tomasc

• Liu, Jiali; Rama, Raquel J.; Cordero-Lanzac, Tomas; Franke, Robert & Flores, Ainara Nova (2024). Outer-sphere CO release mechanism in the methanol to syngas reaction catalyzed by a Ru-PNP pincer complex. ChemRxiv. ISSN 2573-2293. Full text in Research Archive
• Lanzac, Tomas Cordero; Berdiell, Izar Capel; Airi, Alessia; Chung, Sang-Ho; Mancuso, Jenna & Redekop, Evgeniy [Show all 16 contributors for this article] (2024). Transitioning from Methanol to Olefins (MTO) toward a Tandem CO2 Hydrogenation Process: On the Role and Fate of Heteroatoms (Mg, Si) in MAPO-18 Zeotypes. JACS Au. 4(2), p. 744–759. doi: 10.1021/jacsau.3c00768. Full text in Research Archive Show summary

  The tandem CO2 hydrogenation to hydrocarbons over mixed metal oxide/zeolite catalysts (OXZEO) is an efficient way of producing value-added hydrocarbons (platform chemicals and fuels) directly from CO2 via methanol intermediate in a single reactor. In this contribution, two MAPO-18 zeotypes (M = Mg, Si) were tested and their performance was compared under methanol-to-olefins (MTO) conditions (350 °C, PCH3OH = 0.04 bar, 6.5 gCH3OH h–1 g–1), methanol/CO/H2 cofeed conditions (350 °C, PCH3OH/PCO/PH2 = 1:7.3:21.7 bar, 2.5 gCH3OH h–1 g–1), and tandem CO2 hydrogenation-to-olefin conditions (350 °C, PCO2/PH2 = 7.5:22.5 bar, 1.4–12.0 gMAPO-18 h molCO2–1). In the latter case, the zeotypes were mixed with a fixed amount of ZnO:ZrO2 catalyst, well-known for the conversion of CO2/H2 to methanol. Focus was set on the methanol conversion activity, product selectivity, and performance stability with time-on-stream. In situ and ex situ Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), solid-state nuclear magnetic resonance (NMR), sorption experiments, and ab initio molecular dynamics (AIMD) calculations were performed to correlate material performance with material characteristics. The catalytic tests demonstrated the better performance of MgAPO-18 versus SAPO-18 at MTO conditions, the much superior performance of MgAPO-18 under methanol/CO/H2 cofeeds, and yet the increasingly similar performance of the two materials under tandem conditions upon increasing the zeotype-to-oxide ratio in the tandem catalyst bed. In situ FT-IR measurements coupled with AIMD calculations revealed differences in the MTO initiation mechanism between the two materials. SAPO-18 promoted initial CO2 formation, indicative of a formaldehyde-based decarboxylation mechanism, while CO and ketene were the main constituents of the initiation pool in MgAPO-18, suggesting a decarbonylation mechanism. Under tandem CO2 hydrogenation conditions, the presence of high water concentrations and low methanol partial pressure in the reaction medium led to lower, and increasingly similar, methanol turnover frequencies for the zeotypes. Despite both MAPO-18 zeotypes showing signs of activity loss upon storage due to the interaction of the sites with ambient humidity, they presented a remarkable stability after reaching steady state under tandem reaction conditions and after steaming and regeneration cycles at high temperatures. Water adsorption experiments at room temperature confirmed this observation. The faster activity loss observed in the Mg version is assigned to its harder Mg2+-ion character and the higher concentration of CHA defects in the AEI structure, identified by solid-state NMR and XRD. The low stability of a MgAPO-34 zeotype (CHA structure) upon storage corroborated the relationship between CHA defects and instability.

• Berdiell, Izar Capel; Braghin, Giorgio Bruno; Cordero-Lanzac, Tomas; Beato, Pablo; Lundegaard, Lars F. & Wragg, David Stephen [Show all 8 contributors for this article] (2023). Tracking Structural Deactivation of H-Ferrierite Zeolite Catalyst During MTH with XRD. Topics in catalysis. ISSN 1022-5528. 66, p. 1418–1426. doi: 10.1007/s11244-023-01780-0. Full text in Research Archive Show summary

  Abstract We used the methanol-to-hydrocarbon (MTH) reaction as a shape-selective model reaction to investigate coke formation in zeolite H-Ferrierite. Despite being a 2D topology in terms of channel propagation, the FER framework displays a lattice expansion in all three dimensions of space upon deactivation. Therefore, the volume of the unit cell is an excellent X-Ray diffraction (XRD) descriptor for the catalyst deactivation. A model with dummy atoms added, also proved to be an accurate approach to measure the amount of internal coke and/or water inside the pore network correlated with thermogravimetric analysis results. While the catalyst deactivation of the H-Ferrerite during the MTH was fast, a comparably long induction period was observed. We were able to track such fast deactivation with the aforementioned descriptors by means of an operando XRD study by a standard laboratory diffractometer.

• Prodinger, Sebastian; Berdiell, Izar Capel; Cordero-Lanzac, Tomas; Bygdnes, Odd Reidar; Solemsli, Bjørn Gading & Kvande, Karoline [Show all 10 contributors for this article] (2023). Cation-induced speciation of port-size during mordenite zeolite synthesis. Journal of Materials Chemistry A. ISSN 2050-7488. 11(40), p. 21884–21894. doi: 10.1039/d3ta03444e. Full text in Research Archive Show summary

  Mordenite (MOR) zeolite, an important industrial catalyst exists in two, isostructural variants defined by their port-size, small and large-port. Here we show for the first time how a systematic, single-parameter variation influences the synthesis out-come on the final MOR material leading to distinctly different catalysts. The cation identity has a direct impact on the synthesis mechanism with potassium cations generating the more constrained, small-port MOR variant compared to the large-port obtained with sodium cations. This was expressed by different degrees of accessibility ascertained with a combination of toluene breakthrough and temperature programmed desorption (TPD), propylamine TPD, as well as sterically sensitive isobutane conversion. Rietveld refinement of the X-ray diffractograms elucidated the preferential siting of the smaller sodium cations in the constricted 8-ring, from which differences in Al distribution follow. Note, there are no organic structure directing agents utilized in this synthesis pointing at the important role of inorganic structure directing agents (ISDA).

• Cordero-Lanzac, Tomas; Ramirez, Adrian; Cruz-Fernandez, Marta; Zander, Hans-Jörg; Joensen, Finn & Woolas, Steven [Show all 10 contributors for this article] (2023). A CO2 valorization plant to produce light hydrocarbons: Kinetic model, process design and life cycle assessment. Journal of CO2 Utilization. ISSN 2212-9820. 67, p. 102337–102337. doi: 10.1016/j.jcou.2022.102337. Full text in Research Archive Show summary

  Reliable Life Cycle Assessment (LCA) of processes for valorization of CO2-rich off-gas streams requires multidisciplinary contributions that span the development of active and selective catalysts, reactor design, plant modeling and optimization, as well as environmental impact analysis. Herein, we present the design and study of a CO2 valorization plant through methanol-mediated (tandem) hydrogenation to light hydrocarbons, with propane as the most abundant product. A state-of-the-art PdZn/ZrO2 + SAPO-34 catalyst combination was screened for catalytic activity and selectivity in a wide operation range. Optimal process conditions were found at 350 °C, 30–40 bar and co-feeding of CO2/CO. Kinetic parameters for the tandem reaction were extracted and used for the design of a multi-layer reactor, where the two catalysts are distributed according to: (i) CO2-to-methanol catalyst; (ii) mixed catalyst bed, and; (iii) methanol-to-hydrocarbons catalyst. This configuration outperformed the conventional dual bed and mixed bed reactor configurations in terms of process design. A Life Cycle Assessment of the plant suggested that a substantial decrease in the global warming impact of propane production will be highly driven by using green hydrogen from either solar or wind sources, although the comparison with fossil-derived propane indicated already a reasonable improvement even when using grey hydrogen from natural gas.

• Ticali, Pierfrancesco; Salusso, Davide; Airi, Alessia; Morandi, Sara; Borfecchia, Elisa & Ramirez, Adrian [Show all 11 contributors for this article] (2023). From Lab to Technical CO2 Hydrogenation Catalysts: Understanding PdZn Decomposition. ACS Applied Materials & Interfaces. ISSN 1944-8244. 15(4), p. 5218–5228. doi: 10.1021/acsami.2c19357. Full text in Research Archive Show summary

  The valorization of CO2 to produce high-value chemicals, such as methanol and hydrocarbons, represents key technology in the future net-zero society. Herein, we report further investigation of a PdZn/ZrO2 + SAPO-34 catalyst for conversion of CO2 and H2 into propane, already presented in a previous work. The focus of this contribution is on the scale up of this catalyst. In particular, we explored the effect of mixing (1:1 mass ratio) and shaping the two catalyst functions into tablets and extrudates using an alumina binder. Their catalytic performance was correlated with structural and spectroscopic characteristics using methods such as FT-IR and X-ray absorption spectroscopy. The two scaled-up bifunctional catalysts demonstrated worse performance than a 1:1 mass physical mixture of the two individual components. Indeed, we demonstrated that the preparation negatively affects the element distribution. The physical mixture is featured by the presence of a PdZn alloy, as demonstrated by our previous work on this sample and high hydrocarbon selectivity among products. For both tablets and extrudates, the characterization showed Zn migration to produce Zn aluminates from the alumina binder phase upon reduction. Moreover, the extrudates showed a remarkable higher amount of Zn aluminates before the activation rather than the tablets. Comparing tablets and extrudates with the physical mixture, no PdZn alloy was observed after activation and only the extrudates showed the presence of metallic Pd. Due to the Zn migration, SAPO-34 poisoning and subsequent deactivation of the catalyst could not be excluded. These findings corroborated the catalytic results: Zn aluminate formation and Pd0 separation could be responsible for the decrease of the catalytic activity of the extrudates, featured by high methane selectivity and unconverted methanol, while tablets displayed reduced methanol conversion to hydrocarbons mainly attributed to the partial deactivation of the SAPO-34.

• Xie, Jingxiu; Firth, Daniel Sean; Lanzac, Tomas Cordero; Airi, Alessia; Negri, Chiara & Øien-Ødegaard, Sigurd [Show all 9 contributors for this article] (2022). MAPO-18 Catalysts for the Methanol to Olefins Process: Influence of Catalyst Acidity in a High-Pressure Syngas (CO and H2) Environment. ACS Catalysis. 12, p. 1520–1531. doi: 10.1021/acscatal.1c04694. Full text in Research Archive Show summary

  The transition from integrated petrochemical complexes toward decentralized chemical plants utilizing distributed feedstocks calls for simpler downstream unit operations. Less separation steps are attractive for future scenarios and provide an opportunity to design the next-generation catalysts, which function efficiently with effluent reactant mixtures. The methanol to olefins (MTO) reaction constitutes the second step in the conversion of CO2, CO, and H2 to light olefins. We present a series of isomorphically substituted zeotype catalysts with the AEI topology (MAPO-18s, M = Si, Mg, Co, or Zn) and demonstrate the superior performance of the M(II)-substituted MAPO-18s in the conversion of MTO when tested at 350 °C and 20 bar with reactive feed mixtures consisting of CH3OH/CO/CO2/H2. Co-feeding high pressure H2 with methanol improved the catalyst activity over time, but simultaneously led to the hydrogenation of olefins (olefin/paraffin ratio < 0.5). Co-feeding H2/CO/CO2/N2 mixtures with methanol revealed an important, hitherto undisclosed effect of CO in hindering the hydrogenation of olefins over the Brønsted acid sites (BAS). This effect was confirmed by dedicated ethene hydrogenation studies in the absence and presence of CO co-feed. Assisted by spectroscopic investigations, we ascribe the favorable performance of M(II)APO-18 under co-feed conditions to the importance of the M(II) heteroatom in altering the polarity of the M–O bond, leading to stronger BAS. Comparing SAPO-18 and MgAPO-18 with BAS concentrations ranging between 0.2 and 0.4 mmol/gcat, the strength of the acidic site and not the density was found to be the main activity descriptor. MgAPO-18 yielded the highest activity and stability upon syngas co-feeding with methanol, demonstrating its potential to be a next-generation MTO catalyst.

• Mortén, Magnus; Lanzac, Tomas Cordero; Cnudde, Pieter; Redekop, Evgeniy; Svelle, Stian & Speybroeck, Veronique Van [Show all 7 contributors for this article] (2021). Acidity effect on benzene methylation kinetics over substituted H-MeAlPO-5 catalysts. Journal of Catalysis. ISSN 0021-9517. 404, p. 594–606. doi: 10.1016/j.jcat.2021.11.002. Full text in Research Archive Show summary

  Methylation of aromatic compounds is a key reaction step in various industrial processes such as the aromatic cycle of methanol-to-hydrocarbons chemistry. The study of isolated methylation reactions and of the influence of catalyst acidity on their kinetics is a challenging task. Herein, we have studied unidirectional metal-substituted H-MeAlPO-5 materials to evaluate the effect of acid strength on the kinetics of benzene methylation with DME. First-principle simulations showed a direct correlation between the methylation barrier and acid site strength, which depends on the metal substituent. Three H-MeAlPO-5 catalysts with high (Me = Mg), moderate (Me = Si) and low acidity (Me = Zr) were experimentally tested, confirming a linear relationship between the methylation activation energy and acid strength. The effects of temperature and reactant partial pressure were evaluated, showing significant differences in the byproduct distribution between H-MgAlPO-5 and H-SAPO-5. Comparison with propene methylation suggested that the Mg substituted catalyst is also the most active for the selective methylation of alkenes.

• Ramirez, Adrian; Ticali, Pierfrancesco; Salusso, Davide; Lanzac, Tomas Cordero; Ould-Chikh, Samy & Ahoba-Sam, Christian [Show all 13 contributors for this article] (2021). Multifunctional Catalyst Combination for the Direct Conversion of CO<inf>2</inf>to Propane. JACS Au. 1(10), p. 1719–1732. doi: 10.1021/jacsau.1c00302. Full text in Research Archive

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• Gavrilovic, Ljubisa; Kazi, Saima Sultana; Bygdås, Håkon Steinholt; Cordero-Lanzac, Tomas & Olsbye, Unni (2025). Sorption-enhanced methanol synthesis – effect of water removal. Full text in Research Archive
• Gavrilovic, Ljubisa; Kazi, Saima Sultana; Bygdås, Håkon Steinholt; Cordero-Lanzac, Tomas & Olsbye, Unni (2025). Water sorbents for Sorption-enhanced CO2 utilization to methanol. Full text in Research Archive
• Gavrilovic, Ljubisa; Kazi, Saima Sultana; Cordero-Lanzac, Tomas & Olsbye, Unni (2024). Sorption-enhanced methanol synthesis. Full text in Research Archive
• Cordero-Lanzac, Tomas; Ramirez, Adrian; Cruz-Fernandez, Marta; Zander, Hans-Jörg; Joensen, Finn & Meiswinkel, Andreas [Show all 8 contributors for this article] (2023). Kinetic model, process design and LCA of a CO2 valorization plant to produce light hydrocarbon using a PdZn/ZrO2 + SAPO-34 catalyst. Full text in Research Archive
• Lanzac, Tomas Cordero; Ramirez, Adrian; Cruz-Fernandez, Marta; Zander, Hans-Jörg; Joensen, Finn & Meiswinkel, Andreas [Show all 8 contributors for this article] (2023). Kinetic model, process design and LCA of a CO2 valorization plant to produce light hydrocarbon using a PdZn/ZrO2 + SAPO-34 catalyst. Full text in Research Archive
• Cordero-Lanzac, Tomas (2022). KINETIC MODEL, PROCESS DESIGN AND LCA OF A CO2 VALORIZATION PLANT TO PRODUCE LIGHT HYDROCARBON USING A PdZn/ZrO2 + SAPO-34 CATALYST. Full text in Research Archive
• Cordero-Lanzac, Tomas (2022). Kinetic study of the tandem CO2 hydrogenation to C3 hydrocarbons over (Pd)-ZnO:ZrO2 based catalysts with SAPO-18 and SAPO-34. Full text in Research Archive
• Cordero-Lanzac, Tomas (2022). The individual effect of acid strength on benzene methylation kinetics. Full text in Research Archive
• Berdiell, Izar Capel; Braghin, Giorgio Bruno; Cordero-Lanzac, Tomas; Beato, Pablo; Lundegaard, Lars Fahl & Wragg, David Stephen [Show all 8 contributors for this article] (2022). Tracking Structural Deactivation of H-Ferrierite Zeolite Catalyst during MTH with XRD. Full text in Research Archive
• Lanzac, Tomas Cordero; Ramirez, Adrian & Olsbye, Unni (2021). The tandem approach to conversion of CO2 and H2 to light hydrocarbons. Full text in Research Archive

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