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Turning Glycerol to Value-Added Chemicals in the Absence of External Hydrogen over Copper Catalysts Supported on SBA-15-Type Materials Containing Zirconium

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Abstract

Nowadays, many industrial processes depend on fossil resources to obtain high-added-value chemical compounds, bringing with it significant environmental deterioration. Therefore, the implementation of green alternatives considering the use of biomass residues in hydrogen-free catalytic processes is of great relevance. In this work, a set of copper catalysts prepared by impregnating SBA-15 and Zr-SBA-15 (different Si/Zr ratios) supports were catalytically tested in the glycerol dehydration. The copper catalysts were characterized by ICP, SEM-EDS, N2 physisorption, XRD, HRTEM, FT-IR, UV–Vis DRS, XPS, H2-TPR, N2O chemisorption, and TPO analyses. ICP revealed a suitable agreement between nominal and actual copper content in the catalysts. Copper catalysts exhibited textural and structural properties of mesoporous materials which are affected by increasing Zr content. Pyridine FT-IR indicated that copper catalysts with lower Zr content possess the highest values of Lewis acid sites. Higher Zr content makes the copper reduction more difficult, and the dispersion is unfavored. The catalytic system was studied using an 80% wt. aqueous glycerol solution in inert conditions at 220 °C without diffusional limitations according to the Weisz–Prater and Mears criteria. The highest values of specific initial reaction rate and rate constant were obtained in catalysts with zero (Cu/B catalyst, 1.50 × 10−3 molgl/min gcat, 7.79 × 10−4 min−1) and low (Cu/B10 catalyst, 1.53 × 10−3 molgl/min gcat, 8.27 × 10−4 min−1) Zr loading. Hydroxyacetone (HA) and 1,2-propanediol (1,2-PDO) were the main formed products. HA formation reached values greater than 90% selectivity in the first minutes of the reaction, while 1,2-PDO achieved a progressive evolution over time up to 9% selectivity. Initial formation rates of HA (3.29 × 10−4 molHA/min gcat) and 1,2-PDO (2.13 × 10−5 mol1,2−PDO/min gcat) were optimized on the Cu/B10 catalyst containing the lowest Zr load. 1,2-PDO generation in the absence of external hydrogen with a high concentration of glycerol simulating industrial wastes is highlighted. Finally, the Zr load in the copper catalysts modulates the textural, structural, acidic, surface, and reducible properties, which can also be considered as descriptors to understand the catalytic activity together with exposed copper species, stability against copper leaching, sintering, and carbon deposition.

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Acknowledgements

RJC, JG, and JCZ acknowledge the funding provided by Fondecyt with the projects N° 1220355 and N° 1180243. JCZ appreciates the funding provided by the doctoral scholarship No 21201413 awarded by ANID and the internationalization program “UCO 1866”. A.F.P thanks Fundação para a Ciência e a Tecnologia (FCT/MCTES) funding through the projects UIDB/50006/2020 and UIDP/50006/2020. A.F.P. also thanks the work contract under the Scientific Employment Stimulus (2020.01614.CEECIND/CP1596/CT0007). JL is a Serra Húnter Fellow and is grateful to the ICREA Academia program and projects MICINN/FEDER PID2021-124572OB-C31 and GC 2021 SGR 01061.

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Authors and Affiliations

  1. Laboratorio de Investigación de Procesos Catalíticos y Adsorción (LIPROCAD), Departamento de Fisicoquímica, Facultad de Ciencias Químicas, Universidad de Concepción, Casilla 160-C, Concepción, Chile

    Julio Colmenares-Zerpa, Jorge Gajardo & R. J. Chimentão

  2. Laboratorio de Cinética y Catálisis, Departamento de Química, Facultad de Ciencias, Universidad de Los Andes, Mérida, 5101, Venezuela

    Julio Colmenares-Zerpa

  3. LAQV-REQUIMTE, Departamento de Química e Bioquímica, Faculdade de Ciências da, Universidade do Porto, Rua do Campo Alegre, 4169-007, Porto, Portugal

    A. F. Peixoto

  4. Servei de Recursos Científics, Universitat Rovira i Virgili, 43007, Tarragona, Spain

    F. Gispert-Guirado

  5. Department of Chemical Engineering and Barcelona Research Center in Multiscale Science and Engineering, Institute of Energy Technologies, Universitat Politècnica de Catalunya, EEBE, Eduard Maristany 10-14, 08019, Barcelona, Spain

    J. Llorca

  6. Departamento de Engenharia Química, Universidade Federal de São Carlos, São Carlos, Brazil

    E. A. Urquieta-Gonzalez, D. S. A. Silva & J. B. O. Santos

  7. Research Center on Advanced Materials and Energy, Federal University of São Carlos, C. Postal 676, São Carlos, SP, CEP 13565-905, Brazil

    E. A. Urquieta-Gonzalez

Authors
  1. Julio Colmenares-Zerpa
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  2. Jorge Gajardo
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  3. A. F. Peixoto
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  4. F. Gispert-Guirado
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  6. E. A. Urquieta-Gonzalez
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  7. D. S. A. Silva
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  8. J. B. O. Santos
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  9. R. J. Chimentão
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Contributions

JC-Z: conceptualization, methodology, formal analysis and investigation, software, writing—original draft preparation, writing—review and editing, JG: methodology, formal analysis and investigation, AFP: resources, software, writing—review and editing, FG-G: resources, software, writing—review and editing, JL: resources, software, writing—review and editing, EAU-G: resources, writing—review and editing, DSAS: methodology, formal analysis and investigation, JBOS: resources, writing—review and editing, RJC: conceptualization, methodology, software, writing—original draft preparation, writing—review and editing, funding acquisition, resources, supervision.

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Correspondence to R. J. Chimentão.

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In honorary memory of Professor Eduardo José Leonardo Delgado Ramírez.

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Colmenares-Zerpa, J., Gajardo, J., Peixoto, A.F. et al. Turning Glycerol to Value-Added Chemicals in the Absence of External Hydrogen over Copper Catalysts Supported on SBA-15-Type Materials Containing Zirconium. Top Catal 67, 422–453 (2024). https://doi.org/10.1007/s11244-023-01879-4

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