Water Gas Shift Research Articles

Enhanced Oxygen Vacancy Formation in CeO2-Based Materials and the Water–Gas Shift Performance

Enhanced Oxygen Vacancy Formation in CeO2-Based Materials and the Water–Gas Shift Performance

Atomistic Insights Into the Surface Dynamics of Ni(111) During Reverse Water gas Shift Reaction

AbstractThe conversion of CO2‐H2 mixtures on Ni‐based catalysts can proceed through either the reverse water gas shift reaction (RWGS) path to produce CO or the CO2 methanation path to produce CH4. The balance between these competing reactions depends on both the reaction conditions and catalyst structure. In this study, using surface‐sensitive infrared and ambient pressure X‐ray photoelectron spectroscopies, we investigate the effect of reaction conditions on the interaction between CO2 and H2 on a Ni(111) model catalyst. Our findings highlight the occurrence of RWGS, involving direct dissociation of CO2 to CO and atomic oxygen, followed by oxygen reacting with hydrogen to form H2O, and CO and H2O desorption. Hydrogen affects the distribution of CO between hollow and top sites by displacing oxygen from the energetically preferred hollow sites. The overall balance between oxygen production from CO2 dissociation and oxygen removal by hydrogen governs the oxygen coverage and consequently the distribution of CO between top and hollow sites. This balance is significantly influenced by the reaction temperature and the H2/CO2 partial pressures.

Integrated solar system for hydrogen production using steam reforming of methane

Integrating renewable technologies has emerged as a promising option in pursuing sustainable and efficient energy solutions. The primary source of industrial hydrogen is steam methane reforming (SMR); however, this process is based on fossil fuels with massive carbon byproduct emissions. The solar thermal tower appears to be a suitable renewable source for powering SMR by providing high temperature heat to drive the process reactions. This approach aims to harness the abundance of solar energy for natural gas reforming to produce hydrogen at minimum environmental impact. This research establishes the viability of combining external central receiver concentrated solar power with SMR integrated with thermal energy storage (TES), revealing general insights into the system energy and exergy performance. The analysis of the current system is performed using the thermodynamic and thermochemical approaches to conduct a parametric study. A 543 MW central receiver is first modeled with a high-temperature molten salt as a working fluid. The SMR process model is then developed, considering both reforming and shift reactions, and solved using Engineering Equation Solver (EES). The subsystem models are validated before being integrated into the overall system model. The performance of the SMR reactor is found to affect the overall system performance considerably. The results also show that when increasing the temperature above 760 ° C, no remarkable improvement in the reforming process is observed. In contrast, the higher the temperature in the water gas shift reactor, the lower the system's performance. Moreover, the impact of wind velocity on the overall system is considered due to the large central receiver surface area. The overall system performance in terms of energy, exergy, and effectiveness is evaluated for one day of operating through charging and discharging operations. In charging mode, the overall energy and exergy efficiencies are 46.5% and 57.2%, respectively, while the overall effectiveness is 61.8%; on the discharging operation, the overall energy efficiency and effectiveness have a similar definition with a value of 82.4% and the overall exergy efficiency achieves a value of 78.7%. Additionally, the amount of hydrogen produced at a central receiver of 543 MWth capacity is about 7.3 kg/s at a 2.1 steam-to-carbon ratio. This integration mitigates a minimum of 12 kg/s of CO2 emissions that would be generated due to methane combustion.

CFD modeling of a mini-pilot scale CO2 hydrogenation to hydrocarbons reactor using both direct and indirect pathway-based kinetic model

Both indirect CO2 hydrogenation (reverse water gas shift (RWGS) followed by CO-based Fischer-Tropsch synthesis (FTS)) and direct CO2-based FTS were considered for CO2 hydrogenation, and a kinetic model for the chain-length distribution of hydrocarbon products was developed. For independent estimation, the kinetic parameters were estimated by fitting the experimental data using powder catalysts under various conditions, mainly including CO/CO2 ratios. The contribution of indirect CO2 hydrogenation (RWGS followed by CO-FTS) was more favorable than that of direct CO2-FTS, and CO2 conversion and product selectivity were significantly dependent on the temperature and hydrogen fraction. The effectiveness factor was estimated for the pellet-type catalysts, and values less than one validated the existence of mass-transfer resistance. Computational fluid dynamics (CFD) modeling was used to simulate the three-dimensional thermal behaviors of a mini-pilot-scale reactor with a substantially large diameter loaded with a pellet-type catalyst and inert materials. Both a low catalyst loading in the early stage of the reactor and the use of an additional inner cooling tube showed a stable temperature profile, with the peak temperature maintained below 350 °C (the critical temperature to prevent the thermal decomposition of chemicals) and fast heating of cold feed in the early stage. The CFD results with no inner tube showed thermal runaway in the second reactor, and the simulation with arbitrarily reduced heat of the reaction (70 % of the actual value) resulted in a peak temperature higher than 410 °C. Further quantitative analysis indicated that the no-inner-tube case's reduced heat transfer area per unit volume was responsible for its thermally unstable behavior.

Nickel and Iron Biocarbon Catalysts for Water-Gas Shift Reaction

Nickel and Iron Biocarbon Catalysts for Water-Gas Shift Reaction

Temperature effects on chemical reactions and product yields in the Co-pyrolysis of wood sawdust and waste tires: An experimental investigation

This study investigates the effects of varying temperatures on the co-pyrolysis of wood sawdust (WS) and waste tires (WT) within a stainless steel fixed-bed reactor under a nitrogen atmosphere. The experiments were conducted at three different temperatures: 400 °C, 500 °C, and 600 °C, focusing on the thermal behavior and resultant product yields. At 600 °C, WS produced the highest oil yield (63.6 wt%), suggesting a tendency to generate more aqueous and volatile components. Conversely, WT alone showed an optimal oil yield of 46.4 wt% at 500 °C, while the WS-WT blend achieved 55.6 wt%. Gas chromatography-mass spectrometry (GC-MS) analyses of the pyrolytic oils indicated that WS-heavy mixtures were rich in aliphatic compounds, whereas WT-dominant samples had increased aromatic and phenolic contents, demonstrating the potential for creating valuable chemicals from waste. Additionally, gas analysis highlighted significant variations in syngas composition, with increased methane and decreased CO2 levels at higher temperatures, emphasizing the role of the water-gas shift reaction. These findings underscore the critical importance of temperature control in optimizing the efficiency and quality of products from co-pyrolysis, presenting a viable method for enhancing the value derived from waste materials.

Surface oxygen vacancy regulation and active metal doping for Cu-Al based spinel catalysts synthesis toward high-efficiency reverse water-gas shift reaction

The reverse water-gas shift (RWGS) reaction is of great significance to convert CO2 to valuable feedstocks. Reasonable design and preparation of catalysts is necessary to achieve high CO2 conversion and CO selectivity. In this study, a series of Cu-Al based spinel catalysts were synthesized by coprecipitation-calcination method or A-site doped with active metal (Co, Zn, Mg, and Fe) for the RWGS reaction. The results indicated that the surface oxygen vacancies and crystal structure of CuAl2O4 can be regulated by calcination temperature. Remarkably, the CuAl-800 catalyst exhibits the highest CO2 conversion rate (62.7 %) with 100 % CO selectivity at 500 °C. Excessive calcination temperatures (> 800 °C) resulted in a well-defined spinel structure, but decreased surface oxygen vacancies and CO2 conversion rate. At calcination temperatures < 800 °C, surface oxygen vacancies increased, but the formation of CuO impurities which irreversibly converted to Cu2O during reduction, decreased catalytic activity. Compared with Zn, Mg and Fe, Co doping can significantly improved the reactivity of CuAl2O4 catalyst in RWGS reaction at 500 °C, increasing the CO2 conversion rate by 8 % while maintaining 100 % CO selectivity. The main reason is that Co doping not only effectively improves the integrity and stability of spinel structure of CuAl2O4, but also enhances its ability to dissociate and activate H species through interfacial sites of CuO-OV-CuXCo1-XAl2O4, thus further enhancing its catalytic conversion ability of CO2 to CO. These results enrich the understanding of surface chemistry of CuAl2O4 spinel and lay an important theory foundation for design of spinel-based catalysts for RWGS reaction.

Integration of an Autothermal Outer Electrified Reformer Technology for Methanol Production from Biogas: Enhanced Syngas Quality Production and CO2 Capture and Utilization Assessment

Biogas has emerged as a valid feedstock for biomethanol production from steam reforming. This study investigates an alternative layout based on an auto-thermal electrified reforming assuming a 1 MW equivalent anaerobic digestion plant as a source for methanol synthesis. The process considers an oxy-steam combustion of biogas and direct carbon sequestration with the presence of a reverse water–gas shift reactor to convert CO2 and H2 produced by a solid oxide electrolyzer cell to syngas. Thermal auto-sufficiency is ensured for the reverse water–gas shift reaction through the biogas oxy-combustion, and steam production is met with the integration of heat network recovery, with an overall process total electrical demand. This work compares the proposed process of electrification with standard biogas reforming and data available from the literature. To compare the results, some key performance indicators have been introduced, showing a carbon impact of only 0.04 kgCO2/kgMeOH for the electrified process compared to 1.38 kgCO2/kgMeOH in the case of biogas reforming technology. The auto-thermal electrified design allows for the recovery of 66.32% of the carbon available in the biogas, while a similar electrified process for syngas production reported in literature reaches only 15.34%. The overall energy impact of the simulated scenarios shows 94% of the total energy demand for the auto-thermal scenario associated with the electrolyzer. Finally, the introduction of the new layout is taken into consideration based on the country’s carbon intensity, proving carbon neutrality for values lower than 75 gCO2/kWh and demonstrating the role of renewable energies in the industrial application of the process.

Modeling and design of a combined electrified steam methane reforming-pressure swing adsorption process

Steam methane reforming (SMR) is the most widely used hydrogen (H2) production method, converting natural gas and steam into H2 and carbon dioxide (CO2). SMR is a mature industrial technology that burns fossil fuels to provide heat to the endothermic reforming reaction and to generate steam, which contributes to the production of greenhouse gas emissions. In order to reduce heating-based emissions, an electrically-heated steam methane reforming process has been proposed. Conventional SMR uses a packed bed catalyst and receives heat through radiation from hot flames in the surrounding furnace; on the other hand, an electrified SMR employs a washcoated catalyst, and is resistively-heated through the wall of the reactor coil. To gain further insight into the scalability of hydrogen production processes using electrically-heated reformers, this paper takes experimental data from an electrified reformer built at UCLA, extracts kinetic parameters, and uses these parameters to model and scale up a hydrogen production plant with a hydrogen production capacity of 231 kg/h (2607 Nm3/h). The simulated plant includes a reformer, two water gas shift reactors, pressure swing adsorption (PSA) for separation, and a heat exchange network to make steam for the reformer. A two-column-PSA process is dynamically modeled to output 99% H2 purity, and the pressures necessary for separation and H2 recovery are calculated using steady-state simulation data. A sensitivity analysis is conducted for the most energy-efficient H2 production conditions (e.g., operating pressure, heat flux), and CO2 production amounts are compared to a conventional SMR process, demonstrating that electrified SMR can potentially be a significantly cleaner alternative. The optimization of electrified reformers must target high mass and heat transfer along the full length of the reformer to achieve near full methane conversion that will minimize off-gas generation from the PSA unit.

Magnetic capacity in manganese sulfides with rare earth substitution Mn&lt;sub&gt;1–x&lt;/sub&gt;Re&lt;sub&gt;x&lt;/sub&gt;S

Polycrystalline samples Mn1–xGdxS and Mn1–xYbxS with a concentration x = 0.2, near the concentration of ion flow through the fcc lattice, are studied in order to determine fluctuations in the valence of the ytterbium ion on dielectric properties. Dielectric constant and dielectric losses were determined from measurements of capacitance and loss tangent in the frequency range 102–106 Hz at temperatures of 80–500 K without a magnetic field and in a magnetic field. The magnetic capacity and dielectric losses in the magnetic field of the sample were determined from the relative change in the real and imaginary parts of the dielectric constant of the sample in a magnetic field H = 12 kOe applied parallel to the capacitor plates. A temperature range with a sharp increase in dielectric constant and with a maximum dielectric loss has been discovered, which shifts with increasing frequency and magnetic field. An increase in dielectric constant and dielectric losses in a magnetic field above 170 K was found in Mn1-xYbxS. The increase in dielectric losses is explained by an increase in relaxation time, as a result of local deformations near ytterbium ions during valence fluctuations. The mechanism for reducing reactance in a magnetic field in Mn1–xYbxS at low frequencies due to capacitance, and at high frequencies due to inductance, has been determined. In the Mn0.8Gd0.2S compound, the imaginary part of the dielectric constant has two maxima. The low-temperature maximum shifts in a magnetic field towards high temperatures and is described in the model of localized electrons with freezing of dipole moments. Dielectric losses decrease in a magnetic field. The magnetic capacity decreases by an order of magnitude in Mn0.8Gd0.2S compared to Mn0.8Yb0.2S. The dielectric constant in both compounds is described in the Debye model with the activation dependence of the relaxation time on temperature, where the activation energies differ for ytterbium and gadolinium ions.

Silicate minerals enable the efficient photocatalytic RWGS reaction

Silicate minerals are the most abundant minerals on Earth’s crust and can originate from rock-forming minerals with the low risk to the environment. Herein, the chain pyroxene mineral NaFeSi2O6 nanosheets loaded with highly dispersed Cu nanoparticles have been used as an archetype platform for the efficient photocatalytic reverse water gas shift (RWGS) reaction. The resultant Cu/NaFeSi2O6 catalyst demonstrated high performance metrics in the gas-phase photocatalytic hydrogenation of CO2 to CO, with a yield as high as 13144 μmol gcat–1 h–1. It is shown that the coordinately unsaturated Fe atom in NaFeSi2O6 can serve as a robust Lewis acid site for adsorbing and activating CO2 molecules, while the metal/support interface facilitates the formation of intermediate species and the subsequent production of CO products through hydrogen spillover. The surface plasmon resonance (SPR) effect of Cu further promotes the injection of hot electrons into NaFeSi2O6 and the carrier separation and migration at the Schottky heterojunction. This low-cost and earth-abundant mineral-based catalyst exhibits 100 h of long-term photocatalytic stability, indicating its potential as a promising and feasible candidate for the future development of renewable synthetic fuels.

Electrification pathways for sustainable syngas production: A comparative analysis for low-temperature Fischer-Tropsch technology

The electrification of chemical processes holds promise for a sustainable and climate-neutral chemical industry. This study explores pathways for electrifying syngas production, targeting its utilization in low-temperature Fischer-Tropsch (LT-FT) technology with a hydrocarbon production capacity of 222 kton/yr. Three electrified scenarios are juxtaposed against a reference case of autothermal reforming of biomethane. In the first two scenarios, H2 is produced via water electrolysis, with CO obtained either through CO2 electrolysis (Electrolysis case) or electrified reverse water-gas shift (E-rWGS case). The third scenario leverages captured CO2 and biomethane for electrified combined steam and dry reforming of methane (CSDRM case), exhibiting the lowest net emissions of 0.50 tonCO2/tonproduct. All electrified scenarios achieve net negative emissions under the EU's 2030 target of 40% overall renewable energy production. A detailed techno-economic analysis reveals significant feasibility challenges with the Electrolysis, E-rWGS, and CSDRM cases exhibiting a Levelized Cost Of Production (LCOP) of $501, $457, and $251 per barrel (bbl) of Fischer-Tropsch crude, respectively. Future projections suggest considerable capital cost reductions for electrolyzers, potentially rendering the Electrolysis case feasible, particularly under extremely low electricity prices of 3.3 $/MWh. Careful consideration of green electricity and CO2 utilization scenarios is vital for implementing CO2-negative technologies effectively.

Pt single atoms in oxygen vacancies boost reverse water-gas shift reaction by enhancing hydrogen spillover

Pt single atoms in oxygen vacancies boost reverse water-gas shift reaction by enhancing hydrogen spillover

Utilizing Limestone Alone for Integrated CO2 Capture and Reverse Water-Gas Reaction in a Fixed Bed Reactor: Employing Mass and Gas Signal Analysis

The integrated CO2 capture and utilization coupled with the reverse water-gas shift reaction (ICCU-RWGS) presents an alternative pathway for converting captured CO2 into CO in situ. This study investigates the effectiveness of three calcium-based materials (natural limestone, sol-gel CaCO3, and commercial CaCO3) as dual-functional materials (DFMs) for the ICCU-RWGS process at intermediate temperatures (650–750 °C). Our approach involves a fixed-bed reactor coupled with mass spectrometry and in situ Fourier transform infrared (FTIR) measurements to examine cyclic CO2 capture behavior, detailed physical and chemical properties, and morphology. The in situ FTIR results revealed the dominance of the RWGS route and exhibited self-catalytic activity across all calcium-based materials. Particularly, the natural limestone demonstrated a CO yield of 12.7 mmol g−1 with 100% CO selectivity and 81% CO2 conversion. Over the 20th cycle, a decrease in CO2 capture capacity was observed: sol-gel CaCO3, natural limestone, and commercial CaCO3 showed reductions of 44%, 61%, and 59%, respectively. This suggests inevitable deactivation during cyclic reactions in the ICCU-RWGS process, while the skeleton structure effectively prevents agglomeration in Ca-based materials, particularly in sol-gel CaCO3. These insights, coupled with the cost-effectiveness of CaO-alone DFMs, offer promising avenues for efficient and economically viable ICCU-RWGS processes.

Tracking the dynamics of catalytic Pt/CeO2 active sites during water-gas-shift reaction

Understanding the atomistic structure of the active site during catalytic reactions is of paramount importance in both fundamental studies and practical applications, but such studies are challenging due to the complexity of heterogeneous systems. Here, we use Pt/CeO2 as an example to study the dynamic nature of active sites during the water-gas-shift reaction (WGSR) by combining multiple in situ characterization tools. We show that the different concentrations of interfacial Ptδ+ – O – Ce4+ moieties at Pt/CeO2 interfaces are responsible for the rank of catalytic performance of Pt/CeO2 catalysts: Pt/CeO2-rod > Pt/CeO2-cube > Pt/CeO2-oct. For all the catalysts, metallic Pt is formed during the WGSR, leading to the transformation of the active sites to Pt0 – Ov – Ce3+ and interface reconstruction. These findings shed light on the nature of the active site for the WGSR on Pt/CeO2 and highlight the importance of combining complementary in situ techniques for establishing structure-performance relationships.

Theoretical and experimental investigations on single-atom catalysis: Pt1/FeOx for water–gas shift reaction

Theoretical and experimental investigations on single-atom catalysis: Pt1/FeOx for water–gas shift reaction

Graphene-Based Material Supports for Ni- and Ru- Catalysts in CO2 Hydrogenation: Ruling out Performances and Impurity Role.

Laboratory-prepared Gnp using molten salt, commercial Gnp and reduced graphene oxide (rGO) have been characterized and utilized as support for CO2 hydrogenation catalysts. Ni- and Ru- catalysts supported over Gnp, commercial Gnp and rGO have been deeply characterized at different stages using Raman, IR, XRD, FE-SEM-EDXS, SEM-EDXS, XPS, and TEM, also addressing carbon loss before reaction and evolved species, thus allowing a better comprehension of the produced materials. Ni and Ru/rGO were inactive while Gnp-supported ones were active. Ru has been found almost completely selective toward reverse Water Gas Shift to CO, approaching the forecasted thermodynamic equilibrium at 723 K, in the tested conditions (YCO~55 %), with an apparent activation energy in the range of 70-90 kJ/mol. Exhaust catalysts pointed out the presence of sulfur partially linked to the carbon matrix and partially producing the corresponding metal sulfide with the detection of surface oxidized species in the cationic form and adsorbed species as well. The metal-based nanoparticles displayed a quite narrow size distribution, confirming the promising behavior of these catalytic systems for CO2 utilization.

CeO2-Supported Single-Atom Cu Catalysts Modified with Fe for RWGS Reaction: Deciphering the Role of Fe in the Reaction Mechanism by In Situ/Operando Spectroscopic Techniques.

Reverse water-gas shift (RWGS) reaction has attracted much attention as a potential approach for CO2 valorization via the production of synthesis gas, especially over Fe-modified supported Cu catalysts on CeO2. However, most studies have focused solely on investigating the RWGS reaction over catalysts with high Cu and Fe loadings, thus leading to an increase in the complexity of the catalytic system and, hence, preventing the gain of any reliable information about the nature of the active sites and reaction mechanism. In this work, a CeO2-supported single-atom Cu catalyst modified with iron was synthesized and evaluated for the RWGS reaction. The catalytic results reveal a significant synergistic effect between CuCeO2 and Fe, demonstrating an activity up to three times higher than the combined catalytic activities of monometallic catalysts (Fe/CeO2 + CuCeO2) under identical conditions. Various ex situ and in situ/operando techniques are employed to unveil the concealed role of Fe in catalyst activity enhancement. The combined findings from hydrogen temperature-programmed reduction (H2-TPR) and operando electron paramagnetic resonance spectroscopy (EPR) reveal that the added Fe predominantly interacts with Cu-containing surface sites, resulting in the stabilization of higher proportions of Cu single sites. Near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and operando EPR results unveil a synergistic interplay of Fe with Cu-containing sites and CeO x domains, efficiently enhancing both the reoxidation of Cu+ in Cu+-Ov-Ce3+ moieties and the reducibility of Ce4+ in CeO x domains under RWGS conditions. Detailed mechanistic studies reveal that the RWGS reaction predominantly proceeds via the redox mechanism.

Direct reduction of calcium carbonate by coupling with methane dry reforming using NiO/S-1 as catalyst

Thermal decomposition of carbonate is an important process in the production of cement, refractory materials, and steel. Nevertheless, this process requires high temperature and is always accompanied with large amounts of CO2 emission. To reduce the decomposition temperature and simultaneously mitigate CO2 emissions, direct reduction of carbonate under a reducing atmosphere has been proposed as a novel strategy. This work mainly investigated the feasibility of direct reduction of CaCO3 by CH4 in the presence of a highly dispersed NiO/S-1 catalyst. It was found that the introduction of a CH4 atmosphere without a catalyst had little promotion effect on CaCO3 decomposition (as compared to air atmosphere), and no notable conversion of CO2 was observed. However, the presence of a highly dispersed NiO/S-1 catalyst significantly decreased the decomposition temperature of CaCO3 in a CH4 atmosphere, and most of the carbon species in CaCO3 can be converted to CO. To gain a comprehensive understanding of CaCO3 reduction in CH4, the effects of reaction temperature, CH4 concentration, and NiO loading in the NiO/S-1 catalyst were systematically explored. With the best-performing catalyst, i.e., 7NiO/S-1, complete CaCO3 decomposition and approximate 90 % CH4/CO2 conversion can be achieved under the condition of 750 °C and 25 vol% CH4. Characterization results indicated that the CaO particles obtained in the CH4 reducing atmosphere exhibited a more porous structure compared to that attained in air, due to the more intensive CaCO3 decomposition in CH4. Further data analysis revealed that reverse water-gas shift reaction also contributed to CO2 conversion during the reduction of CaCO3 in CH4. The findings obtained in this research can provide new perspectives for CO2 emission control and energy saving in traditional heavy-emission and high energy consumption industries.

Supported Inverse MnOx/Pt Catalysts Facilitate Reverse Water Gas Shift Reaction

Catalytic conversion of CO2 to CO via the reverse water gas shift (RWGS) reaction has been identified as a promising approach for CO2 utilization and mitigation of CO2 emissions. Bare Pt shows low activity for the RWGS reaction due to its low oxophilicity, with few research works having concentrated on the inverse metal oxide/Pt catalyst for the RWGS reaction. In this work, MnOx was deposited on the Pt surface over a SiO2 support to prepare the MnOx/Pt inverse catalyst via a co-impregnation method. Addition of 0.5 wt% Mn to 1 wt% Pt/SiO2 improved the intrinsic reaction rate and turnover frequency at 400 °C by two and twelve times, respectively. Characterizations indicate that MnOx partially encapsulates the surface of the Pt particles and the coverage increases with increasing Mn content, which resembles the concept of strong metal–support interaction (SMSI). Although the surface accessible Pt sites are reduced, new MnOx/Pt interfacial perimeter sites are created, which provide both hydrogenation and C-O activation functionalities synergistically due to the close proximity between Pt and MnOx at the interface, and therefore improve the activity. Moreover, the stability is also significantly improved due to the coverage of Pt by MnOx. This work demonstrates a simple method to tune the oxide/metal interfacial sites of inverse Pt-based catalyst for the RWGS reaction.