TY - GEN A1 - Baena-Moreno, Francisco Manuel A1 - González-Castaño, Miriam A1 - Arellano-García, Harvey A1 - Ramirez Reina, Tomas T1 - Exploring profitability of bioeconomy paths: Dimethyl ether from biogas as case study T2 - Energy N2 - Herein a novel path is analysed for its economic viability to synergize the production of biomethane and dimethyl ether from biogas. We conduct a profitability analysis based on the discounted cash flow method. The results revealed an unprofitable process with high cost/revenues ratios. Profitable scenarios would be reached by setting prohibitive DME prices (1983–5566 €/t) or very high feed-in tariffs subsidies (95.22 €/MWh in the best case scenario). From the cost reduction side, the analysis revealed the need of reducing investment costs. For this purpose, we propose a percentage of investment as incentive scheme. Although the size increase benefits cost/revenues ratio, only the 1000 m3/h biogas plant size will reach profitability if 90% of the investment is subsidized. A sensitivity analysis to check the influence of some important economical parameters is also included. Overall this study evidences the big challenge that our society faces in the way towards a circular economy. KW - Biomethane production KW - Biogas upgrading KW - CO2 utilization KW - Green energy production KW - Waste valorization KW - Dimethyl ether Y1 - 2021 U6 - https://doi.org/10.1016/j.energy.2021.120230 SN - 0360-5442 VL - 225 ER - TY - GEN A1 - González-Castaño, Miriam A1 - Saché, Estelle le A1 - Berry, Cameron A1 - Pastor-Pérez, Laura A1 - Arellano-García, Harvey A1 - Wang, Qiang A1 - Ramirez Reina, Tomas T1 - Nickel Phosphide Catalysts as Efficient Systems for CO2 Upgrading via Dry Reforming of Methane T2 - Catalysts N2 - This work establishes the primordial role played by the support’s nature when aimed at the constitution of Ni2P active phases for supported catalysts. Thus, carbon dioxide reforming of methane was studied over three novel Ni2P catalysts supported on Al2O3, CeO2 and SiO2-Al2O3 oxides. The catalytic performance, shown by the catalysts’ series, decreased according to the sequence: Ni2P/Al2O3 > Ni2P/CeO2 > Ni2P/SiO2-Al2O3. The depleted CO2 conversion rates discerned for the Ni2P/SiO2-Al2O3 sample were associated to the high sintering rates, large amounts of coke deposits and lower fractions of Ni2P constituted in the catalyst surface. The strong deactivation issues found for the Ni2P/CeO2 catalyst, which also exhibited small amounts of Ni2P species, were majorly associated to Ni oxidation issues. Along with lower surface areas, oxidation reactions might also affect the catalytic behaviour exhibited by the Ni2P/CeO2 sample. With the highest conversion rate and optimal stabilities, the excellent performance depicted by the Ni2P/Al2O3 catalyst was mostly related to the noticeable larger fractions of Ni2P species established KW - Ni2P KW - supported catalysts KW - dry reforming of methane KW - Al2O3 KW - CeO2 KW - SiO2-Al2O3 Y1 - 2021 U6 - https://doi.org/10.3390/catal11040446 SN - 2073-4344 VL - 11 IS - 4 ER - TY - BOOK A1 - Odriozola, José Antonio A1 - Ramirez Reina, Tomas A1 - Arellano-García, Harvey T1 - Engineering Solutions for CO2 Conversion N2 - A comprehensive guide that offers a review of the current technologies that tackle CO2 emissionsThe race to reduce CO2 emissions continues to be an urgent global challenge. "Engineering Solutions for CO2 Conversion" offers a thorough guide to the most current technologies designed to mitigate CO2 emissions ranging from CO2 capture to CO2 utilization approaches.... KW - CO2 conversion KW - CO2 emissions KW - reduce CO2 emissions KW - CO2 capture KW - computer modeling Y1 - 2021 SN - 978-3-527-34639-4 SN - 3-527-34639-2 PB - Wiley-VCH CY - Berlin ; Boston ER - TY - GEN A1 - Sebastia-Saez, Daniel A1 - Ramirez Reina, Tomas A1 - Silva, Ravi A1 - Arellano-García, Harvey T1 - Synthesis and characterisation of n‐octacosane@silica nanocapsules for thermal storage applications T2 - International Journal of Energy Research N2 - This work reports the synthesis and characterisation of a core‐shell n‐octacosane@silica nanoencapsulated phase‐change material obtained via interfacial hydrolysis and polycondensation of tetraethyl orthosilicate in miniemulsion. Silica has been used as the encapsulating material because of its thermal advantages relative to synthesised polymers. The material presents excellent heat storage potential, with a measured melting latent heat varying between 57.1 and 89.0 kJ kg−1 (melting point between 58.2°C and 59.9°C) and a small particle size (between 565 and 227 nm). Degradation of the n‐octacosane core starts between 150°C and 180°C. Also, the use of silica as shell material gives way to a heat conductivity of 0.796 W m−1 K−1 (greater than that of nanoencapsulated materials with polymeric shell). Charge/discharge cycles have been successfully simulated at low pressure to prove the suitability of the nanopowder as phase‐change material. Further research will be carried out in the future regarding the use of the synthesised material in thermal applications involving nanofluids. Y1 - 2019 UR - https://onlinelibrary.wiley.com/doi/10.1002/er.5039 U6 - https://doi.org/10.1002/er.5039 SN - 1099-114X SN - 0363-907X VL - 44 IS - 3 SP - 2306 EP - 2315 ER - TY - GEN A1 - Baena-Moreno, Francisco Manuel A1 - Cid-Castillo, N. A1 - Arellano-García, Harvey A1 - Ramirez Reina, Tomas T1 - Towards emission free steel manufacturing – Exploring the advantages of a CO2 methanation unit to minimize CO2 emissions T2 - Science of The Total Environment N2 - This paper demonstrates the benefits of incorporating CO2 utilisation through methanation in the steel industry. This approach allows to produce synthetic methane, which can be recycled back into the steel manufacturing process as fuel and hence saving the consumption of natural gas. To this end, we propose a combined steel-making and CO2 utilisation prototype whose key units (shaft furnace, reformer and methanation unit) have been modelled in Aspen Plus V8.8. Particularly, the results showed an optimal performance of the shaft furnace at 800°C and 6 bar, as well as 1050°C and atmospheric pressure for the reformer unit. Optimal results for the methanation reactor were observed at 350°C. Under these optimal conditions, 97.8% of the total CO2 emissions could be mitigated from a simplified steel manufacturing scenario and 89.4% of the natural gas used in the process could be saved. A light economic approach is also presented, revealing that the process could be profitable with future technologic developments, natural gas prices and forthcoming increases of CO2 emissions taxes. Indeed, the cash-flow can be profitable (325 k€) under the future costs: methanation operational cost at 0.105 €/Nm³; electrolysis operational cost at 0.04 €kWh, natural gas price at 32 €/MWh; and CO2 penalty at 55€/MWh. Hence this strategy is not only environmentally advantageous but also economically appealing and could represent an interesting route to contribute towards steel-making decarbonisation. Y1 - 2021 UR - https://www.sciencedirect.com/science/article/pii/S0048969721018441?via%3Dihub U6 - https://doi.org/10.1016/j.scitotenv.2021.146776 SN - 1879-1026 SN - 0048-9697 VL - 781 ER - TY - GEN A1 - Ketabchi, Elham A1 - Ramirez Reina, Tomas A1 - Dorneanu, Bogdan A1 - Arellano-García, Harvey T1 - An identification approach to a reaction network for an ABE catalytic upgrade T2 - Computer Aided Chemical Engineering N2 - This contribution presents a kinetic study for the identification of the complex reaction mechanism occurring during the ABE upgrading, and the development of a kinetic model. Employing graph theory analysis, a directed bipartite graph is constructed to reduce the complexity of the reaction network, and the reaction rate constants and reaction orders are calculated using the initial rate method, followed by the calculation of the activation energy and frequency factor for an Arrhenius-type law. Subsequently, using general mass balancing a proposed mathematical model is produced to determine the apparent reaction rates, which are successfully in line with the experimental results. Y1 - 2021 UR - https://www.sciencedirect.com/science/article/abs/pii/B9780323885065501029?via%3Dihub U6 - https://doi.org/10.1016/B978-0-323-88506-5.50102-9 SN - 1570-7946 VL - 50 SP - 643 EP - 648 ER - TY - GEN A1 - Tarifa, Pilar A1 - Ramirez Reina, Tomas A1 - González-Castaño, Miriam A1 - Arellano-García, Harvey T1 - Catalytic Upgrading of Biomass-Gasification Mixtures Using Ni-Fe/MgAl₂O₄ as a Bifunctional Catalyst T2 - Energy and Fuels N2 - Biomass gasification streams typically contain a mixture of CO, H2, CH4, and CO2 as the majority components and frequently require conditioning for downstream processes. Herein, we investigate the catalytic upgrading of surrogate biomass gasifiers through the generation of syngas. Seeking a bifunctional system capable of converting CO2 and CH4 to CO, a reverse water gas shift (RWGS) catalyst based on Fe/MgAl2O4 was decorated with an increasing content of Ni metal and evaluated for producing syngas using different feedstock compositions. This approach proved efficient for gas upgrading, and the incorporation of adequate Ni content increased the CO content by promoting the RWGS and dry reforming of methane (DRM) reactions. The larger CO productivity attained at high temperatures was intimately associated with the generation of FeNi3 alloys. Among the catalysts' series, Ni-rich catalysts favored the CO productivity in the presence of CH4, but important carbon deposition processes were noticed. On the contrary, 2Ni-Fe/MgAl2O4 resulted in a competitive and cost-effective system delivering large amounts of CO with almost no coke deposits. Overall, the incorporation of a suitable realistic application for valorization of variable composition of biomass-gasification derived mixtures obtaining a syngas-rich stream thus opens new routes for biosyngas production and upgrading. Y1 - 2022 UR - https://pubs.acs.org/doi/10.1021/acs.energyfuels.2c01452 U6 - https://doi.org/10.1021/acs.energyfuels.2c01452 SN - 1520-5029 SN - 0887-0624 VL - 36 IS - 15 SP - 8267 EP - 8273 ER - TY - GEN A1 - Bobadilla, Luis F. A1 - Azancot, Lola A1 - Luque-Alvarez, Ligia A. A1 - Torres-Sempere, Guillermo A1 - Gonzalez-Castano, Miriam A1 - Pastor-Perez, Laura A1 - Yu, Jie A1 - Ramirez Reina, Tomas A1 - Ivanova, Svetlana A1 - Centeno, Miguel Angel A1 - Odriozola, José Antonio T1 - Development of Power-to-X Catalytic Processes for CO2 Valorisation: From the Molecular Level to the Reactor Architecture T2 - Chemistry N2 - Nowadays, global climate change is likely the most compelling problem mankind is facing. In this scenario, decarbonisation of the chemical industry is one of the global challenges that the scientific community needs to address in the immediate future. Catalysis and catalytic processes are called to play a decisive role in the transition to a more sustainable and low-carbon future. This critical review analyses the unique advantages of structured reactors (isothermicity, a wide range of residence times availability, complex geometries) with the multifunctional design of efficient catalysts to synthesise chemicals using CO2 and renewable H2 in a Power-to-X (PTX) strategy. Fine-chemistry synthetic methods and advanced in situ/operando techniques are essential to elucidate the changes of the catalysts during the studied reaction, thus gathering fundamental information about the active species and reaction mechanisms. Such information becomes crucial to refine the catalyst’s formulation and boost the reaction’s performance. On the other hand, reactors architecture allows flow pattern and temperature control, the management of strong thermal effects and the incorporation of specifically designed materials as catalytically active phases are expected to significantly contribute to the advance in the valorisation of CO2 in the form of high added-value products. From a general perspective, this paper aims to update the state of the art in Carbon Capture and Utilisation (CCU) and PTX concepts with emphasis on processes involving the transformation of CO2 into targeted fuels and platform chemicals, combining innovation from the point of view of both structured reactor design and multifunctional catalysts development. Y1 - 2022 UR - https://www.mdpi.com/2624-8549/4/4/83 U6 - https://doi.org/10.3390/chemistry4040083 SN - 2624-8549 VL - 4 IS - 4 SP - 1250 EP - 1280 ER - TY - GEN A1 - Ketabchi, Elham A1 - Pastor-Perez, Laura A1 - Arellano-García, Harvey A1 - Ramirez Reina, Tomas T1 - Influence of Reaction Parameters on the Catalytic Upgrading of an Acetone, Butanol and Ethanol (ABE) Mixture: Exploring New Routes for Modern Biorefineries T2 - Frontiers in Chemistry N2 - Here we present a comprehensive study on the effect of reaction parameters on the upgrade of an acetone, butanol and ethanol mixture – key molecules and platform products of great interest within the chemical sector. Using a selected high performing catalyst, Fe/MgO-Al2O3, the variation of temperature, reaction time, catalytic loading and reactant molar ratio have been examined in this reaction. This work is aiming to not only optimise the reaction conditions previously used, but to step towards using less energy, time and material by testing those conditions and analysing the sufficiency of the results. Herein we demonstrate that this reaction is favoured at higher temperatures and longer reaction time. Also, we observe that increasing the catalyst loading had a positive effect on the product yields, while reactant ratios have shown to produce varied results due to the role of each reactant in the complex reaction network. In line with the aim of reducing energy and costs, this work showcases that the products from the upgrading route have significantly higher market value than the reactants; highlighting that this process represents an appealing route to be implemented in modern biorefineries. Y1 - 2020 UR - https://www.frontiersin.org/articles/10.3389/fchem.2019.00906/full U6 - https://doi.org/10.3389/fchem.2019.00906 SN - 2296-2646 VL - 7 ER - TY - GEN A1 - Ketabchi, Elham A1 - Pastor-Perez, Laura A1 - Ramirez Reina, Tomas A1 - Arellano-García, Harvey T1 - Catalytic upgrading of acetone, butanol and ethanol (ABE): A step ahead for the production of added value chemicals in bio-refineries T2 - Renewable Energy N2 - With the aim of moving towards sustainability and renewable energy sources, we have studied the production of long chain hydrocarbons from a renewable source of biomass to reduce negative impacts of greenhouse gas emissions while providing a suitable alternative for fossil fuel-based processes. Herein we report a catalytic strategy for Acetone, Butanol and Ethanol (ABE) upgrading using economically viable catalysts with potential impact in modern bio-refineries. Our catalysts based on transition metals such as Ni, Fe and Cu supported on MgO–Al2O3 have been proven to perform exceptionally with outstanding conversions towards the production of a broad range of added value chemicals from C2 to C15. Although all catalysts displayed meritorious performance, the Fe catalyst has shown the best results in terms conversion (89%). Interestingly, the Cu catalyst displays the highest selectivity towards long chain hydrocarbons (14%). Very importantly, our approach suppresses the utilization of solvents and additives resulting directly in upgraded hydrocarbons that are of use in the chemical and/or the transportation industry. Overall, this seminal work opens the possibility to consider ABE upgrading as a viable route in bio-refineries to produce renewably sourced added value products in an economically favorable way. In addition, the described process can be envisaged as a cross-link stream among bio and traditional refineries aiming to reduce fossil fuel sources involved and incorporate “greener” solutions. Y1 - 2020 UR - https://www.sciencedirect.com/science/article/pii/S096014812030690X?via%3Dihub U6 - https://doi.org/10.1016/j.renene.2020.04.152 SN - 1879-0682 SN - 0960-1481 VL - 156 SP - 1065 EP - 1075 ER - TY - GEN A1 - Ramirez Reina, Tomas A1 - Ketabchi, Elham A1 - Arellano-García, Harvey A1 - Pastor-Perez, Laura T1 - The Production of Long Chain Hydrocarbons through the Catalytic Upgrade of Biomass-Based Acetone, Butanol and Ethanol (ABE) T2 - 2019 AIChE Annual Meeting N2 - One of the main issues that many industrial sectors such as oil refineries have been facing nowadays is their sole dependency on fossil fuel. Not only have price fluctuations affected the products, but their environmental impact is an ever present problem that should be addressed. This has led to the search for alternatives such as biomass based processes in order to reduce the dependency on fossil fuel. Bio-refinery processes, fed by biomass, produce high value chemicals and materials with the advantage of reduced environmental drawbacks, such as CO2 emissions, when compared to the conventional refinery. For the benefit of both systems, an integration approach has been considered connecting bio-refining and conventional refining processes together. In this work we focus on the production of long chain hydrocarbons while maintaining production of chemicals that already originate from biomass such as Acetone, Butanol and Ethanol (ABE). The ABE used for this process is obtained as a product of sugar fermentation using the bacteria genus Clostridium. Through the upgrading and conversion of ABE, the products obtained will then be incorporated in the proposed integration system, connecting the conventional oil refinery to this process. A reaction involving a complex reaction network towards upgrading ABE with the aim of producing valuable products using economically viable catalysts has been carried out. The vast majority of research in this area either involves the separation of ABE after fermentation to be used in the chemical/or transportation industry that incurs large costs, or noble metal catalysts are used to upgrade this feed, which would also not be economically viable. However, our research has surpassed the necessity of noble metals, leading to a significant cost decrease that also produces outstanding results. The catalysts required for this process were synthesised successfully through the wetness incipient method and characterised by XRD, Raman, BET, TPR and N2 Isotherm. The reaction consists of the self-condensation and cross condensation of the alcohols and acetone, respectively, using a variety of active metals on basic supports as catalysts, at high temperatures and pressure in a batch reactor. The results have shown exceptional performance for the catalysts in terms of conversion and selectivity, having conversions as high as 90%. The catalysts have proven to yield a range of C3-C15 hydrocarbons identified to be of need in the chemical industry. In conclusion, our route has produced valuable chemicals proven to have a considerably higher market value than the simple alcohol reactants, useful for both the petrochemical and the transportation industries, through the use of novel and economically favourable catalysts. Y1 - 2019 UR - https://www.aiche.org/conferences/aiche-annual-meeting/2019/proceeding/paper/39f-production-long-chain-hydrocarbons-through-catalytic-upgrade-biomass-based-acetone-butanol-and SN - 978-0-8169-1112-7 ER - TY - GEN A1 - Gonzalez-Arias, Judith A1 - Torres-Sempere, Guillermo A1 - Gonzalez-Castano, Miriam A1 - Baena-Moreno, Francisco Manuel A1 - Ramirez Reina, Tomas T1 - Hydrochar and synthetic natural gas co-production for a full circular economy implementation via hydrothermal carbonization and methanation: An economic approach T2 - Journal of Environmental Sciences N2 - Herein we study the economic performance of hydrochar and synthetic natural gas co-production from olive tree pruning. The process entails a combination of hydrothermal carbonization and methanation. In a previous work, we evidenced that standalone hydrochar production via HTC results unprofitable. Hence, we propose a step forward on the process design by implementing a methanation, adding value to the gas effluent in an attempt to boost the overall process techno-economic aspects. Three different plant capacities were analyzed (312.5, 625 and 1250 kg/hr). The baseline scenarios showed that, under the current circumstances, our circular economy strategy in unprofitable. An analysis of the revenues shows that hydrochar selling price have a high impact on NPV and subsidies for renewable coal production could help to boost the profitability of the process. On the contrary, the analysis for natural gas prices reveals that prices 8 times higher than the current ones in Spain must be achieved to reach profitability. This seems unlikely even under the presence of a strong subsidy scheme. The costs analysis suggests that a remarkable electricity cost reduction or electricity consumption of the HTC stage could be a potential strategy to reach profitability scenarios. Furthermore, significant reduction of green hydrogen production costs is deemed instrumental to improve the economic performance of the process. These results show the formidable techno-economic challenge that our society faces in the path towards circular economy societies. Y1 - 2023 UR - https://www.sciencedirect.com/science/article/pii/S1001074223001766 U6 - https://doi.org/10.1016/j.jes.2023.04.019 SN - 1878-7320 VL - Vol. 140(2024) SP - 69 EP - 78 ER -