Article
Green & Sustainable Science & Technology
Anjani R. K. Gollakota, Chi-Min Shu, Prakash Kumar Sarangi, Krushna Prasad Shadangi, Sudip Rakshit, John F. Kennedy, Vijai Kumar Gupta, Minaxi Sharma
Summary: The quest for renewable and sustainable alternatives, especially biomass/bio waste, has been prompted by rising environmental concerns and the depletion of natural fossil fuels. Converting biomass residues into liquid fuels using thermochemical means seems promising, but the poor quality of bio-oil produced through pyrolysis poses challenges. Hydrodeoxygenation (HDO) offers a cutting-edge method for upgrading bio-oil into sustainable fuels that can compete with traditional fossil fuels. However, producing high-performance catalysts and understanding the physico-chemical aspects of bio-oil remain difficult. Research on upgrading pyrolysis bio-oil to gasoline is crucial for biorefineries, and this review provides detailed information on HDO mechanisms, biofuels, model compounds, and catalyst suitability for biofuels obtained from various feedstock.
RENEWABLE & SUSTAINABLE ENERGY REVIEWS
(2023)
Review
Chemistry, Multidisciplinary
Lu Qu, Xia Jiang, Zihao Zhang, Xiang-gang Zhang, Guo-yong Song, Hua-lin Wang, Yuan-ping Yuan, Yu-long Chang
Summary: This article reviews the model compounds, catalysts, and equipment involved in the hydrodeoxygenation (HDO) of bio-oils, aiming to summarize the progress in the utilization of the HDO process and provide useful insights for the efficient practical application of bio-oils.
Article
Energy & Fuels
Mingxing Zhao, Jun Hu, Ping Lu, Shiliang Wu, Chao Liu, Yahui Sun
Summary: Efficient conversion of lignin-derived bio-oils to cycloalkanes was achieved using bifunctional RuCoWx/NC catalyst prepared by in situ pyrolysis method. The catalyst exhibited excellent hydrodeoxygenation (HDO) activity towards 4-propylguaiacol and rice husk bio-oil, leading to high yields of propylcyclohexane and hydrocarbons, respectively. The stability of RuCoW0.03/NC catalyst was also confirmed after four cycles.
Article
Chemistry, Applied
Wajahat Waheed Kazmi, Ji-Yeon Park, Ghazaleh Amini, In-Gu Lee
Summary: In this study, the influence of reaction parameters (temperature, holding time, and biooil concentration) on the upgrading of esterified CG-BO over MgNiMo/AC catalyst in supercritical ethanol was investigated. The MgNiMo/AC catalyst played a crucial role in hydrogen production and hydrodeoxygenation reactions of CG-EBO during the supercritical upgrading. The optimized conditions for the upgrading process were determined as 375 degrees C, 2 h holding time, and 20 wt% CG-EBO concentration, which resulted in a biofuel product with high yield and low oxygen content.
FUEL PROCESSING TECHNOLOGY
(2023)
Article
Energy & Fuels
Xiangchen Kong, Chao Liu, Xing Wang, Yuyang Fan, Weicong Xu, Rui Xiao
Summary: This study presents a practical and economical method for upgrading lignin bio-oil by supercritical methanol hydrodeoxygenation (SCM-HDO) using a Cu/CuZnAlO(x) catalyst. The selective production of oxygen-containing fuel was achieved through the hydrogenation of aromatic rings and inhibition of over-deoxygenation reactions. The catalyst activity could be easily recovered through a calcination-reduction process, offering potential opportunities for the production of alternative biofuels from lignin bio-oil.
Review
Chemistry, Multidisciplinary
Jing Cao, Youming Zhang, Li Wang, Cen Zhang, Congshan Zhou
Summary: This mini-review focuses on the recent development of unsupported MoS2-based HDO catalysts from the understanding of catalyst design. The three aspects including morphology and defect engineering, metal doping, and deactivation mechanism are highlighted in adjusting the HDO performance of MoS2-based catalysts. Finally, the key challenges and future perspectives about how to design efficient catalysts are also summarized in the conclusions.
FRONTIERS IN CHEMISTRY
(2022)
Article
Chemistry, Applied
I Vazquez-Garrido, A. Lopez-Benitez, A. Guevara-Lara, G. Berhault
Summary: The addition of 1 mol% manganese to Al2O3 support has been shown to enhance the performance of NiMo catalysts for the hydroconversion of soybean oil, due to the stabilization of manganese oxide species aiding in the redispersion of the active phase.
Article
Energy & Fuels
Sasiradee Jantasee, Nattawut Rodtuk, Weerinda Mens, Chaiyan Chaiya
Summary: The characteristics of bio-oil derived from soybean meal were improved through hydrodeoxygenation using monometallic and bimetallic catalysts. The oxygen content was reduced and the heating value of the bio-oil increased. The Ni/gamma-Al2O3 catalyst was found to be more effective in reducing oxygen content and increasing the heating value.
Article
Chemistry, Applied
Denise Cavuoto, Antonella Gervasini, Federica Zaccheria, Nicola Scotti, Marcello Marelli, Chiara Bisio, Federico Begni, Nicoletta Ravasio
Summary: This paper proposes the synthesis of green solvents N-alkyl-pyrrolidinones from gamma-valerolactone using non-noble, supported copper catalysts. The reaction setup has been improved to limit harsh conditions and auxiliaries, as well as avoid catalyst pretreatment or high hydrogen pressure. A CuO/Al2O3 catalyst with high metal phase dispersion and low Cu nanoparticle size proved to be the best for the process. The catalytic system is also suitable for other lactones such as gamma-butyrolactone, gamma-caprolactone, epsilon-caprolactone, and dihydrocoumarin.
Article
Engineering, Chemical
Isaac Yeboah, Yahao Li, Kishore Rajendran, Kumar R. Rout, De Chen
Summary: The study presented an efficient tandem catalytic system for converting bio-oil to hydrocarbons with enhanced C4+ fuel yield. The multifunctional catalytic approach has potential applications in the emerging biorefinery concept.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2021)
Article
Green & Sustainable Science & Technology
Quoc Khanh Tran, Hoang Vu Ly, Byeongwan Kwon, Seung-Soo Kim, Jinsoo Kim
Summary: The study prepared Ni/γ-Al2O3 and Fe/activated carbon catalysts for the hydrodeoxygenation (HDO) of guaiacol, showcasing different conversion rates under varying calcination temperatures and metal loadings.
Article
Engineering, Environmental
Humair Ahmed Baloch, Sabzoi Nizamuddin, M. T. H. Siddiqui, Sajid Riaz, Kristina Konstas, N. M. Mubarak, M. P. Srinivasan, G. J. Griffin
Summary: The study demonstrated that upgrading bio-oil in sub-supercritical ethanol using Pt/AC and Pd/AC as catalysts is effective, reducing acid fractions, increasing solution pH, and improving the heating value of the bio-oil.
JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING
(2021)
Review
Biochemistry & Molecular Biology
Yanfan Yang, Xuan Xu, Haodong He, Dan Huo, Xiaoyun Li, Lin Dai, Chuanling Si
Summary: The depletion of oil resources and environmental problems caused by fossil energy usage have led to the search for alternative energy sources, with bio-oil being a promising option. However, bio-oil cannot be directly utilized due to its high proportion of oxygenated compounds with low calorific value and poor thermal stability. Catalytic hydrodeoxygenation (HDO), with various catalyst systems like noble/non-noble metal catalysts, porous organic polymer catalysts, and polar solvents, is an effective method to refine oxygenated compounds from bio-oil. This review discusses the HDO process, different catalytic materials, mechanisms, and future challenges and opportunities for bio-oil upgradation.
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
(2023)
Article
Green & Sustainable Science & Technology
Athanasios Dimitriadis, Loukia P. Chrysikou, George Meletidis, George Terzis, Milos Auersvald, David Kubicka, Stella Bezergianni
Summary: This study investigated the upgrading of pyrolysis bio-oil through mild hydrotreatment, finding that the longest catalyst life was achieved under specific operating conditions. Furthermore, several properties of the initial bio-oil were improved during the upgrading process.
Article
Energy & Fuels
Xing Zhang, Jingfeng Wu, Lingjun Zhu, Shurong Wang
Summary: A novel strategy was proposed to produce diesel-like liquid fuel from lignin-derived bio-oil and plant/animal oil through hydrodeoxygenation-in situ esterification. The utilization of both aromatic units and -OCH3 groups of lignin was achieved. Model compounds, guaiacol and lauric acid, successfully produced cyclohexyl laurate and methyl laurate, satisfying the biodiesel standard. The yield of esters reached 112.5 mol % with nearly complete conversion of guaiacol. The presence of an additional -OCH3 group hindered the formation of cyclohexanol while increasing the yield of methanol. Lignin-derived dimers were also efficiently converted into diesel-like liquid fuel rich in esters and cycloalkanes.
Article
Chemistry, Applied
Chao-Wei Lee, Po-Yi Lin, Bing-Hung Chen, Roman G. Kukushkin, Vadim A. Yakovlev
Summary: By utilizing the Ni-Mo(R)/ZSM-5 catalyst, hydrogenation-deoxygenation of palmitic acid can achieve conversion rates close to 99% with significant production of isomerized paraffins.
Article
Chemistry, Applied
B. N. Kuznetsov, V. Sharypov, S. Baryshnikov, A. Miroshnikova, O. P. Taran, V. A. Yakovlev, A. Lavrenov, L. Djakovitch
Summary: Catalytic hydrogenolysis in supercritical ethanol using bifunctional catalysts such as Ru/C and Pt/ZrO2 enables the effective fractionation of aspen wood biomass into cellulose and liquid products enriched with propyl syringol and propyl guaiacol. The yield of alkyl derivatives of methoxyphenols is higher in the liquid products of wood compared to ethanol lignin hydrogenolysis. The catalysts also shift the molecular weight distribution of liquid products towards lower molecular mass according to GPC data.
Article
Chemistry, Applied
Petr M. Yeletsky, Yury V. Dubinin, Nikolay A. Yazykov, Roman B. Tabakaev, Konstantin A. Okotrub, Vadim A. Yakovlev
Summary: The study investigated the development of porosity in porous carbons from vegetable biomass through the leaching of mineral phases from the carbonized feedstock. The research found that the method of removing mineral template phases via acid leaching can result in porous carbons with high porosity, with biomass feedstocks showing more effective porosity development.
FUEL PROCESSING TECHNOLOGY
(2022)
Article
Chemistry, Physical
Alexey A. Philippov, Nikolai N. Nesterov, Vera P. Pakharukova, Oleg N. Martyanov
Summary: The transfer hydrogenation of anisole in 2-PrOH was studied as a model reaction for lignocellulose processing. It was found that the oxide support significantly affects the structure, activity, and selectivity of the catalysts. The Ni catalyst supported on alumina showed the best performance in the transfer hydrodeoxygenation of anisole due to the highest dispersion of Ni-0 particles and the highest concentration of acid centers.
APPLIED CATALYSIS A-GENERAL
(2022)
Article
Chemistry, Physical
K. S. Shinkevich, R. G. Kukushkin, O. A. Bulavchenko, O. O. Zaikina, M. V. Alekseeva, P. S. Ruvinskiy, V. A. Yakovlev
Summary: The effects of different supports and modifiers on the performance of catalysts for hydroprocessing of fatty acids were investigated, and it was found that the ZSM-5 supported catalytic system had the highest conversion rate. Leaching of active components from the surface of all catalysts was observed, and modification with molybdenum did not improve their stability.
APPLIED CATALYSIS A-GENERAL
(2022)
Article
Chemistry, Physical
Sergey A. Stepanenko, Danil M. Shivtsov, Anton P. Koskin, Igor P. Koskin, Roman G. Kukushkin, Petr M. Yeletsky, Vadim A. Yakovlev
Summary: This study focuses on the development of liquid organic hydrogen carriers (LOHC) based on N-heterocyclic compounds. The advantage of these LOHC-substrates is their low hydrogen extraction temperature and high purity of hydrogen gas. Among the studied heterocyclic compounds, 8HMI showed the highest reactivity and hydrogen storage performance in the presence of a palladium catalyst.
Article
Chemistry, Physical
Alexey Philippov, Nikolay Nesterov, Vera Pakharukova, Ivan Kozhevnikov, Oleg Martyanov
Summary: This study investigates the effect of Cu on the catalytic activity and selectivity of Ni-Cu catalysts in transfer hydrogenation, and finds that the addition of Cu leads to deactivation of the catalyst during the conversion of anisole.
Article
Chemistry, Physical
Nikolay S. Nesterov, Vera P. Pakharukova, Alexey A. Philippov, Evgeny Y. Gerasimov, Sergey V. Tsybulya, Oleg N. Martyanov
Summary: The synthesis and properties of different Ni-Al oxide catalytic precursors were investigated, and the most active catalyst was found in the hydrogenation reaction of anisole.
Article
Chemistry, Physical
Alexey Philippov, Nikolay Nesterov, Oleg Martyanov
Summary: Transfer hydrogenation (TH) using high-loaded Ni-based catalysts was studied under supercritical conditions for phenolic compounds, showing that the addition of Cu increases specific catalytic activity.
Article
Chemistry, Multidisciplinary
Nikolay Nesterov, Vera Pakharukova, Svetlana Cherepanova, Stanislav Yakushkin, Evgeniy Gerasimov, Dmitry Balaev, Sergei Semenov, Andrey Dubrovskii, Oleg Martyanov
Summary: Mixed Co-Ni bimetallic systems with solid substitution structure were synthesized using the supercritical antisolvent precipitation method, and their properties were characterized. It was found that Co-enriched systems have a defective hexagonal close-packed structure, and an increase in water content affects their structure and distribution. The mixed systems showed the highest coercivity, while the Ni-enriched systems had a cubic close-packed structure with modified lattice parameters.
Article
Chemistry, Inorganic & Nuclear
Maxim D. Mikhnenko, Svetlana V. Cherepanova, Evgeny Yu Gerasimov, Alena A. Pochtar, Maria V. Alekseeva (Bykova), Roman G. Kukushkin, Vadim A. Yakovlev, Olga A. Bulavchenko
Summary: The structural features of NiO-SiO2 nanocrystalline catalyst synthesized by sol-gel method were investigated. XRD, TEM, and DD were used to study the structure. XRD simulations based on conventional Rietveld analysis and statistical models of 1D disordered crystals were conducted to extract structural information. The results showed the presence of two NiO-like oxides with different lattice constants and different average sizes in NiO-SiO2 catalyst.
Article
Chemistry, Multidisciplinary
S. G. Zavarukhin, Yu. V. Dubinin, N. A. Yazykov, V. A. Yakovlev
Summary: This paper proposes a method for estimating the heat of combustion of sewage sludge under the condition of lack of air, based on the modification of the Mendeleev formula and the calculation of chemical equilibrium in an initial mixture. The equilibrium composition of the mixture can be calculated using applied programs or chemical equilibrium equations. Test calculations and comparisons show satisfactory agreement between the results obtained by both methods, indicating the feasibility of this procedure.
SOLID FUEL CHEMISTRY
(2022)
Article
Thermodynamics
S. F. Tikhov, K. R. Valeev, Yu Dubinin, N. A. Yazykov, S. Cherepanova, A. N. Salanov, V. A. Yakovlev, V. A. Sadykov
Summary: Honeycomb cermet catalysts were studied before and after stability tests in a fluidized-bed coal reactor. The decrease in catalytic activity was observed with decreasing strength. The predicted operating time of the catalyst was at least two winter seasons.
COMBUSTION EXPLOSION AND SHOCK WAVES
(2022)
Article
Chemistry, Inorganic & Nuclear
Maria Alekseeva (Bykova), Yuliya K. Gulyaeva, Olga A. Bulavchenko, Andrey A. Saraev, Anna M. Kremneva, Sergey A. Stepanenko, Anton P. Koskin, Vasily V. Kaichev, Vadim A. Yakovlev
Summary: The addition of zinc hinders the reducibility of nickel and weakens its interaction with the silica matrix, leading to the formation of solid oxide nickel-zinc solutions. Zn-modified catalysts exhibit significantly better catalytic properties in the dehydrogenation of methylcyclohexane compared to Ni-Cu counterparts. The selectivity towards toluene formation increases noticeably with a decrease in the Ni : Zn mass ratio, attributed to the promoting geometric and electronic effects from the formation of bimetallic Ni-Zn solid solutions.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Applied
Qingyuan Zheng, Jack H. Williams, Scott Elgersma, Mick D. Mantle, Andrew J. Sederman, G. Leendert Bezemer, Constant M. Guedon, Lynn F. Gladden
Summary: In this study, a pilot-scale fixed-bed reactor compatible with NMR/MRI was developed for Fischer-Tropsch synthesis. Multiple magnetic resonance techniques were applied to quantitatively characterize different product species within catalyst pellets, providing valuable information for catalyst and reactor optimization.
Article
Chemistry, Applied
Lisa Ramisch, Sebastian Pfaff, Sabrina M. Gericke, Edvin Lundgren, Johan Zetterberg
Summary: We present a combination of optical operando techniques that allow simultaneous measurement of adsorbed species on catalyst surfaces, monitoring of surface oxide formation, and imaging of the gas phase above the catalyst surface. The experimental setup was validated by studying CO oxidation on Pd(100) at different pressures, revealing the effects of pressure on the heterogeneous catalytic reaction.
Article
Chemistry, Applied
Marta Paniagua, Gabriel Morales, Juan A. Melero, Daniel Garcia-Salgado
Summary: The influence of common impurities in levulinic acid on the catalytic performance of different acid catalysts for bio-jet fuel production was studied. It was found that furfural had the greatest detrimental effect on catalyst performance, while propyl-sulfonic acid-modified SBA-15 and sulfonic acid resin Amberlyst-70 showed good regeneration ability.
Article
Chemistry, Applied
Jesus Tapiador, Pedro Leo, Guillermo Calleja, Gisela Orcajo
Summary: This study presents a new MOF material, Zn-URJC-13, with acid and basic sites, permanent porosity, and high affinity to CO2 molecules. The Zn-URJC-13 catalyst exhibits efficient performance in CO2 cycloaddition reactions and can be reused multiple times.
Article
Chemistry, Applied
Dan Zhao, Vita A. Kondratenko, Dmitry E. Doronkin, Shanlei Han, Jan-Dierk Grunwaldt, Uwe Rodemerck, David Linke, Evgenii V. Kondratenko
Summary: This study demonstrates the potential of cheap and commercially available Zr or Ti-based supports and ZnO to serve as active and selective catalysts for propane dehydrogenation (PDH). The catalytically active species formed in situ under PDH conditions consist of isolated ZnOx. ZnOx on the surface of LaZrOx shows the highest rate of propene formation.
Article
Chemistry, Applied
Hanbyeol Kim, Jung Rae Kim, Young-Kwon Park, Jeong-Myeong Ha, Jungho Jae
Summary: In this study, metal phosphates were used as catalysts for biomass conversion to produce sustainable aromatics through DielsAlder cycloaddition reactions. The effects of synthesis method, activation method, and P/Ti molar ratio on the structure and acid properties of titanium phosphate catalysts were systematically studied. The mesoporous titanium phosphate catalyst synthesized by hydrothermal method at 180℃ for 12 h followed by ethanol refluxing at 60℃ for 24 h at a molar P/Ti ratio of 1 showed the highest surface area and acid site density.
Article
Chemistry, Applied
Yasin Khani, Sumin Pyo, Kwang-Eun Jeong, Chul-Ung Kim, Moonis Ali Khan, Byong-Hun Jeon, Kun-Yi Andrew Lin, Siyoung Q. Choi, Young-Kwon Park
Summary: A protonated form of Zeolite Socony Mobil-5 (H-ZSM-5) catalyst was synthesized through a hydrothermal method using different sources of silica. The effect of loading the catalyst with yttrium, samarium, and gadolinium on the acidic properties was investigated. Among the metal-loaded catalysts, the Sm/LHZ catalyst showed the best performance in the methanol to propylene conversion due to its high amount of weak and intermediate acid sites, while the Gd-LHZ catalyst increased the selectivity towards ethane and propane.
Article
Chemistry, Applied
Michael Franc, Ivana Cisarova, Jan Vesely
Summary: The present study investigates an enantioselective cyclization of enals with imidazolone derivatives catalyzed by a combination of achiral Pd(0) complex and chiral secondary amine. Corresponding spirocyclic imidazolones were produced in high yields with moderate diastereoselectivity and excellent enantioselectivity. The developed co-operative catalytic methodology provides a highly substituted spirocyclic scaffold with four stereogenic centers under mild conditions.
Article
Chemistry, Applied
Mauro Alvarez, Jennifer Cueto, David P. Serrano, Pablo Marin, Salvador Ordonez
Summary: This study focuses on improving the formulation and preparation methods of catalysts for the production of dimethyl carbonate. By using suitable catalyst preparation methods and copper salt precursors, the researchers successfully produced catalysts with optimal performance for dimethyl carbonate formation.
Article
Chemistry, Applied
Claudia J. Keijzer, Luc C. J. Smulders, Dennie Wezendonk, Jan Willem de Rijk, Petra E. de Jongh
Summary: This study investigates the catalytic behavior of alpha-alumina supported silver catalysts in the presence of chloride. It is found that the particle size of silver can affect the selectivity of the catalyst, but different strategies lead to different results. In this size range, the selectivity of ethylene oxide is correlated to the Ag : Al2O3 surface ratio.
Article
Chemistry, Applied
Takeshi Aihara, Wataru Aoki, Michikazu Hara, Keigo Kamata
Summary: The development of acid-base bifunctional catalysts is important for promoting specific chemical transformations. In this study, Ti-based perovskite oxides were synthesized and used as catalysts for two C-C bond-forming reactions (cyanosilylation and Knoevenagel condensation). The highly pure SrTiO3 nanoparticles with a high specific surface area exhibited the highest catalytic performance, and could be easily recovered and reused.
Article
Chemistry, Applied
Olga Gorlova, Petra Pribylova, Eliska Vyskocilova, Katerina Peroutkova, Jan Kohout, Iva Paterova
Summary: This study investigates the Baeyer-Villiger oxidation of beta-cyclocitral using tin-modified mixed oxides as catalysts. The optimal reaction conditions and the effects of various factors on the reaction course and selectivity were determined. The results show that tin-modified mixed oxides exhibit high activity and selectivity in the oxidation reaction.
Article
Chemistry, Applied
M. I. Avila, M. M. Alonso-Doncel, L. Briones, G. Gomez-Pozuelo, J. M. Escola, D. P. Serrano, A. Peral, J. A. Botas
Summary: The catalytic fast pyrolysis of lignin using ion-exchanged zeolite catalysts showed significant improvements in bio-oil quality and the production of aromatic hydrocarbons and oxygenated compounds.
Article
Chemistry, Applied
Enrico Catizzone, Giorgia Ferrarelli, Paolo Bruno, Girolamo Giordano, Massimo Migliori
Summary: The acid-catalysed alcohol conversion reaction is a promising route for de-fossilization strategies. Research on pure alcohol conversion and simultaneous dehydration of mixed alcohols have shown different product compositions, with the type and distribution of acid sites affecting the reaction mechanism.
Article
Chemistry, Applied
Alireza Ranjbari, Juho Kim, Jihee Yu, Jiyun Kim, Mireu Park, Nayoung Kim, Kristof Demeestere, Philippe M. Heynderickx
Summary: This study investigated a novel kinetic model for the adsorption and photocatalytic degradation of methyl orange using commercial ZnO and reduced ZnO photocatalysts. The results provided new insights into the interaction of catalysts with molecules of different charges and compared with a previous study on methylene blue. The presence of oxygen vacancies in ZnO and their effects on adsorption and photocatalytic degradation were analyzed, and the photocatalytic degradation rate of reduced ZnO was found to increase significantly.