High-temperature Water Gas Shift Reaction Research Articles

Investigating the effects of synthesis parameter on textural and catalytic properties of ZnO-CuO-Al2O3-Cr2O3 mixed oxide in water gas shift reaction

The present study has investigated the influence of preparing conditions, including aging temperature and time, pH, and Tcalcination, on the co-precipitated ZnO-CuO-Al2O3-Cr2O3 mixed oxide at a high-temperature water gas shift reaction. XRD, BET, FTIR, TG-DTA, SEM, TEM, and H2-TPR were used to characterize the relationships between the synthesis parameters and the physicochemical features. The investigation proved that the activity in aging 5 h could be related to higher pore volume and lower crystalline size of 0.24 cm3g-1 and 6.4nm, respectively. Also found that increasing the aging temperature to 60°C results in a rise in the surface area and particle size of less than 6nm, enhancing the catalyst activity. The findings showed that raising the Tcalcination reduced the surface area from 132 to 65m2 g-1. It has been concluded that the CO conversion of 70% was obtained at a pH of 10 when aged at 60°C for 5 hours and calcination temperature of 400°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

Enhanced activity of bimetallic Fe-Cu catalysts supported on ceria toward water gas shift reaction: synergistic effect

Within the “hydrogen chain”, the hight-emperature water gas shift reaction represents a key step to improve the H2 yield and adjust the H2/COx ratio to fit the constraints of downstream processes. Despite the commercial application of the high-temperature water gas shift, novel catalysts characterized by higher intrinsic activity (especially at low temperatures), good thermal stability, and no chromium content are needed. In this work, we propose bimetallic iron-copper catalysts supported on ceria, characterized by low active phase content (iron oxide + copper oxide < 5 wt %). Fresh and used samples were characterized by inductively coupled plasma mass spectrometry, X-ray diffraction, nitrogen physisorption, scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy, and temperature programmed reduction in hydrogen to relate physicochemical features and catalytic activity. The sample with iron/copper ≈ 1 and 4 wt % active phase content showed the best catalytic properties in terms of turnover frequency, no methane formation, and stability. Its unique properties were due to both strong iron-copper interaction and strong metal-support interaction, leading to outstanding redox behavior.

An investigation of water gas shift reaction in a Pd-alloy membrane reactor with an optimized crossflow configuration

In this study, the performance of a high-temperature water gas shift reaction (WGSR) using a Fe-Cr catalyst along with a Pd alloy membrane was simulated by computational fluid dynamics (CFD). The influences of using Pd membranes, catalytic layer thickness ratio (R/R0), Reynolds number, and steam-to-CO ratio (S/C) on the reaction were investigated by comparing CO conversion and hydrogen recovery (HR). In the CFD simulation, one-tube and four-tube systems were simulated at 500 °C. This study also compared the performance between tandem and optimized configurations. The results show that the CO conversion can be improved up to 22.9% when the WGSR reactor system uses a Pd membrane compared to the system without a Pd membrane. The system has the best hydrogen recovery performance at S/C = 4 and R/R0 larger than 1.5. At Re=5, the optimized configuration for CO conversion has better performance when R/R0 is larger than 1.75. Compared to the tandem configuration, the optimized configuration also shows better performance for HR at every R/R0. The results indicate that a Pd membrane and optimized configuration can significantly improve CO conversion and that R/R0 and S/C optimization is very important for effective reactor performance.

NiCx/Ni-foam discovered as a promising high-temperature WGSR catalyst

Water gas shift reaction (WGSR) is urgently calling for an alternative to the Fe-Cr catalyst. Ni-based catalysts are taken into consideration but remain challenging because of their high methanation activity. Here we report a highly active and selective NiCx/Ni-foam catalyst with clearly detectable Ni3C phase, facilely obtainable by endogenous growth of NiC2O4 onto a Ni-foam and subsequent H2-reduction treatment. The preferred catalyst with high content of NiCx is capable of converting 63.6% or 94.3% CO at 350 °C or 400 °C with trace or < 0.8% CH4 formation for a feed gas with H2O/CO/Ar molar ratio of 4/1/9, and is stable for at least 110 h. It is experimentally and theoretically unveiled that the Ni3C facilitates the dissociative activation of H2O and favors CO to form carboxylate species (favorable for CO2 formation) rather than active Ni(CO)n intermediates for CH4 formation thereby enabling the catalyst with high WGSR activity and selectivity.

Hydrogen production from waste-derived synthesis gas over Ni(x)Fe(3-x)-CeO2 catalyst: optimization of Ni/Fe ratio

In this study, the effect of the Ni/Fe molar ratio on the Ni(x)Fe(3-x)-CeO2 catalyst was investigated for the high-temperature water-gas shift reaction, which produces hydrogen from waste-derived synthesis gas. The catalysts were synthesized via a co-precipitation method, using different Ni/Fe molar ratios (0.5:2.5, 1.0:2.0, 1.5:1.5, 2.0:1.0, and 2.5:0.5). The physicochemical properties of these catalysts were analyzed by Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), temperature-programmed reduction using hydrogen (H2-TPR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and H2-O2 pulse analyses to determine their reaction performance. The Ni1.0Fe2.0-CeO2 catalyst exhibited the highest activity (Xco = 88%, T = 500 °C) without any side reactions at a high gas hourly space velocity of 41,823 mL·g−1 h−1, compared to the other catalysts tested, owing to its high oxygen vacancies and oxygen storage capacity (OSC). In addition, when the Ni/Fe molar ratio was higher than 1, a side reaction (methanation) occurred. Therefore, it was concluded that the Ni1.0Fe2.0-CeO2 catalyst is optimal for hydrogen production via the high-temperature water-gas shift reaction from waste-derived synthesis gas.

Effect of Stoichiometry and Method of Synthesis of Powdered Cu–Fe–Al Precursors on the Stability and Activity of CuFeAlO/CuFeAl Ceramometals in the High-Temperature Water Gas Shift Reaction

Effect of Stoichiometry and Method of Synthesis of Powdered Cu–Fe–Al Precursors on the Stability and Activity of CuFeAlO/CuFeAl Ceramometals in the High-Temperature Water Gas Shift Reaction

Facile synthesis of M-CuFe2O4 (M= Al2O3, CeO2, La2O3, ZrO2, Mn2O3) catalysts using a one-pot method and their applications in high-temperature water gas shift reaction

Water gas shift reaction is an essential process of hydrogen production and carbon monoxide removal from syngas. In this study, the promotional effect of ZrO2, CeO2, La2O3, Al2O3, and Mn2O3 was investigated on the CO conversion and thermal stability of the copper ferrite in high-temperature water gas shift reaction (HTSR) and hydrogen purification. The powders were synthesized by a simple solid-state route and characterized by XRD, H2-TPR, SEM, FT-IR, TG-DTA, and BET analyses. Promoters (ZrO2, CeO2, La2O3, Al2O3, and Mn2O3) could affect the WGSR performance in activity and stability. In the M-CuFe2O4 catalyst, alumina acts as a texture promoter and aids in the fine dispersion of copper ferrite. The results indicated that the surface area of the Al2O3–CuFe2O4 (210 m2/g) catalyst was higher than the other samples. This catalyst presented higher CO conversion in HTSR and had higher stability at 1000 min on stream. It was found that the incorporation of different contents of alumina had a significant influence on the textural and catalytic properties of the CuFe2O4-based catalysts. The 30%Al2O3–70%CuFe2O4 catalyst exhibited the highest CO conversion of 65% at 350 °C, uniform pore size distribution, and intense interaction between copper ferrite and alumina, causing the effective stabilization of the active phase in the catalyst structure. The findings of this study represent that the solid-state method, due to its simplicity and creation of a mesoporous structure, can also be applied for the preparation of many heterogeneous metal oxide catalysts.

Substituting Chromium in Iron-Based Catalysts for the High-Temperature Water-Gas Shift Reaction.

A set of doped iron oxides (chromium, aluminum, gallium, indium, manganese, zinc, niobium) were prepared by a one-step coprecipitation/calcination approach evaluated for their WGS activity under industrially relevant conditions and characterized in detail. The WGS activity after ageing the doped catalyst for 4 days at 25 bar follows the order chromium ≈ aluminum > gallium > indium > manganese > zinc > niobium for copper-codoped catalysts. The activated catalysts predominantly consist of magnetite, irrespective of the dopant. Mössbauer spectra of aged catalysts showed that aluminum and zinc occupy both tetrahedral and octahedral sites of magnetite, while chromium, gallium, indium, manganese, and niobium preferentially substitute octahedral iron. The incorporation of trivalent metal ions of similar size to octahedral Fe3+ (i.e., chromium, aluminum, gallium) results in moderate to high CO conversion, irrespective of incorporation in tetrahedral or octahedral sites. The substitution of Fe2+ with Mn2+ results in an increased Fe3+/Fe2+ ratio. Incorporation of Zn2+ in tetrahedral sites (replacing Fe3+ ions) leads to a complex structure where the charge balance is compensated from the octahedral sites. Separate dopant metal oxide phases were observed in indium- and niobium-doped catalysts. XPS shows that copper is present as a separate phase in activated copper-codoped catalysts. Aluminum is identified as the most promising promoter for substituting chromium in commercial high-temperature WGS catalysts on the basis of their similar high CO conversion although incorporation of these dopants into the magnetite structure differed substantially.

Waste to worth: A high-temperature water-gas shift magnetite catalyst with encapsulated core-shell structure from coal fly ash

In this paper, we demonstrate the synthesis of magnetite-based, encapsulated catalyst with a core-shell structure from coal fly ash, an industrial solid waste, and its application to industrially important high temperature water-gas shift reaction (HT-WGSR). The catalyst precursor was first synthesized through a leaching-precipitation-hydrothermal process, leading to the formation of a nanosheet-like hematite precursor consisting of Fe3+ as primary element and minor cations including Al3+, Mg2+ and other cations (e.g. Ca2+ and Ti4+). During the WGSR, the nanosheets broke into smaller particles with a core of magnetite with a diameter of ~20 nm, whereas the inherent impurity elements were activated and migrated to the outer surface forming a shell with a thickness of ~4 nm. Due to the protection of shell, the as-synthesized catalyst exhibited improved activity, thermal stability and long-term durability for HT-WGSR at 400 °C and 450 °C. Compared to the pure hematite, this catalyst exhibited much higher activity and stability, i.e., increased CO conversion and decreased deactivation rate constant, by a factor of four and three, respectively. Additionally, through a bottom-up reverse synthesis, we have confirmed that Al3+ functioned as a textual promoter enhancing the interfacial area of the catalyst. On the other hand, the presence of minor impurity elements, in particular 2.58 wt% Mg2+ and 0.18 wt% Ti4+, were found to increase the basicity, and promote the adsorption rate of CO, the redox of catalysts, and the alteration of the reaction mechanism from regenerative to associative with the formation of a strong intermediate formate. This study not only opens a new direction on the valorization of solid waste into high-value catalysts, promoting the sustainability of solid waste management, but also provides an alternative, cost-effective and scalable approach for the design and fine-tuning of encapsulated catalysts.

Effect of ZrO2 on the performance of Co–CeO2 catalysts for hydrogen production from waste-derived synthesis gas using high-temperature water gas shift reaction

In this study, highly active and stable CeO 2 , ZrO 2 , and Zr (1- x ) Ce ( x ) O 2 -supported Co catalysts were prepared using the co-precipitation method for the high-temperature water gas shift reaction to produce hydrogen from waste-derived synthesis gas. The physicochemical properties of the catalysts were investigated by carrying out Brunauer-Emmet-Teller, X-ray diffraction, CO-chemisorption, Raman spectroscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and H 2 -temperature-programmed reduction measurements. With an increase in the ZrO 2 content, the surface area and reducibility of the catalysts increased, while the interaction between Co and the support and the dispersion of Co deteriorated. The Co–Zr 0.4 Ce 0·6 O 2 and Co–Zr 0.6 Ce 0·4 O 2 catalysts showed higher oxygen storage capacity than that of the others because of the distortion of the CeO 2 structure due to the substitution of Ce 4+ by Zr 4+ . The Co–Zr 0.6 Ce 0·4 O 2 catalyst with high reducibility and oxygen storage capacity exhibited the best catalytic performance and stability among all the catalysts investigated in this study. • CeO 2 , ZrO 2 , and Zr (1-x) Ce (x) O 2 -supported Co catalysts were prepared. • WGS reaction was carried out over the catalysts to produce hydrogen from syngas. • Oxygen storage capacity and reducibility were dependent on the ratio of Ce/Zr. • Co–Zr 0.4 Ce 0·6 O 2 showed the best performance among the prepared catalysts. • This performance was relating to its high oxygen storage capacity and reducibility.

Promotion of methanation suppression by alkali and alkaline earth metals in Ni-CeO2 catalysts for water–gas shift reaction using waste-derived synthesis gas

In this study, alkali and alkaline earth metal-promoted Ni-CeO2 catalysts were developed for the high-temperature water–gas shift reaction of waste-derived synthesis gas in which hydrogen is produced. The elements K, Ca, Mg, and Ba were selected to repress methanation, which is a major side reaction of Ni-based catalysts. The prepared catalysts were characterized using different techniques including the Brunauer–Emmett–Teller method, X-ray diffraction, H2-temperature programmed reduction, CO2-temperature programmed desorption, H2-chemisorption, and X-ray photoelectron spectroscopy to determine the correlations between the catalyst activity and their properties. The results show that the alkali and alkaline earth metal-promoted Ni-CeO2 catalyst effectively suppressed methanation. Among the promoted catalysts, the Ca/Ni-CeO2 catalyst exhibited the highest activity and stability for 18 h at a very high gas hourly space velocity of 1,050,957 h−1, which is mainly due to the high oxygen storage capacity.

Partially sintered copper\u2012ceria as excellent catalyst for the high-temperature reverse water gas shift reaction

For high-temperature catalytic reaction, it is of significant importance and challenge to construct stable active sites in catalysts. Herein, we report the construction of sufficient and stable copper clusters in the copper‒ceria catalyst with high Cu loading (15 wt.%) for the high-temperature reverse water gas shift (RWGS) reaction. Under very harsh working conditions, the ceria nanorods suffered a partial sintering, on which the 2D and 3D copper clusters were formed. This partially sintered catalyst exhibits unmatched activity and excellent durability at high temperature. The interaction between the copper and ceria ensures the copper clusters stably anchored on the surface of ceria. Abundant in situ generated and consumed surface oxygen vacancies form synergistic effect with adjacent copper clusters to promote the reaction process. This work investigates the structure-function relation of the catalyst with sintered and inhomogeneous structure and explores the potential application of the sintered catalyst in C1 chemistry.

Water Gas Shift Reaction Activity on Fe (110): A DFT Study

Metal Fe is one of the phases existing on iron-based catalysts for a high-temperature water gas shift reaction (WGSR), but research on the activity of metal Fe in WGSR is almost not reported. In this work, the density functional theory (DFT) method was used to systematically study the reaction activity and mechanisms of WGSR on metal Fe (110), including the dissociation of H2O, the transformation of CO and the formation of H2, as well as the analysis of surface electronic properties. The results show that (1) the direct dissociation of H2O occurs easily on Fe (110) and the energy barrier is less than 0.9 eV; (2) the generation of CO2 is difficult and its energy barrier is above 1.8 eV; (3) H migrates easily on the Fe surface and the formation of H2 also occurs with an energy barrier of 1.47 eV. Combined with the results of Fe3O4, it can be concluded that the active phase should be Fe3O4 with O vacancy defects, and the iron-rich region plays an important role in promoting the formation of H2 in WGSR.

Ce/Cr and Ce/Co modified ferrite catalysts for high temperature water-gas shift reaction at elevated pressures

In this work, Ce and Cr/Co co-doped iron oxide (FeCeMOx, where M = Cr or Co) ferrites were investigated for high-temperature water-gas shift (HT-WGS) under industrially relevant pressures (20 bars). The Ce and Cr/Co bi-doping has greatly promoted the catalytic performance in comparison to the single Ce-doping. Especially, the FeCeCoOx ferrite demonstrated the best HT-WGS activity without any deactivation at a steam to CO ratio of 3.5. The ternary FeCeCrOx and FeCeCoOx catalysts also exhibited reasonably stable performance with a slight methanation activity (<2.5%) even under low steam to CO ratio of 1.5. The hematite phase (Fe2-xCex/2Mx/2O3, where M = Cr or Co and × = 0.33) of the fresh (calcined) catalysts became [A(1-δ)Bδ]T[AδB(2-δ)]OO4 type magnetite spinel structure (Fe3-xCex/2Mx/2O4, where M = Cr or Co and × = 0.5) during the activation process, which is regarded as the active phase for the WGS reaction. The co-doping of Cr or Co increased the stability of the active magnetite phase against sintering and suppressed the coke formation during the WGS reaction, which should be responsible for the stable activity. The addition of Cr or Co to iron oxide also delays the formation and over-reduction of active magnetite phase. Mössbauer spectra confirmed that the Cr or Co ions were incorporated into the octahedral sites of [A(1-δ)Bδ]T[AδB(2-δ)]OO4 spinel framework during the activation and modifies the local structure. The superparamagnetic behavior of the spinel ferrites has significantly enhanced upon the co-doping of Ce and Cr/Co into the iron oxide lattice, indicating a high fraction of nanoparticles in the ternary spinel ferrites. The Cr or Co addition resulted in the decreased surface Fe3+/Fe2+ ratio which could be due to the replacement of Fe3+ ions by Cr or Co ions. Most importantly, no evident change was observed in the surface structure of ternary spinel ferrites even after the reaction, which could be responsible the stable performance of the catalysts.

First-principles study on the mechanism of water-gas shift reaction on the Fe3O4 (111)-Fetet1

Water-gas shift reaction (WGSR) is an important means for the production of H2 in industry, but the understanding of high-temperature WGSR on iron oxide catalysts is not sufficient, especially the relationship between crystal planes of Fe3O4 and reaction mechanisms and activity. In this paper, the three mechanisms of WGSR on Fe3O4 (111)-Fetet1 have been systematically studied by the density functional theory (DFT) considering spin polarization, and the whole reaction paths of three mechanisms were calculated in detail. The results indicate that association mechanism and regeneration mechanism are coexisted, and the effective energy barrier of the association mechanism is the lowest of 0.45 eV. For the step of H2 formation, the activity is affected by the coverage of surface *H and the O defects concentration. High surface H coverage and a lot of O defects are beneficial to the H2 formation. These results are helpful for further understanding the mechanism of WGSR on Fe3O4 catalyst.

Improved Catalytic Activity of the High-Temperature Water Gas Shift Reaction on Metal-Exsolved La0.9Ni0.05Fe0.95O3 by Controlling Reduction Time

The catalyst exsolved from nickel-doped perovskite oxide, La0.9Ni0.05Fe0.95O3, has been proven to be effective for gas-phase reactions. To obtain the optimum amount of exsolved nanoparticles from the parent perovskite oxide, control of the reduction treatment condition is vital. Here, the effect of reduction time on the exsolved nanoparticle distribution, and thus the catalytic activity of the high-temperature water gas shift reaction (WGSR), was investigated. Upon conducting a wide range of characterizations, we assumed that the exsolution process might be a two-step process. Firstly, the surface oxygen is extracted. Secondly, due to the unstable perovskite structure, the Ni ions in the bulk La0.9Ni0.05Fe0.95O3 continuously diffuse toward the surface and, as the reduction progresses, more nuclei are generated to form a greater number of nanoparticles. This assumption is proven by the fact that, with an increase in the exsolution treatment time, the population of exsolution nanoparticles increases. Moreover, as the reduction time increases, the high-temperature WGSR activity also increases. The temperature-programmed measurements suggest that the exsolved nanoparticles are the active reaction sites. We believe that this study is helpful for understanding exsolution behavior during reduction treatment and, thus, developing a perovskite exsolution catalyst for the WGSR.

Exsolved metal-boosted active perovskite oxide catalyst for stable water gas shift reaction

We designed a Ni-exsolved perovskite catalyst for the high-temperature water–gas shift reaction. The perovskite particle has the formula of La0.9Fe0.95Ni0.05O3 and has metal nanoparticles (NPs) exsolved on its surface after reduction treatment. XRD, SEM, HR-TEM and XPS analyses were used to confirm the existence of the exsolved Ni metal NPs. This catalyst provided higher CO conversion and H2 yield, and exceptionally better catalytic stability than the commercial catalyst. Temperature-programmed desorption and reduction measurements revealed the active sites for the enhanced activity. Density functional theory calculations and DRIFT results elucidated the reaction mechanism on this catalyst. We believe that our results can increase the possibility of achieving an effective and economical catalyst for a wide range of heterogeneous catalytic reactions.

Ecofriendly K-decorated ZnO/Zn(Al,La)2O4 catalyst for hydrogen production – Effect of heterostructure on catalyst activity at steam‐lean process gas

The effect of ZnAlLa-LDHs calcinations temperature on physicochemical and catalytic properties of K-decorated Zn-Al-La mixed oxides for water-gas shift reaction was investigated. The fresh and spent catalysts were characterized using various methods including XRF, N2 adsorption, TG/DTG/MS, XRD, FT-IR, STEM-EDS and HRTEM. Catalysts activity tests were carried out in high-temperature water-gas shift (HT-WGS) reaction in kinetic regime within the temperature range of 330–400 °C and H2O/dry gas molar ratio in the range of 0.5–1. The relationship between the structural, surface morphology of catalysts and the activity in the HT-WGS reaction was studied. The presence of ZnO-Zn(AlLa)2O4 heterostructure decorated with potassium species enhances HT-WGS activity. Calcinations of ZnAlLa-LDH precursor at mild conditions creates a favorable morphology of the surface and results in relatively high activity similar to the standard HT-WGS catalyst (Fe-Cr-Cu). The highest activity in the HT-WGS reaction at lower steam/dry gas ratios was obtained for the ZnAlLa_600_K.

Effects of niobium addition on active metal and support in Co–CeO2 catalyst for the high temperature water gas shift reaction

Nb promoter was introduced in the Co–CeO2 catalyst to improve its catalytic performance in the high temperature water gas shift (HT-WGS) reaction, which involves the production of hydrogen from waste-derived synthesis gas. Thereafter, the physicochemical properties of the promoter as well as those of the catalyst were investigated using various techniques. Thus, it was confirmed that the Nb promoter affects the key properties related to catalytic performance, including oxygen storage capacity (OSC) and dispersion. To maximize the positive effect of the Nb promoter, we further investigated the effect of the Nb loading amount on the performance of the catalyst. The results obtained showed that the 1.5NbCo catalyst exhibited the highest catalytic performance (XCO = 89% at 450 °C) under very severe conditions (gas hourly space velocity (GHSV) = 637,320 h−1). Additionally, this catalyst exhibited stable activity for 50 h. This its high catalytic performance could be attributed to its high OSC and Co dispersion. Therefore, it is a promising catalyst for hydrogen production via the HT-WGS reaction.