52 research outputs found

    Effect of Co incorporation and support selection on deoxygenation selectivity and stability of (Co)Mo catalysts in anisole HDO

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    A series of supported Co modified Mo catalysts was prepared by varying the Co/Mo ratio in the range from 0 to 1 while maintaining the Mo loading at ca. 10 wt%. A sequential incipient wetness impregnation method, with Mo being introduced first, using aqueous solutions of the corresponding precursor salts was employed during the synthesis procedure. Three supports, i.e., Al2O3, ZrO2, and TiO2 differing in textural and acidic properties were investigated. Material physicochemical characteristics were evaluated through ICP-OES, N2-sorption, XRD, H2-TPR, NH3-TPD, O2-TPO, STEM-EDX and XPS techniques. The anisole HDO performance of these CoMo catalysts was evaluated at gas phase conditions in a fixed bed tubular reactor in plug flow regime. The catalysts performance is correlated with properties such as reducibility, acidity, and metal-support interactions. Cobalt addition enhanced the total HDO selectivity by 45% as compared to Mo catalysts. Alumina catalysts displayed higher initial activity (Xanisole≈97%) relative to titania and zirconia supported variants (Xanisole <40%) at identical operating conditions. Titania supported catalysts exhibited rather higher stability compared to zirconia and alumina catalysts over 50 h time on stream (TOS), while zirconia catalysts displayed the highest HDO selectivity (up to 86%). Characterization studies of pre and post-reaction catalysts indicate Mo5+ to be the main active phase while over-reduction to lower Mo states (Mo4+ and Mo3+) as well as carbon deposition are identified as the cause for catalyst activity decrease with TOS.publishedVersio

    Catalytic cracking of cycloparaffins admixed with Olefins: 2. Single-Event Microkinetic (SEMK) assessment

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    The developed SEMK model is used to provide an insight into the contribution of individual reactions in the cracking of methylcyclohexane as well as the site coverage by various carbenium ions. The preferred reaction pathways for the conversion of methylcyclohexane are hydride transfer reactions followed by PCP-isomerizations, deprotonation and endocyclic beta-scission, accounting for 61%, 22% and 12% of its disappearance, respectively, at 693 K and 30% conversion of methylcyclohexane. Protolysis plays a minor role in the cracking of methylcyclohexane. Once cyclic diolefins are formed, all of them can be instantaneously transformed to aromatics, which are easily interconverted via disproportionation. Judging from the carbenium ion concentrations it is evident that, at the investigated operating conditions, less than 5% of the acid sites are covered by carbenium ions, less than 2% of which corresponds to cyclic type species including allylic ones

    Recent advances in the use of Steady-State Isotopic Transient Kinetic Analysis data in (micro)kinetic modeling for catalyst and process design

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    Developing new catalysts with improved performance is crucial for establishing a sustainable chemical industry and requires atomic-scale knowledge of the relevant catalyst-species interactions. A powerful experimental technique to gather such detailed knowledge is Steady-State Isotopic Transient Kinetic Analysis (SSITKA). By combining SSITKA with (micro)kinetic modeling, the observed catalyst performance can be rationalized to advance the development of structure-activity relationships, and to obtain fundamental insights in complex reaction pathways. In turn, tailored experimental and computational methodologies provide the tools to access this detailed information. This mini review summarizes the developments that have been made in these fields during the last decade

    Effect of Co incorporation and support selection on deoxygenation selectivity and stability of (Co)Mo catalysts in anisole HDO

    No full text
    A series of supported Co modified Mo catalysts was prepared by varying the Co/Mo ratio in the range from 0 to 1 while maintaining the Mo loading at ca. 10 wt%. A sequential incipient wetness impregnation method, with Mo being introduced first, using aqueous solutions of the corresponding precursor salts was employed during the synthesis procedure. Three supports, i.e., Al2O3, ZrO2, and TiO2 differing in textural and acidic properties were investigated. Material physicochemical characteristics were evaluated through ICP-OES, N2-sorption, XRD, H2-TPR, NH3-TPD, O2-TPO, STEM-EDX and XPS techniques. The anisole HDO performance of these CoMo catalysts was evaluated at gas phase conditions in a fixed bed tubular reactor in plug flow regime. The catalysts performance is correlated with properties such as reducibility, acidity, and metal-support interactions. Cobalt addition enhanced the total HDO selectivity by 45% as compared to Mo catalysts. Alumina catalysts displayed higher initial activity (Xanisole≈97%) relative to titania and zirconia supported variants (Xanisole <40%) at identical operating conditions. Titania supported catalysts exhibited rather higher stability compared to zirconia and alumina catalysts over 50 h time on stream (TOS), while zirconia catalysts displayed the highest HDO selectivity (up to 86%). Characterization studies of pre and post-reaction catalysts indicate Mo5+ to be the main active phase while over-reduction to lower Mo states (Mo4+ and Mo3+) as well as carbon deposition are identified as the cause for catalyst activity decrease with TOS
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