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.

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.

EFFECT OF Fe ON SURFACE REACTION OF Co_(3)Ti WITH WATER VAPOR

The surface reaction of Co 3Ti alloys (with and without Fe) with water vapor was investigated by using Auger electron spectroscopy (AES). The results showed that the rate of the surface reaction is much lower in Co 21 5Ti 3Fe alloy as compared with Co 3Ti (Co 23Ti) alloy. The surface reaction of Co 21 5Ti 3Fe alloy with water vapor saturates at exposure of 2×10 -3 Pa·s, but it does not saturate even at 0 1 Pa·s exposure for Co 3Ti alloy without Fe. The results also indicated that the kinetic of the surface reaction of Co 21 5Ti 3Fe with water vapor is much smaller than that of Co 3Ti at the same exposure. All the above results illustrate that the suppression of environmental embrittlement by addition of Fe to Co 3Ti alloy is attributed to its reduction of the surface reaction kinetics with water vapor.

Recent progress on bimetallic NiCo and CoFe based electrocatalysts for alkaline oxygen evolution reaction: A review

The deployment of hydrogen as an energy carrier is found to be a vital alternative fuel for the future. It is expected that water electrolysis, powered by renewable energy sources, be able to scale-up hydrogen production. However, the reaction kinetic of oxygen evolution reaction(OER) is a sluggish process, which predominantly limits the efficiency of water electrolysis. This review recapitulates the recent progress and efforts made in the design and development of two selected earth-abundant bimetallic electrocatalysts(Ni Co and Co Fe) for alkaline OER. Each bimetal electrocatalyst is thoroughly outlined and discussed in five sub-sections, including bimetal(oxy) hydroxides, Layered double hydroxides(LDHs) structures,oxides, composites, alloy and nanostructured electrocatalysts, and assembled with heteroatoms.Furthermore, a brief introduction to an in situ/operando characterization techniques and advantages for monitoring the structure of the electrocatalysts is provided. Finally, a summary outlining the challenges and conceivable approaches to advance OER performance is highlighted and discussed.

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.

A Study on the Dissolution Kinetics of Basalt-Water Interaction under Different pH Conditions I: Release of Elements and pH Neutralization Effect

Experimental research on the chemical weathering of alkaline-olivine basalt from Huangyi Mountain,Kuandain County,Liaoning.Province and olivine basalt from Dayangke,Mingxi County,Fujian Province has shown that the acidity of the solution tends to become neutral regardless of what the acidity of the starting solution would be during basalt0-water interaction.We call this phenome-non“pH neutralized Effect”.The dissolved species in the solution were determined and unreacted and reacted sample-surface chemical components involved or uninvolved in reaction were analyzed using X-ray photoelectron spectroscopy(XPS).The results revealed two different mechanisms of dissolution of basalt in acidic and basic solutions.

Mechanistic understanding on oxygen evolution reaction on γ-Fe OOH(010) under alkaline condition based on DFT computational study

An efficient and economical oxygen evolution reaction(OER)catalyst is critical to the widespread application of solar energy to fuel conversion.Among many potential OER catalysts,the metal oxyhydroxides,especially FeOOH,show promising OER reactivity.In the present work,we performed a DFT+U study of the OER mechanism on theγ‐FeOOH(010)surface.In particular,we established the chemical potential of the OH?and hole pair and included the OH?anion in the reaction pathway,accounting to the alkaline conditions of anodic OER process.We then analyzed the OER pathways on the surface with OH‐,O‐and Fe‐terminations.On the surface with OH‐and O‐terminations,the O2molecule could form from either OH reacting with the surface oxygen species(-OH*and-O*)or the combination of two surface oxygen species.On the Fe‐terminated surface,O2can only form by adsorbing OH on the Fe sites first.The potential‐limiting step of the oxygen evolution with different surface terminations was determined by following the free‐energy change of the elementary steps along each pathway.Our results show that oxygen formation requires recreating the surface Fe sites,and consequently,the condition that favors the partially exposed Fe sites will promote oxygen formation.

The Mitigation of Alkali-Silica Reactions by Aluminum-Bearing Substances

An ability of aluminum-bearing substances-amorphous aluminum hydroxide, aluminum sulphate and basic aluminum sulphate to mitigate alkali-silica reactions in Portland cement mortars has been studied. At equivalent dosages in terms of Al2O3, these substances are ranged in the following order in respect of inhibiting effect: Al(OH)1.78(SO4)0.61 ≥ Al2(SO4)3 > Al(OH)3. It is found that the plasticizing agents of the main types used in cement compositions have no influence on the inhibiting effect of aluminum-bearing admixtures. To control the setting time of cement paste, iron(II) sulphate may be used for partial substitution of Al2SO4·18H2O, and this operation is not influence on the results of ASR expansion test.

Density Functional Study on the Mechanism of Collision Reaction among Protons, N_2 and Water Vapor

The mechanism of collision reaction among protons, N2 and water vapor was theoretically studied using Den-sity Functional Theory. The geometries of reactants, transition states, intermediates and products were optimized at the B3LYP/6-311+G** level by the BERNY gradient analysis method. Transition states and intermediates have been identified by vibrational frequency analysis. The relationship among reactants, intermediates, transition states and products was affirmed by IRC calculation. The variations of energy and geometry along the IRC-determined reaction paths were described. The possible reaction pathways were represented and the optimal one was decided from the viewpoint of energy.

Promoter effect on the CO_2-H_2O formation during Fischer-Tropsch synthesis on iron-based catalysts

The effects of Mg,La and Ca promoters on primary and secondary CO2 and H2O formation pathways during Fischer-Tropsch synthesis on precipitated Fe/Cu/SiO2 catalysts are investigated.The chemisorbed oxygen atoms in the primary pathway formed in the CO dissociation steps reacted with co-adsorbed hydrogen or carbon monoxide to produce H2O and CO2,respectively.The secondary pathway was the water-gas shift reaction.The results indicated that the CO2 production led to an increase in both primary and secondary pathways,and H2O production decreased when surface basicity of the catalyst increased in the order Ca 〉 Mg 〉 La.

An unexpected iron(Ⅱ)-promoted reaction of N-arylprop-2-yn-1-imines with water:Facile assembly of multi-substituted pyrroles

Generation of multi-substituted pyrroles is accomplished through an unexpected iron(Ⅱ)-promoted reaction of N-arylprop-2-yn-1-imines with wate r.This transformation proceeds smoothly with excellent chemoselectivityand regioselectivity.A stoichiometric amount of Fe(OTf)_(2) is necessary for the succes s ful conversion.A Lewis acid-promoted tandem reaction pathway is proposed.

电解水析氢反应的铁基非晶合金薄带催化剂研究进展

Pt基电催化剂是析氢反应的基准,然而低丰度和高成本制约了此类贵金属基催化剂的大规模应用,从而促使了替代材料的探索。铁基非晶合金具有无序原子排布结构,表现出独特的物理化学性质。受碱性溶液中的高效析氢反应启发,简述了铁基非晶合金薄带电催化剂的常见反应机理和设计策略,旨在为制备高性能电催化剂提供指导,包括杂原子掺杂、异质面构筑、应变及空位缺陷构建等。此外,原位表征技术和密度泛函理论在铁基非晶合金薄带电催化剂理论设计、反应过程、动态结构演变和机理揭示等方面发挥了重要作用。最后简要介绍了铁基电催化剂目前存在的挑战和未来的研究方向。

天然氢气规模生成的成因类型与成藏特点

目前对全球天然氢气资源的估量十分巨大,寻找天然氢气的规模聚集区有赖于对其形成机理和富集规律的不断认识。通过对国内外典型天然氢气显示的数据统计,系统总结了全球天然氢气规模聚集的成因类型、并分析了天然氢气藏的分布和成藏特征。研究结果表明:①天然氢气的成因复杂多样,主要包括水岩反应、地幔脱氢、水的辐解、岩石破碎、有机质热解以及微生物作用等,其中,水岩反应生氢和地幔脱气生氢在自然界中普遍发生,在各种地质环境中广泛存在,且其生氢速率高、生氢量大,因此是天然氢气规模生成最重要的2种成因类型。②天然氢气藏的赋存环境集中体现于三大地质背景中:板块俯冲带、前寒武纪富铁地层发育区以及裂谷构造系统。③天然氢气藏的盖层条件受多个因素的影响,不仅要考虑盖层本身的封盖能力,还要考虑由于氢活跃的物理化学性质导致盖层机械性能发生的变化,影响其脆性-韧性行为形成新的裂缝而产生氢气的逃逸。④地下微生物利用氢气进行代谢活动、中深层的加氢生烃作用等耗烃作用不利于氢气规模聚集,因此在寻找天然氢气生成有利区时,应该避开氢被大量消耗的区域。⑤天然氢气的生成时间尺度短和易扩散性等因素,使得天然氢气成藏表现出动态成藏的特征,只要氢生成与散失始终处于一种动态平衡,就能够富集成藏。地下水是水岩反应生氢的必要条件,国外发现的很多天然氢气藏都分布在地下水循环较好的地区。

反应温度及压力对三塘湖盆地褐煤热解产物分布影响

煤在气化通道中气化反应效率是影响煤炭地下气化气体组分与热值的关键问题。为揭示反应温度和压力对三塘湖盆地褐煤在水蒸气中气化行为和产物分布特征影响,基于固定床热解炉对三塘湖盆地西山窑组褐煤进行不同反应温度和压力热解试验。结果表明:随反应温度升高(300~900℃),气体质量分数由3.84%增至24.29%,水和焦油质量分数先增后减;高温下反应温度升高,加剧二次反应,H_(2)和CH_(4)体积显著增加,900℃体积最大分别为100.89、106.09 mL/g,污染物总质量减少,900℃质量分数相对小,17.72 mg/g。增加反应压力(1.5~3.0 MPa),利于提高半焦转化率和增加气体质量分数。高温下反应压力增加,加剧二次反应,利于反应加氢气化和甲烷化发生,导致CH_(4)体积显著增加,700℃CH_(4)体积最多增加26.89 mL/g,但在700℃会促进自由基加氢饱和反应,污染物总质量增加。建议在实际生产中,通过控制注汽移动速度适当增加反应温度并提高反应压力,且控制气化反应区的温度远离700℃,利于H_(2)和CH_(4)生成,以提高煤炭地下气化工艺高效清洁开发。研究成果可为三塘湖盆地西山窑组褐煤煤炭地下气化工艺提供指导。

Iron-doped nickel disulfide nanoarray： A highly efficient and stable electrocatalyst for water splitting

Developing efficient water-splitting electrocatalysts, particularly for the anodic oxygen evolution reaction （OER）, is an important challenge in energy conversion technologies. In this study, we report the development of iron-doped nickel disulfide nanoarray on Ti mesh （Fe0.1-NiS2 NA/Ti） via the sulfidation of its nickel-iron-layered double hydroxide precursor （NiFe-LDH NAFFi）. As a three-dimensional OER anode, Fe0.1NiS2 NA/Ti exhibits remarkable activity and stability in 1.0 M KOH, with the requirement of a low overpotential of 231 mV to achieve 100 mA·cm^-2. In addition, it exhibits excellent activity and durability in 30 wt.% KOH. Notably, this electrode is also efficient for the cathodic hydrogen evolution reaction under alkaline conditions.

泡沫镍原位生长普鲁士蓝类似物构筑镍铁双金属氧化物催化剂的氧析出反应性能研究

开发高性能、低成本的氧析出反应(OER)催化剂对促进电解水制氢降低电耗、提高经济性具有重要意义。以导电泡沫镍为基底,采用冰水浴法原位生长镍铁普鲁士蓝类似物,氧化制备了镍铁双金属氧化物催化剂。分别采用X射线衍射、扫描电镜、高分辨率透射电镜和X射线光电子能谱方法对催化剂的物相组成、微观形貌和表面化学状态进行了表征,并采用电化学测试表征了催化剂的OER催化性能。结果表明,当氧化温度为200℃、氧化时间为2 h时,制备的催化剂中镍铁双金属氧化物高度分散在泡沫镍基底上,纳米颗粒最小,平均粒径为71 nm,可暴露的催化反应活性位点多,表现出最优的OER催化性能。该催化剂在1.0 mol/L的KOH电解液中,电流密度为10 mA/cm^(2)时,过电位仅为272 mV,并在电流密度为100 mA/cm^(2)时稳定运行了40 h,表现出优异的OER电化学稳定性。

硫酸-氨水体系回收磷铁渣制备电池级磷酸铁实验研究

研究采用硫酸-氨水体系,分别考察了浸取反应阶段的n(H_(2)SO_(4))∶n(Fe)、反应温度、反应时间对铁磷回收率的影响;以及合成反应阶段氨水加入时间和体系pH对磷酸铁指标的影响。实验结果表明,先在n(H_(2)SO_(4))∶n(Fe)=1.5,反应温度80℃,反应时间2 h条件下浸出铁、磷;再在10%氨水50 min匀速加入,生成碱式磷酸铁,在pH=1.5的条件下进行合成反应。可制备各项物化及电性能指标优异的电池级磷酸铁。

锌铝镁表面腐蚀黑斑缺陷研究

本文通过对光伏支架用锌铝镁产品在使用时表面出现的腐蚀黑斑缺陷进行分析,采用SEM和EDS方式检测黑斑处的组织结构及成分,研究锌铝镁在加工运输过程中黑斑产生的机理及原因。结果表明:锌铝镁产品由于在存储过程中进水或水汽凝结在表面未及时进行加工处理和通风干燥,局部发生电化学腐蚀反应,生成程度不一的腐蚀产物,宏观上表现为变色、发黑等现象,形成腐蚀黑斑缺陷。

水蒸气对甲烷在金属铁表面还原NO行为的影响

采用程序控温电加热水平陶瓷管反应器,在N2气氛和模拟烟气气氛中、300-1100℃下,研究了水蒸气对甲烷在金属铁表面还原NO行为的影响,并对反应前、后铁样品进行了X光衍射（XRD）、扫描电子显微镜（SEM）及X光电子能谱（XPS）等表征。结果表明,水蒸气对甲烷在金属铁表面还原NO行为的影响较小。在N2气氛中,水蒸气参与了金属铁的氧化;与无水蒸气时相比,水蒸气存在时NO还原效率有所下降。当水蒸气含量从2.5%增加到7%时,由于水蒸气对金属铁的氧化导致其表面形成疏松的微观孔隙,使得NO的还原效率随水蒸气含量的增加而提高。甲烷则参与了铁氧化物的还原,使铁样品表面形成相对致密的Fe3O4和FeO氧化层,不利于NO与金属铁的接触,使得NO的还原效率低于无甲烷时的结果。在模拟烟气条件下,水蒸气使得甲烷在金属铁表面还原NO的效率增加;在1050℃下,反应段过量空气系数SR1=0.7和燃尽段过量空气系数SR2=1.2时,含7%的H2O和无H2O条件下脱硝效率分别为96.7%和90.6%。而在湿烟气中SO2使NO还原效率略有下降。持久性脱硝实验结果表明,当反应温度为1050℃时,在含7%的H2O、0.02%的SO2的模拟烟气中,1.14%的甲烷在金属铁表面持续50h都能保持90%以上的脱硝效率。

水蒸气对煤焦恒温下燃烧特性的影响

利用自制的恒温热重测量实验台,研究了水蒸气对煤焦燃烧特性的影响规律。结果表明:在低氧浓度下,水蒸气对煤焦燃烧影响显著,使燃烧失重速率增大,燃尽时刻提前,影响程度随氧气浓度的增加而减弱,主要是由于在低氧浓度下,水蒸气与煤焦发生了气化反应,并且反应随着氧浓度的增加而减弱;反应温度越高,水蒸气对煤焦燃烧特性影响越显著;气氛中存在二氧化碳,水蒸气仍能改善煤焦的燃烧特性;原煤煤化程度越高,水蒸气对煤焦燃烧特性的影响越小,即水蒸气对反应活性高的煤焦燃烧影响明显。