Abdelgaid, Mona
(2024)
Catalyst Design for Dehydrogenation of Light Alkanes
to Olefins.
Doctoral Dissertation, University of Pittsburgh.
(Unpublished)
Abstract
Light olefins are versatile building blocks to produce petrochemicals, plastics, and polymers. Currently, there is a rapidly increasing gap between global demand and supply for olefins. The abundance of light alkanes from shale gas reserves offers an excellent opportunity for “on-purpose” production of light olefins through catalytic nonoxidative dehydrogenation (DH) of alkanes. The discovery of active catalysts plays a critical role in reducing the energy input required in DH processes. Heterogeneous catalysts, such as metal oxides and nitrides, can selectively activate the C–H bonds of alkanes due to their characteristic Lewis acidity (metal) and basicity (oxygen or nitrogen). However, discovering efficient DH catalysts has traditionally relied on trial-and-error experimentation. Alternatively, developing structure-activity relationships (SARs) based on first-principles calculations can accelerate the screening of active and selective catalysts for the production of olefins.
This work developed and applied DH SARs for the discovery of active and selective DH catalysts. First, we provided mechanistic insights into alkane DH reactions on pristine and gallium-doped γ-Al2O3 using Density Functional Theory (DFT) and developed SARs based on fundamental properties of the catalyst and reacting hydrocarbons. Following an initial catalyst screening approach followed by detailed DFT calculations and microkinetic modeling, we revealed pristine aluminum nitride (AlN) as an efficient DH catalyst. Lastly, we employed heterometal doping as a strategy to enhance the DH performance of pristine AlN. We showcased that Zn-doped AlN exhibits high DH activity and olefin selectivity compared to pristine AlN and other oxides reported in the literature. Importantly, we elucidated very complex hydrocarbon DH mechanisms on novel, previously untested AlN catalysts. Overall, this dissertation provides important insights into designing highly active DH catalysts for industrial applications, while revealing rich information on DH mechanisms.
Share
| Citation/Export: |
|
| Social Networking: |
|
Details
| Item Type: |
University of Pittsburgh ETD
|
| Status: |
Unpublished |
| Creators/Authors: |
|
| ETD Committee: |
|
| Date: |
6 September 2024 |
| Date Type: |
Publication |
| Defense Date: |
31 May 2024 |
| Approval Date: |
6 September 2024 |
| Submission Date: |
3 June 2024 |
| Access Restriction: |
2 year -- Restrict access to University of Pittsburgh for a period of 2 years. |
| Number of Pages: |
154 |
| Institution: |
University of Pittsburgh |
| Schools and Programs: |
Swanson School of Engineering > Chemical Engineering |
| Degree: |
PhD - Doctor of Philosophy |
| Thesis Type: |
Doctoral Dissertation |
| Refereed: |
Yes |
| Uncontrolled Keywords: |
structure-activity relationships, propane dehydrogenation, olefins, metal oxides, metal nitrides, density functional theory, microkinetic modeling, aluminum nitride, heterometal doping, reactivity descriptors, C−H bond activation, catalyst screening |
| Date Deposited: |
06 Sep 2024 19:54 |
| Last Modified: |
06 Sep 2024 19:54 |
| URI: |
http://d-scholarship.pitt.edu/id/eprint/46464 |
Metrics
Monthly Views for the past 3 years
Plum Analytics
Actions (login required)
 |
View Item |
![[img]](https://d-scholarship.pitt.edu/style/images/fileicons/application_pdf.png)
![[feed]](/images/feed-icon-32x32.png){kind=icon}