Water Gas Shift Research Articles

Tailoring the A and B site of Fe-based perovskites for high selectivity in the reverse water-gas shift reaction

The reverse water-gas shift reaction (rWGS) is of particular interest as it is the first step to producing high-added-value products from carbon dioxide (CO2) and renewable hydrogen (H2), such as synthetic fuels or other chemical building blocks (e.g. methanol) through a modified Fischer-Tropsch process. However, side reactions and material deactivation issues, depending on the conditions used, still make it challenging. Efforts have been put into developing and improving scalable catalysts that can deliver high selectivity while at the same time being able to avoid deactivation through high temperature sintering and/or carbon deposition. Here we design a set of perovskite ferrites specifically tailored to the hydrogenation of CO2 via the reverse water-gas shift reaction. We tailor the oxygen vacancies, proven to play a major role in the process, by partially substituting the primary A-site element (Barium, Ba) with Praseodymium (Pr) and Samarium (Sm), and also dope the B-site with a small amount of Nickel (Ni). We also take advantage of the exsolution process and manage to produce highly selective Fe-Ni alloys that suppress the formation of any by-products, leading to up to 100% CO selectivity.

Onboard pre-combustion carbon capture with combined-cycle gas turbine power plant architectures for LNG-fuelled ship propulsion

This paper investigates the concept of pre-combustion carbon capture (Pre-CCS) with a combined cycle gas turbine (CCGT) propulsion system to achieve energy efficient carbon capture onboard a Liquid Natural Gas fuelled vessel. A basic CCGT model with energy efficiency of 51.6 % when using LNG as fuel was integrated with a Pre-CCS system composed of a steam methane reformer, water–gas shift reactors, pressure swing adsorption (SMR-PSA), and liquid CO2 storage. Various waste heat utilisation schemes integrated with the CCGT-reformer were modelled in Aspen HYSYS. The modelling of the waste heat recovery networks as energy streams integrating between various processes and unit of operations has facilitated a closed-loop simulation of various systems. It was concluded that a proper utilisation of the high-grade heat from the gas turbine (GT) exhaust and from the reformer is crucial to improve the overall energy efficiency and carbon capture rate, exemplified by a scheme where the heating needs for the SMR and the cooling needs from the water–gas-shift reactors are fully integrated. When optimised, the integrated system had an overall energy efficiency of 41.5 % and 43.2 % (i.e. an efficiency loss of 10.2–10.5 percentage points from the base CCGT system) accompanied with specific GHG emission reduction of 51.2 % and 52.3 % for operation of the GT at a turbine entry temperature of 1700 K and 1850 K, respectively. Intermediate levels of reforming, where the GT uses a mix of LNG and reformate gases, were also simulated, showing an almost linear evolution from the 100 % LNG feed to the GT to the 100 % reformate case. Such a strategy could be used for gradual evolution to meet the required CO2 reduction timeline. It was determined that the 100 % reformate case provides the highest CO2 capture rate. Estimates of other emissions from the GT assuming typical combustor residence times for the whole range of fuel blends were also carried out, showing that the overall greenhouse gas emission is dominated by CO2, given that the GT emits negligible N2O and unburnt methane. Some capital cost estimates were also made to determine the unit price of hydrogen fuel produced onboard, suggesting that the CAPEX was not prohibitive. These findings support the pre-combustion CCS − CCGT integrated system as a promising long-term decarbonisation and propulsion strategy to comply with emissions regulations, displaying good performance in terms of cost, energy consumption, and CO2 reduction. The scalability and adaptability of the proposed system for existing and new-built ships across the decarbonisation timeline is also discussed.

The role of Ga and Y on binary Al2O3-Y2O3 and Al2O3-Ga2O3 mixed oxides nanoparticles towards potential Ni water-gas shift catalysts

This work focuses on the study of binary Al2O3-Y2O3-x and Al2O3-Ga2O3-x mixed oxides with varying Y2O3 or Ga2O3 nominal loading (x=25, 50) prepared by hydrothermal synthesis assisted by Triton X-100. The mixed oxides were used to prepare Ni-based (5 wt%) catalysts for the Water Gas Shift Reaction. The Al2O3 sample presented urchin-like hollow nanosphere morphology, which evolved to solid nanospheres with Y2O3 or Ga2O3 in the mixed oxides. The physicochemical characterization indicated good integration of the mixed oxides, especially on the low-content additive oxides. The theoretical results confirmed that Ga goes deeper into the alumina matrix than Y, partially explaining the XPS and HRTEM results in which the Ni dispersion was better in the Ni/AlGa-x samples. The FTIR in-situ measurements of the reaction allowed us to propose that the reaction occurs minimally through the carbonyl mechanism at low temperatures (<300 °C) and the formate mechanism at high temperatures (>300 °C).

Volcano-Shaped Correlation Dictated Superior Activity for Ultralow Al-Doped Iron Oxide toward High-Temperature Water–Gas Shift Reaction

Volcano-Shaped Correlation Dictated Superior Activity for Ultralow Al-Doped Iron Oxide toward High-Temperature Water–Gas Shift Reaction

Modeling of water gas shift reaction using neural network trained on detailed kinetic mechanisms

For the optimization of a chemical reactor or its control, computational fluid dynamics (CFD) that considers accurate reaction models is effective. Although detailed kinetic mechanisms can accurately predict gas-phase reactions, integrating them with CFD is too computationally expensive. In contrast, global reactions have lower computational costs but significantly reduced accuracy outside of tuned conditions. This study proposes a method for constructing a model using a neural network to predict the reaction rate of water gas shift reaction based on detailed kinetic mechanisms. It includes techniques to avoid unrealistic solutions inherent to detailed kinetic mechanisms and methods to minimize biases in training data. The neural network input was log-transformed concentrations and inverse temperatures, and the output was the logarithm of the absolute value of the reaction rate and direction, enabling the prediction of bidirectional reactions over a wide temperature range. The quality of the dataset significantly impacted the accuracy of the neural network. Using a dataset with less bias in chemical species concentrations, the model achieved accuracy similar to detailed models while facilitating an over 400 times faster computation. The study also discussed the impact of temperature change rate, showing that at about 72 K/min, the detailed kinetic mechanism's solution can be accurately replicated. Still, at 720 K/min, the radical concentration deviates from the quasi-steady state, leading to discrepancies. This study opens up new possibilities for computational methods in the prediction and optimization of chemical reactions.

Modeling and experimental analysis of CO2 methanation reaction using Ni/CeO2 monolithic catalyst

In this study, the effect of the cell density of monolithic catalysts was investigated and further mathematically modeled on cordierite supports used in CO2 methanation. Commercial cordierite monoliths with 200, 400, and 500 cpsi cell densities were coated by immersion into an ethanolic suspension of Ni/CeO2 active phase. SEM–EDS analysis confirmed that, owing to the low porosity of cordierite (surface area < 1 m2 g−1), the Ni/CeO2 diffusion into the walls was limited, especially in the case of low and intermediate cell density monoliths; thus, active phase was predominantly loaded onto the channels’ external surface. Nevertheless, despite the larger exposed surface area in the monolith with high cell density, which would allow for better distribution and accessibility of Ni/CeO2, its higher macro-pore volume resulted in some introduction of the active phase into the walls. As a result, the catalytic evaluation showed that it was more influenced by increments in volumetric flow rates. The low cell density monolith displayed diffusional control at flow rates below 500 mL min−1. In contrast, intermediate and high cell density monoliths presented this behavior up to 300 mL min−1. These findings suggest that the interaction reactants-catalyst is considerably more affected by a forced non-uniform flow when increasing the injection rate. This condition reduced the transport of reactants and products within the catalyst channels and, in turn, increased the minimum temperature required for the reaction. Moreover, a slight diminution of selectivity to CH4 was observed and ascribed to the possible formation of hot spots that activate the reverse water–gas shift reaction. Finally, a mathematical model based on fundamental momentum and mass transfer equations coupled with the kinetics of CO2 methanation was successfully derived and solved to analyze the fluid dynamics of the monolithic support. The results showed a radial profile with maximum fluid velocity located at the center of the channel. A reactive zone close to the inlet was obtained, and maximum methane production (4.5 mol m−3) throughout the monolith was attained at 350 °C. Then, linear streamlines of the chemical species were developed along the channel.

Experimental assessment of reverse water gas shift integrated with chemical looping for low-carbon fuels

Chemical looping integrated with reverse water gas (CL-RWGS) shift is presented in this study using Cu-based oxygen carrier (OC) supported on Al2O3 has been used to convert the CO2 and H2 mixture stream into a syngas stream with a tailored H2 to CO ratio and relevant conditions. The results demonstrated consistent breakthrough curves during redox cycles, confirming the chemical stability of the material. In 10 consecutive cycles at 600 °C and 1 bar, bed temperatures increased by 184 °C and 132 °C across the bed during oxidation and reduction stages respectively. The cooling effects during RWGS showed a decline in solid temperatures demonstrating the effectiveness of the heat removal strategy while attaining a CO2-to-CO conversion close >48%. The outlet gas maintains a H2/CO ratio above 2, confirming the material's dual role as OC and catalyst. During complete CL-RWGS cycles, varying temperature from 500 °C to 600 °C at a constant H2/CO2 molar ratio (1.3) and pressure (1 bar) reduces the H2/CO molar ratio from 3.14 to 2.35, respectively with a remarkable continuous CO2-to-CO conversion > 40%. The decrease in H2/CO molar ratio with the increase in temperature is consistent with the expected results of equilibrium limited conditions. Additionally, in CL-RWGS cycles, pressure insignificantly affects product molar composition. The study showed the capability of Cu material in converting CO2 into syngas through the CL-RWGS technique.

Insights into Fischer–Tropsch catalysis: current perspectives, mechanisms, and emerging trends in energy research

Fischer–Tropsch (FT) synthesis is an important module for the production of clean and sustainable fuels and chemicals, making it a topic of considerable interest in energy research. This mini-review covers the current literature on FT catalysis and offers insights into the primary products, the nuances of the FT reaction, and the product distribution, with particular attention to the Anderson–Schulz–Flory distribution (ASFD) and known deviations from this fundamental concept. Conventional FT catalysts, particularly Fe- and Co-based catalysis systems, are reviewed, highlighting their central role and the influence of water and water–gas shift (WGS) activity on their catalytic behavior. Various mechanisms of catalyst deactivation are also investigated, and the high methanation activity of Co-based catalysts is illustrated. To make this complex field accessible to a broader audience, we explain conjectured reaction mechanisms, namely, the carbide mechanism and CO insertion. We discuss the complex formation of a wide range of products, including olefins, kerosenes, branched hydrocarbons, and by-products such as alcohols and oxygenates. The article goes beyond the traditional scope of FT catalysis by addressing topics of current interest, including the direct hydrogenation of CO2 for power-to-X applications and the use of bifunctional catalysts to produce tailored FT products, most notably for the production of sustainable aviation fuel (SAF). This mini-review provides a holistic overview of the evolving landscape of FT catalysts and is aimed at both experienced researchers and those new to the field while covering current and emerging trends in this important area of energy research.

Optimized Pt-Co Alloy Nanoparticles for Reverse Water-Gas Shift Activation of CO2.

Different Co contents were used to tune bimetallic Pt-Co nanoparticles with a diameter of 8 nm, resulting in Pt:Co ratios of 3.54, 1.51, and 0.96. These nanoparticles were then applied to the MCF-17 mesoporous silica support. The synthesized materials were characterized with HR-TEM, HAADF-TEM, EDX, XRD, BET, ICP-MS, in situ DRIFTS, and quasi in situ XPS techniques. The catalysts were tested in a thermally induced reverse water-gas shift reaction (CO2:H2 = 1:4) at atmospheric pressure in the 200-700 °C temperature range. All bimetallic Pt-Co particles outperformed the pure Pt benchmark catalyst. The nanoparticles with a Pt:Co ratio of 1.51 exhibited 2.6 times higher activity and increased CO selectivity by 4% at 500 °C. Experiments proved that the electron accumulation and alloying effect on the Pt-Co particles are stronger with higher Co ratios. The production of CO followed the formate reaction pathway on all catalysts due to the face-centered-cubic structure, which is similar to the Pt benchmark. It is concluded that the enhanced properties of Co culminate at a Pt:Co ratio of 1.51 because decreasing the ratio to 0.96 results in lower activity despite having more Co atoms available for the electronic interaction, resulting in the lack of electron-rich Pt sites.

Alkali treatment modulated borate anions in layered double hydroxides as precursors of highly efficient Au-based catalysts for water-gas shift reaction

Layered double hydroxides (LDHs) as an adjustable layered materials were considered as good candidates for the supports of water-gas Shift (WGS) catalysts. However, there is rare report about the exfoliation preparation and WGS application of LDHs containing BO33− as intercalated anions. Herein, we reported a mild alkali treatment modulation of the intercalated borate anions in LDHs for improving the WGS catalytic performance of Au-based catalysts. Compared with inactive Au supported LDHs without alkali treatment, the moderate alkali treatment consumes intercalated BO33− anions in LDHs, arousing the WGS activities of Au-based catalysts. Among the different alkali treatment concentration, Au-LDHs-1M treated with 1 M NaOH present the highest WGS activity and excellent stability with a reduction of only 10 % for 60 h. The moderate alkali treatment promotes the exfoliation of LDHs into nanosheets covered Co3O4 small nanoparticles, which facilitated the high dispersion of Au species and also easily converted into active Fe3O4 and metallic Co phases. While Au-LDHs-5M presents such large Au particles that it exhibits low activity, and Au-LDHs-0M is inactive due to the formation of B2O and Fe23B6 poison phases for the WGS reaction.

Mo-based bimetallic oxide catalysts for the reverse water gas shift reaction

The reverse water gas shift (RWGS) is of great significance to the resource utilization of CO2. In this paper, based on the features of MoO3, the Mo-based catalysts doped with Ga, Ti and Ce were prepared, and the effects of oxygen vacancies and basic sites on the RWGS reaction were studied. When the volume ratio of H2 and CO2 is 1 : 1, the yield of CO can reach 26.66%. Because it exposes higher concentration of Ce sites and moderate alkaline active sites on the surface. When the proportion of H2 in the reaction gas increases, the highest yield of CO can reach 54.53%, which is mainly attributed to a large number of oxygen vacancies on the surface of MoTi. This study can be used as a reference for the design of catalysts for RWGS reaction under different reaction conditions.

Highly Efficient Layered Double Hydroxide-Derived Bimetallic Cu–Co Alloy Catalysts for the Reverse Water–Gas Shift Reaction

Highly Efficient Layered Double Hydroxide-Derived Bimetallic Cu–Co Alloy Catalysts for the Reverse Water–Gas Shift Reaction

On the benefits of Counter-Current regeneration on a partial pressure swing Adsorptive reactor (PPSAR) with application to the Water Gas Shift reaction

This work demonstrates the benefits of carrying out counter-current over co-current regeneration during the operation of a Partial Pressure Swing Adsorptive Reactor with application to the Water Gas Shift reaction. Our previously introduced dynamic, multidomain, multiscale model is used to compare two theoretical case studies employing co-current and counter-current regeneration modes, respectively. The process conditions for the two regeneration case studies remain identical apart from the employed regeneration modality. This allows for the elucidation of the process performance benefits arising solely from the adaptation of the employed regeneration mode.

Intensification of the CO2-capturing methanol steam reforming process: A comprehensive analysis of energy, economic and environmental impacts

The methanol (MeOH) steam reforming (MSR) process plays an important role in the MeOH-based international renewable energy supply chain. To address the challenges related to the high cost and substantial CO2 emissions linked to the state-of-the-art integrated MSR process, this study aims to propose and enhance an intensified MSR process focusing on energy utilization, economic viability and environmental impact. Aside from the MSR process, the overall scenario also includes the water–gas-shift reaction (WGS) process, CO2 capture using amine-based methods, liquefaction, and hydrogen purification through pressure-swing adsorption. Based on this study, apparent enhancements of the state-of-the-art MSR process can be achieved by adjusting key process variables, especially those related to the CO2 capture process, and by incorporating various intensification strategies, including heat integration (with feed-effluent heat exchangers) between the MSR and the WGS processes, implementing a side-draw intercooling structure of the CO2 absorber, splitting the rich solvent flow to the CO2 stripper, and employing a multi-stage CO2 stripper with vapor recompression. Compared to the state-of-the-art MSR process in the literature, the intensified MSR process produces ultra-pure hydrogen (99.99 mol%) as a main product while reduces 6.2 % of the shared cost (from 191.0 USD/t-MeOH to 179.1 USD/t-MeOH), increases the overall carbon capture rate by 3 % (from 86.73 % to 89.99 %), and reduces the direct CO2 emission by approximately 25 % (from 1.41 t-CO2/ t-MeOH to 1.06 t-CO2/ t-MeOH). Within a MeOH-based international renewable energy supply chain, these enhancements can also significantly lower the imported cost of electricity from 105.9 USD/MWh to 95.5 USD/MWh.

Pt Molecularly Defined Precursors to Tune Particle Size and Speciation: Impact on the Reverse Water Gas Shift Reaction

Pt Molecularly Defined Precursors to Tune Particle Size and Speciation: Impact on the Reverse Water Gas Shift Reaction

Revealing the effect of synthetic method on integrated CO2 capture and conversion performance of Ni-Na2ZrO3 bifunctional materials

Integrated CO2 capture and utilization by reverse water gas shift (ICCU-RWGS) reaction for syngas production for C1 chemical industry has gained increasing attention. Designing highly active bifunctional materials that enables CO2 adsorption and in-situ conversion is essential. In this work, Ni-Na2ZrO3 bifunctional materials are prepared by different synthetic methods for ICCU-RWGS. N2 physisorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), CO2 temperature-programmed desorption (CO2-TPD) and H2 temperature-programmed reduction (H2-TPR) analysis reveals that Ni-Na2ZrO3-CP prepared by the co-precipitation (CP) method shows small Ni crystalline size, moderate surface basicity, and excellent reducibility. ICCU-RWGS performance is investigated under isothermal conditions of 650 °C, 10 %CO2 and 35 %H2. The results indicate that Ni-Na2ZrO3-CP demonstrates excellent performance in ICCU-RWGS, with a notable CO2 capture capacity of 3.76 mmol CO2/g and a CO production rate of 3.10 mmol CO/g. Additionally, it exhibits relatively good operational stability. Detailed reaction paths of the ICCU-RWGS procedure for the Ni-Na2ZrO3 bifunctional materials are proposed. The findings will shed new perspectives on the design of synthetic bifunctional catalysts for ICCU-RWGS.

Unlocking the Potential of Cu/Ti3C2Tx MXene Catalyst in Plasma Catalytic CO2 Hydrogenation

Plasma catalytic CO2 hydrogenation has emerged as a promising approach for converting CO2 into valuable chemicals such as CO, offering a potential solution to mitigate greenhouse gas emissions. In this study, we investigate the synergistic effect between plasma and a Cu/Ti3C2Tx MXene catalyst for CO2 hydrogenation via the reverse water gas shift (RWGS) reaction in a dielectric barrier discharge (DBD) reactor. Our findings reveal a significant enhancement in CO2 conversion (33.1%) and CO yield (31.9%) when using the Cu/Ti3C2Tx catalyst compared to plasma alone or with a Ti3C2Tx foam. Plasma treatment creates unsaturated Ti sites on the Ti3C2Tx surface, dramatically improving CO2 adsorption and activation, while Cu nanoparticles significantly enhances the activation and dissociation of H2 molecules on the catalyst surface. These surface adsorbed hydrogen species readily hydrogenate adsorbed CO2 molecules through the Langmuir-Hinshelwood mechanism. Furthermore, these surface hydrogen species can also participate in the conversion of gas-phase CO2 molecules through the Eley-Rideal pathway. This work sheds light on the synergistic plasma catalytic mechanism and provide insights for optimizing CO2 hydrogenation processes using MXene catalysts.

In situ/operando spectroscopic evidence on associative redox mechanism for periodic unsteady-state water–gas shift reaction on Au/CeO2 catalyst

Cyclic and repeatable CO2/H2 formation under periodic CO ↔ H2O feeds, that is unsteady-state water–gas shift reaction (uss-WGS), was found to be catalyzed by a gold nanoparticles-loaded CeO2 (Au/CeO2) catalyst. Kinetics of the CO-reduction of Ce4+ to Ce3+ and Ce3+ reoxidation by H2O in combination with transient CO2/H2 formation over Au/CeO2 were studied by operando ultraviolet–visible (UV–vis) and infrared (IR) spectroscopies at 175 °C. The Ce4+–OH species were reduced by CO to give Ce3+-□-Ce3+ (□: oxygen vacancy) and gas phase products (H2, CO2). The Ce3+-□-Ce3+ species were oxidized by H2O to give H2 and Ce4+–OH species. The reduction and reoxidation rates of Ce4+/Ce3+ redox couple were close to the rates of transient CO2/H2 formation. The X-ray absorption spectroscopy results showed that the oxidation states of Au remained unchanged during the redox reactions. These results indicate that the uss-WGS is primary driven by the Ce4+/Ce3+ redox couple. Combined with the observation of adsorbed carboxylate intermediates as a precursor of H2 and CO2, associative redox mechanism is proposed as the main pathway for the unsteady-state WGS reaction on Au/CeO2 at 175 °C.

Enhanced CO2 capture and reverse water gas shift reaction using CaO in NaCl-CaCl2 molten salt medium

This study introduces an Integrated Carbon Capture and Utilisation-Reverse Water Gas Shift (ICCU-RWGS) approach, a novel method for in situ CO2 adsorption and conversion, leveraging the synergistic effects of CaO within a NaCl-CaCl2 molten salt blend to enhance CO2 capture and conversion efficiency. Building upon this foundation, we optimize CaO concentration and operating temperature to maximize CO2 uptake and conversion performance. The research focuses on integrating CaO with a NaCl-CaCl2 molten salt blend (mass ratio 4:6) to improve CO2 sorption and conversion performance. Findings show significant enhancements in CO2 uptake and CO yield with the presence of molten salt compared to systems without it. The optimal operating temperature and CaO concentration are identified for maximum CO yield. Characterisation techniques like in-situ infrared spectroscopy, XRD, and SEM provide insights into the behavior of CaO in the molten salt, revealing the solubility of the partial carbonate formed from CO2 and CaO, dispersion of CaO particles, and their morphological characteristics. Overall, the study demonstrates the potential of CaO-molten salt integration in improving ICCU-RWGS process efficiency and contributes to the development of more effective and sustainable ICCU technologies.

Reverse water gas-shift reaction product driven dynamic activation of molybdenum nitride catalyst surface

In heterogeneous catalysis catalyst activation is often observed during the reaction process, which is mostly attributed to the induction by reactants. In this work we report that surface structure of molybdenum nitride (MoNx) catalyst exhibits a high dependency on the partial pressure or concentration of reaction products i.e., CO and H2O in reverse water gas-shift reaction (RWGS) (CO2:H2 = 1:3) but not reactants of CO2 and H2. Molybdenum oxide (MoOx) overlayers formed by oxidation with H2O are observed at reaction pressure below 10 mbar or with low partial pressure of CO/H2O products, while CO-induced surface carbonization happens at reaction pressure above 100 mbar and with high partial pressure of CO/H2O products. The reaction products induce restructuring of MoNx surface into more active molybdenum carbide (MoCx) to increase the reaction rate and make for higher partial pressure CO, which in turn promote further surface carbonization of MoNx. We refer to this as the positive feedback between catalytic activity and catalyst activation in RWGS, which should be widely present in heterogeneous catalysis.