Engineering Commons^™

Hydrodeoxygenation Of Biomass Derived Sugar Alcohols To Platform Chemicals Using Heterogeneous Catalysts, Blake Macqueen

Theses and Dissertations

This work set out to investigate biomass derived sugar alcohol upgrading via the removal of oxygen and hydroxyl groups via the hydrodeoxygenation reaction utilizing heterogeneous catalysts. The importance of reaction conditions, catalyst meal loadings, catalyst structure and properties were probed using techniques such as design of experiments, and spectroscopic techniques including Raman and DRIFTS. The state of the art simultaneous hydrodeoxygenation (S-HDO) catalyst ReO_x-Pd/CeO₂ was investigated and optimized for various sugar alcohol substrates. The kinetics and associated mass transfer were also investigated to give further insight into the reaction over the ReO_xPd/CeO₂ catalyst.

First, …

Kinetics Study Of The Hydrodeoxygenation Of Xylitol Over A ReoX-Pd/Ceo2 Catalyst, Blake Macqueen, Michael Royko, Bradie S. Crandall, Andreas Heyden, Yomaira J. Pagán-Torres, Jochen A. Lauterbach

Faculty Publications

In this study, we elucidate the reaction kinetics for the simultaneous hydrodeoxygenation of xylitol to 1,2-dideoxypentitol and 1,2,5-pentanetriol over a ReOx-Pd/CeO2 (2.0 weight% Re, 0.30 weight% Pd) catalyst. The reaction was determined to be a zero-order reaction with respect to xylitol. The activation energy was elucidated through an Arrhenius relationship as well as non-Arrhenius kinetics. The Arrhenius relationship was investigated at 150–170◦ C and a constant H2 pressure of 10 bar resulting in an activation energy of 48.7 ± 10.5 kJ/mol. The investigation of non-Arrhenius kinetics was conducted at 120–170◦ C and a sub-Arrhenius relation was elucidated with activation energy …

Kinetics Study Of The Hydrodeoxygenation Of Xylitol Over A ReoX-Pd/Ceo2 Catalyst, Blake Macqueen, Michael Royko, Bradie S. Crandall, Andreas Heyden, Yomaira J. Pagán-Torres, Jochen A. Lauterbach

Faculty Publications

In this study, we elucidate the reaction kinetics for the simultaneous hydrodeoxygenation of xylitol to 1,2-dideoxypentitol and 1,2,5-pentanetriol over a ReOx-Pd/CeO2 (2.0 weight% Re, 0.30 weight% Pd) catalyst. The reaction was determined to be a zero-order reaction with respect to xylitol. The activation energy was elucidated through an Arrhenius relationship as well as non-Arrhenius kinetics. The Arrhenius relationship was investigated at 150–170◦ C and a constant H2 pressure of 10 bar resulting in an activation energy of 48.7 ± 10.5 kJ/mol. The investigation of non-Arrhenius kinetics was conducted at 120–170◦ C and a sub-Arrhenius relation was elucidated with activation energy …

Theoretical Investigation Of The Biomass Conversion On Transition Metal Surfaces Based On Density Functional Theory Calculations And Machine Learning, Wenqiang Yang

Theses and Dissertations

During the past decades, heterogenous catalyzed conversion of biomass to hydrocarbons with similar or identical properties to conventional fossil fuels has gained significantly academic and industrial interest. However, the conventional heterogeneous catalysts such as sulfided NiMo/Al₂O₃ and CoMo/Al₂O₃ used have various drawbacks, such as short catalyst lifetime and high sulfur content of product. To overcome the limitations of the conventional sulfided catalysts, new catalysts must be developed, which requires a better understanding of the reaction mechanism of the biomass conversion. Based on density functional theory, in this thesis, we reported a computational calculation study …

Liquid Phase Modeling In Heterogeneous Catalysis, Mohammad Shamsus Saleheen

Theses and Dissertations

Conversion of lignocellulosic biomass into transportation fuels or commodity and specialty chemicals will be an important and fast-growing industry within the United States over the coming decades. Its growth will be driven by a variety of factors, including increased energy demands, environmental considerations, national security, and government mandates. To achieve the desired energy efficiency and economic impact, the emerging biorefining industries need novel heterogeneous catalysts with exceptional activity, selectivity, and stability. Catalytic materials developed in the petrochemical industries are generally not suitable for processing highly functionalized feedstocks typical of the biorefinery landscape. Due to the characteristics of this biomass feedstock …

Heterogeneous Catalysis For The Upgrading Of Biomass Derived Chemicals Via Hydrodeoxygenation, Elizabeth Barrow

Theses and Dissertations

An important step in the upgrading of biomass derived chemicals is the removal of excess oxygen. The works reported here are focused on studying the heterogeneous catalysts that can be utilized for that upgrading through hydrodeoxygenation. This work begins with a discussion of the alkylation of short chain platform chemicals for chain growth and also demonstrates the proof of concept of combining alkylation and hydrodeoxygenation in a single step. Then, because of the promising nature of ReOx- Pd/CeO2 for selective hydrodeoxygenation, a detailed study of ReOx/CeO2 is presented. Finally, a new surface structure interpretation is presented for P/Ni(111) which could …

Hydrodeoxygenation Of Acetic Acid Using Monometallic And Bimetallic Catalysts Supported On Carbon, José Luis Contreras Mora

Theses and Dissertations

Heterogeneous catalytic hydrodeoxygenation (HDO) of biomass-derived feeds is a deoxygenation process that is of highly interest. Carboxylic acids are one of the main components of bio-oils and acetic acid is one of the most abundant of these carboxylic acids. This acid is rich in oxygen, therefore a lot of research to produce fuel and other valuable chemicals such as ethanol is of interest.

This dissertation explores the gas-phase catalytic HDO of AA over catalysts supported on activated carbon (Cp-97). Temperature-dependent conversion and selectivity were studied at 1 atm from 200-400⁰C with an AA concentration of 1.1% and 20% …

Theoretical Investigation Of The Catalytic Hydrodeoxygenation Of Levulinic Acid Over Ru (0001) Catalyst Surface, Osman Mamun

Theses and Dissertations

Due to the rapidly declining fossil fuel reserves and the onset of global climate change, the development of active, selective, and stable catalytic materials for the efficient production of biomass derived platform chemicals, i.e., levulinic acid (LA), succinic acid (SA), γ-valerolactone (GVL) etc., is receiving considerable attention in order to produce second generation biofuels and commodity chemicals. Though solid lignocellulosic biomass is significantly cheaper than petroleum; however, the available technology is the significant barrier for large scale utilization of biomass for the production of biofuels. The development of biomass conversion technology requires, 1) identification of potential biomass chemicals that can …

Gas-Phase, Catalytic Hydrodeoxygenation Of Propanoic Acid Over Supported Group Viii Noble Metals, Yuliana K. Lugo José

Theses and Dissertations

Recent advances for the deoxygenation of biomass, have demonstrated that hydrodeoxygenation (HDO) is one of the most promising route for the upgrading pyrolysis bio-oils. Catalytic hydrodeoxygenation of pyrolysis bio-oil have shown to be an efficient and economical process, since the raw materials consist mainly of waste. Propanoic Acid (PAc) is considered as one of the main constituents of pyrolysis bio-oils. However, these carboxylic acids are extremely corrosive and difficult to deoxygenate. Therefore, much effort have been given to the development of novel catalytic techniques, to improve the activity, stability and selectivity for the HDO of carboxylic acids.

This dissertation explores …