Hydrogen Utilization in Green Fuel Synthesis via CO2 Conversion to Methanol over New Cu-Based Catalysts

Abstract

Abstract:The use of hydrogen as an energy vector and raw material for "very clean liquid fuels" manufacturing has been assessed by the catalytic conversion of CO 2 to methanol over copper based catalysts. A systematic evaluation of copper based catalysts, prepared varying the chemical composition, has been carried out at 0.1-5.0 MPa of total pressure and in the range of 453-513 K by using a semi-automated LAB-microplant, under CO 2 /H 2 reactant mixture (1/3), fed at GHSV of 8.8 NL·kg cat −1 ·h −1 . Material's properties have been investigated by the means of chemical-physical studies. The findings disclose that the addition of structure promoters (i.e., ZrO 2 /CeO 2 ) strongly improves the textural properties of catalysts, in term of total surface area and exposure of metal surface area (MSA), also reducing the sintering phenomena. The results of the catalytic study clearly prove a structure-activity relationship at low reaction pressure (0.1 MPa), while at higher pressure (3.0-5.0 MPa) the reaction path is insensitive to structure and chemical composition.

Totally-green Fuels via CO2 Hydrogenation

“…On this account, ZrO2 has been shown to positively affect morphology and texture of Cu-ZnO based catalysts, favoring also CO2 adsorption / activation and methanol selectivity, while CeO2 could act as both electronic promoter and improver of surface functionality of Cu phase. As reported in our preliminary works, we have proved a greater specific activity of CuZnO-CeO2 catalyst with respect to that of similar catalytic systems containing ZrO2 or other promoter oxides, facing several electronic and structural effects [14,15,18]. In spite of a generally higher specific activity, we have evidenced that CuZ-nO-Ceria catalyst suffers from several practical limitations, such as: a lower surface area, especially compared to that of ZrO2 and Al2O3 promoted catalysts.…”

“…Differently from fossil, a totallygreen fuel does not give rise to extra CO2 emission in atmosphere, because its combustion, in the well-to-wheel cycle, generates a CO2 release equal to that necessary for its manufacturing, closing the CO2 balance, on the other words a fuel at zero-charge of carbon dioxide. On the other hand, besides the efforts to limit the presence of CO2 in the atmosphere by CCUS tech-nologies, CO2 is assuming an even more important and strategic play-role in the energy field, as well as in the synthesis of industrial relevant products and chemicals [8,9,[14][15][16][17][18][19][20][21]. As new raw material, the direct utilization of CO2 for industrial purposes finds commercial applications in the synthesis of methanol and other chemical compounds such as olefins and aromatics, which are a rapidly growing field, since CO2 represents an abundant and economic carbon source [10,22,23].…”

A novel Core–Shell structured CuIn@SiO2 catalyst for CO2 hydrogenation to methanol

“…Finally, the catalyst was reduced again in 10 vol % H 2 /He at 350°C, and the amount of consumed H 2 was denoted as n H2 . The D Cu and S Cu were calculated by the following equations: D Cu (%) = [(2 n H2 × M Cu )/( W × X Cu )] × 100 and S Cu (m 2 /g) = (2 n H2 × N a )/( W × 1.46 × 10), where n H2 is the molar number of consumed H 2 , M Cu is the relative atomic mass (63.456 g·mol −1 ), W is the catalyst weight, X Cu is the stoichiometric composition of Cu (wt %), N a is the Avogadro's constant (6.02 × 10 23 atoms·mol −1 ), and 1.46 × 10 19 is the number of copper atoms per square meter . X‐ray photoelectron spectroscopy (XPS) was collected using a Thermo Scientific ESCALAB 250Xi spectrometer featuring monochromatic Al‐K α radiation (hν = 1486.6 eV) under ultrahigh vacuum (1.3 × 10 −6 Pa).…”

“…Hence, low‐cost, highly efficient and sustainable catalysts for methanol synthesis are required to better utilize CO 2 . Metallic Cu, Co, and Ni are widely used as the active species for CO 2 hydrogenation reaction and Cu is especially more beneficial for methanol formation from CO 2 hydrogenation than Co and Ni . However, the catalytic activity of a pure copper catalyst is almost negligible.…”

Combination of Chemo- and Biocatalysis: Conversion of Biomethane to Methanol and Formic Acid

“…Moreover, methane from mimicked biogas (CH 4 :CO 2 = 1:1) was utilized in this work to further explore this renewable feedstock, which is produced at a scale of Gm 3 •a −1 [41]. The following results should be also set into context of presently discussed methanol production routes from biogas which follow the conventional syngas strategy [42] or might use the hydrogenation of carbon dioxide [43][44][45][46]. Clearly, the following results represent insights of a new, alternative route to already existing methods from biomethane to methanol.…”