Open Access
Acoustic and psychoacoustic levels from an internal combustion engine fueled by hydrogen vs. gasoline
(Elsevier, 2022) Arana Burgui, Miguel; San Martín Murugarren, Ricardo; Urroz Unzueta, José Carlos; Diéguez Elizondo, Pedro; Gandía Pascual, Luis; Zientziak; Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias; Ingeniería; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
Whereas noise generated by road traffic is an important factor in urban pollution, little attention has been paid to this issue in the field of hydrogen-fueled vehicles. The objective of this study is to analyze the influence of the type of fuel (gasoline or hydrogen) on the sound levels produced by a vehicle with an internal combustion engine. A Volkswagen Polo 1.4 vehicle adapted for its bi-fuel hydrogen-gasoline operation has been used. Tests were carried out with the vehicle when stationary to eliminate rolling and aerodynamic noise. Acoustics and psychoacoustics levels were measured both inside and outside the vehicle. A slight increase in the noise level has only been found outside when using hydrogen as fuel, compared to gasoline. The increase is statistically significant, can be quantified between 1.1 and 1.7 dBA and is mainly due to an intensification of the 500 Hz band. Loudness is also higher outside the vehicle (between 2 and 4 sones) when the fuel is hydrogen. Differences in sharpness and roughness values are lower than the just-noticeable difference (JND) values of the parameters. Higher noise levels produced by hydrogen can be attributed to its higher reactivity compared to gasoline.
Open Access
Conversion of a commercial gasoline vehicle to run bi-fuel (hydrogen-gasoline)
(Elsevier, 2012) Sáinz Casas, David; Diéguez Elizondo, Pedro; Sopena Serna, Carlos; Urroz Unzueta, José Carlos; Gandía Pascual, Luis; Ingeniería; Ingeniaritza
Bi-fuel internal combustion engine vehicles allowing the operation with gasoline or diesel and hydrogen have great potential for speeding up the introduction of hydrogen in the transport sector. This would also contribute to alleviate the problem of urban air pollution. In this work, the modifications carried out to convert a Volkswagen Polo 1.4 into a bi-fuel (hydrogen-gasoline) car are described. Changes included the incorporation of a storage system based on compressed hydrogen, a machined intake manifold with a low-pressure accumulator where the hydrogen injectors were assembled, a new electronic control unit managing operation on hydrogen and an electrical junction box to control the change from a fuel to another. Change of fuel is very simple and does not require stopping the car. Road tests with hydrogen fuel gave a maximum speed of 125 km/h and an estimated consumption of 1 kg of hydrogen per 100 km at an average speed of 90 km/h. Vehicle conversion to bi-fuel operation is technically feasible and cheap.
Open Access
Conversion of a gasoline engine-generator set to a bi-fuel (hydrogen/gasoline) electronic fuel-injected power unit
(Elsevier, 2011) Sáinz Casas, David; Diéguez Elizondo, Pedro; Urroz Unzueta, José Carlos; Sopena Serna, Carlos; Guelbenzu, E.; Pérez Ezcurdia, Amaya; Benito Amurrio, Marta; Marcelino Sádaba, Sara; Arzamendi Manterola, Gurutze; Gandía Pascual, Luis; Ingeniería; Ingeniaritza
The modifications performed to convert a gasoline carbureted engine-generator set to a bi-fuel (hydrogen/gasoline) electronic fuel-injected power unit are described. Main changes affected the gasoline and gas injectors, the injector seats on the existing inlet manifold, camshaft and crankshaft wheels with their corresponding Hall sensors, throttle position and oil temperature sensors as well as the electronic management unit. When working on gasoline, the engine-generator set was able to provide up to 8 kW of continuous electric power (10 kW peak power), whereas working on hydrogen it provided up to 5 kW of electric power at an engine speed of 3000 rpm. The air-to-fuel equivalence ratio (λ) was adjusted to stoichiometric (λ = 1) for gasoline. In contrast, when using hydrogen the engine worked ultra-lean (λ = 3) in the absence of connected electric load and richer as the load increased. Comparisons of the fuel consumptions and pollutant emissions running on gasoline and hydrogen were performed at the same engine speed and electric loads between 1 and 5 kW. The specific fuel consumption was much lower with the engine running on hydrogen than on gasoline. At 5 kW of load up to 26% of thermal efficiency was reached with hydrogen whereas only 20% was achieved with the engine running on gasoline. Regarding the NOx emissions, they were low, of the order of 30 ppm for loads below 4 kW for the engine-generator set working on hydrogen. The bi-fuel engine is very reliable and the required modifications can be performed without excessive difficulties thus allowing taking advantage of the well-established existing fabrication processes of internal combustion engines looking to speed up the implementation of the energetic uses of hydrogen.
Open Access
The 3D-printing fabrication of multichannel silicone microreactors for catalytic applications
(MDPI, 2023) Ibáñez de Garayo Quilchano, Alejandro; Imizcoz Aramburu, Mikel; Maisterra Udi, Maitane; Almazán, Fernando; Sanz Carrillo, Diego; Bimbela Serrano, Fernando; Cornejo Ibergallartu, Alfonso; Pellejero, Ismael; Gandía Pascual, Luis; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
Microstructured reactors (MSRs) are especially indicated for highly demanding heterogeneous catalysis due to the small channel dimensions that minimize diffusional limitations and enhance mass and heat transport between the fluid and the catalyst. Herein, we present the fabrication protocol of the fused filament 3D printing of silicone monolithic microreactors based on a multichannel design. Microchannels of 200 to 800 µm in width and up to 20 mm in length were developed following the scaffold-removal procedure using acrylonitrile butadiene styrene (ABS) as the material for the 3D-printed scaffold fabrication, polydimethylsiloxane (PDMS) as the building material, and acetone as the ABS removing agent. The main printing parameters such as temperature and printing velocity were optimized in order to minimize the bridging effect and filament collapsing and intercrossing. Heterogeneous catalysts were incorporated into the microchannel walls during fabrication, thus avoiding further post-processing steps. The nanoparticulated catalyst was deposited on ABS scaffolds through dip coating and transferred to the microchannel walls during the PDMS pouring step and subsequent scaffold removal. Two different designs of the silicone monolithic microreactors were tested for four catalytic applications, namely liquid-phase 2-nitrophenol photohydrogenation and methylene blue photodegradation in aqueous media, lignin depolymerization in ethanol, and gas-phase CO2 hydrogenation, in order to investigate the microreactor performance under different reaction conditions (temperature and solvent) and establish the possible range of applications.
Open Access
Three-dimensional printing of acrylonitrile butadiene styrene microreactors for photocatalytic applications
(American Chemical Society, 2020) Cabrera Barrios, Aarón; Pellejero, Ismael; Oroz Mateo, Tamara; Salazar, Cristina; Navajas León, Alberto; Fernandez Acevedo, Claudio; Gandía Pascual, Luis; Institute for Advanced Materials and Mathematics - INAMAT2; Gobierno de Navarra / Nafarroako Gobernua, PC003-004; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
Miniaturization is a key aspect for many technological applications and the use of microreactors is an excellent solution for the intensification of chemical processes for a variety of applications. However, standard microfabrication requires large facilities and intricate fabrication protocols, and consequently it is not easily available, generally resulting in high production costs. Herein, we present a very cheap, fast and easy microreactor design for photocatalytic applications based on direct fused filament 3D printing as a facilitating and widespread technology. The microreactor consists of three bodies directly printed in ABS (Acrylonitrile Butadiene Styrene): a main body with a serpentine microchannel pattern where the photocatalyst is placed, a top holder with a transparent polymer window, and a base to clamp the parts. Several microreactor units were coated with TiO2 doped with Cu (2.4 wt.%) nanoparticles synthesized by FSP (Flame Spray Pyrolysis) and tested for the photocatalytic degradation of two water pollutants showing excellent performance.
Open Access
UiO-66 MOF-Derived Ru@ZrO2 catalysts for photo-thermal CO2 hydrogenation
(MDPI, 2023) Almazán, Fernando; Lafuente Adiego, Marta; Echarte Villeras, Amaya; Imizcoz Aramburu, Mikel; Pellejero, Ismael; Gandía Pascual, Luis; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
The use of metal–organic frameworks (MOFs) as templates or precursors in the manufacture of heterogeneous catalysts is highly attractive due to the transfer of MOFs’ inherent porosity and homogeneous metallic distribution to the derived structure. Herein, we report on the preparation of MOF-derived Ru@ZrO2 catalysts by controlled thermal treatment of zirconium-based MOF UiO66 with ruthenium moieties. Ru3+ (3 or 10 mol%) precursor was added to UiO-66 synthesis and, subsequently, the as-synthesized hybrid structure was calcined in flowing air at different temperatures (400–600 ◦C) to obtain ZrO2 -derived oxides doped with highly dispersed Ru metallic clusters. The materials were tested for the catalytic photo-thermal conversion of CO2 to CH4 . Methanation experiments were conducted in a continuous flow (feed flow rate of 5 sccm and 1:4 CO2 to H2 molar ratio) reactor at temperatures from 80 to 300 ◦C. Ru0.10@ZrO2 catalyst calcined at 600 ◦C was able to hydrogenate CO2 to CH4 with production rates up to 65 mmolCH4·gcat. –1 ·h –1, CH4 yield of 80% and nearly 100% selectivity at 300 ◦C. The effect of the illumination was investigated with this catalyst using a high-power visible LED. A CO2 conversion enhancement from 18% to 38% was measured when 24 sun of visible LED radiation was applied, mainly due to the increase in the temperature as a result of the efficient absorption of the radiation received. MOF-derived Ru@ZrO2 catalysts have resulted to be noticeably active materials for the photo-thermal hydrogenation of CO2 for the purpose of the production of carbon-neutral methane. A remarkable effect of the ZrO2 crystalline phase on the CH4 selectivity has been found, with monoclinic zirconia being much more selective to CH4 than its cubic allotrope.
Open Access
Innovative catalyst integration on transparent silicone microreactors for photocatalytic applications
(Elsevier, 2022) Pellejero, Ismael; Clemente, Alberto; Navajas León, Alberto; Vesperinas Oroz, José Javier; Urbiztondo, Miguel A.; Gandía Pascual, Luis; Institute for Advanced Materials and Mathematics - INAMAT2; Gobierno de Navarra / Nafarroako Gobernua; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
Reproducible and controllable incorporation and immobilization of catalysts and other active particles onto silicone microreactor channels is still challenging. In this work, we present an innovative fabrication protocol to attain affordable, custom-designed photocatalytic microreactors in a fast and simple manner. In this protocol, a 3D-printed ABS microreactor mold is first dip-coated with the photocatalyst, and subsequently, the catalytic layer is transferred onto the microchannel walls by indirect immobilization during the silicone casting and scaffold removal step. Serpentine-shaped microreactors have been satisfactorily fabricated with Au@POM-impregnated TiO2 nanoparticles (Au@POM/TiO2; Au 0.18 % w/w, POM: H3PW12O40) as the integrated photocatalytic layer. The suitability of our fabrication method has been validated on the basis of the excellent photocatalytic performance shown by the microreactors in a model test reaction such as the continuous-flow photoreduction of 4-nitrophenol to 4-aminophenol with NaBH4 and monitored by UV-Vis spectroscopy.
Open Access
Performance comparison between washcoated and packed-bed monolithic reactors for the low-temperature Fischer-Tropsch synthesis
(Elsevier, 2021) Ibáñez Borde, María; Sanz Iturralde, Oihane; Egaña, Ane; Reyero Zaragoza, Inés; Bimbela Serrano, Fernando; Gandía Pascual, Luis; Montes, Mario; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
Washcoating and packing of Co-Re catalyst particles have been employed as structuring methods of parallel channel monoliths used in the low-temperature Fischer-Tropsch synthesis (FTS). These methods were compared with regard to catalyst hold-up, heat transfer properties and pressure drop. Reactors output was assessed in terms of CO conversion, CH4 selectivity and productivity of C5+ hydrocarbons. Washcoating led to much lower pressure drops, but also resulted in considerably lower catalyst inventory. As for the reactors performance (volumetric and per catalyst mass C5+ productivities), the washcoated monoliths were more effective than the packed-bed ones. This has been attributed to their more favorable hydrodynamic behavior that facilitates the drainage of the reaction products (liquids and waxes) through the central hollow of the channels thus reducing the extra-pellet diffusional limitations. For both catalyst configurations, it has been found that the productivity of C5+ per catalyst mass unit increases as the characteristic diffusion length increases within the range of values considered in this study (below 150 µm). This indicates that a moderate level of internal mass transport restrictions is beneficial for the low-temperature FTS, which has been explained in terms of the effects of diffusional limitations on the H2/CO molar ratio, and that of this ratio on the FTS kinetics. The possible influence of thermal effects on these results has been numerically and experimentally discarded.
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 Jr, 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.
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.