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Keywords = real bio-oil upgrading

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22 pages, 2707 KiB  
Review
Metal-Based Heterogeneous Catalysts for the Synthesis of Valuable Chemical Blends via Hydrodeoxygenation of Lignin-Derived Fractions
by Marvin Chávez-Sifontes and María Ventura
Catalysts 2024, 14(2), 146; https://doi.org/10.3390/catal14020146 - 16 Feb 2024
Cited by 2 | Viewed by 3107
Abstract
Currently, many research projects are focused on the conversion of renewable raw materials into chemicals and fuels. Lignocellulosic biomass is a raw material used for the production of bio-oils and black liquors. These biomass-derived fractions offer promising paths for the production of valuable [...] Read more.
Currently, many research projects are focused on the conversion of renewable raw materials into chemicals and fuels. Lignocellulosic biomass is a raw material used for the production of bio-oils and black liquors. These biomass-derived fractions offer promising paths for the production of valuable chemical products. Various catalytic methods have been investigated for upgrading the biomass-derived fractions. Researchers are interested in the hydrodeoxygenation process (HDO); in this process, the oxygen groups are eliminated by breaking the C-O bonds and water as a product. Incorporating heterogeneous catalysts (i.e., noble metals, transition metals, and metal sulfides) improves this process. Most HDO review articles describe catalytic results for model phenolic compounds. However, there is also a need to investigate the catalytic activity of real biomass-derived fractions. This paper explains research results regarding the upgrading of lignin-derived fractions (i.e., black liquors) by HDO. The paper has been organized according to the type of heterogeneous catalyst and shows compelling results based on different experimental conditions. The final sections present an analysis of the documented results and outline perspectives about integrating lignin into the biorefinery framework. Full article
(This article belongs to the Special Issue New Advances in Metal Oxide Catalysts)
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21 pages, 7140 KiB  
Article
Hydrodeoxygenation of Oxygenates Derived from Biomass Pyrolysis Using Titanium Dioxide-Supported Cobalt Catalysts
by Surachet Hongkailers, Adisak Pattiya and Napida Hinchiranan
Molecules 2023, 28(22), 7468; https://doi.org/10.3390/molecules28227468 - 7 Nov 2023
Cited by 7 | Viewed by 2093
Abstract
Bio-oil upgrading to produce biofuels and chemicals has become an attractive topic over the past decade. However, the design of cost- and performance-effective catalysts for commercial-scale production remains a challenge. Herein, commercial titania (TiO2) was used as the support of cobalt [...] Read more.
Bio-oil upgrading to produce biofuels and chemicals has become an attractive topic over the past decade. However, the design of cost- and performance-effective catalysts for commercial-scale production remains a challenge. Herein, commercial titania (TiO2) was used as the support of cobalt (Co)-based catalysts (Co/TiO2) due to its low cost, high availability, and practicability for commercialization in the future. The Co/TiO2 catalysts were made with two different forms of TiO2 (anatase [TiO2–A] and rutile [TiO2–R]) and comparatively evaluated in the hydrodeoxygenation (HDO) of 4-propylguaicol (4PG), a lignin-derived model compound. Both Co/TiO2 catalysts promoted the HDO of 4PG following a similar pathway, but the Co/TiO2–R catalyst exhibited a higher activity in the early stages of the reaction due to the formation of abundant Ti3+ species, as detected by X-ray photoelectron spectroscopy (XPS) and hydrogen–temperature programed reduction (H2–TPR) analyses. On the other hand, the Co/TiO2–A catalyst possessed a higher acidity that enhanced propylcyclohexane production at prolonged reaction times. In terms of reusability, the Co/TiO2–A catalyst showed a higher stability (less Co leaching) and reusability compared to Co/TiO2–R, as confirmed by transmission electron microscopy (TEM) and inductively coupled plasma optical emission spectroscopy (ICP-OES) analyses. The HDO of the real bio-oil derived from pyrolysis of Leucaena leucocephala revealed that the Co/TiO2–A catalyst could convert high oxygenated aromatics (methoxyphenols, dimethoxyphenols, and benzenediols) to phenols and enhanced the phenols content, hinting at its potential to produce green chemicals from bio-feedstock. Full article
(This article belongs to the Special Issue Research on Heterogeneous Catalysis)
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30 pages, 3233 KiB  
Review
Current and Future Trends for Crude Glycerol Upgrading to High Value-Added Products
by Muhammad Harussani Moklis, Shou Cheng and Jeffrey S. Cross
Sustainability 2023, 15(4), 2979; https://doi.org/10.3390/su15042979 - 7 Feb 2023
Cited by 46 | Viewed by 10662
Abstract
Crude glycerol is the main byproduct of biodiesel manufacturing from oleaginous crops and other biomass-derived oils. Approximately 10% crude glycerol is produced with every batch of biodiesel. Worldwide, there is a glut of glycerol and the price of it has decreased considerably. There [...] Read more.
Crude glycerol is the main byproduct of biodiesel manufacturing from oleaginous crops and other biomass-derived oils. Approximately 10% crude glycerol is produced with every batch of biodiesel. Worldwide, there is a glut of glycerol and the price of it has decreased considerably. There are real opportunities for valorizing crude glycerol into higher value-added chemicals which can improve the economic viability of biodiesel production as an alternative fuel. Exploring new potential applications of glycerol in various sectors is needed such as in pharmaceuticals, food and beverages, cosmetics, and as a transportation fuel. However, crude glycerol produced directly from biodiesel often contains impurities that hinder its direct industrial usage and thus, a refining process is needed which is typically expensive. Hence, this review reports on current upgrading crude glycerol technologies—thermo-, bio-, physico-, and electrochemical approaches—that valorize it into higher value-added chemicals. Through comparison between those viable upgrading techniques, future research directions, challenges, and advantages/disadvantage of the technologies are described. Electrochemical technology, which is still underdeveloped in this field, is highlighted, due to its simplicity, low maintenance cost, and it working in ambient condition, as it shows promising potential to be applied as a major glycerol upgrading technique. Full article
(This article belongs to the Special Issue Frontiers in Bio-Energy Production and Applications)
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18 pages, 1439 KiB  
Article
Structural Evolution of Molybdenum Carbides in Hot Aqueous Environments and Impact on Low-Temperature Hydroprocessing of Acetic Acid
by Jae-Soon Choi, Viviane Schwartz, Eduardo Santillan-Jimenez, Mark Crocker, Samuel A. Lewis, Michael J. Lance, Harry M. Meyer and Karren L. More
Catalysts 2015, 5(1), 406-423; https://doi.org/10.3390/catal5010406 - 13 Mar 2015
Cited by 16 | Viewed by 6995
Abstract
We investigated the structural evolution of molybdenum carbides subjected to hot aqueous environments and their catalytic performance in low-temperature hydroprocessing of acetic acid. While bulk structures of Mo carbides were maintained after aging in hot liquid water, a portion of carbidic Mo sites [...] Read more.
We investigated the structural evolution of molybdenum carbides subjected to hot aqueous environments and their catalytic performance in low-temperature hydroprocessing of acetic acid. While bulk structures of Mo carbides were maintained after aging in hot liquid water, a portion of carbidic Mo sites were converted to oxidic sites. Water aging also induced changes to the non-carbidic carbon deposited during carbide synthesis and increased surface roughness, which in turn affected carbide pore volume and surface area. The extent of these structural changes was sensitive to the initial carbide structure and was lower under actual hydroprocessing conditions indicating the possibility of further improving the hydrothermal stability of Mo carbides by optimizing catalyst structure and operating conditions. Mo carbides were active in acetic acid conversion in the presence of liquid water, their activity being comparable to that of Ru/C. The results suggest that effective and inexpensive bio-oil hydroprocessing catalysts could be designed based on Mo carbides, although a more detailed understanding of the structure-performance relationships is needed, especially in upgrading of more complex reaction mixtures or real bio-oils. Full article
(This article belongs to the Special Issue Feature Papers to Celebrate the Landmarks of Catalysts)
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20 pages, 405 KiB  
Article
Catalytic Conversion of Bio-Oil to Oxygen-Containing Fuels by Acid-Catalyzed Reaction with Olefins and Alcohols over Silica Sulfuric Acid
by Zhijun Zhang, Shujuan Sui, Fengqiang Wang, Qingwen Wang and Charles U. Pittman
Energies 2013, 6(9), 4531-4550; https://doi.org/10.3390/en6094531 - 2 Sep 2013
Cited by 20 | Viewed by 9074
Abstract
Crude bio-oil from pine chip fast pyrolysis was upgraded with olefins (1-octene, cyclohexene, 1,7-octadiene, and 2,4,4-trimethylpentene) plus 1-butanol (iso-butanol, t-butanol and ethanol) at 120 °C using a silica sulfuric acid (SSA) catalyst that possesses a good catalytic activity and stability. [...] Read more.
Crude bio-oil from pine chip fast pyrolysis was upgraded with olefins (1-octene, cyclohexene, 1,7-octadiene, and 2,4,4-trimethylpentene) plus 1-butanol (iso-butanol, t-butanol and ethanol) at 120 °C using a silica sulfuric acid (SSA) catalyst that possesses a good catalytic activity and stability. Gas chromatography-mass spectrometry (GC-MS), Fourier transform infrared spectroscopy (FT-IR) and proton nuclear magnetic resonance (1H-NMR) analysis showed that upgrading sharply increased ester content and decreased the amounts of levoglucosan, phenols, polyhydric alcohols and carboxylic acids. Upgrading lowered acidity (pH value rose from 2.5 to >3.5), removed the unpleasant odor and increased hydrocarbon solubility. Water content dramatically decreased from 37.2% to about 7.0% and the heating value increased from 12.6 MJ·kg−1 to about 31.9 MJ·kg−1. This work has proved that bio-oil upgrading with a primary olefin plus 1-butanol is a feasible route where all the original heating value of the bio-oil plus the added olefin and alcohol are present in the resulting fuel. Full article
(This article belongs to the Special Issue Biomass and Biofuels 2013)
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