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This study presents an integrated approach combining aqueous phase reforming (APR) and hydrodeoxygenation (HDO) for the hydrotreatment of guaiacol, a model compound representing lignin-derived phenols in pyrolysis bio-oils. The APR process enables in-situ H2 generation, eliminating the need for an external hydrogen source. We examine the interplay between metal species, the Pt-promoting effect on Ni–Pt catalyst supported on activated carbon (AC), and the choice of hydrogen source (methanol or glycerol). Amongst the monometallic catalysts, a 1% Pt/AC catalyst notably achieved over 96% guaiacol conversion at 300 °C with either hydrogen source. Interestingly, when 0.5–1% of the Ni loading is replaced with Pt, the resulting bimetallic Ni–Pt/AC catalysts demonstrate a significant improvement in guaiacol conversion, reaching 70% when methanol is employed as the hydrogen source. Surprisingly, no comparable enhancement in guaiacol conversion is observed when employing glycerol as the hydrogen source. This observation underlines one of the pivotal effects of the hydrogen source on catalyst performance. X-ray photoemission spectroscopy (XPS) pinpointed strong Ni–Pt interactions in the catalyst. It also revealed distinctive electronic features of Ni–Pt/AC, which are favourable for steering selectivity towards cyclohexanol rather than phenol when Pt loading is increased from 0.5 to 1%. Moreover, Pt enhanced catalyst stability by inhibiting the oxidation of Ni sites and mitigating Ni–Pt phase sintering. Overall, our findings offer important insights into integrating APR and HDO processes, the promotion effect of Pt, and the importance of hydrogen source selection in terms of guaiacol conversion and catalyst stability.

In-situ hydrodeoxygenation of guaiacol over Ni-based nitrogen-doped activated carbon supported catalysts is presented in this paper as an economically viable route for bio-resources upgrading. The overriding concept of this paper is to use water as hydrogen donor for the HDO reaction suppressing the input of external high-pressure hydrogen. The effect of nitrogen sources, including polyporrole (PPy), polyaniline (PANI) and melamine (Mel) on the structural, electronic and ultimately of catalytic features of the design materials have been addressed. Nitrogen-doped samples, are more active than the undoped counterparts in the “H2-free” HDO process. For instance, the conversion of guaiacol increased by 8% for Ni/PANI-AC compared to that of Ni/AC catalysts. The superior performance of Ni/NC can be attributed to the acid-base properties and modified electronic properties which favours the C-O cleavage and water activation as well as enhances dispersion of Ni particles on the catalysts’ surface

Herein we analyze the profitability of a novel regenerative process to synergize biogas upgrading and carbon dioxide utilization. Our proposal is a promising alternative which allows to obtain calcium carbonate as added value productwhile going beyond traditional biogas upgrading methodswith high thermal energy consumption. Recently we have demonstrated the experimental viability of this route. In this work, both the scale-up and the profitability of the process are presented. Furthermore, we analyze three representative scenarios to undertake a techno-economic study of the proposed circular economy process. The scale-up results demonstrate the technical viability of our proposal. The precipitation efficiency and the product quality are still remarkable with the increase of the reactor size. The techno-economic analysis reveals that the implementation of this circular economy strategy is unprofitable without subsidies. Nonetheless, the results are somehow encouraging as the subsides needed to reach profitability are lower than in other biogas upgrading and carbon dioxide utilization proposals. Indeed, for the best-case scenario, a feed-in tariff incentive of 4.3 €/MWh makes the approach profitable. A sensitivity study through tornado analysis is also presented, revealing the importance of reducing bipolarmembrane electrodialysis energy consumption. Overall our study envisages the big challenge that the EU faces during the forthcoming years. The evolution towards bio-based and circular economies requires the availability of economic resources and progress on engineering technologies

Catalytic hydrodeoxygenation (HDO) is a fundamental and promising route for bio-oil upgrading to produce petroleum-like hydrocarbon fuels or chemical building blocks. One of the main challenges of this technology is the demand of high-pressure H, which poses high costs and safety concerns. Accordingly, developing cost-effective routes for biomass or bio-oil upgrading without the supply of commercial H is essential to implement the HDO at commercial scale. This article critically reviewed the very recent studies relating to the novel strategies for upgrading the biofeedstocks with ‘green’ H generated from renewable sources. More precisely, catalytic transfer hydrogenation/hydrogenolysis, combined reforming and HDO, combined metal hydrolysis and HDO, water-assisted in-situ HDO and nonthermal plasma technology and self-supported hydrogenolysis are reviewed herein. Current challenges and research trends of each strategy are also proposed aiming to motivate further improvement of these novel routes to become competitive alternatives to conventional HDO technology.

In this work a novel strategy for bio-methane production and magnesium chloride waste valorization is addressed. The proposed process is a potential alternative path to the already existing biogas upgrading technologies by carbon dioxide mineralization into valuable magnesium carbonate. The main parameters affecting the precipitation efficiency (reaction time, reaction temperature, and molar ratio reactant/precipitator) are studied, leading to promising results which spark further investigation in this innovative route. Additionally the purity and the morphology of the obtained solid product was accurately analysed through different physicochemical characterization techniques such as Raman, X-Ray diffraction and Scanning electron microscope. The characterisation study reveals a mixture of Nesqueonite and Dypingite carbonate phases obtained in the process being the later the dominant phase in the resulting precipitate. Overall, the results discussed herein confirmed the technical feasibility of this innovative strategy for synergizing carbon dioxide mineralization and renewable energy production.

Clean hydrogen production via WGS is a key step in the development of hydrogen fuel processors. Herein, we have designed a new family of highly effective catalysts for low-temperature WGS reaction based on gold modified copper-zinc mixed oxides. Their performance was controlled by catalysts’ composition and the Au-Cu synergy. The utilization of hydrotalcite precursors leads to an optimal microstructure that ensures excellent Au and Cu dispersion and favors their strong interaction. From the application perspective these materials succeed to overcome the major drawback of the commercial WGS catalysts: resistance towards start/stop operations, a mandatory requisite for H-powered mobile devices.

Outstanding catalysts for the water was shift reaction are reported in this work. The combination of gold nanoparticles with Cu/ZnO/AlO prepared from hydrotalcite-like precursors leads to very promising systems for pure hydrogen production. Full CO conversion is reached at temperatures as low as 180 °C. The key point seems to be the cooperation of Au and Cu and the optimal metal-oxide contact derived from the synthesis method. The high activity of gold for low temperature CO oxidation and the suitability of copper for the WGS results in a perfect synergy. Moreover the materials developed in this work present good stability and tolerance towards start/stop cycles an indispensable requisite for a realistic application in an integrated hydrogen fuel processor.

A copper-ceria bulk catalyst has been compared to a series of catalysts designed according to the as called “supported approach”, corresponding to the dispersion of low content mixed copper-ceria oxide on alumina matrix. The principal characteristics of both types of catalysts are contemplated and the differences in their electronic and redox properties discussed in details. As a plus, the gold metal promotion of the catalysts is also envisaged. The advantages of the systems in the CO clean up reactions, WGS and CO-PrOx are commented. While the WGS activity appears to be ruled especially by the Cu/Ce surface to volume ratio, the CO-PrOx reaction is governed by the CuO loading. Gold addition provides benefits only at the low temperature WGS regime. Very importantly, the supported systems are always superior to the bulk configuration in terms of specific activity, a key factor from the catalyst's design perspective.

The WGS reaction over multicomponent Au/Ce1-xCuxO2/Al2O3 catalysts is studied in this work. The systems are carefully designed aiming to take advantage of every active phase included in the formulation: gold, ceria and copper. Special emphasis is given to the CeO2-CuO synergy and its influence on the displayed catalytic performance with and without gold. To this aim a meaningful correlation between the physicochemical properties of the mixed materials and their activity/stability is proposed. In general terms the developed catalysts present high activity under realistic WGS reaction conditions, with fairly good long term stability. In addition, the systems successfully withstand start-up/shut-downs situations, indispensable requisite for real applications in the field of pure hydrogen production for fuel cell goals.

Platinum and gold structured catalysts were compared as active phases in classical and O2-assisted Water Gas Shift (WGS) reaction. Both metals were supported on iron-doped ceria mixed oxide and then, structured on metallic micromonolithic devices. As expected the WGS activity of both micromonoliths is conditioned by the nature of the noble metals being Pt the most active metal in traditional conditions. However, the addition of oxygen to the classical water gas feed turns the balance in favor of the gold based catalysts, being the presence of gold responsible for an excessive improvement of the catalytic activity.

Herein, a series of highly efficient gold based catalysts supported on mesoporous CeO2-Fe2O3 mixed oxides for CO elimination reactions have been developed. The materials have been fully characterized by means of XRD, Raman and UV-Vis spectroscopies among other techniques. We identify the Ce-Fe synergism as a fundamental factor controlling the catalytic performance. Our data clearly reveal that the CO oxidation activity is maximized when the electronic and structural properties of the support are carefully controlled. In this situation, fairly good catalysts for environmental applications as for example H2 streams purification for fuel cell goals or CO abatement at room temperature can be designed

A new approach for understanding PrOx reaction over gold catalysts is proposed in this work. The competition between H2 and CO oxidation has been studied over a series of Au/MOx/Al2O3 (M = Ce and Co) catalysts in simulated post-reforming gas stream, containing H2O and CO2 for H2 cleanup goals. The catalysts’ behavior is correlated to their oxygen storage capacity, redox behavior, and oxidation ability. The estimation of the reaction rates reveals that in these solids the H2 combustion, the selectivity limiting factor in the PrOx process, is mainly controlled by the support and not by the gold presence. The possible use of the hydrogen oxidation reaction as a catalyst selection criterion is discussed.

The water-gas shift (WGS) reaction over structured Cu, Ni, and bimetallic Cu-Ni supported on active carbon (AC) catalysts was investigated. The structured catalysts were prepared in pellets form and applied in the medium range WGS reaction. A good activity in the 180–350 °C temperature range was registered being the bimetallic Cu-Ni:2-1/AC catalyst the best catalyst. The presence of Cu mitigates the methanation activity of Ni favoring the shift process. In addition the active carbon gasification reaction was not observed for the Cu-containing catalyst converting the active carbon in a very convenient support for the WGS reaction. The stability of the bimetallic Cu-Ni:2-1/AC catalyst under continuous operation conditions, as well as its tolerance towards start/stop cycles was also evaluated.

Herein a strategy to design highly efficient Au/CeO2/Al2O3 based WGS catalysts is proposed. The inclusion of transition metals, namely Fe, Cu and Zn as CeO2 dopant is considered. All the promoters successfully increased the WGS performance of the undoped sample. The activity improvement can be correlated to structural and/or redox features induced by the dopants. The comparative characterization of the doped samples by means of XRD, Raman spectroscopy and OSC evaluation permits an accurate understanding of the boosted WGS activity arising from the Ce-promoter interaction. This study establishes distinction among both, structural and redox sources of promotion and provides a useful strategy to develop highly active Au/CeO2 based catalysts for the WGS reaction.

A series of ZnO and Fe 2O 3 modified ceria/alumina supports and their corresponding gold catalyst were prepared and studied in the CO oxidation reaction. ZnO-doped solids show a superior catalytic activity compared to the bare CeO 2-Al 2O 3, which is attributed to the intimate contact of the ZnO and CeO 2 phases, since an exchange of the lattice oxygen occurs at the interface. In a similar way, Fe 2O 3-modified supports increase the ability of the CeO 2-Al 2O 3 solids to eliminate CO caused by both the existence of Ce-Fe contact surface and the Fe 2O 3 intrinsic activity. All of the gold catalysts were very efficient in oxidising CO irrespective of the doping metal oxide or loading, with the ZnO containing systems better than the others. The majority of the systems reached total CO conversion below room temperature with the ZnO and Fe 2O 3 monolayer loaded systems the most efficient within the series. © 2012 Elsevier B.V. All rights reserved.