Open Access
Outstanding performance of rehydrated Mg-Al hydrotalcites as heterogeneous methanolysis catalysts for the synthesis of biodiesel
(Elsevier, 2018) Navajas León, Alberto; Campo Aranguren, Idoia; Moral Larrasoaña, Ainara; Echave, Javier; Sanz, Oihane; Montes, Mario; Odriozola, José A.; Arzamendi Manterola, Gurutze; Gandía Pascual, Luis; Química Aplicada; Kimika Aplikatua; Institute for Advanced Materials and Mathematics - INAMAT2
There is still a need for active, selective and stable heterogeneous catalysts for the synthesis of biodiesel. In this work, magnesium-aluminium hydrotalcites with Mg/Al molar ratios within the 1.5–5 range were synthesized by coprecipitation and used as transesterification catalysts for the synthesis of biodiesel. The mixed oxides obtained after calcination recovered the hydrotalcite structure in the form of meixnerite after rehydration in boiling water. The solids were characterized by XRD, TGA, N2 adsorption-desorption, and SEM. Basic properties were assessed by means of Hammett indicators and CO2-TPD. Rehydrated materials with the highest Mg/Al ratios showed some distinctive features: low surface area, well defined flake-like crystals, high basicity and strong basic sites with H_ values above 11. They were also the most active catalysts allowing to achieve 51–75% sunflower oil methanolysis conversion after 8 h of reaction under mild conditions (60 °C, 1 atm), methanol/oil molar ratio of 12 using between 2 and 6 wt% of catalyst. The conversion increased up to 96% (92% fatty acid methyl esters yield) using 2 wt% catalyst and methanol/oil molar ratio of 48. Catalyst leaching was not a serious problem with these solids that could be reutilized maintaining very good activities. A general accordance between solids basic properties and their catalytic performance has been observed. These results are among the best reported in the literature for heterogeneous methanolysis catalysts and have been attributed to the high basicity of the rehydrated solids and the presence of strong and accessible basic sites probably consisting in interlayer hydroxide anions at the edges of the crystals.
Open Access
Life cycle assessment of wheat straw pyrolysis with volatile fractions chemical looping combustion
(MDPI, 2024) Mendiara, Teresa; Navajas León, Alberto; Abad, Alberto; Pröll, Tobias; Munárriz Tabuenca, Mikel; Gandía Pascual, Luis; García-Labiano, Francisco; Diego, Luis F. de; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
Among the approaches to facilitating negative CO2 emissions is biochar production. Biochar is generated in the pyrolysis of certain biomasses. In the pyrolysis process, carbon in the biomass is turned into a solid, porous, carbon-rich, and stable material that can be captured from the soil after a period of from a few decades to several centuries. In addition to this long-term carbon sequestration role, biochar is also beneficial for soil performance as it helps to restore soil fertility and improves the retention and diffusion of water and nutrients. This work presents a Life Cycle Assessment of different pyrolysis approaches for biochar production. Biomass pyrolysis is performed in a fixed-bed reactor, which operates at a mild temperature (550 °C). Biochar is obtained as solid product of the pyrolysis, but there are also liquid (bio-oil) and gaseous products (syngas). The pyrolysis gas is partly used to fulfil the energy demand of the pyrolysis process, which is highly endothermic. In the conventional approach, CO2 is produced during the combustion of syngas and emitted to the atmosphere. Another approach to facilitate CO2 capture and thus obtain more negative CO2 emissions in the pyrolysis process is burning syngas and bio-oil in a Chemical Looping Combustion unit. Life Cycle Assessment was performed of these approaches toward biomass pyrolysis to evaluate their environmental impact. The Chemical Looping Combustion approach significantly reduced the values of 7 of the 16 environmental impact indicators studied, along with the Global Warming Potential among them, it slightly increased the value of one indicator related to the use of fossil resources, and it maintained the values of the remaining 8 indicators. Environmental impact reduction occurs due to the avoidance of CO2 and NOx emissions with Chemical Looping Combustion. The CO2 balances of the different pyrolysis approaches with Chemical Looping Combustion configurations were compared with a base case, which constituted the direct combustion of wheat straw to obtain thermal energy. Direct biomass combustion for the production of 17.1 MJ of thermal energy had CO2 positive emissions of 0.165 kg. If the gaseous fraction was burned by Chemical Looping Combustion, CO2 was captured and the emissions became increasingly negative, until a value of -3.30 kg/17.1 MJ was generated. If bio-oil was also burned by this technology, the negative trend of CO2 emissions continued, until they reached a value of -3.66 kg.
Open Access
Experimental study of the performance and emission characteristics of an adapted commercial four-cylinder spark ignition engine running on hydrogen-methane mixtures
(Elsevier, 2014) Diéguez Elizondo, Pedro; Urroz Unzueta, José Carlos; Marcelino Sádaba, Sara; Pérez Ezcurdia, Amaya; Benito Amurrio, Marta; Sáinz Casas, David; Gandía Pascual, Luis; Ingeniería; Ingeniaritza
The use of hydrogen/methane mixtures with low methane contents as fuels for internal combustion engines (ICEs) may help to speed up the development of the hydrogen energy market and contribute to the decarbonization of the transportation sector. In this work, a commercial 1.4 L four-cylinder Volkswagen spark-ignition engine previously adapted to operate on pure hydrogen has been fueled with hydrogen/methane mixtures with 5–20 vol.% methane (29.6–66.7 wt.%). An experimental program has been executed by varying the fuel composition, air-to-fuel ratio (λ), spark advance and engine speed. A discussion of the results regarding the engine performance (brake torque, brake mean effective pressure, thermal efficiency) and emissions (nitrogen oxides, CO and unburned hydrocarbons) is presented. The results reveal that λ is the most influential variable on the engine behavior due to its marked effect on the combustion temperature. As far as relatively high values of λ have to be used to prevent knock, the effect on the engine performance is negative. In contrast, the specific emissions of nitrogen oxides decrease due to a reduced formation of thermal NOx. A clear positive effect of reducing the spark advance on the specific NOx emissions has been observed as well. As concerns CO and unburned hydrocarbons (HCs), their specific emissions increase with the methane content of the fuel mixture, as expected. However, they also increase as λ increases in spite of the lower fuel concentration due to a proportionally higher reduction of the power. Finally, the effect of the increase of the engine speed is positive on the CO and HCs emissions but negative on that of NOx due to improved mixing and higher temperature associated to intensified turbulence in the cylinders.
Open Access
Highly selective CO formation via CO2 hydrogenation over novel ceria-based high-entropy oxides (HEOs)
(Elsevier, 2025-03-01) Cortázar, María; Lafuente Adiego, Marta; Navarro Puyuelo, Andrea; García, Xènia; Llorca Piqué, Jordi; Reyero Zaragoza, Inés; Bimbela Serrano, Fernando; Gandía Pascual, Luis; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
In the present study, new ceria-based high-entropy oxides (HEOs) were investigated as CO2 hydrogenation catalysts. The nominal composition was (Ce0.5Ni0.1Co0.1Cu0.1Zn0.1Mg0.1)Ox and the synthesis was accomplished through the citrate complexing sol-gel method. Characterization techniques utilized including ICP-AES, in situ XRD and in situ XPS, SEM-EDS, HR-TEM and HAADF-STEM, Raman spectroscopy, H2-TPR, CO2-TPD and N2 physical adsorption. The physicochemical characterization and the catalytic results revealed that the conditions of the thermal treatments at which the oxides were subjected critically determined the catalytic performance, especially the CO2 hydrogenation products selectivities. Calcination in air and/or reduction in hydrogen conducted at temperatures below 500 °C led to active but poorly selective catalysts that produced both methane and CO with significant yields. This was mainly attributed to the presence of metallic Cu, Ni and Co on the catalysts that appeared to be supported on ceria doped with the rest of the formulation elements. In contrast, thermal treatments at 750 °C favored the formation of a rocksalt entropy-stabilized (NiCoCuZnMg)Ox HEO supported on ceria that has stood out for showing an excellent selectivity towards the reverse water¿gas shift (RWGS) reaction. This catalyst led to CO selectivities of almost 100 % over a very wide range of reaction temperatures (300-700 °C). Long-term stability tests (100 h) showed only a slight decrease in CO2 conversion, while CO selectivity remained stable at nearly 100 % at 400 °C. XRD characterization of the used catalysts evidenced that, whereas the basic catalyst structure remained, some metallic copper exsolved during reduction and reaction period. These results are relevant and very promising, opening a door to the development of new catalysts for the valorization of CO2 through the RWGS reaction, thus expanding the low-temperature limit at which this process can be carried out selectively.
Open Access
Oak wood extracts applied to the grapevine. An alternative to obtain quality Garnacha wines
(Elsevier, 2018) Jiménez Moreno, Nerea; Moler Cuiral, José Antonio; Urmeneta Martín-Calero, Henar; Suberviola Ripa, Julián; Cibriain Sabalza, Félix; Gandía Pascual, Luis; Ancín Azpilicueta, Carmen; Química Aplicada; Kimika Aplikatua; Institute for Advanced Materials and Mathematics - INAMAT2; Estadística e Investigación Operativa; Estatistika eta Ikerketa Operatiboa
Open Access
Gaseous fueling of an adapted commercial automotive spark-ignition engine: simplified thermodynamic modeling and experimental study running on hydrogen, methane, carbon monoxide and their mixtures
(Elsevier, 2023) Urroz Unzueta, José Carlos; Diéguez Elizondo, Pedro; Arzamendi Manterola, Gurutze; Arana Burgui, Miguel; Gandía Pascual, Luis; Ingeniería; Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias; Zientziak; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
In the present work, methane, carbon monoxide, hydrogen and the binary mixtures 20 % CH4–80 % H2, 80 % CH4–20 % H2, 25 % CO–75 % H2 (by volume) were considered as fuels of a naturally aspirated port-fuel injection four-cylinder Volkswagen 1.4 L spark-ignition (SI) engine. The interest in these fuels lies in the fact that they can be obtained from renewable resources such as the fermentation or gasification of residual biomasses as well as the electrolysis of water with electricity of renewable origin in the case of hydrogen. In addition, they can be used upon relatively easy modifications of the engines, including the retrofitting of existing internal combustion engines. It has been found that the engine gives similar performance regardless the gaseous fuel nature if the air–fuel equivalence ratio (λ) is the same. Maximum brake torque and mean effective pressure values within 45–89 N⋅m and 4.0–8.0 bar, respectively, have been obtained at values of λ between 1 and 2 at full load, engine speed of 2000 rpm and optimum spark-advance. In contrast, the nature of the gaseous fuel had great influence upon the range of λ values at which a fuel (either pure or blend) could be used. Methane and methane-rich mixtures with hydrogen or carbon monoxide allowed operating the engine at close to stoichiometric conditions (i.e. 1 < λ < 1.5) yielding the highest brake torque and mean effective pressure values. On the contrary, hydrogen and hydrogen-rich mixtures with methane or carbon monoxide could be employed only in the very fuel-lean region (i.e. 1.5 < λ < 2). The behavior of carbon monoxide was intermediate between that of methane and hydrogen. The present study extends and complements previous works in which the aforementioned fuels were compared only under stoichiometric conditions in air (λ = 1). In addition, a simple zero-dimensional thermodynamic combustion model has been developed that allows describing qualitatively the trends set by the several fuels. Although the model is useful to understand the influence of the fuels properties on the engine performance, its predictive capability is limited by the simplifications made.
Open Access
Comparative performance of coke oven gas, hydrogen and methane in a spark ignition engine
(Elsevier, 2020) Ortiz Imedio, Rafael; Ortiz, A.; Urroz Unzueta, José Carlos; Diéguez Elizondo, Pedro; Gorri, D.; Gandía Pascual, Luis; Ortiz, I.; Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2; Ingeniería
In this study, coke oven gas (COG), a by-product of coke manufacture with a high volumetric percentage of H2 and CH4, has been identified as auxiliary support and promising energy source in stationary internal combustion engines. Engine performance (power and thermal efficiency) and emissions (NOx, CO, CO2 and unburned hydrocarbons) of COG, pure H2 and pure CH4 have been studied on a Volkswagen Polo 1.4 L port-fuel injection spark ignition engine. Experiments have been done at optimal spark advance and wide open throttle, at different speeds (2000–5000 rpm) and various air-fuel ratios (λ) between 1 and 2. The obtained data revealed that COG combines the advantages of pure H2 and pure CH4, widening the λ range of operation from 1 to 2, with very good performance and emissions results comparable to pure gases. Furthermore, it should be highlighted that this approach facilitates the recovery of an industrial waste gas.
Open Access
Innovative flow-through reaction system for the sustainable production of phenolic monomers from lignocellulose catalyzed by supported Mo2C
(Wiley, 2024) Maisterra Udi, Maitane; Atienza Martínez, María; Hablich Alvarracin, Karina Lissett; Moreira, Rui; Martínez Merino, Víctor; Gandía Pascual, Luis; Cornejo Ibergallartu, Alfonso; Bimbela Serrano, Fernando; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra - Nafarroako Unibertsitate Publikoa
Molybdenum carbide supported on activated carbon (β-Mo2C/AC) has been tested as catalyst in the reductive catalytic fractionation (RCF) of lignocellulosic biomass both in batch and in Flow-Through (FT) reaction systems. High phenolic monomer yields (34 wt.%) and selectivity to monomers with reduced side alkyl chains (up to 80 wt.%) could be achieved in batch in the presence of hydrogen. FT-RCF were made with no hydrogen feed, thus via transfer hydrogenation from ethanol. Similar selectivity could be attained in FT-RCF using high catalyst/biomass ratios (0.6) and high molybdenum loading (35 wt.%) in the catalyst, although selectivity decreased with lower catalyst/biomass ratios or molybdenum contents. Regardless of these parameters, high delignification of the lignocellulosic biomass and similar monomer yields were observed in the FT mode (13-15 wt.%) while preserving the holocellulose fractions in the delignified pulp. FT-RCF system outperforms the batch reaction mode in the absence of hydrogen, both in terms of activity and selectivity to reduced monomers that is attributed to the two-step non-equilibrium processes and the removal of diffusional limitations that occur in the FT mode. Even though some molybdenum leaching was detected, the catalytic performance could be maintained with negligible loss of activity or selectivity for 15 consecutive runs.
Open Access
Kinetic analysis and CFD simulations of the photocatalytic production of hydrogen in silicone microreactors from water-ethanol mixtures
(Elsevier, 2017) Castedo, Alejandra; Uriz Doray, Irantzu; Soler, Lluís; Gandía Pascual, Luis; Llorca Piqué, Jordi; Kimika Aplikatua; Institute for Advanced Materials and Mathematics - INAMAT2; Química Aplicada
Silicone microreactors containing microchannels of 500 μm width in a single or triple stack configuration have been manufactured, coated with an Au/TiO2 photocatalyst and tested for the photocatalytic production of hydrogen from water-ethanol gaseous mixtures under UV irradiation. Computational fluid dynamics (CFD) simulations have revealed that the design of the distributing headers allowed for a homogeneous distribution of the gaseous stream within the channels of the microreactors. A rate equation for the photocatalytic reaction has been developed from the experimental results obtained with the single stack operated under different ethanol partial pressures, light irradiation intensities and contact times. The hydrogen photoproduction rate has been expressed in terms of a Langmuir-Hinshelwood-type equation that accurately describes the process considering that hydrogen is produced through the dehydrogenation of ethanol to acetaldehyde. This equation incorporates an apparent rate constant (kapp) that has been found to be proportional to the intrinsic kinetic rate constant (k), and that depends on the light intensity (I) as follows: kapp = k·I0.65. A three-dimensional isothermal CFD model has been developed in which the previously obtained kinetic equation has been implemented. The model adequately describes the production of hydrogen of both the single and triple stacks. Moreover, the specific hydrogen productions (i.e. per gram of catalyst) are very close for both stacks thus suggesting that the scaling-up of the process could be accomplished by simply numbering-up. However, small deviations between the experimental and predicted hydrogen production suggest that a fraction of the radiation is absorbed by the microreactor components which should be taken into account for scaling-up purposes.
Open Access
Renewable hydrocarbon production from waste cottonseed oil pyrolysis and catalytic upgrading of vapors with Mo-Co and Mo-Ni catalysts supported on γ-Al2O3
(MDPI, 2021) Alves Melo, Josué; Santana de Sá, Mirele; Moral Larrasoaña, Ainara; Bimbela Serrano, Fernando; Gandía Pascual, Luis; Wisniewski, Alberto; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
In this work, the production of renewable hydrocarbons was explored by the means of waste cottonseed oil (WCSO) micropyrolysis at 500◦C. Catalytic upgrading of the pyrolysis vapors was studied using α-Al2O3, γ-Al2O3, Mo-Co/γ-Al2O3, and Mo-Ni/γ-Al2O3 catalysts. The oxygen removal efficiency was much lower in non-catalytic pyrolysis (18.0%), whilst γ-Al2O3 yielded a very high oxygen removal efficiency (91.8%), similar to that obtained with Mo-Co/γ-Al2O3 (92.8%) and higher than that attained with Mo-Ni/γ-Al2O3 (82.0%). Higher conversion yields into total renewable hydrocarbons were obtained with Mo-Co/γ-Al2O3 (61.9 wt.%) in comparison to Mo-Ni/γ-Al2O3 (46.6%). GC/MS analyses showed a relative chemical composition of 31.3, 86.4, and 92.6% of total renewable hydrocarbons and 58.7, 7.2, and 4.2% of oxygenated compounds for non-catalytic bio-oil (BOWCSO), BOMoNi and BOMoCo, respectively. The renewable hydrocarbons that were derived from BOMoNi and BOMoCo were mainly composed by olefins (35.3 and 33.4%), aromatics (31.4 and 28.9%), and paraffins (13.8 and 25.7%). The results revealed the catalysts’ effectiveness in FFA decarbonylation and decarboxylation, as evidenced by significant changes in the van Krevelen space, with the lowest O/C ratio values for BOMoCo and BOMoNi (O/C = 0–0.10) in relation to the BOWCSO (O/C = 0.10–0.20), and by a decrease in the presence of oxygenated compounds in the catalytic bio-oils.