2026-09-20T08:38:59Zhttps://dspace.mit.edu/server/oai/requestoai:dspace.mit.edu:1721.1/1202102026-06-17T14:47:29Zcom_1721.1_7582com_1721.1_7581col_1721.1_131022
Klavs F. Jensen.
Lusardi, Marcella R. (Marcella Rose)
Massachusetts Institute of Technology. Department of Materials Science and Engineering.
Massachusetts Institute of Technology. Department of Materials Science and Engineering
2019-02-05T15:58:04Z
2019-02-05T15:58:04Z
2018
2018
http://hdl.handle.net/1721.1/120210
1082848364
Thesis: Ph. D., Massachusetts Institute of Technology, Department of Materials Science and Engineering, 2018.
Cataloged from PDF version of thesis.
Includes bibliographical references (pages 129-137).
The aromatization of acetaldehyde derived from bio-based feedstocks offers a sustainable route to obtaining valuable BTX (benzene, toluene, and xylenes)-like platform chemicals traditionally produced from petroleum naphtha. The acid-base properties of the catalyst must be carefully designed in order to selectively promote the multiple condensation-cyclodehydration mechanisms, yet it is not clear what the active sites actually are. To investigate this, we built a microreactor/flow system with flame ionization detector (FID)-quantification sensitivities and residence times ([tau]) on the orders of 10 ppm and 1 ms, respectively. Pure and Al-substituted (molar Mg/Al = 1, 2, and 3) MgOs were synthesized using a co-precipitation-calcination technique. The physicochemical properties of the catalysts were studied using X-ray diffraction (XRD), ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, inductively coupled plasma atomic emission spectroscopy (ICP-AES), and N₂ adsorption-desorption experiments at 77 K. The acid-base character of the MgO-based materials was analyzed using a homemade temperature programmed desorption-mass spectrometry (TPD-MS) system as well as diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) experiments. Benzene activity on these catalysts at the reaction conditions investigated (250 °C, 10 ms [tau]) is low and is attributed to strong basic sites (low-coordinated surface O₂⁻). Two isomers (ortho- and para-) of tolualdehyde, a drop-in replacement for xylene, were found to form via the self-condensation of the acetaldehyde dimer. Condensation experiments, in-situ acid-base titration studies, and CO2 DRIFTS comparisons on the spent oxides revealed that the same active site, a medium strength M-O type basic site in specific coordination, is responsible for the formation of both isomers. The amount of Al incorporation did not alter the condensation activity, despite changing the densities of acid and base site types. However, we found that, compared to pure MgO, the Al-substituted samples shifted the selectivity towards the significantly more valuable para- isomer. This is likely due to an increase in the kinetic favorability of one of the para-forming routes, induced by the carbonyl oxygen interactions with acid sites that arise from surface-exposed Al³⁺ , cations. These results can inform next generation catalyst design for improved selectivity and active site stability with time on stream.
by Marcella R. Lusardi.
Ph.D.
137 pages
eng
Massachusetts Institute of Technology
MIT theses are protected by copyright. They may be viewed, downloaded, or printed from this source but further reproduction or distribution in any format is prohibited without written permission.
http://dspace.mit.edu/handle/1721.1/7582
Materials Science and Engineering.
Understanding the active sites of Mg-Al oxide catalysts in the formation of aromatic platform chemicals from acetaldehyde
Thesis
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<Abstract>The aromatization of acetaldehyde derived from bio-based feedstocks offers a sustainable route to obtaining valuable BTX (benzene, toluene, and xylenes)-like platform chemicals traditionally produced from petroleum naphtha. The acid-base properties of the catalyst must be carefully designed in order to selectively promote the multiple condensation-cyclodehydration mechanisms, yet it is not clear what the active sites actually are. To investigate this, we built a microreactor/flow system with flame ionization detector (FID)-quantification sensitivities and residence times ([tau]) on the orders of 10 ppm and 1 ms, respectively. Pure and Al-substituted (molar Mg/Al = 1, 2, and 3) MgOs were synthesized using a co-precipitation-calcination technique. The physicochemical properties of the catalysts were studied using X-ray diffraction (XRD), ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, inductively coupled plasma atomic emission spectroscopy (ICP-AES), and N₂ adsorption-desorption experiments at 77 K. The acid-base character of the MgO-based materials was analyzed using a homemade temperature programmed desorption-mass spectrometry (TPD-MS) system as well as diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) experiments. Benzene activity on these catalysts at the reaction conditions investigated (250 °C, 10 ms [tau]) is low and is attributed to strong basic sites (low-coordinated surface O₂⁻). Two isomers (ortho- and para-) of tolualdehyde, a drop-in replacement for xylene, were found to form via the self-condensation of the acetaldehyde dimer. Condensation experiments, in-situ acid-base titration studies, and CO2 DRIFTS comparisons on the spent oxides revealed that the same active site, a medium strength M-O type basic site in specific coordination, is responsible for the formation of both isomers. The amount of Al incorporation did not alter the condensation activity, despite changing the densities of acid and base site types. However, we found that, compared to pure MgO, the Al-substituted samples shifted the selectivity towards the significantly more valuable para- isomer. This is likely due to an increase in the kinetic favorability of one of the para-forming routes, induced by the carbonyl oxygen interactions with acid sites that arise from surface-exposed Al³⁺ , cations. These results can inform next generation catalyst design for improved selectivity and active site stability with time on stream.</Abstract>
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