Menú secundario

Artículos SCI



2024


Química de Superficies y Catálisis

Synthetic natural gas production using CO2-rich waste stream from hydrothermal carbonization of biomass: Effect of impurities on the catalytic activity

González-Arias, J; Torres-Sempere, G; Villora-Picó, JJ; Reina, TR; Odriozola, JA
Journal of CO2 Utilization, 79 (2024) 102653

Show abstract ▽

The utilization of biomass and bio-waste, particularly through hydrothermal processes, has shown promise as a technology for converting these materials into valuable products. While most research has traditionally focused on the solid and liquid byproducts of these hydrothermal treatments, the gaseous phase has often been over-looked. This study specifically investigates the conversion of off-gases produced during hydrothermal carbonation (HTC) into synthetic natural gas, offering a readily marketable product with economic potential. Although the methanation of conventional flue gases has been extensively studied, dealing with non-standard off-gases from processes like HTC presents challenges due to the presence of minor impurities like CO and CH4. This novel research seeks to experimentally evaluate the methanation of HTC off-gases using nickel-based catalysts and analyze how these impurities affect the catalytic performance. The studied catalysts include nickel supported by ceria and alumina, as well as alumina supported nickel-cobalt systems. The results demonstrate that these catalysts exhibit high CO2 conversion and CH4 selectivity under ideal gas conditions. However, when real gas compositions with impurities are considered, CO2 conversion decreases at lower temperatures (ca. 20% lower conversion for real gas vs. ideal), probably due to side reactions such as CH4 cracking. This difference becomes less pronounced at higher temperatures. Nevertheless, the catalysts perform satisfactorily, especially at temperatures exceeding 350 degrees C. In conclusion, this study sheds light on the methanation of HTC off-gases and underscores the significance of understanding how impurities in real gases impact the process, providing potential directions for future research.


Enero, 2024 | DOI: 10.1016/j.jcou.2023.102653

Química de Superficies y Catálisis

Boosting Low-Temperature CO2 Hydrogenation over Ni-based Catalysts by Tuning Strong Metal-Support Interactions

Ye, RP; Ma, LX; Hong, XL; Reina, TR; Luo, WH; Kang, LQ; Feng, G; Zhang, RB; Fan, MH, Zhang, RG
Angewandte Chemie-International Edition,

Show abstract ▽

Rational design of low-cost and efficient transition-metal catalysts for low-temperature CO2 activation is significant and poses great challenges. Herein, a strategy via regulating the local electron density of active sites is developed to boost CO2 methanation that normally requires >350 °C for commercial Ni catalysts. An optimal Ni/ZrO2 catalyst affords an excellent low-temperature performance hitherto, with a CO2 conversion of 84.0 %, CH4 selectivity of 98.6 % even at 230 °C and GHSV of 12,000 mL g−1 h−1 for 106 h, reflecting one of the best CO2 methanation performance to date on Ni-based catalysts. Combined a series of in situ spectroscopic characterization studies reveal that re-constructing monoclinic-ZrO2 supported Ni species with abundant oxygen vacancies can facilitate CO2 activation, owing to the enhanced local electron density of Ni induced by the strong metal-support interactions. These findings might be of great aid for construction of robust catalysts with an enhanced performance for CO2 emission abatement and beyond.


Enero, 2024 | DOI: 10.1002/anie.202317669

Materiales y Procesos Catalíticos de Interés Ambiental y Energético

CuO-TiO2 pilot-plant system performance for solar photocatalytic hydrogen production

Villachica-Llamosas, JG; Ruiz-Aguirre, A; Colón, G; Peral, J; Malato, S
International Journal of Hydrogen Energy, 51 (2024) 1069-1077

Show abstract ▽

 

The main goal of the present study was to explore photocatalytic performance of the TiO2 -CuO mixture, for solar to hydrogen conversion at pilot plant scale under two different irradiation conditions (sunny and partly cloudy), focusing on high-temperature pretreat-ment of the catalyst mixture to try to improve TiO2 doping with copper. P25-TiO2 and commercial CuO were used with different amounts of Cu (2 wt% or 7 wt% Cu) calcined at 200-400 degrees C during several hours. Catalysts were tested at pilot plant scale using solar compound parabolic collectors, with glycerol as the sacrificial agent. The photocatalyst prepared after heating at 200 degrees C for 3 h and with 7 wt% Cu, resulted in higher hydrogen production than under the other heating conditions, and results were slightly better (5 -10%) than the reference values with the untreated catalysts. Photocatalytic efficiency was slightly lower at the higher calcination temperature (400 degrees C). CO2 production and formation of formate and glycolate clearly demonstrated glycerol photoreforming. The Cu from the calcined catalyst remaining on the solid was significantly less (2.5%) than on the non -calcined catalyst (4.2%), with an important fraction of lixiviated copper and copper deposition on the reactor walls. This is a critical drawback that must be considered for large-scale applications.


Enero, 2024 | DOI: 10.1016/j.ijhydene.2023.07.149



2023


Materiales y Procesos Catalíticos de Interés Ambiental y Energético

Photoreforming of glycerol to produce hydrogen from natural water in a compound parabolic collector solar photoreactor

Villachica-Llamosas, JG; Sowik, J; Ruiz-Aguirre, A; Colón, G; Peral, J; Malato, S
Journal of Environmental Chemical Engineering, 11 (2023) 111216

Show abstract ▽

To improve TiO2 for H2 generation, one strategy for the separation of photogenerated charges is the formation of heterostructures with other materials. In particular, NiO is a photocatalyst known for its good stability and low cost. However, no studies at pilot scale using solar energy have been described. Consequently, an evaluation of a physical NiO:TiO2 mixture at pilot scale (25 L) with natural irradiation (2.10 m2 of sun-exposed surface) and with simultaneous glycerol photoreforming was explored. NiO:TiO2 50 mg & sdot;L- 1 resulted in the highest hydrogen production, showing an STH = 1.44%, considering only the UV fraction of the solar irradiation. H2 and CO2 production were analysed by on-line GC; Glycerol, dissolved organic carbon, carboxylic acids and nickel leaching were also evaluated. The NiO:TiO2 mixtures rendered a systematically lower H2 production in natural water than in high-purity water. The increase of ionic strength increased the mean size of particle clusters, promoting rapid sedimentation. All this indicates the importance of testing under real field conditions for attaining reliable solar to hydrogen (STH) efficiency.


Diciembre, 2023 | DOI: 10.1016/j.jece.2023.111216

Química de Superficies y Catálisis

Effect of zeolite topological structure in bifunctional catalyst on direct conversion of syngas to light olefins

Meng, FH; Gong, ZY; Yang, LL; Wang, Q; Xing, MQ; Nawaz, MA; Li, Z
Microporous and Mesoporous Materials, 362 (2023) 112792

Show abstract ▽

Bifunctional catalyst composed of metal oxide and zeolite (OX-ZEO) is a promising strategy for the direct conversion of syngas to light olefins (STO), where the structure of zeolite plays a vital role in determining the selectivity of product. Herein, three kinds of silicoaluminophosphate zeolites with different topological structures, i.e., the ERI(SP17), AEI(SP18) and CHA(SP34), were hydrothermally synthesized, after the combination with Mn-Ga oxide, the prepared OX-ZEO was applied for STO reaction. The variation in the crystallization time for SP17 synthesis has a great impact on the generation of impurity phase of SAPO-5, where a crystallization time of 48-96 h is found to be beneficial in synthesizing SP17 zeolite with pure phase. SP17 zeolite with a crystallization time of 96 h, possesses the micropores and columnar morphology, where the small cage-defining 8-ring size of SP17 shows the olefins selectivity of 87.0% at a low CO conversion of 19.4%, significantly deviating towards the major fraction of ethylene (45.6%) than that of butene (8.2%). In a contrast, SP18 and SP34 zeolites with the same and large cage-defining 8-ring size, are richer in propylene and butene fractions than that of ethylene in overall similar olefins selectivity of 87.0% and 87.1% at CO conversion of 28.7% and 28.5%, respectively. Interestingly, it is further interpreted that the SP17 sample generated more carbon species during the reaction due to the small 8-ring size, while those amounts of carbon species were restricted in the hierarchical pore structure and plate-like morphology in SP18 and SP34 samples.


Diciembre, 2023 | DOI: 10.1016/j.micromeso.2023.112792

 

 

 

 

 

icms