Subscriber access provided by Northwestern Univ Library Article Microkinetic model of propylene oligomerization on Brønsted acidic zeolites at low conversion Sergio Vernuccio, Elizabeth Bickel, Rajamani Gounder, and Linda J Broadbelt ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.9b02066 • Publication Date (Web): 21 Aug 2019 Downloaded from pubs.acs.org on September 2, 2019 Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication They are posted online prior to technical editing, formatting for publication and author proofing The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record They are citable by the Digital Object Identifier (DOI®) “Just Accepted” is an optional service offered to authors Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts is published by the American Chemical Society 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society Copyright © American Chemical Society However, no copyright claim is made to original U.S Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties Page of 68 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 ACS Catalysis Microkinetic model of propylene oligomerization on Brønsted acidic zeolites at low conversion Sergio Vernuccioa, Elizabeth E Bickelb, Rajamani Gounderb, Linda J Broadbelta* aDepartment of Chemical and Biological Engineering, Northwestern University, Evanston, IL, 60208, United States bDavidson School of Chemical Engineering, Purdue University, West Lafayette, IN, 47907, United States Abstract The construction of a computational framework that describes the kinetic details of the propylene oligomerization reaction network on Brønsted acidic zeolites is particularly challenging due to the considerable number of species and reaction steps involved in the mechanism This work presents a detailed microkinetic model at the level of elementary steps that includes 4,243 reactions and 909 ionic and molecular species within the C2-C9 carbon number range An automated generation procedure using a set of eight reaction families was applied to construct the reaction network The kinetic ACS Paragon Plus Environment ACS Catalysis 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 Page of 68 parameters for each elementary step were estimated using transition state theory, Evans-Polanyi relationships, and thermodynamic data The reaction mechanism and its governing kinetic parameters were embedded into the design equation of a plug-flow reactor, which was the reactor configuration used to experimentally measure reactant and product concentrations as a function of propylene conversion and temperature on a representative H-ZSM-5 (MFI) zeolite The resulting mechanistic model is able to accurately describe the experimental data over a wide range of operating conditions in the low propylene conversion
Subscriber access provided by Northwestern Univ Library Article Microkinetic model of propylene oligomerization on Brønsted acidic zeolites at low conversion Sergio Vernuccio, Elizabeth Bickel, Rajamani Gounder, and Linda J Broadbelt ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.9b02066 • Publication Date (Web): 21 Aug 2019 Downloaded from pubs.acs.org on September 2, 2019 Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication They are posted online prior to technical editing, formatting for publication and author proofing The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record They are citable by the Digital Object Identifier (DOI®) “Just Accepted” is an optional service offered to authors Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts is published by the American Chemical Society 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society Copyright © American Chemical Society However, no copyright claim is made to original U.S Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties Page of 68 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 ACS Catalysis Microkinetic model of propylene oligomerization on Brønsted acidic zeolites at low conversion Sergio Vernuccioa, Elizabeth E Bickelb, Rajamani Gounderb, Linda J Broadbelta* aDepartment of Chemical and Biological Engineering, Northwestern University, Evanston, IL, 60208, United States bDavidson School of Chemical Engineering, Purdue University, West Lafayette, IN, 47907, United States Abstract The construction of a computational framework that describes the kinetic details of the propylene oligomerization reaction network on Brønsted acidic zeolites is particularly challenging due to the considerable number of species and reaction steps involved in the mechanism This work presents a detailed microkinetic model at the level of elementary steps that includes 4,243 reactions and 909 ionic and molecular species within the C2-C9 carbon number range An automated generation procedure using a set of eight reaction families was applied to construct the reaction network The kinetic ACS Paragon Plus Environment ACS Catalysis 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 Page of 68 parameters for each elementary step were estimated using transition state theory, Evans-Polanyi relationships, and thermodynamic data The reaction mechanism and its governing kinetic parameters were embedded into the design equation of a plug-flow reactor, which was the reactor configuration used to experimentally measure reactant and product concentrations as a function of propylene conversion and temperature on a representative H-ZSM-5 (MFI) zeolite The resulting mechanistic model is able to accurately describe the experimental data over a wide range of operating conditions in the low propylene conversion (