Reverse water gas shift reaction over Co-precipitated Ni-CeO_2 catalysts

The Ni-CeO2 catalysts with different Ni contents were prepared by a co-precipitation method and used for Reverse Water Gas Shift （RWGS） reaction. 2wt.%Ni-CeO2 showed excellent catalytic performance in terms of activity, selectivity, and stability for RWGS reaction. Characterizations of the catalyst samples were conducted by XRD and TPR. The results indicated that, in Ni-CeO2 catalysts, there were three kinds of nickel, nickel ions in ceria lattice, highly dispersed NiO and bulk NiO. Oxygen vacancies were formed in CeO2 lattice due to the incorporation of Ni^2＋ ions into ceria lattice. Oxygen vacancies formed in ceria lattice and highly dispersed Ni were key active components for RWGS, and bulk Ni was key active component for methanation of CO2.

A Novel γ-Alumina Supported Fe-Mo Bimetallic Catalyst for Reverse Water Gas Shift Reaction

In reverse water gas shift （RWGS） reaction COa is converted to CO which in turn can be used to pro- duce beneficial chemicals such as methanol. In the present study, Mo/AlaO3, Fe/AlaO3 and Fe-Mo/Al2O3 catalysts were synthesised using impregnation method. The structures of catalysts were studied using X-ray diffraction （XRD）, Brunauer-Emmett-Teller （BET） method, inductively coupled plasma atomic emission spectrometer （ICP-AES）, temperature programmed reduction （H2-TPR）, CO chemisorption, energy dispersive X-ray （EDX） and scanning electron microscopy （SEM） techniques. Kinetic properties of all catalysts were investigated in a batch re- actor for RWGS reaction. The results indicated that Mo existence in structure of Fe-Mo/AlzO3 catalyst enhances its activity as compared to Fe/AlaO3. This enhancement is probably due to better Fe dispersion and smaller particle size of Fe species. Stability test of Fe-Mo/AlzO3 catalyst was carried out in a fixed bed reactor and a high CO yield for 60 h of time on stream was demonstrated. Fez（MoO4）3 phase was found in the structures of fresh and used catalysts. TPR results also indicate that Fez（MoO4）3 phase has low reducibility, therefore the Fe2（MoO4）3 phase significantly inhibits the reduction of the remaining Fe oxides in the catalyst, resulted in high stability of Fe-Mo/Al2O3 catalyst. Overall, this study introduces Fe-Mo/Al2O3 as a novel catalyst with high CO yield, almost no by-products and fairly stable for RWGS reaction.

For more and purer hydrogen-the progress and challenges in water gas shift reaction

The water gas shift(WGS) reaction is a standard reaction that is widely used in industrial hydrogen production and removal of carbon monoxide. The improved catalytic performance of WGS reaction also contributes to ammonia synthesis and other reactions. Advanced catalysts have been developed for both high and low-temperature reactions and are widely used in industry. In recent years, supported metal nanoparticle catalysts have been researched due to their high metal utilization. Low-temperature catalysts have shown promising results, including high selectivity, high shift rates, and higher activity potential. Additionally, significant progress has been made in removing trace CO through the redox reaction in electrolytic cell. This paper reviews the development of WGS reaction catalysts, including the reaction mechanism, catalyst design, and innovative research methods. The catalyst plays a crucial role in the WGS reaction, and this paper provides an instant of catalyst design under different conditions. The progress of catalysts is closely related to the development of advanced characterization techniques.Furthermore, modifying the catalyst surface to enhance activity and significantly increase reaction kinetics is a current research direction. This review goals to stimulate a better understanding of catalyst design, performance optimization, and driving mechanisms, leading to further progress in this field.

Boosting the water gas shift reaction on Pt/CeO_(2)-based nanocatalysts by compositional modification: Support doping versus bimetallic alloying

The water gas shift reaction is of vital significance for the generation and transition of energy due to the application in hydrogen production and industries such as ammonia synthesis and fuel cells.The influence of support doping and bimetallic alloying on the catalytic performance of Pt/Ce O_(2)-based nanocatalysts in water gas shift reaction was reported in this work.Various lanthanide ions and 3d transition metals were respectively introduced into the Ce O_(2)support or Pt to form Pt/Ce O_(2):Ln(Ln=La,Nd,Gd,Tb,Yb)and Pt M/Ce O_(2)(M=Fe,Co,Ni)nanocatalysts.The sample of Pt/Ce O_(2):Tb showed the highest activity(TOF at 200℃=0.051 s^(-1))among the Pt/Ce O_(2):Ln and the undoped Pt/Ce O_(2)catalysts.Besides,the sample of Pt Fe/Ce O_(2)exhibited the highest activity(TOF at 200℃=0.12 s^(-1))among Pt M/Ce O_(2)catalysts.The results of the multiple characterizations indicated that the catalytic activity of Pt/Ce O_(2):Ln catalysts was closely correlated with the amount of oxygen vacancies in doped ceria support.However,the different activity of Pt M/Ce O_(2)bimetallic catalysts was owing to the various Pt oxidation states of the bimetals dispersed on ceria.The study of the reaction pathway indicated that both the samples of Pt/Ce O_(2)and Pt/Ce O_(2):Tb catalyzed the reaction through the formate pathway,and the enhanced activity of the latter derived from the increased concentration of oxygen vacancies along with promoted water dissociation.As for the sample of Pt Fe/Ce O_(2),its catalytic mechanism was the carboxyl route with a higher reaction rate due to the moderate valence of Pt along with improved CO activation.

Copper Promoted Au/ZnO-CuO Catalysts for Low Temperature Water-gas Shift Reaction

Various copper promoted Au/ZnO-CuO catalysts with different atomic ratios of Cu to Zn prepared by means of co-precipitation were tested for the low temperature water-gas shift（WGS） reaction. The catalytic activity of the catalyst depends largely on the ratio of Cu to Zn. The addition of an appropriate amount of copper can considerably improve both the catalytic activity and the stability of the catalyst in comparison with those of copper-free Au/ZnO cata- lysts. The enhanced reducibility of copper oxide in the Au/ZnO-CuO ternary-component catalysts, which was confirmed by H2-TPR, may be related to the high activity and stability of the catalyst for the low temperature WGS reaction.

Effects of the partial replacement of La by M(M=Ce,Ca and Sr) in La_(2-x)M_xCuO_4 perovskites on catalysis of the water-gas shift reaction

The performance of La2-x M x CuO4 perovskites （where M=Ce,Ca or Sr） as catalysts for the water-gas shift reaction was investigated at 290℃ and 360℃.The catalysts were characterized by EDS,XRD,N2 adsorption-desorption,XPS and XANES.The XRD results showed that all the perovskites exhibited a single phase （the presence of perovskite structure）,suggesting the incorporation of metals in the perovskite structure.The XPS and XANES results showed the presence of Cu2＋ on the surface.The perovskites that exhibited the best catalytic performance were La 2 x Ce x CuO 4 perovskites,with CO conversions of 85% 90%.Moreover,these perovskites have higher surface areas and larger amounts of Cu on the surface.And Ce has a higher filled energy level than the other metals,increasing the energy of the valence band of Ce and providing more electrons for the reaction.Besides,the La1.80Ca0.20CuO4 perovskite showed a good catalytic performance.

Kinetics of the water-gas shift reaction in Fischer-Tropsch synthesis over a nano-structured iron catalyst

Based on formate and direct oxidation mechanisms,three Langmuir-Hinshelwood-Hougen-Watson （LHHW） kinetic models of the water-gasshift （WGS） reaction over a nano-structured iron catalyst under Fischer-Tropsch synthesis （FTS） reaction conditions were derived and compared with those over the conventional catalyst.The conventional and nanostructured Fe/Cu/La/Si catalysts were prepared by co-precipitation of Fe and Cu nitrates in aqueous media and water-oil micro-emulsion,respectively.The WGS kinetic data were measured by experiments over a wide range of reaction conditions and comparisons were also made for various rate equations.WGS rate expressions based on the formate mechanism with the assumption that the formation of formate is rate determining step were found to be the best.

Selective synthesis of carbon monoxide via formates in reverse water–gas shift reaction over alumina-supported gold catalyst

Thermal decomposition of formic acid on SiO2, CeO2 and γ-Al2O3 was studied as an elementary step of reverse water–gas shit reaction（RWGS） over supported Au catalysts. γ-Al2O3 showed the highest CO selectivity among the tested oxides in the decomposition of formic acid. Infrared spectroscopy showed the formation of four formate species on γ-Al2O3： three η~1-type and one μ~2-type species, and these formates decomposed to CO at 473 K or higher. Au-loaded γ-Al2O3 samples were prepared by a depositionprecipitation method and used as catalysts for RWGS. The supported Au catalyst gave CO with high selectivity over 99% from CO2 and H2, which is attributed to the formation of formates on Au and subsequent decomposition to CO on γ-Al2O3.

Effect of Addition Sequence during Neutralization and Precipitation on Iron-based Catalysts for High Temperature Shift Reaction

The preparation of the iron-based catalysts promoted by cobalt with a small amount of copper and aluminum for the high temperature shift reaction （HTS） with different sequences of adding catalyst raw materials during neutralization and precipitation was investigated. XRD, BET and particle size distribution （PSD） were used to characterize the prepared catalysts. It was found that the catalyst crystals were all γ-Fe2O3, and the intermediate of the catalyst after aging was Fe3O4. The crystallographic form of the catalyst and its intermediate was not affected by the addition sequence in the neutralization and precipitation process. The results showed that the specific surface area and the particle size of the catalysts depended on the addition sequence to the mother liquor. Cobalt with a small amount of copper and aluminum could increase the specific surface area and decrease the particle size of catalysts.

Preparation and characterization of Cu-Ce-La mixed oxide as water-gas shift catalyst for fuel cells application

Cu-Ce-La mixed oxides were prepared by three precipitation methods （coprecipitation, homogeneous precipitation, and deposition precipitation） with variable precipitators and characterized using X-ray diffraction, BET, temperature-programmed reduction, and catalytic reaction for the water-gas shift. The Cu-Ce-La mixed oxide prepared by coprecipitation method with NaOH as precipitator presented the highest activity and thermal stability. Copper ion substituted quadrevalent ceria entered CeO2 （111） framework was in favor of activity and thermal stability of catalyst. The crystallinity of fresh catalysts increased with the reduction process. La^3＋ or Ce^4＋ substituted copper ion entered the CeO2 framework during reduction process. The coexistence of surface copper oxide （crystalline） and pure bulk crystalline copper oxide both contributed to the high activity and thermal stability of Cu-Ce-La mixes oxide catalyst.

Model for Reduction of Iron Oxide Pellet with a C-O-H-N Gas Mixture Considering Water Gas Shift Equilibrium in the Gas While It Diffuses through the Product Layer

In metallurgical processes, more and more usage of hydrocarbons is encouraged to bring down the carbon emissions. In this regard, numerous investigations on reduction of oxides by C-O-H-N gas mixture have been reported. Attempts to simulate these reduction processes using shrinking core model, one of the common models used for such studies, have under predicted the reduction rates. This may be owing to the fact that the homogeneous reaction in the gas phase is not being considered. If the reaction temperatures are above 1,000 K, generally so for many reduction processes, the homogeneous gas reaction rates are expected to be high enough that local equilibrium in the gas phase can be assumed. In the present study, reduction of wustite in a C-O-H-N gas mixture has been modeled using shrinking core model considering the water gas shift equilibrium in the gas while it diffuses through the product layer.

Computational Screening of Pt1@Ti_(3)C_(2)T_(2)(T=O,S)MXene Catalysts for Water-Gas Shift Reaction

Single-atom catalysts(SACs)provide an oppor-tunity to elucidate the catalytic mechanism of complex reactions in heterogeneous catalysis.The low-temperature water-gas shift(WGS)reaction is an important industrial technology to obtain high purity hydrogen.Herein,we study the catalytic activity of Pt1@Ti_(3)C_(2)T_(2)(T=O,S)SACs,where one subsurface Ti atom with three T vacancies in the functionalized Ti_(3)C_(2)T_(2)(T=O,S)MXene is substituted by one Pt atom,for the low-temperature show that Pt1@Ti_(3)C_(2)T_(2)provides an excellent platform for the WGS reaction by its bowl-shaped vacancy derived from the Pt1 single atom and three T defects surrounding it.Especially,Pt1@Ti_(3)C_(2)S_(2)SAC has higher catalytic performance for the WGS reaction,due to the weaker electronegativity of the S atom than the O atom,which significantly reduces the energy barrier of H*migration in the WGS reaction,which is often the rate-determining step.In the most favorable redox mechanism of the WGS reaction on Pt1@Ti_(3)C_(2)S_(2),the rate-determining step is the dissociation of OH*into O*and H*with the energy barrier as low as 1.12 eV.These results demonstrate that Pt1@Ti_(3)C_(2)S_(2)is promising in the application of MXenes for low-temperature WGS reactions.

Influence of Reaction Conditions on Methanol Synthesis and WGS Reaction in the Syngas-to-DME Process

A series of CuO-ZnO catalysts （with different Cu/Zn molar ratios） were prepared, and evaluated under the reaction conditions of syngas-to-dimethyl ether （DME） with three sorts of feed gas and different space velocity. The catalysts were characterized by X-ray diffraction （XRD） and temperatureprogrammed reduction （TPR）. The experiment results showed that the reaction conditions of syngas-to- DME process greatly affected the methanol synthesis and WGS reaction. The influence caused by Cu/Zn molar ratio was quite different on the two reactions; increasing of percentage of CO2 in feed gas was unfavorable for catalyst activity, and also inhibited both reactions; enhancement of reaction space velocity heavily influenced the performance of the catalyst, and the benefits were relatively less for methanol synthesis than for the WGS reaction.

Theoretical and Experimental Study on Reaction Coupling: Dehydrogenation of Ethylbenzene in the Presence of Carbon Dioxide

Dehydrogenation of ethylbenzene （EB） to styrene （ST） in the presence of CO2, in which EB dehydrogenation is coupled with the reverse water-gas shift （RWGS）, was investigated extensively through both theoretical analysis and experimental characterization. The reaction coupling proved to be superior to the single dehydrogenation in several respects. Thermodynamic analysis suggests that equilibrium conversion of EB can be improved greatly by reaction coupling due to the simultaneous elimination of the hydrogen produced from dehydrogenation. Catalytic tests proved that iron and vanadium supported on activated carbon or Al2O3 with certain promoters are potential catalysts for this coupling process. The catalysts of iron and vanadium are different in the reaction mechanism, although ST yield is always associated with CO2 conversion over various catalysts. The two-step pathway plays an important role in the coupling process over Fe/Al2O3, while the one-step pathway dominates the reaction over V/Al2O3. Coke deposition and deep reduction of active components are the major causes of catalyst deactivation. CO2 can alleviate the catalyst deactivation effectively through preserving the active species at high valence in the coupling process, though it can not suppress the coke deposition.

Adsorption Properties of Water Vapor on Iron Oxide Containing Cerium Oxide

The properties of adsorption of water vapor on iron oxide containing CeO 2 have been studied by pulse gas chromatography(GC) with the method of retention volume It was found that the adsorption heat of water vapor on the catalyst decreased and the number of adsorption centers did not change as the amount of cerium oxide increasing in the samples However, the adsorption heat increased somewhat as the sample contains enough amount of cerium oxide The activities of the samples catalyzing the water gas shift(WGS) reaction were measured The results showed that the lower the adsorption heat of a sample was, the higher its activity became It was proved that cerium oxide was a catalyst accelerator in the WGS catalysis

基于反应耦合的低能耗水合氯化钙脱水制无水氯化钙

在降低工业热脱水工艺能耗的迫切需求下,基于反应耦合基本原理,报道了一种低温水煤气变换反应耦合水合氯化钙低能耗脱水的新策略。以工业水合氯化钙为原料,将其中具有一定化学反应活性的结晶水作为反应物与CO耦合反应,在413 K下即可制备得到符合国家标准(GB/T 26520—2021)要求的Ⅰ型工业无水氯化钙产品(CaCl_(2)·0.38H_(2)O),较在N_(2)条件下获得同等结晶水含量产品的处理时间缩短了1/3,说明耦合催化脱水策略在降低过程能耗方面具有优势。原位FTIR和CO-TPD-MS实验研究表明,CO可化学吸附或准化学吸附于水合氯化钙样品表面,结合MS分析在脱水产物中检测到CO_(2)和H_(2),说明发生了一定程度的耦合催化脱水。进一步,对所得无水氯化钙样品进行SEM、压汞测试及水蒸气吸附测试,结果表明,与CO耦合反应使得无水CaCl_(2)样品形成了较为丰富的孔结构,在作为干燥剂使用时有利于增加与水的接触面积,从而使其表现出比商用无水氯化钙更快的吸水速率。本工作报道的低能耗耦合催化脱水策略有望拓展至更多材料的脱水环节。

神华上湾煤在含CO气氛下的直接液化行为研究

本研究通过对比CO、H_(2)、N_(2)三种气氛下的液化行为,探究了CO对神华上湾煤液化过程的影响,并进一步研究不同CO/H_(2)比以及催化剂对合成气条件下液化过程的影响。结果显示,在CO气氛下煤直接液化的油产率达到43.1%,比H_(2)气氛中低4.2%,但比N_(2)气氛下高10.2%,添加神华863催化剂后液化效果得到进一步的提升,表明,CO在液化过程中可通过水煤气变换反应和CO与煤有机结构间的反应促进煤液化。对液化产物进行GC-MS、FT-IR等分析发现,CO使液化油中苯系物、脂肪烃与含氧化合物同时增多,对液化残渣中官能团与自由基浓度的影响不明显。在CO+H_(2)合成气下的实验结果表明,在20%CO的合成气中煤液化具有最高的油产率,达到57.4%;适当提高煤的含水量能够提升液化效果;神华863催化剂对液化过程与水煤气变换反应均具有良好的催化作用。

吸附强化水气变换制氢复合催化剂研究进展

吸附强化水气变换反应(SEWGS)是实现高纯氢制备及二氧化碳(CO_(2))减排的关键反应之一。SEWGS借助复合催化剂将水气变换反应(制氢)和原位移除CO_(2)反应(脱碳)耦合,打破热力学限制使反应平衡向制氢侧移动。SEWGS具有一步制取高纯氢气的特点,但复合催化剂在连续操作过程中由于烧结和CO_(2)扩散受阻存在循环稳定性下降的问题,进而影响制氢效率。本文阐述了高温Ni/CaO基复合催化剂吸附强化制氢的研究现状,简述了Fe/CaO基复合催化剂SEWGS制氢面临的主要问题,回顾了中温Cu/MgO基和Cu/类水滑石基复合催化剂的SEWGS制氢现状及现阶段的核心问题。从复合催化剂的催化组分和吸附组分角度,分析了SEWGS制氢过程中复合催化剂循环稳定性降低的原因,简述了现阶段最有效的改性手段。进一步从增强CO_(2)扩散和改善烧结角度入手,围绕复合催化剂设计、操作条件和床层装填方式等方面探讨提高复合催化剂循环稳定性的策略。指出设计开发组成简单、易制备、兼具高活性和高稳定性的复合催化剂实现制氢和脱碳耦合是今后SEWGS制氢的研究方向。

铝源对Cu-Al尖晶石物化性质和逆水煤气变换性能的影响

基于高能球磨和固相焙烧的方法,采用杂质元素(Na、Fe、Si和S)含量不等的四种拟薄水铝石和氢氧化铜制备了Cu-Al尖晶石固溶体催化剂,通过ICP-AES、TG、XRD、H2-TPR和BET表征了催化剂的物化性质,并考察了对逆水煤气变换反应的催化性能。结果表明,拟薄水铝石中的杂质元素对于Cu-Al尖晶石催化剂的物相性质、还原性能、织构性质和催化性能有显著的影响,Si有助于合成高比表面积的催化剂,但不利于Cu-Al尖晶石生成,导致催化活性低;含有少量Na和Fe的尖晶石的催化活性较低;S物种经高温焙烧后分解,对催化活性没有影响;基于杂质元素含量最低的拟薄水铝石合成的催化剂中难还原尖晶石含量最高,表现出最高的逆水煤气变换催化活性。此外,基于活性最优样品的CO_(2)-TPDMS和In-situ DRIFTS分析表明,Al上形成的双齿甲酸盐是Cu-Al尖晶石固溶体催化CO_(2)加氢生成CO的主要中间产物,其含量与催化活性随反应时间的变化规律一致。

Influence of preparation method on performance of Ni-CeO_2 catalysts for reverse water-gas shift reaction

This study investigated 1 wt.% Ni-CeO2 catalysts that were prepared using co-precipitation, deposition-precipitation, and impregnation methods for the reverse water-gas shift （RWGS） reaction. Characterizations of the catalyst samples were conducted by Brumauer-Emmett-Teller （BET）, atomic absorption spectrophotometer （AAS）, X-ray diffraction （XRD）, transmission electron microscopy （TEM）, high-resolution transmission electron microscopy （HR-TEM） and temperature programmed reduction （TPR）. The results showed that the Ni-CeO2 catalyst prepared using the co-precipitation method exhibited the best catalytic performance. In the Ni-CeO2 catalyst prepared using co-precipitation method, a combination of highly dispersed NiO and abundant oxygen vacancies was assumed to play a crucial role in determining the catalytic activity and selectivity of the RWGS reaction.