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Among the approaches to facilitating negative CO2 emissions is biochar production. Biochar is generated in the pyrolysis of certain biomasses. In the pyrolysis process, carbon in the biomass is turned into a solid, porous, carbon-rich, and stable material that can be captured from the soil after a period of from a few decades to several centuries. In addition to this long-term carbon sequestration role, biochar is also beneficial for soil performance as it helps to restore soil fertility and improves the retention and diffusion of water and nutrients. This work presents a Life Cycle Assessment of different pyrolysis approaches for biochar production. Biomass pyrolysis is performed in a fixed-bed reactor, which operates at a mild temperature (550 °C). Biochar is obtained as solid product of the pyrolysis, but there are also liquid (bio-oil) and gaseous products (syngas). The pyrolysis gas is partly used to fulfil the energy demand of the pyrolysis process, which is highly endothermic. In the conventional approach, CO2 is produced during the combustion of syngas and emitted to the atmosphere. Another approach to facilitate CO2 capture and thus obtain more negative CO2 emissions in the pyrolysis process is burning syngas and bio-oil in a Chemical Looping Combustion unit. Life Cycle Assessment was performed of these approaches toward biomass pyrolysis to evaluate their environmental impact. The Chemical Looping Combustion approach significantly reduced the values of 7 of the 16 environmental impact indicators studied, along with the Global Warming Potential among them, it slightly increased the value of one indicator related to the use of fossil resources, and it maintained the values of the remaining 8 indicators. Environmental impact reduction occurs due to the avoidance of CO2 and NOx emissions with Chemical Looping Combustion. The CO2 balances of the different pyrolysis approache

The success of catalytic schemes for the large-scale valorization of CO2 does not only depend on the development of active, selective and stable catalytic materials but also on the overall process design. Here we present a multidisciplinary study (from catalyst to plant and techno-economic/lifecycle analysis) for the production of green methanol from renewable H-2 and CO2. We combine an in-depth kinetic analysis of one of the most promising recently reported methanol-synthesis catalysts (InCo) with a thorough process simulation and techno-economic assessment. We then perform a life cycle assessment of the simulated process to gauge the real environmental impact of green methanol production from CO2. Our results indicate that up to 1.75 ton of CO2 can be abated per ton of produced methanol only if renewable energy is used to run the process, while the sensitivity analysis suggest that either rock-bottom H-2 prices (1.5 $ kg(-1)) or severe CO2 taxation (300 $ per ton) are needed for a profitable methanol plant. Besides, we herein highlight and analyze some critical bottlenecks of the process. Especial attention has been paid to the contribution of H-2 to the overall plant costs, CH4 trace formation, and purity and costs of raw gases. In addition to providing important information for policy makers and industrialists, directions for catalyst (and therefore process) improvements are outlined.

TGA curves of Sn-In-MCM-41: as synthesized, calcined, and after four catalytic cycles; XRD patterns of as-synthesized and calcined Sn-In-MCM-41; XRD patterns of as-synthesized and calcined In-MCM-41; FTIR spectra of calcined Sn-In-MCM-41, Sn-MCM-41, and In-MCM-41; FTIR spectra of Sn-In-MCM-41, Sn-MCM-41, and In-MCM-41 before and after pyridine adsorption and heating at 353 K; nitrogen adsorption–desorption isotherms of Sn-In-MCM-41, Sn-MCM-41, and In-MCM-41; BJH adsorption of Sn-In-MCM-41, Sn-MCM-41, and In-MCM-41; complete XPS spectra of Sn-In-MCM-41 fresh and after four catalytic cycles, Sn-MCM-41, and In-MCM-41; XPS spectra of Sn-MCM-41 fresh and after four catalytic cycles; catalytic results obtained for sugar conversion with Sn-In-MCM-41 in catalytic cycles (160 °C for 20 h, 160 mg of catalyst, and 225 mg of glucose); reaction mechanism; inputs for the LCA calculations on GaBi Software; flowchart for the production of 1 kg of glucose (Ecoinvent); environmental impact indicators (EIIs), units, and recommendation level; environmental impact indicator values; and contribution of the different processes to the EII values for the biochemical and chemical routes.

The use of biomass for the production of energy and higher added value products is a topic of increasing interest in line with growing environmental concerns and circular economy. Mesoporous material Sn-In-MCM-41 was synthesized for the first time and used as a catalyst for the transformation of sugars to methyl lactate (ML). This catalyst was characterized in depth by various techniques and compared with Sn-MCM-41 and In-MCM-41 catalysts. In the new Sn-In-MCM-41 material, both metals, homogeneously distributed throughout the mesoporous structure of MCM-41, actuate in a cooperative way in the different steps of the reaction mechanism. As a result, yields to ML of 69.4 and 73.9% in the transformation of glucose and sucrose were respectively reached. In the case of glucose, the ML yield 1.5 and 2.6 times higher than those of Sn-MCM-41 and In-MCM-41 catalysts, respectively. The Sn-In-MCM-41 catalyst was reused in the transformation of glucose up to four cycles without significant loss of catalytic activity. Finally, life cycle assessment comparison between chemical and biochemical routes to produce ML allowed us to conclude that the use of Sn-In-MCM-41 reduces the environmental impacts compared to Sn-MCM-41. Nevertheless, to make the chemical route comparable to the biochemical one, improvements in the catalyst and ML synthesis have to be achieved.

Non-edible vegetable oils are characterized by high contents of free fatty acids (FFAs) that prevent from using the conventional basic catalysts for the production of biodiesel. In this work, solid acid catalysts are used for the simultaneous esterification and transesterification with methanol of the FFAs and triglycerides contained in sunflower oil acidified with oleic acid. Molybdenum oxide (MoO3), which has been seldom considered as a catalyst for the production of biodiesel, was used in bulk and alumina-supported forms. Results showed that bulk MoO3 is very active for both transesterification and esterification reactions, but it suffered from severe molybdenum leaching in the reaction medium. When supported on Al2O3, the MoO3 performance improved in terms of active phase utilization and stability though molybdenum leaching remained significant. The improvement of catalytic performance was ascribed to the establishment of MoO3Al2O3 interactions that favored the anchorage of molybdenum to the support and the formation of new strong acidic centers, although this effect was offset by a decrease of specific surface area. It is concluded that the development of stable catalysts based on MoO3 offers an attractive route for the valorization of oils with high FFAs content.

Non-edible vegetable oils are characterized by high contents of free fatty acids (FFAs) that prevent from using the conventional basic catalysts for the production of biodiesel. In this work, solid acid catalysts are used for the simultaneous esterification and transesterification with methanol of the FFAs and triglycerides contained in sunflower oil acidified with oleic acid. Molybdenum oxide (MoO3), which has been seldom considered as a catalyst for the production of biodiesel, was used in bulk and alumina-supported forms. Results showed that bulk MoO3 is very active for both transesterification and esterification reactions, but it suffered from severe molybdenum leaching in the reaction medium. When supported on Al2O3, the MoO3 performance improved in terms of active phase utilization and stability though molybdenum leaching remained significant. The improvement of catalytic performance was ascribed to the establishment of MoO3- Al2O3 interactions that favored the anchorage of molybdenum to the support and the formation of new strong acidic centers, although this effect was offset by a decrease of specific surface area. It is concluded that the development of stable catalysts based on MoO3 offers an attractive route for the valorization of oils with high FFAs content.

The catalytic performance of a CuOx/CeO2 powder catalyst and that of a microchannel reactor or microreactor (MR) coated with the same solid was determined and compared. The catalytic activity measurements were carried out with varying O2/CO molar ratios in the feed-stream. In addition, the influence of the presence of CO2 and H2O in the reaction mixture was studied. Some discrepancies were observed between the performances of the powder catalyst and the MR depending on the O2/CO ratio. The MR presented a very good performance with a superior selectivity for CO conversion. This behaviour was due to a more efficient heat removal in the case of the MR that inhibited the H2 oxidation reaction and the r-WGS. The isothermicity of the microreactor during the process was demonstrated through the monitoring of the MR inlet and outlet temperatures. Concerning the presence of CO2 or H2O in the feed-stream, both compounds gave rise to a decrease of the CO conversion. The negative effect on the catalytic performance was more marked when both compounds were fed together, although the principal inhibitor effect was associated to the CO2. This seems to be related with the formation of stable carbonates at the catalyst surface.