CO2 Recycling to Dimethyl Ether: State-of-the-Art and Perspectives.

This review reports recent achievements in dimethyl ether (DME) synthesis via CO2 hydrogenation. This gas-phase process could be considered as a promising alternative for carbon dioxide recycling toward a (bio)fuel as DME. In this view, the production of DME from catalytic hydrogenation of CO2 appears as a technology able to face also the ever-increasing demand for alternative, environmentally-friendly fuels and energy carriers. Basic considerations on thermodynamic aspects controlling DME production from CO2 are presented along with a survey of the most innovative catalytic systems developed in this field. During the last years, special attention has been paid to the role of zeolite-based catalysts, either in the methanol-to-DME dehydration step or in the one-pot CO2-to-DME hydrogenation. Overall, the productivity of DME was shown to be dependent on several catalyst features, related not only to the metal-oxide phase-responsible for CO2 activation/hydrogenation-but also to specific properties of the zeolites (i.e., topology, porosity, specific surface area, acidity, interaction with active metals, distributions of metal particles, …) influencing activity and stability of hybridized bifunctional heterogeneous catalysts. All these aspects are discussed in details, summarizing recent achievements in this research field.

Process Simulation and Environmental Aspects of Dimethyl Ether Production from Digestate-Derived Syngas.

The production of dimethyl ether from renewables or waste is a promising strategy to push towards a sustainable energy transition of alternative eco-friendly diesel fuel. In this work, we simulate the synthesis of dimethyl ether from a syngas (a mixture of CO, CO2 and H2) produced from gasification of digestate. In particular, a thermodynamic analysis was performed to individuate the best process conditions and syngas conditioning processes to maximize yield to dimethyl etehr (DME). Process simulation was carried out by ChemCAD software, and it was particularly focused on the effect of process conditions of both water gas shift and CO2 absorption by Selexol® on the syngas composition, with a direct influence on DME productivity. The final best flowsheet and the best process conditions were evaluated in terms of CO2 equivalent emissions. Results show direct DME synthesis global yield was higher without the WGS section and with a carbon capture equal to 85%. The final environmental impact was found equal to -113 kgCO2/GJ, demonstrating that DME synthesis from digestate may be considered as a suitable strategy for carbon dioxide recycling.

Purification of Wastewater from Biomass-Derived Syngas Scrubber Using Biochar and Activated Carbons.

Phenol is a major component in the scrubber wastewater used for syngas purification in biomass-based gasification plants. Adsorption is a common strategy for wastewater purification, and carbon materials, such as activated carbons and biochar, may be used for its remediation. In this work, we compare the adsorption behavior towards phenol of two biochar samples, produced by pyrolysis and gasification of lignocellulose biomass, with two commercial activated carbons. Obtained data were also used to assess the effect of textural properties (i.e., surface area) on phenol removal. Continuous tests in lab-scale columns were also carried out and the obtained data were processed with literature models in order to obtain design parameters for scale-up. Results clearly indicate the superiority of activated carbons due to the higher pore volume, although biomass-derived char may be more suitable from an economic and environmental point of view. The phenol adsorption capacity increases from about 65 m/g for gasification biochar to about 270 mg/g for the commercial activated carbon. Correspondingly, service time of commercial activated carbons was found to be about six times higher than that of gasification biochar. Finally, results indicate that phenol may be used as a model for characterizing the adsorption capacity of the investigated carbon materials, but in the case of real waste water the carbon usage rate should be considered at least 1.5 times higher than that calculated for phenol.

Techno-Economic Assessment of Bio-Syngas Production for Methanol Synthesis: A Focus on the Water-Gas Shift and Carbon Capture Sections.

The biomass-to-methanol process may play an important role in introducing renewables in the industry chain for chemical and fuel production. Gasification is a thermochemical process to produce syngas from biomass, but additional steps are requested to obtain a syngas composition suitable for methanol synthesis. The aim of this work is to perform a computer-aided process simulation to produce methanol starting from a syngas produced by oxygen-steam biomass gasification, whose details are reported in the literature. Syngas from biomass gasification was compressed to 80 bar, which may be considered an optimal pressure for methanol synthesis. The simulation was mainly focused on the water-gas shift/carbon capture sections requested to obtain a syngas with a (H2 - CO2)/(CO + CO2) molar ratio of about 2, which is optimal for methanol synthesis. Both capital and operating costs were calculated as a function of the CO conversion in the water-gas shift (WGS) step and CO2 absorption level in the carbon capture (CC) unit (by Selexol® process). The obtained results show the optimal CO conversion is 40% with CO2 capture from the syngas equal to 95%. The effect of the WGS conversion level on methanol production cost was also assessed. For the optimal case, a methanol production cost equal to 0.540 €/kg was calculated.

The Effect of Zeolite Features on the Dehydration Reaction of Methanol to Dimethyl Ether: Catalytic Behaviour and Kinetics.

The synthesis of dimethyl ether (DME) is an important step in the production of chemical intermediate because it is possible to prepare it by direct hydrogenation of CO2. This paper reports the effect of different zeolitic frameworks (such as: BEA, EUO, FER, MFI, MOR, MTW, TON) on methanol conversion, DME selectivity and catalyst deactivation. The effect of crystal size, Si/Al ratio and acidity of the investigated catalysts have been also studied. Finally, the kinetic parameters (such as: ∆H, ∆S and ∆G) have been evaluated together with pre-exponential factor and activation energy for catalysts with FER and MFI structure topology.

Mesoporous silica-based hybrid materials for bone-specific drug delivery.

A mesoporous silica-based drug delivery device potentially useful for bone-specific drug delivery has been designed, developed and characterized starting from MSU-type mesoporous silica. The proposed system consists of a mesoporous silica nanoparticles (MSN) based vehicle, presenting alendronate as a targeting functionality for bone tissue while ibuprofen is used as a model molecule for the drugs to be delivered. The particles are functionalized on the external surface using a propionitrile derivative that is successively hydrolyzed to a carboxylic group. Alendronate, one of the most used member of the diphosphonate drug class, is electrostatically bonded to the external carboxyl functionalities of mesoporous silica. The obtained material has been characterized by powder X-ray diffraction, N2 adsorption-desorption porosimetry, UV-vis spectrophotometry, FT-IR spectrometry and MAS-NMR 13C and 29Si. Hydroxyapatite, which simulates the bone matrix, has been synthesized with the aim of testing the targeting activity of the obtained device. In a separate test, the MSNs have been loaded with ibuprofen, a non-steroidal anti-inflammatory drug (NSAID), and its release has been determined under neutral conditions by HPLC. Moreover, biological tests were carried out. The tested devices did not show any toxicity towards normal cells, confirming their high biocompatibility and the lack of off-target effects.

In Situ FT-IR Characterization of CuZnZr/Ferrierite Hybrid Catalysts for One-Pot CO2-to-DME Conversion.

CO2 hydrogenation to dimethyl ether (DME) is a promising strategy to drive the current chemical industry towards a low-carbon scenario since DME can be used as an eco-friendly fuel as well as a platform molecule for chemical production. A Cu‒ZnO‒ZrO2/ferrierite (CZZ/FER) hybrid grain was recently proposed as a catalyst for CO2-to-DME one-pot conversion exhibiting high DME productivity thanks to the unique shape-selectivity offered by ferrierite zeolite. Nevertheless, such a catalyst deactivates but no direct evidence has been reported of activity loss over time. In this work, CZZ/FER catalysts with different acidity levels were characterized with the FTIR technique before and after reactions, aiming to give new insights about catalyst deactivation. Results show that activity loss can be related to both (i) copper particle sintering, which decreases CO2 activation towards methanol, and (ii) acidity loss due to H⁺/Cu2+ ion exchange.