Carlos Henriques
@tecnico.ulisboa.pt
Department of Chemical Engineering
Instituto Superior Técnico, Universidade de Lisboa
RESEARCH, TEACHING, or OTHER INTERESTS
Chemical Engineering, Catalysis, Process Chemistry and Technology, Renewable Energy, Sustainability and the Environment
Scopus Publications
Scopus Publications
Frédéric Thibault-Starzyk, Ana Neto, Sébastien Thomas, Carlos Henriques, and Gary Bond
Elsevier BV
Domenico Aceto, Maria Carmen Bacariza, Arnaud Travert, Carlos Henriques, and Federico Azzolina-Jury
MDPI AG
The Editorial Office and Editorial Board are announcing the finished post-publication review process, as well as an update to the original publication [...]
Rosana V. Pinto, Chen‐Chen Cao, Pengbo Lyu, Iurii Dovgaliuk, William Shepard, Eric Rivière, Cheng‐Yong Su, Guillaume Maurin, Fernando Antunes, João Pires,et al.
Wiley
AbstractNitric oxide (NO), a key element in the regulation of essential biological mechanisms, presents huge potential as therapeutic agent in the treatment and prevention of chronic diseases. Metal‐organic frameworks (MOFs) with open metal sites are promising carriers for NO therapies but delivering it over an extended period in biological media remains a great challenge due to i) a fast degradation of the material in body fluids and/or ii) a rapid replacement of NO by water molecules onto the Lewis acid sites. Here, a new ultra‐narrow pores Fe bisphosphonate MOF, denoted MIP‐210(Fe) or Fe(H2O)(Hmbpa) (H4mbpa = p‐xylenediphosphonic acid) is described that adsorbs NO due to an unprecedented sorption mechanism: coordination of NO through the Fe(III) sites is unusually preferred, replacing bound water, and creating a stable interaction with the free H2O and P‐OH groups delimiting the ultra‐narrow pores. This, associated with the high chemical stability of the MOF in body fluids, enables an unprecedented slow replacement of NO by water molecules in biological media, achieving an extraordinarily extended NO delivery time over at least 70 h, exceeding by far the NO kinetics release reported with others porous materials, paving the way for the development of safe and successful gas therapies.
Luísa Marques, Maria Vieira, José Condeço, Carlos Henriques, and Maria Mateus
MDPI AG
The cement industry significantly impacts the environment due to natural resource extraction and fossil fuel combustion, with carbon dioxide (CO2) emissions being a major concern. The industry emits 0.6 tons of CO2 per ton of cement, accounting for about 8% of global CO2 emissions. To meet the 13th United Nations Sustainable Development Goal, cement plants aim for carbon neutrality by 2050 through reducing CO2 emissions and adopting Carbon Capture and Utilization (CCU) technologies. A promising approach is converting CO2 into valuable chemicals and fuels, such as methanol (MeOH), using Power-to-Liquid (PtL) technologies. This process involves capturing CO2 from cement plant flue gas and using hydrogen from renewable sources to produce renewable methanol (e-MeOH). Advancing the development of novel, efficient catalysts for direct CO2 hydrogenation is crucial. This comprehensive mini-review presents a holistic view of recent advancements in CO2 catalytic conversion to MeOH, focusing on catalyst performance, selectivity, and stability. It outlines a long-term strategy for utilizing captured CO2 emissions from cement plants to produce MeOH, offering an experimental roadmap for the decarbonization of the cement industry.
Luísa Marques, Maria Vieira, José Condeço, Henrique Sousa, Carlos Henriques, and Maria Mateus
MDPI AG
The cement industry is a significant contributor (around 8%) to CO2 global emissions. About 60% of the industry’s emissions come from limestone calcination, which is essential for clinker production, while 40% are the result of fuel combustion. Reducing these emissions is challenging due to limestone’s role as the primary raw material for cement. Cement plants are required to achieve carbon neutrality by 2050, as outlined in the 13th United Nations Sustainable Goals. One strategy to achieve this goal, involves Carbon Capture and utilization (CCU). Among the options for CO2 utilization, the Power-to-Liquid (PtL) strategy offers a means to mitigate CO2 emissions. In PtL, the CO2 captured from cement industrial flue gas is combined with the hydrogen generated by renewable electrolysis (green hydrogen) and is catalytically converted into renewable methanol (e-MeOH). In this sense, this review provides a comprehensive overview of the worldwide existing pilot and demonstration units and projects funded by the EU across several industries. It specifically focuses on PtL technology worldwide within cement plants. This work covers 18 locations worldwide, detailing technology existent at plants of different capacities, location, and project partners. Finally, the review analyses techno-economic assessments related to e-MeOH production processes, highlighting the potential impact on achieving carbon neutrality in the cement industry.
Daniela Spataru, Gilda Carvalho, Adrián Quindimil, José M. Lopes, Carlos Henriques, and Carmen Bacariza
Elsevier BV
Daniela Spataru, Diogo Canastreiro, Katarzyna Świrk Da Costa, Adrián Quindimil, José M. Lopes, Patrick Da Costa, Carlos Henriques, and Carmen Bacariza
Elsevier BV
Antoine Salden, Maik Budde, Carolina A. Garcia-Soto, Omar Biondo, Jairo Barauna, Marzia Faedda, Beatrice Musig, Chloé Fromentin, Minh Nguyen-Quang, Harry Philpott,et al.
Elsevier BV
Filipe Mateus, Paula Teixeira, José M. Lopes, Carlos Henriques, and Carmen Bacariza
American Chemical Society (ACS)
Domenico Aceto, Maria Carmen Bacariza, Arnaud Travert, Carlos Henriques, and Federico Azzolina-Jury
MDPI AG
CO2 methanation is an attractive reaction to convert CO2 into a widespread fuel such as methane, being the combination of catalysts and a dielectric barrier discharge (DBD) plasma responsible for synergistic effects on the catalyst’s performances. In this work, a Ru-based zeolite catalyst, 3Ru/CsUSY, was synthesized by incipient wetness impregnation and characterized by TGA, XRD, H2-TPR, N2 sorption and CO2-TPD. Catalysts were tested under thermal and plasma-assisted CO2 methanation conditions using in-situ operando FTIR, with the aim of comparing the mechanism under both types of catalysis. The incorporation of Ru over the CsUSY zeolite used as support induced a decrease of the textural properties and an increase of the basicity and hydrophobicity, while no zeolite structural damage was observed. Under thermal conditions, a maximum CO2 conversion of 72% and CH4 selectivity above 95% were registered. These promising results were ascribed to the presence of small Ru0 nanoparticles over the support (16 nm), catalyst surface hydrophobicity and the presence of medium-strength basic sites in the catalyst. Under plasma-catalytic conditions, barely studied in similar setups in literature, CO2 was found to be excited by the plasma, facilitating its adsorption on the surface of 3Ru/CsUSY in the form of oxidized carbon species such as formates, aldehydes, carbonates, or carbonyls, which are afterwards progressively hydrogenated to methane. Adsorption and surface reaction of key intermediates, namely formate and aldehydic groups, was observed even on the support alone, an occurrence not reported before for thermal catalysis. Overall, similar reaction mechanisms were proposed for both thermal and plasma-catalysis conditions.
Rita Martinho, Jéssica Lopes, Diogo Jorge, Luís Caldas de Oliveira, Carlos Henriques, and Paulo Peças
MDPI AG
This work responds to the gap in integrating the Internet-of-Things in Continuous Improvement processes, especially to facilitate diagnosis and problem-solving activities regarding manufacturing workstations. An innovative approach, named Automatic Detailed Diagnosis (ADD), is proposed: a non-intrusive, easy-to-install and use, low-cost and flexible system based on industrial Internet-of-Things platforms and devices. The ADD requirements and architecture were systematized from the Continuous Improvement knowledge field, and with the help of Lean Manufacturing professionals. The developed ADD concept is composed of a network of low-power devices with a variety of sensors. Colored light and vibration sensors are used to monitor equipment status, and Bluetooth low-energy and time-of-flight sensors monitor operators’ movements and tasks. A cloud-based platform receives and stores the collected data. That information is retrieved by an application that builds a detailed report on operator–machine interaction. The ADD prototype was tested in a case study carried out in a mold-making company. The ADD was able to detect time performance with an accuracy between 89% and 96%, involving uptime, micro-stops, and setups. In addition, these states were correlated with the operators’ movements and actions.
Carmen Bacariza, Leila Karam, Nissrine El Hassan, José M. Lopes, and Carlos Henriques
MDPI AG
As the utilization of zeolites has become more frequent in the dry reforming of methane (DRM) reaction, more systematic studies are required to evaluate properly the influence of zeolites’ composition and framework type on the performance. Therefore, in this work, a step-by-step study was performed with the aim of analyzing the effects of Ni loading (5, 10 or 15 wt.% over USY(3) zeolite), Si/Al ratio (3, 15 or 38 on USY zeolites with 15 wt.% Ni) and framework type (USY, BEA, ZSM-5 or MOR for 15 wt.% Ni and Si/Al ratios of ≈40) on catalysts’ properties and performances. Increasing Ni loadings enhanced CH4 and CO2 conversions even though the catalysts’ stability was decreasing over the time. The variation of the Si/Al ratio on USY and the use of different zeolites had also a remarkable impact on the catalytic performance. For instance, at 500–600 °C reaction temperatures, the catalysts with higher basicity and reducibility exhibited the best results. However, when the temperature was further increased, catalysts presenting stronger metal–support interactions (nickel nanoparticles located in mesoporous cavities) displayed the highest conversions and stability over time. In brief, the use of 15 wt.% Ni and a USY zeolite, with both micro- and mesopores and high surface area, led to the best performances, mainly attributed to a favorable number of Ni0 active sites and the establishment of stronger metal–support interactions (due to nanoparticles confinement inside the mesopores).
Golshid Hasrack, Maria Carmen Bacariza, Carlos Henriques, and Patrick Da Costa
MDPI AG
In recent years, carbon dioxide hydrogenation leading to synthetic fuels and value-added molecules has been proposed as a promising technology for stabilizing anthropogenic greenhouse gas emissions. Methanation or Sabatier are possible reactions to valorize the CO2. In the present work, thermal CO2 methanation and non-thermal plasma (NTP)-assisted CO2 methanation was performed over 15Ni/CeO2 promoted with 1 and 5 wt% of cobalt. The promotion effect of cobalt is proven both for plasma and thermal reaction and can mostly be linked with the basic properties of the materials.
Patrick Da Costa, Goshid Hasrack, Jérôme Bonnety, and Carlos Henriques
Elsevier BV
Adrián Quindimil, M. Carmen Bacariza, José A. González-Marcos, Carlos Henriques, and Juan R. González-Velasco
Elsevier BV
M. Carmen Bacariza, Cláudia Grilo, Paula Teixeira, José M. Lopes, and Carlos Henriques
MDPI AG
CO2 methanation is typically carried out using Ni-supported catalysts containing promoters such as alkali or alkali-earth metals to improve their properties. In this work, bimetallic Ni-based USY zeolite catalysts containing alkali (Li, K and Cs) and alkali-earth (Mg, Ca) metal compounds were prepared using the same conditions (15 wt% of metals; co-impregnation), characterized by N2 sorption, XRD, TGA, CO2 adsorption–desorption, DRS UV-Vis and H2-TPR, and finally applied in CO2 methanation reaction (86,100 mL h−1 g−1, PCO2 = 0.16 bar, H2:CO2 = 4:1). For each group, the effects of the second metal nature on the properties and performances were assessed. Alkali metals incorporation induced considerably low catalytic performances (CH4 yields < 26%), attributed to their negative impact on zeolite structure preservation. On the contrary, alkali-earth metal-containing catalysts exhibited lower structural damage. However, the formation of Ni-Mg mixed oxides in Ni-Mg/USY catalyst and CaCO3 during the reaction in Ni-Ca/USY sample could explain their performances, similar or lower than those obtained for Ni/USY catalyst. Among the studied metals, calcium was identified as the most interesting (CH4 yield of 65% at 415 °C), which was ascribed to the slight improvement of the Ni0 dispersion.
Leila Karam, Maria C. Bacariza, José M. Lopes, Carlos Henriques, Julien Reboul, Nissrine El Hassan, and Pascale Massiani
Elsevier BV
Zhi Lin, Rosana V. Pinto, Carlos Henriques, Fernando Antunes, João Pires, Moisés L. Pinto, and João Rocha
Elsevier BV
M. Carmen Bacariza, Daniela Spataru, Leila Karam, José M. Lopes, and Carlos Henriques
MDPI AG
The increasing utilization of renewable sources for electricity production turns CO2 methanation into a key process in the future energy context, as this reaction allows storing the temporary renewable electricity surplus in the natural gas network (Power-to-Gas). This kind of chemical reaction requires the use of a catalyst and thus it has gained the attention of many researchers thriving to achieve active, selective and stable materials in a remarkable number of studies. The existing papers published in literature in the past few years about CO2 methanation tackled the catalysts composition and their related performances and mechanisms, which served as a basis for researchers to further extend their in-depth investigations in the reported systems. In summary, the focus was mainly in the enhancement of the synthesized materials that involved the active metal phase (i.e., boosting its dispersion), the different types of solid supports, and the frequent addition of a second metal oxide (usually behaving as a promoter). The current manuscript aims in recapping a huge number of trials and is divided based on the support nature: SiO2, Al2O3, CeO2, ZrO2, MgO, hydrotalcites, carbons and zeolites, and proposes the main properties to be kept for obtaining highly efficient carbon dioxide methanation catalysts.
Maria C. Bacariza, Salman Amjad, Paula Teixeira, José M. Lopes, and Carlos Henriques
American Chemical Society (ACS)
Leila Karam, M. Carmen Bacariza, José M. Lopes, Carlos Henriques, Pascale Massiani, and Nissrine El Hassan
Elsevier BV
Esther Bailón-García, Ewelina Drwal, Teresa Grzybek, Carlos Henriques, and M. Filipa Ribeiro
Elsevier BV
Esther Bailón-García, Abdelhakim Elmouwahidi, Filipa Ribeiro, Carlos Henriques, Agustín F. Pérez-Cadenas, Francisco Carrasco-Marín, and Francisco J. Maldonado-Hódar
Elsevier BV
M. Carmen Bacariza, Acácio Nobre Mendes, Cansu Ozhan, Patrick Da Costa, and Carlos Henriques
American Chemical Society (ACS)
This work reports an exploratory study in terms of monoliths preparation for application in NOx CH4 selective catalytic reduction (NOx CH4-SCR), a promising route for treating the exhaust gas emiss...