Enhancement for the Oxidative Coupling of Methane in Adiabatic Layered-Bed Reactors Pirro, Laura; Mendes, Pedro S. F.; De Keulenaer, Joris ACS Engineering Au, Vol. 1, Issue 1 https://doi.org/10.1021/acsengineeringau.1c00008	journal	August 2021
Autothermal oxidative coupling of methane on the SrCO3/Sm2O3 catalysts Wang, Kai; Ji, Shengfu; Shi, Xuejun Catalysis Communications, Vol. 10, Issue 6 https://doi.org/10.1016/j.catcom.2008.12.001	journal	February 2009
Analysis of volume‐to‐surface ratio effects on methane oxidative coupling using microkinetic modeling Alexiadis, V. I.; Serres, T.; Marin, G. B. AIChE Journal, Vol. 64, Issue 7 https://doi.org/10.1002/aic.16152	journal	March 2018
Strategies To Improve the Activity While Maintaining the Selectivity of Oxidative Coupling of Methane at La ₂ O ₃ : A Density Functional Theory Study Wang, Zhi-Qiang; Wang, Dong; Gong, Xue-Qing ACS Catalysis, Vol. 10, Issue 1 https://doi.org/10.1021/acscatal.9b03066	journal	November 2019
Catalyst ignition and extinction: A microkinetics-based bifurcation study of adiabatic reactors for oxidative coupling of methane Vandewalle, Laurien A.; Lengyel, Istvan; West, David H. Chemical Engineering Science, Vol. 199 https://doi.org/10.1016/j.ces.2018.08.053	journal	May 2019
Characterisation and design of single pellet string reactors using numerical simulation Fernengel, Johanna; Bolton, Leslie; Hinrichsen, Olaf Chemical Engineering Journal, Vol. 373 https://doi.org/10.1016/j.cej.2019.03.114	journal	October 2019
Scaled-up production of C2 hydrocarbons by the oxidative coupling of methane over pelletized Na2WO4/Mn/SiO2 catalysts: Observing hot spots for the selective process Lee, Jong Yeol; Jeon, Wonjin; Choi, Jae-Wook Fuel, Vol. 106 https://doi.org/10.1016/j.fuel.2013.01.026	journal	April 2013
Wärmeleitfähigkeit von Schüttungen bei mäßigen Temperaturen: Wärmeleitfähigkeit von Schüttungen bei mäßigen Temperaturen Zehner, P.; Schlünder, E. U. Chemie Ingenieur Technik, Vol. 42, Issue 14 https://doi.org/10.1002/cite.330421408	journal	July 1970
A meta-analysis of catalytic literature data reveals property-performance correlations for the OCM reaction Schmack, Roman; Friedrich, Alexandra; Kondratenko, Evgenii V. Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-08325-8	journal	January 2019
Oxidative coupling of methane: catalytic behaviour assessment via comprehensive microkinetic modelling Alexiadis, V. I.; Thybaut, J. W.; Kechagiopoulos, P. N. Applied Catalysis B: Environmental, Vol. 150-151 https://doi.org/10.1016/j.apcatb.2013.12.043	journal	May 2014
Model-Based Catalyst Selection for the Oxidative Coupling of Methane in an Adiabatic Fixed-Bed Reactor Pirro, Laura; Obradović, Ana; Vandegehuchte, Bart D. Industrial & Engineering Chemistry Research, Vol. 57, Issue 48 https://doi.org/10.1021/acs.iecr.8b04242	journal	November 2018
Fixed bed catalytic reactor modelling-the radial heat transfer problem Dixon, Anthony G. The Canadian Journal of Chemical Engineering, Vol. 90, Issue 3 https://doi.org/10.1002/cjce.21630	journal	December 2011
Experimental determination of La2O3 thermal conductivity and its application to the thermal analysis of a-Ge/La2O3/c-Si laser annealing Fornarini, L.; Conde, J. C.; Alvani, C. Thin Solid Films, Vol. 516, Issue 21 https://doi.org/10.1016/j.tsf.2008.02.032	journal	September 2008
Chemical Reactor Design, Optimization, and Scaleup Nauman, E. Bruce https://doi.org/10.1002/9780470282076	book	October 2007
Numerical simulation of a structured catalytic methane reformer by DUO: The new computational interface for OpenFOAM® and DETCHEM™ Hettel, Matthias; Diehm, Claudia; Bonart, Henning Catalysis Today, Vol. 258 https://doi.org/10.1016/j.cattod.2015.02.011	journal	December 2015
A review of correlations to model the packing structure and effective thermal conductivity in packed beds of mono-sized spherical particles van Antwerpen, W.; du Toit, C. G.; Rousseau, P. G. Nuclear Engineering and Design, Vol. 240, Issue 7 https://doi.org/10.1016/j.nucengdes.2010.03.009	journal	July 2010
CFD testing of the pointwise use of the Zehner–Schlünder formulas for fixed-bed stagnant thermal conductivity Dixon, Anthony G.; Gurnon, A. Kate; Nijemeisland, Michiel International Communications in Heat and Mass Transfer, Vol. 42 https://doi.org/10.1016/j.icheatmasstransfer.2012.12.013	journal	March 2013
Carman–Kozeny Equation Kruczek, Boguslaw Encyclopedia of Membranes https://doi.org/10.1007/978-3-642-40872-4_1995-1	book	January 2014
High-Throughput Experimentation and Catalyst Informatics for Oxidative Coupling of Methane Nguyen, Thanh Nhat; Nhat, Thuy Tran Phuong; Takimoto, Ken ACS Catalysis, Vol. 10, Issue 2 https://doi.org/10.1021/acscatal.9b04293	journal	December 2019
Enhanced Voidage Correlations for Packed Beds of Various Particle Shapes and Sizes Benyahia, F.; O'Neill, K. E. Particulate Science and Technology, Vol. 23, Issue 2 https://doi.org/10.1080/02726350590922242	journal	April 2005
Catalyst screening for the oxidative coupling of methane: from isothermal to adiabatic operation via microkinetic simulations Pirro, Laura; Mendes, Pedro S. F.; Vandegehuchte, Bart D. Reaction Chemistry & Engineering, Vol. 5, Issue 3 https://doi.org/10.1039/C9RE00478E	journal	January 2020
Estimation of effective thermal conductivity of packed beds incorporating effects of primary and secondary parameters Jayachandran, S.; Reddy, K. S. Thermal Science and Engineering Progress, Vol. 11 https://doi.org/10.1016/j.tsep.2018.12.011	journal	June 2019
Sub-grid scale modeling of heterogeneous chemical reactions and transport in full-scale catalytic converters Mazumder, Sandip; Sengupta, Debasis Combustion and Flame, Vol. 131, Issue 1-2 https://doi.org/10.1016/S0010-2180(02)00392-9	journal	October 2002
Studies on effective thermal conductivities in packed beds Yagi, Sakae; Kunii, Daizo AIChE Journal, Vol. 3, Issue 3 https://doi.org/10.1002/aic.690030317	journal	September 1957
Bifurcation analysis of methane oxidative coupling without catalyst Sun, Zhe; Kota, Arun; Sarsani, Sagar Chemical Engineering Journal, Vol. 343 https://doi.org/10.1016/j.cej.2018.02.004	journal	July 2018
Products of catalytic oxidative coupling of methane to improve thermal efficiency in natural gas engines Cho, Seokwon; Lee, Hyewon; Lin, Ying Energy Conversion and Management, Vol. 268 https://doi.org/10.1016/j.enconman.2022.116030	journal	September 2022
Heat transfer characteristics of porous rocks Kunii, Daizo; Smith, J. M. AIChE Journal, Vol. 6, Issue 1 https://doi.org/10.1002/aic.690060115	journal	March 1960
CFD Study of Heat Transfer near and at the Wall of a Fixed Bed Reactor Tube: Effect of Wall Conduction Dixon, Anthony G.; Nijemeisland, Michiel; Stitt, E. Hugh Industrial & Engineering Chemistry Research, Vol. 44, Issue 16 https://doi.org/10.1021/ie049183e	journal	April 2005
Recent advances and future prospect in catalysts for oxidative coupling of methane to ethylene: A review Gambo, Y.; Jalil, A. A.; Triwahyono, S. Journal of Industrial and Engineering Chemistry, Vol. 59 https://doi.org/10.1016/j.jiec.2017.10.027	journal	March 2018
Oxidative Coupling of Methane: A Microkinetic Model Accounting for Intraparticle Surface-Intermediates Concentration Profiles Kechagiopoulos, Panagiotis N.; Thybaut, Joris W.; Marin, Guy B. Industrial & Engineering Chemistry Research, Vol. 53, Issue 5 https://doi.org/10.1021/ie403160s	journal	December 2013
Synthetic Packed-Bed Generation for CFD Simulations: Blender vs. STAR-CCM+ Flaischlen, Steffen; Wehinger, Gregor D. ChemEngineering, Vol. 3, Issue 2 https://doi.org/10.3390/chemengineering3020052	journal	May 2019
In situ adaptive tabulation for the CFD simulation of heterogeneous reactors based on operator-splitting algorithm Bracconi, Mauro; Maestri, Matteo; Cuoci, Alberto AIChE Journal, Vol. 63, Issue 1 https://doi.org/10.1002/aic.15441	journal	August 2016
Numerical simulations of single phase reacting flows in randomly packed fixed-bed reactors and experimental validation Freund, Hannsjörg; Zeiser, Thomas; Huber, Florian Chemical Engineering Science, Vol. 58, Issue 3-6 https://doi.org/10.1016/S0009-2509(02)00622-X	journal	February 2003
A Lumped-Parameter Model for Stagnant Thermal Conductivity of Spatially Periodic Porous Media Hsu, C. T.; Cheng, P.; Wong, K. W. Journal of Heat Transfer, Vol. 117, Issue 2 https://doi.org/10.1115/1.2822515	journal	May 1995
Scale‐up analysis of autothermal operation of methane oxidative coupling with La₂O₃/CaO catalyst Sun, Zhe; West, David H.; Gautam, Pankaj AIChE Journal, Vol. 66, Issue 6 https://doi.org/10.1002/aic.16949	journal	February 2020
Systematic mesh development for 3D CFD simulation of fixed beds: Contact points study Dixon, Anthony G.; Nijemeisland, Michiel; Stitt, E. Hugh Computers & Chemical Engineering, Vol. 48 https://doi.org/10.1016/j.compchemeng.2012.08.011	journal	January 2013
Influence of Macroscopic Wall Structures on the Fluid Flow and Heat Transfer in Fixed Bed Reactors with Small Tube to Particle Diameter Ratio Eppinger, Thomas; Jurtz, Nico; Kraume, Matthias Processes, Vol. 9, Issue 4 https://doi.org/10.3390/pr9040689	journal	April 2021
Evaluating Catalytic Fixed‐Bed Reactors for Dry Reforming of Methane with Detailed CFD Wehinger, Gregor D.; Eppinger, Thomas; Kraume, Matthias Chemie Ingenieur Technik, Vol. 87, Issue 6 https://doi.org/10.1002/cite.201400153	journal	March 2015
Flow and Transport in Porous Formations Dagan, Gedeon https://doi.org/10.1007/978-3-642-75015-1	book	January 1989
CFD analysis of fluid flow and particle-to-fluid heat transfer in packed bed with radial layered configuration Guo, Zehua; Sun, Zhongning; Zhang, Nan Chemical Engineering Science, Vol. 197 https://doi.org/10.1016/j.ces.2018.12.034	journal	April 2019
CFD Simulation of Reaction and Heat Transfer Near the Wall of a Fixed Bed Dixon, Anthony G.; Nijemeisland, Michiel; Stitt, Hugh International Journal of Chemical Reactor Engineering, Vol. 1, Issue 1 https://doi.org/10.2202/1542-6580.1069	journal	July 2003
The Radiant Heat Transfer in the High Temperature Reactor Core after Failure of the Afterheat Removal Systems Breitbach, G.; Barthels, H. Nuclear Technology, Vol. 49, Issue 3 https://doi.org/10.13182/NT80-A17687	journal	August 1980

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Title: Computational Study on the Effect of Thermal Boundary Conditions and Axial Aspect Ratio on Catalytic Oxidative Coupling of Methane

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