Article
Chemistry, Multidisciplinary
Puhua Sun, Wenxiang Zhang, Xiao Yu, Jie Zhang, Ningkun Xu, Zhichao Zhang, Mengyuan Liu, Dongpei Zhang, Guangyu Zhang, Ziyuan Liu, Chaohe Yang, Wenjuan Yan, Xin Jin
Summary: Hydrogenolysis of glycerol to propylene glycol is a promising biomass conversion technology. However, conventional hydrogenolysis processes are energy-intensive, catalyst deactivates quickly and safety risks exist. Catalytic transfer hydrogenolysis shows high energy and atom efficiency. We studied novel solid catalysts for glycerol transfer hydrogenolysis and found that it requires less energy and capital investment. This study provides valuable information for the design and implementation of novel hydrogenolysis technologies for other energy and environmental applications.
FRONTIERS IN CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Georgy S. Dmitriev, Ilia S. Melchakov, Vadim O. Samoilov, Dzhamalutdin N. Ramazanov, Leonid N. Zanaveskin
Summary: This study investigated the hydrogenolysis of glycerol to 1,2-propylene glycol using a continuous down-flow fixed-bed reactor with 60%Cu/Al2O3 catalyst. The effect of catalyst particle size on the reaction mode was examined, and the routes of product formation were proposed. The optimal conditions for the reaction were determined.
Article
Biochemistry & Molecular Biology
Iuliana Porukova, Vadim Samoilov, Dzhamalutdin Ramazanov, Mariia Kniazeva, Anton Maximov
Summary: The present study experimentally verifies a concept for the hydrogenolysis of glycerol using in situ-generated copper dispersed particles (Cu-DP). It shows that the selectivity between 1,2-propylene glycol and lactic acid can be tuned by adjusting hydrogen pressure or alkalinity. The activity of the in situ-generated Cu-DP catalyst is comparable to that of an industrial Cu-Cr2O3 catalyst.
Article
Chemistry, Multidisciplinary
Alba N. Ardila A, Erasmo Arriola-Villasenor, Rolando Barrera-Zapata, Jose Hernandez, Gustavo A. Fuentes
Summary: The kinetics of glycerol hydrodeoxygenation (HDO) to 1,2-propanediol (1,2-PDO) in the liquid phase using Cu-Pd/TiO2 catalysts was studied. The absence of mass transfer resistance artifacts was observed at a stirring speed above 480 rpm and catalyst particle diameter below 89.5 μm. Higher temperatures and H2 concentrations enhanced glycerol conversion and selectivity towards 1,2-PDO while reducing selectivity towards acetol. Empirical kinetic pseudo-homogeneous expressions were proposed based on experimental data for glycerol disappearance, 1,2-PDO formation, and acetol formation in the catalytic system. The activation energies for glycerol disappearance (77.8 kJ/mol), 1,2-PDO formation (51.2 kJ/mol), and acetol formation (84.6 kJ/mol) indicated the selective formation of 1,2-PDO in this catalytic system.
Article
Chemistry, Physical
Victor G. S. Mendonca, Isabelle C. Freitas, Robinson L. Manfro, Mariana M. V. M. Souza
Summary: Cu-Ni / xMgO-Al2O3 catalysts were used for the hydrogenolysis of glycerol to produce 1,2-propanediol without the addition of external hydrogen. The addition of MgO to alumina improved the yield of 1,2-propanediol. The rate limiting step for MgO-Al2O3 catalysts is the hydrogenation of acetol, while Cu-Ni / MgO catalysts follow a basic route.
APPLIED CATALYSIS A-GENERAL
(2022)
Review
Chemistry, Physical
Martin N. Gatti, Federico M. Perez, Gerardo F. Santori, Nora N. Nichio, Francisco Pompeo
Summary: Research on the utilization of biomass resources for energy and chemical compounds attracts worldwide attention. The biodiesel industry, as it grows, generates a parallel market for glycerol, its major by-product. Glycerol, with its wide availability and low cost, becomes a fundamental component for the production of various chemical products, thus enabling the development of a biorefinery around biodiesel plants through the integration of different production processes. This study offers a comprehensive review of the hydrogenolysis of glycerol to 1,2-propylene glycol, a reaction of interest in the biorefinery context. The article analyzes over 300 references spanning approximately 20 years, focusing on the heterogeneous catalysts employed for glycol production.
Article
Chemistry, Multidisciplinary
Ram Singh, Prakash Biswas, Prateek K. Jha
Summary: Quantum chemistry calculations were used to evaluate the efficacy of Cu-based catalysts in the glycerol hydrogenolysis reaction. The results showed that the conversion of glycerol to 1,2-propanediol was favored in the catalyzed system. Additionally, the doping of Zn or ZnO had an influence on the activation barriers of the reaction.
Article
Chemistry, Multidisciplinary
Lujie Liu, Ji Cao, Yoshinao Nakagawa, Mii Betchaku, Masazumi Tamura, Mizuho Yabushita, Keiichi Tomishige
Summary: This study investigated the hydrodeoxygenation of erythritol, xylitol, and sorbitol over a Pt-WOx/SiO2 catalyst and found that high yields of 1,4-butanediol, pentanols, and other mono-alcohols can be selectively produced. The catalyst showed differences in activity towards mono-alcohols and polyols, and the Pt-WOx interfacial site was suggested to be the active site for the reactions.
Article
Chemistry, Physical
Mukesh Kumar Poddar, Ankit Pandey, Mukund Kumar Jha, Suresh Chandra Andola, Syed Saif Ali, Sonu Bhandari, Govind Kumar Sahani, Rajaram Bal
Summary: This study investigated the effect of Cu and Ni on the hydrogenolysis of glycerol to produce 1, 2-Propanediol, finding that Cu nanoparticles are critical for the selective production of the desired product. The mesoporous alumina support played a crucial role in enhancing the performance of Cu and Ni oxide particles, with both acid and metal functions contributing to increasing selectivity for 1, 2-Propanediol.
MOLECULAR CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Taemin Kim, Andre L. Boehman
Summary: A life-cycle greenhouse gas emissions assessment was conducted on a novel, stable DME-glycerol blend, showing that using high-purity crude glycerol for purification and producing DME from animal manure led to the lowest GHG emissions. For fossil-based DME scenarios, pump-to-wheels combustion was the biggest GHG emitting process, while crude glycerol production was the biggest emitter for renewable DME cases. Adopting regenerative farming methods, using less carbon-intensive hydrogen for PG production, and optimizing material and thermal energy utilization are suggested to further reduce GHG emissions for the Michigan DME blend II.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2021)
Review
Chemistry, Physical
Yangzi Liu, Jiayu Liu, Zhihao Xing, Xueqian Zhang, Chen Luo, Wenjuan Yan, Xin Jin
Summary: In this work, a comprehensive summary on the kinetic modeling of glycerol hydrogenolysis has been conducted, which reveals the possible mechanism involved in the activation of the C-H and C-O bond in glycerol molecules. The study offers alternative views on the scale-up design of glycerol hydrogenolysis to glycols, as well as the hydrogenolysis of various other bio-derived compounds to value-added chemicals.
Article
Chemistry, Multidisciplinary
Nat Phongprueksathat, Atul Bansode, Takashi Toyao, Atsushi Urakawa
Summary: In this study, sodium- and nitrate-free hydroxy-carbonate precursors were successfully prepared via urea hydrolysis co-precipitation of acetate salt, simplifying the catalyst preparation process and making the synthesis more sustainable. The Cu/ZnO catalysts derived from these precursors showed comparable catalytic performance to commercial catalysts in CO2 hydrogenation, even without the need for a washing step and pH control.
Article
Chemistry, Physical
Arindam Modak, Deepika Gill, Komal Sharma, Vidha Bhasin, Kamal K. Pant, S. N. Jha, Dibyendu Bhattacharyya, Saswata Bhattacharya
Summary: A new microwave route has been developed for the one-pot conversion of pentose and hexose sugars into glycol and hexitol without pressurized hydrogen reactors. The hydrogenolysis of sugars to glycols is achieved using a Ru single atom catalyst on a phosphine-modified silica carrier under mild conditions.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Energy & Fuels
Rafael Belo Duarte, Marcos Lucio Corazza, Joao Lourenco Castagnari Willimann Pimenta, Luiz Mario de Matos Jorge
Summary: A kinetic study of glycerol hydrodeoxygenation (HDO) on NiMo2C/Al2O3 and Al2O3 catalysts, prepared by sol-gel technique, was conducted at high glycerol concentration (95wt%) in a batch reactor, from 250 degrees C to 285 degrees C. The catalysts' structural and surface properties were characterized, and it was found that impregnation of alumina with Ni and Mo followed by carburization increased crystallite sizes and reduced total acidity. The reactions followed a zeroth order model and had no diffusion limitation. The main products were propanediols, ethylene glycol, long-chain molecules, as well as methane, ethane, and propane.
Article
Chemistry, Inorganic & Nuclear
Fiseha Bogale Gebretsadik, Javier Ruiz-Martinez, Maria Dolores Gonzalez, Pilar Salagre, Yolanda Cesteros
Summary: The study investigated the effect of Ni-Cu bimetallic catalysts with different Ni:Cu ratios on the liquid phase hydrogenolysis of glycidol, showing that the addition of Cu and higher reaction temperatures decreased diol formation while increasing the 1,3-propanediol/1,2-propanediol ratio. This suggests that an appropriate amount of Cu enhances the collaborative effect between Ni and H+ ions, favoring the formation of 1,3-propanediol.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Physical
C. Garcia-Sancho, C. P. Jimenez-Gomez, N. Viar-Antunano, J. A. Cecilia, R. Moreno-Tost, J. M. Merida-Robles, J. Requies, P. Maireles-Torres
Summary: ZrO2, Al2O3, and ZrO2/Al2O3 catalysts with different Zr/Al molar ratios were synthesized and characterized. The Zr5Al5 catalyst with a Zr/Al ratio of 1 exhibited the highest conversion and yield in the reduction of furfural reaction due to its abundant acid sites, specific surface area, and pore volume.
APPLIED CATALYSIS A-GENERAL
(2021)
Article
Chemistry, Physical
David Mendez-Mateos, V. Laura Barrio, Jesus M. Requies, Jose F. Cambra
Summary: This study investigates the effects of adding alkaline earth metals and lanthanides on the conversion of CO2 to methane in catalysts. The inclusion of La improves methane yield and enhances resistance to H2S deactivation.
Article
Engineering, Chemical
Jon Solar, Blanca M. Caballero, Alexander Lopez-Urionabarrenechea, Esther Acha, Pedro L. Arias
Summary: The pyrolysis of woody biomass waste can produce gas, solid, and liquid products, with different temperatures affecting the product yields and composition. Higher temperatures lead to increased gas yield, decreased solid and liquid yields, and changes in the composition of charcoal obtained.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2021)
Article
Thermodynamics
Nerea Viar, Jesus M. Requies, Ion Agirre, Aitziber Iriondo, Cristina Garcia-Sancho, Pedro L. Arias
Summary: In this study, catalysts supported on biomass-derived carbon were used for the hydrogenolysis of HMF to produce DMF and DMTHF in a continuous flow reactor. The carbon-supported catalysts showed good activity and selectivity, outperforming commercial carbon-supported catalysts in terms of selectivity and stability.
Article
Chemistry, Physical
A. Barranca, I Gandarias, P. L. Arias, I Agirrezabal-Telleria
Summary: This study provides new evidence for the one-pot production of 1,5-pentanediol from sustainable sources. The researchers found that by studying the catalysts and reaction conditions, it is possible to directly produce 1,5-pentanediol from furfural at lower temperatures with high productivity. The presence of Co2+ sites in the catalysts showed significant differences compared to other bivalent metals, possibly due to differences in the adsorption positions of reaction intermediates.
Article
Energy & Fuels
Daniel Bielsa, Mikel Oregui, Pedro L. Arias
Summary: This study investigated an established granulation technique using Si-doped manganese oxide as the active material to determine critical parameters for achieving the best chemical and mechanical stability of the granules. The positive effect of decreasing the bath temperature on increasing the volumetric energy density of the granules was identified.
Article
Green & Sustainable Science & Technology
Jorge Blanco, Maria Linares, Manuel Lopez Granados, Ion Agirre, Inaki Gandarias, Pedro Luis Arias, Jose Iglesias, Jovita Moreno, Alicia Garcia
Summary: This study compares the production of maleic anhydride from different feedstock using life cycle analysis and exergy analysis. The results show that the gas phase oxidation of furfural is competitive with petrochemical technologies, while the aqueous phase process is not viable due to energy and environmental concerns. The environmental footprint of the starting raw material is the major drawback for the new furfural-to-maleic anhydride production processes. The use of environmentally friendly furfural production technologies at the commercial scale can improve the environmental performance of gas phase maleic anhydride production.
ADVANCED SUSTAINABLE SYSTEMS
(2022)
Article
Chemistry, Physical
Francesco Torre, Teresa Aguilar Sanchez, Stefania Doppiu, Mikel Oregui Bengoechea, Pedro Luis Arias Ergueta, Elena Palomo del Barrio
Summary: This study investigates the effect of atomic substitution on the MnFe2O4-Na2CO3 thermochemical cycle for H-2 production. It is found that Na2CO3 substitution for Li2CO3 decreases the decarbonation onset temperature but does not improve the reversibility. Among the substitutions of Mn with Ca, Ni, and Zn, the 5% Zn mixture exhibits the best reversibility and stable H-2 production.
MATERIALS TODAY ENERGY
(2022)
Article
Chemistry, Multidisciplinary
Alberto Barranca, Iker Agirrezabal-Telleria, Marcos Rellan-Pineiro, Manuel A. Ortuno, Inaki Gandarias
Summary: The selective hydrogenolysis of C-OH bond without the hydrogenation of the furan ring is essential in converting biomass-derived platform chemicals. By adjusting the concentration of HCl during catalyst synthesis, the amount of surface chlorine can be fine-tuned, promoting the formation of 2-methylfuran and inhibiting undesired furan ring hydrogenation. Under optimized conditions, a yield of 94% 2-methylfuran and a productivity of approximately 18 mol(2MF) kg(cat)(-1) h(-1) were achieved.
REACTION CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Physical
M. El Doukkali, S. Paul, F. Dumeignil
Summary: This study proposes a rationalized approach to develop catalysts for glycerol-to-propylene routes. The use of hydrophobic-inert silica supports protects reactive Mo particles against leaching and sintering. Carburizing MoOx nanoparticles to beta-Mo2C leads to an extremely efficient HDO catalyst with high propylene yield.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2023)
Review
Chemistry, Physical
Mohamed El Doukkali, Meryem Bahlouri, Sebastien Paul, Franck Dumeignil
Summary: GTP routes are being developed as a bridge between the biorefinery and polyolefin industries. This review discusses developments in GTP catalysis, including catalyst design, active site elucidation, and reaction mechanisms. It also compares GTP configurations based on thermodynamic and operating conditions, and evaluates various criteria such as process configuration, energy consumption, and propylene production.
Review
Chemistry, Physical
Ane Bueno, Asier Barredo, Nerea Viar, Jesus Requies
Summary: The production of FDCA from sugars is an important challenge in reducing dependence on fossil fuels. Various strategies, including physical separation and one-pot transformation, have been investigated to achieve efficient conversion of sugars to FDCA. The development of catalytic systems functional for both dehydration and oxidation reactions is crucial. This review summarizes recent research on the catalytic systems for the direct production of FDCA from sugars, including both one-step and two-step integrated systems.
Review
Polymer Science
Patricia Ares-Elejoste, Ruben Seoane-Rivero, Inaki Gandarias, Aitziber Iturmendi, Koldo Gondra
Summary: The concerns over the environmental impact of thermoset composites and new legislation have driven the scientific sector to search for sustainable alternatives. Sustainable reinforcements have been widely used to manufacture more sustainable composites, but new alternatives such as bio-based thermosetting resins and recyclable systems have emerged. This review explores these new systems as well as sustainable reinforcements and discusses the biocomposites market and its impact. While significant improvements have been made, further research into alternative solutions is necessary.
Article
Chemistry, Multidisciplinary
L. Ouayloul, M. El Doukkali, M. Jiao, F. Dumeignil, I. Agirrezabal-Telleria
Summary: This study investigates the role of Bronsted- and Lewis-acid sites in the conversion of ethanol to ethylene at low temperature. The results show that the cooperative effect between these acid sites is crucial for ethylene formation.