Within the Waste2Fuel project, innovative, high-performance, and cost-effective fuel production methods are developed to target the “closed carbon cycle”. The catalysts supported on different metal oxides were characterized by XRD, XPS, Raman, UV-Vis, temperature-programmed techniques; then, they were tested in CO₂ hydrogenation at 1 bar. Moreover, the V₂O₅ promotion was studied for Ni/Al₂O₃ catalyst. The precisely designed hydrotalcite-derived catalyst and vanadia-promoted Ni-catalysts deliver exceptional conversions for the studied processes, presenting high durability and selectivity, outperforming the best-known catalysts. The equilibrium conversion was reached at temperatures around 623 K, with the primary product of reaction CH₄ (>97% CH₄ yield). Although the Ni loading in hydrotalcite-derived NiWP is lower by more than 40%, compared to reference NiR catalyst and available commercial samples, the activity increases for this sample, reaching almost equilibrium values (GHSV = 1.2 × 10⁴ h^–1, 1 atm, and 293 K).

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CO₂ methanation is a very promising technology for the production of alternative fuels with the simultaneous use of greenhouse gases. Therefore, intensive research is carried out on the optimization of catalysts with excellent properties for operation in the area of low temperatures. Here, we present research on a catalyst composed of 19 wt % NiO supported on alumina/calcium aluminate. The catalyst was modified with V₂O₅ in order to be suited for extrusion and scale-up in the frame of power to gas technology. Samples with various vanadium contents (Ni–xV, where x represents the amount of vanadium) were prepared in the form of ground granules obtained from 0.5 mm diameter spherical grains. X-ray diffraction (XRD), transmission electron microscopy (TEM), skeletal infrared (IR), diffuse reflectance ultraviolet–visible-near-infrared (DR-UV–vis-NIR), and X-ray photoelectron (XPS) spectroscopies, as well as H₂ temperature-programmed reduction (H₂-TPR), were used to characterize the samples. Catalytic performances of the catalyst samples were tested in CO₂ hydrogenation at 1 atm. Among the many supported Ni catalysts tested in our laboratories, the catalysts of 0.5 and 1 wt % V showed very high activity, with the highest CH₄ yield of 97% at 623 K. These catalysts exhibited 100% CH₄ selectivity up to 673 K. The excellent performances of the studied catalysts are attributed to the possible formation of Ni–V solid solution alloy nanoparticles.

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This research was supported by receiving funding from the Foundation for Polish Science Reintegration/2016-1/5 Project “Waste to fuel—Catalyst and process development for waste biomass valorization”, cofinanced by the European Regional Development Fund under the Intelligent Development Operational Program 2014–2020 (POIR), Axis IV: Increasing the scientific and research potential, Measure 4.4: Increasing the human potential in the R&D sector, awarded to I.S.P., with connected subcontracting agreement 1414/2018 given to G.G. for the Task “CO₂ valorization over V-modified Ni catalyst supported on various supports”. I.S.P. gratefully acknowledges support from the French Government for collaboration with Sorbonne University Project “Catalytic conversion of CO₂ to hydrocarbons: The Ni–V catalyst selectivity and durability in in plasma assisted hydrogenation of CO₂ to methane”

Owner IPC PAS

Pieta, I. S.; Pieta, P.; Nowakowski, R. Nickel-vanadium catalyst for the valorization of carbon dioxide, a method of obtaining a nickel-vanadium catalyst and the use of a nickel-vanadium catalyst in the processes of carbon dioxide hydrogenation and reforming.

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Within the ongoing project, related to fuels and energy production from biomass, agricultural and other wastes, the technology based on SOFC stack and steam reforming is under development. The project aims to present an efficient technology for biogas reforming and continuous supply of reformate fuel to the working SOFC stack. The decision, concerning reforming unit and the stack separation, has been made after detailed analysis of advantages and disadvantages of internal reforming. The set of Ni-based catalysts was prepared and investigated for the external biogas steam reforming. To determine the optimal condition of the reforming process the effect of reaction temperature (RT–773 K) for steam to carbon (S/C) molar ratio of 2.5 in the feedstock was investigated. Conversions rates and H₂/CO ratios in the produced syngas were influenced by the feedstock composition and catalyst used. The increase in the catalyst activity can be attributed to the specific catalyst–promoter interactions such as the redox capacity of V₂O₅ and its influence on surface Ni-species.

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Targeting CO2 hydrogenation and oxygenated reforming  – our Ni and stabilized Ni-V catalysts ready for purchase.

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Our Ni/CaO-Al₂O₃  and stabilized Ni-V catalysts tested for CO2 cold plasma hydrogenation.

Thank you to French Government scholarships for supporting bilateral cooperation with Paris-Sorbonne University.

Dimethyl ether (DME) as a potential chemical storage of renewable energy was studied for decomposition and steam reforming (DME SR) to produce hydrogen-rich streams over V-Ni/Al₂O₃ catalysts. The extent of DME decomposition, DME hydrolysis, and subsequent methanol steam reforming was examined during this study, focusing on the redox and acid/base properties of catalyst surface species. The results show that the DME SR performance depended on the acid-redox character of the Ni-O-Ni/V-O-Ni species dispersed onto alumina. For S/C ratio close to 2.5, for relative V-rich catalysts, DME hydrolysis reaction over the Lewis acid sites was found a rate-determining step and then, metallic centers being responsible for H₂ and CO₂ production. For 3V-Ni/Al₂O₃ DME SR with low selectivity towards methane and direct H₂ and CO₂ production (H₂/CO₂ ratios close to 3), with near-complete DME conversion was obtained above 673 K.

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The authors acknowledge the National Science Centre Poland for funding through project SONATA-2013/11/D/ST5/03007 ‘Second generation of biofuel and near future alternative fuels - development of stable, selective and highly active for steam reforming process’ awarded to I.S.P with connected contracting agreement 2012/10/11 for “DME process and material development’ given to C.H., M.L., L.A., and SONATA scholarship contracts no. 2014/12/15 and 2015/06/01 given to R.G.G. C.H., M.L., L.A. gratefully acknowledge the contract no. 20170000000000998 ‘Development and characterization of advanced catalytic materials’ trough Reintegration FNP 2016/1-5 ‘Waste into fuel - catalyst and process development for waste biomass valorization’. The UBA is acknowledged for TPR.

Owner IN

Pieta, I.S. The method and installation for continuous multi-parameter analysis of gaseous fuel conversion including reforming and measurement of post-reaction gas pollutants nitrogen, carbon and sulfur oxides, and chlorine.

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