Acid Functionalized Mesoporous Ordered Materials for the Production of 5-Hydroxymethyfurfural from Carbohydrates
- Degree Grantor:
- University of California, Santa Barbara. Chemistry
- Degree Supervisor:
- Susannah L. Scott
- Place of Publication:
- [Santa Barbara, Calif.]
- Publisher:
- University of California, Santa Barbara
- Creation Date:
- 2012
- Issued Date:
- 2012
- Topics:
- Engineering, Materials Science, Chemistry, Inorganic, and Chemistry, Organic
- Keywords:
- 5-hydroxymethylfurfural,
SBA-15.,
Functionalized Silica,
Biomass, and
Mesoporous Ordered Silica - Genres:
- Online resources and Dissertations, Academic
- Dissertation:
- Ph.D.--University of California, Santa Barbara, 2012
- Description:
Solid acid catalysts were designed for the conversion of fructose to 5-hydroxymethylfurfural (HMF). Some of the catalysts incorporate thioether groups to promote the tautomerization of fructose to its furanose form, as well as sulfonic acid groups to catalyze its dehydration. A bifunctional silane, 3-((3-(trimethoxysilyl)propyl)thio)propane-1-sulfonic acid (TESAS), was designed for incorporation into SBA-15-type silica by co-condensation. To achieve mesopore ordering in the functionalized silica, the standard SBA-15 synthetic protocol was modified, resulting in well-formed hexagonal particles. Functional groups incorporated into mesoporous silica by co-condensation are more robust under the reaction conditions than those grafted onto a non-porous silica. In a variation, the thioether group of TESAS was oxidized by H2O 2 to the sulfone during the synthesis of the modified SBA-15. The materials were tested in batch reactors and compared in the selective dehydration of fructose to 5-hydroxymethylfurfural (HMF). Compared to benchmark catalysts, the thioether-containing TESAS-SBA-15 showed the highest activity in the dehydration of aqueous fructose, as well as the highest selectivity towards HMF (71 % at 84 % conversion).
In addition, the stability of several supported acid catalysts was evaluated in tubular reactors designed to produce 5-hydroxymethylfurfural (HMF) continuously. The reactors, packed with the solid catalysts, were operated at 403 K for extended periods, up to 180 h. The behaviors of three propylsulfonic acid-functionalized, ordered porous silicas (one inorganic SBA-15-type silica, and two ethane-bridged SBA-15-type organosilicas) were compared with that of a propylsulfonic acid-modified, non-ordered porous silica. The HMF selectivity of the catalysts with ordered pore structures ranged from 60 to 75 %, while the selectivity of the non-ordered catalyst peaked at 20 %. The latter was also the least stable, deactivating with a first-order rate constant of 0.152 h-1. The organosilicas are more hydrothermally stable and maintained a steady catalytic activity longer than inorganic SBA-15-type silica. The organosilica with an intermediate framework ethane content of 45 mol % was the most stable, with a first-order deactivation rate constant of only 0.012 h-1. Deactivation under flow conditions is caused primarily by hydrolytic cleavage of acid sites, which can be (to some extent) recaptured by the free surface hydroxyl groups of the silica surface.
- Physical Description:
- 1 online resource (246 pages)
- Format:
- Text
- Collection(s):
- UCSB electronic theses and dissertations
- Other Versions:
- http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&res_dat=xri:pqm&rft_dat=xri:pqdiss:3540173
- ARK:
- ark:/48907/f31c1ttz
- ISBN:
- 9781267648358
- Catalog System Number:
- 990038915210203776
- Copyright:
- Anthony Crisci, 2012
- Rights:
- In Copyright
- Copyright Holder:
- Anthony Crisci
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