The increase in atmospheric carbon dioxide is linked to climate changes; hence there is an urgent need to reduce the accumulation of CO2 in the atmosphere. The utilization of CO2 as a raw material in the synthesis of chemicals and liquid energy carriers offers a way to mitigate the increasing CO2 buildup. This review covers six important CO2 transformations namely: chemical transformations, photochemical reductions, chemical and electrochemical reductions, biological conversions, reforming and inorganic transformations. Furthermore, the vast research area of carbon capture and storage is reviewed briefly. This review is intended as an introduction to CO2, its synthetic reactions and their possible role in future CO2 mitigation schemes that has to match the scale of man-made CO2 in the atmosphere, which rapidly approaches 1 teraton.

The teraton challenge. A review of fixation and transformation of carbon dioxide

Beyond Oil and Gas: The Methanol Economy

Global challenges and strategies for control, conversion and utilization of CO2 for sustainable development involving energy, catalysis, adsorption and chemical processing

Dry (CO2) reforming of methane (DRM) is a well-studied reaction that is of both scientific and industrial importance. This reaction produces syngas that can be used to produce a wide range of products, such as higher alkanes and oxygenates by means of Fischer–Tropsch synthesis. DRM is inevitably accompanied by deactivation due to carbon deposition. DRM is also a highly endothermic reaction and requires operating temperatures of 800–1000 °C to attain high equilibrium conversion of CH4 and CO2 to H2 and CO and to minimize the thermodynamic driving force for carbon deposition. The most widely used catalysts for DRM are based on Ni. However, many of these catalysts undergo severe deactivation due to carbon deposition. Noble metals have also been studied and are typically found to be much more resistant to carbon deposition than Ni catalysts, but are generally uneconomical. Noble metals can also be used to promote the Ni catalysts in order to increase their resistance to deactivation. In order to design catalysts that minimize deactivation, it is necessary to understand the elementary steps involved in the activation and conversion of CH4 and CO2. This review will cover DRM literature for catalysts based on Rh, Ru, Pt, and Pd metals. This includes the effect of these noble metals on the kinetics, mechanism and deactivation of these catalysts.

A review of dry (CO2) reforming of methane over noble metal catalysts

CO2 conversion covers a wide range of possible application areas from fuels to bulk and commodity chemicals and even to specialty products with biological activity such as pharmaceuticals. In the present review, we discuss selected examples in these areas in a combined analysis of the state-of-the-art of synthetic methodologies and processes with their life cycle assessment. Thereby, we attempted to assess the potential to reduce the environmental footprint in these application fields relative to the current petrochemical value chain. This analysis and discussion differs significantly from a viewpoint on CO2 utilization as a measure for global CO2 mitigation. Whereas the latter focuses on reducing the end-of-pipe problem “CO2 emissions” from todays’ industries, the approach taken here tries to identify opportunities by exploiting a novel feedstock that avoids the utilization of fossil resource in transition toward more sustainable future production. Thus, the motivation to develop CO2-based chemistry does...

Sustainable Conversion of Carbon Dioxide: An Integrated Review of Catalysis and Life Cycle Assessment

Although technological practice should minimize environmental impact, this is not always economically feasible. During the past decade, for example, there has been increasing global concern over th...

CO2 Reforming of CH4

The reforming of methane with carbon dioxide was studied over nickel supported on MgO, TiO2, SiO2, and activated carbon. The influence of the support on catalyst activity and carbon deposition resistivity was markedly different ineach case. Although considerable formation of filamentous carbon was observed over Ni/SiO2 (confirmed by TEM and TPO), there was negligible initial loss of catalytic activity. The catalytic activity of Ni/C was very similar to that of Ni/SiO2, but no filamentous carbon appeared to be formed. In contrast to Ni/SiO2, substantially less coking was observed over either the Ni/TiO2 or the Ni/MgO catalysts. Evidence of strong metal-support interaction (SMSI) in the Ni/TiO2 catalyst indicated that large ensembles of nickel atoms, active for carbon deposition, are deactivated or removed by the presence of mobile TiOx species. The identification of two TiOx phases and a Ni5TiO7 phase was made possible by direct measurement of crystalline d spacings with TEM. The Ni/MgO catalyst was both active and very stable for up to 44 h time on stream. Chemisorption, XRD and TEM results indicate the formation of a partially reducible NiO—MgO solid solution, which appears to stabilize the reduced nickel surfaces and provide resistance to carbon deposition.

Catalytic reforming of methane with carbon dioxide over nickel catalysts I. Catalyst characterization and activity

The reforming of methane with carbon dioxide was studied over nickel supported on SiO2, TiO2, MgO and activated carbon. Specific activities on a turnover frequency basis were in the order: Ni/TiO2 > Ni/C > Ni/SiO2 > Ni/MgO. Interestingly, a 2-fold increase in activation energy for this reaction was observed over Ni/TiO2 after several hours time on stream. The reverse water-gas shift reaction was found to be close to thermodynamic equilibrium over all catalysts. Partial pressure dependencies were obtained with the Ni/C and Ni/SiO2 catalysts at 723 K for comparative purposes only, but a more thorough kinetic analysis was made with the Ni/MgO and Ni/TiO2 catalysts, which were shown previously to strongly inhibit carbon deposition. Partial pressure dependencies were obtained at 673, 698, and 723 K for Ni/TiO2 and at 773, 798, and 823 K for Ni/MgO. In situ DRIFTS studies clearly showed the presence of both linear and bridged carbon monoxide adsorption on Ni/SiO2 under reaction conditions; however, adsorbed carbon monoxide could not be identified on Ni/TiO2. A reaction model for CH4—CO2 reforming, based on CH4 activation to form CHx and CHxO decomposition as the slow kinetic steps, successfully correlated the rate data.

Michael C. Bradford

Papers

CO2 Reforming of CH4

Catalytic reforming of methane with carbon dioxide over nickel catalysts I. Catalyst characterization and activity

Catalytic reforming of methane with carbon dioxide over nickel catalysts II. Reaction kinetics

CO2Reforming of CH4over Supported Pt Catalysts

The role of metal–support interactions in CO2 reforming of CH4