The SUPREN SUstainable PRocess ENgineering research group is integrated in the Department of Chemical and Environmental Engineering of the Bilbao School of Engineering (University of the Basque Country). Its different R&D activities are briefly described in what follows:
Physicochemical characterization of fuels and urban or industrial wastes to design their valorization.
The development of thermochemical and valorization processes to valorize and recycle organic wastes through pyrolysis or gasification.
The development of hydrometallurgical processes to valorize and recycle industrial wastes.
The preparation, characterization and testing of heterogeneous catalysts for reforming, oxidation, hydrotreating, dehydration and hydrogenolysis processes of both fossil (oil fractions, NG) or renewable (biomass) resources.
The application of advanced and innovative approaches from chemical reaction engineering to develop microreaction systems or other ones with coupled selective separations (reactive distillation, membrane modules). These technologies use to be applied to hydrogen production technologies and to biorefinery processes development (biofuels and added-value intermediates or products).
All the expertise accumulated working in all the previously indicated areas allows at present the development of research projects within the following lines of R&D:
Design of innovative reaction systems
Development of biorefinery processes
Waste to resource (W2R)
Development of hydrometallurgical processes
The R&D researchers have also experience in modeling and simulation in process engineering: experimental data processing, model tuning, process scale-up or design and optimization of real processes. Both commercial simulators and specifically developed tools use to be applied in this field.
Publication in Nature Communications: Taming defective porous materials for robust and selective heterogeneous catalysis
First publication date:10/06/2019
Precise engineering of defects transforms metal–organic frameworks into selective heterogeneous catalysts for ethylene dimerization without activators or solvent
The production of 1-butene via ethylene dimerization is one of the few industrial processes that employs homogeneous catalysis due to their high selectivity—despite the massive amounts of activators and solvents required.
Now, a new paper by the University of the Basque Country (UPV/EHU), in collaboration with the López group at the Institute of Chemical Research of Catalonia (ICIQ) and RTI International, shows a more sustainable alternative via metal–organic frameworks (MOFs), a family of porous materials formed by metallic nodes connected through organic ligands.
The scientists demonstrate that tailored MOFs under condensation regimes catalyze the ethylene dimerization to 1-butene with high selectivity and stability in the absence of activators and solvent. The research, published in Nature Communications, opens new avenues to develop robust heterogeneous catalysts for a wide variety of gas-phase reactions.
Know your defects…
The researchers have engineered defects in the MOF (Ru)HKUST-1 without compromising the framework structure via two strategies: a conventional ligand exchange approach during MOF synthesis and a pioneering post-synthetic thermal approach. The researchers then characterized the defects — which have been shown to be catalytically active for ethylene dimerization.
Thanks to the computational resources of the Barcelona Supercomputing Center (BSC), which belongs to the ”Red Española de Supercomputación” (RES), the researchers were able to simulate realistic MOF systems to characterize the defects and compute the reaction mechanism. They found that unsaturated metal centers induced by defects drive activity, while the bimetallic nature of the node controls selectivity. After testing the catalytic performance of the system, they next improved the recyclability and robustness of the catalyst through one crucial condition: intrapore condensation.
…and fill the pores
Production of 1-butene via ethylene dimerization occurs in gas phase. When the reaction happens at low reactant pressure, some catalytic sites get deactivated due to the coordination of oligomers. But as pressure increases, the reactant molecules can condensate inside the pores of the material. Such a concentration effect avoids deactivation thus enhancing the stability of the catalyst.
The next steps of the project would involve the use of MOF catalysts based on first-row transition metals as well as the application of the novel intrapore condensation strategy to other gas-phase reactions.
I. Agirrezabal-Telleria, I. Luz, M. A. Ortuño, M. Oregui-Bengoecheaa, I. Gandariasa, N. Lópezc, M. Lailb, M. SoukribGas reactions under intrapore condensation regime within tailored Metal–Organic Framework catalystsNature Communications.DOI: 10.1038/s41467-019-10013-6