• Login
    View Item 
    •   Home
    • Research
    • Articles
    • View Item
    •   Home
    • Research
    • Articles
    • View Item
    JavaScript is disabled for your browser. Some features of this site may not work without it.

    Browse

    All of KAUSTCommunitiesIssue DateSubmit DateThis CollectionIssue DateSubmit Date

    My Account

    Login

    Quick Links

    Open Access PolicyORCID LibguidePlumX LibguideSubmit an Item

    Statistics

    Display statistics

    Catalytic hydrogenation of levulinic acid to ɣ-valerolactone: Insights into the influence of feed impurities on catalyst performance in batch and flow

    • CSV
    • RefMan
    • EndNote
    • BibTex
    • RefWorks
    Thumbnail
    Name:
    cccatalytic hydrogenation.pdf
    Size:
    1.422Mb
    Format:
    PDF
    Description:
    Accepted manuscript
    Embargo End Date:
    2021-03-25
    Download
    Type
    Article
    Authors
    Genuino, Homer C.
    van de Bovenkamp, Henk H.
    Wilbers, Erwin
    Winkelman, Jozef G. M.
    Goryachev, Andrey
    Hofmann, Jan P.
    Hensen, Emiel J.M.
    Weckhuysen, Bert M.
    Bruijnincx, Pieter C.A.
    Heeres, Hero Jan
    KAUST Department
    KAUST Catalysis Center (KCC)
    Physical Science and Engineering (PSE) Division
    Date
    2020-03-25
    Online Publication Date
    2020-03-25
    Print Publication Date
    2020-04-20
    Embargo End Date
    2021-03-25
    Permanent link to this record
    http://hdl.handle.net/10754/662452
    
    Metadata
    Show full item record
    Abstract
    γ-Valerolactone (GVL) is readily obtained by the hydrogenation of levulinic acid (LA) and is considered a sustainable platform chemical for the production of bio-based chemicals. Herein the performance and stability of Ru-based catalysts (1 wt.% Ru) supported on TiO2 (P25) and ZrO2 (monoclinic) for LA hydrogenation to GVL was investigated in the liquid phase in batch and continuous-flow reactors using water and dioxane as solvents. Particular attention is paid to the influence of both process-derived and biogenic impurities on LA hydrogenation performance. Benchmark continuous-flow experiments at extended times on stream (i.e., 190 h, 10 wt.% LA, 50 bar H2, 150 oC in dioxane, 90 oC in water, WSHV of 2.4 gfeed gcat·h-1 in dioxane, 3.6 gfeed gcat·h-1 in water) showed that the deactivation profiles are distinctly different for both solvents. In dioxane, the Ru/ZrO2 catalyst is clearly more stable than Ru/TiO2, whereas the latter is slightly more stable in water. Detailed characterization of spent catalysts after long-term stability runs showed that deactivation of Ru/TiO2 is strongly linked to reduction of the TiO2 support and a reduction of the specific surface area. Ru/ZrO2 showed no signs of support reduction and displayed morphological and structural stability, although some deposition of carbonaceous material was observed. Impurities in the LA feed such as HCOOH, H2SO4, furfural (FFR), 5-hydroxymethylfurfural (HMF), humins, and sulfur-containing amino acids impacted catalyst performance differently. Results reveal rapid, yet reversible loss of activity for both catalysts upon HCOOH addition to LA, attributed to its preferential adsorption on Ru sites and possible CO poisoning. A more gradual drop in activity was found when co-feeding HMF, FFR, and humins for both solvents. The presence of H2SO4, cysteine, and methionine all resulted in irreversible deactivation of the Ru catalysts. The results obtained provide new insights into the (ir)reversible (in)sensitivity of Ru-based hydrogenation catalysts to potential impurities in LA feeds, knowledge essential for next-generation catalyst development.
    Citation
    Genuino, H. C., van de Bovenkamp, H. H., Wilbers, E., Winkelman, J. G. M., Goryachev, A., Hofmann, J. P., … Heeres, H. J. (2020). Catalytic hydrogenation of levulinic acid to ɣ-valerolactone: Insights into the influence of feed impurities on catalyst performance in batch and flow. ACS Sustainable Chemistry & Engineering. doi:10.1021/acssuschemeng.9b07678
    Publisher
    American Chemical Society (ACS)
    Journal
    ACS Sustainable Chemistry & Engineering
    DOI
    10.1021/acssuschemeng.9b07678
    Additional Links
    https://pubs.acs.org/doi/10.1021/acssuschemeng.9b07678
    ae974a485f413a2113503eed53cd6c53
    10.1021/acssuschemeng.9b07678
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

    entitlement

     
    DSpace software copyright © 2002-2021  DuraSpace
    Quick Guide | Contact Us | Send Feedback
    Open Repository is a service hosted by 
    Atmire NV
     

    Export search results

    The export option will allow you to export the current search results of the entered query to a file. Different formats are available for download. To export the items, click on the button corresponding with the preferred download format.

    By default, clicking on the export buttons will result in a download of the allowed maximum amount of items. For anonymous users the allowed maximum amount is 50 search results.

    To select a subset of the search results, click "Selective Export" button and make a selection of the items you want to export. The amount of items that can be exported at once is similarly restricted as the full export.

    After making a selection, click one of the export format buttons. The amount of items that will be exported is indicated in the bubble next to export format.