甲烷二氧化碳重整镍基催化剂的研究进展

甲烷二氧化碳重整制合成气是对甲烷、二氧化碳这2种温室气体资源化利用的有效途径。近年来,研究最多的领域是关于该反应催化剂的开发,其中镍基催化剂的研究最广泛。为了全面了解甲烷二氧化碳重整反应及镍基催化剂的应用,介绍了甲烷二氧化碳重整反应的热力学研究及机理;分析了镍基催化剂的积碳原因及消碳途径;论述了镍基催化剂的载体、助剂、制备方法对催化剂催化性能的影响;最后对镍基催化剂未来的研究方向进行了展望。热力学研究结果显示,高温低压有利于甲烷二氧化碳重整反应的进行;针对甲烷二氧化碳重整反应的机理尚没有统一的定论,不同催化剂应用于该反应,作用机理也不同;镍基催化剂积碳主要由甲烷裂解反应、一氧化碳歧化反应及一氧化碳氧化还原反应产生,为解决积碳问题,从催化剂方面着手,通过调控催化剂性质抑制积碳;载体性质、助剂类型、制备方法不同会对镍基催化剂产生不同作用;镍基催化剂距离工业化应用还有一段距离,在未来发展中可优化催化剂制备条件,深入探究催化剂的积碳机理,理论与实践相结合,进一步探究镍基催化剂的性能。     

催化剂颗粒形状对甲烷水蒸气重整反应的影响及工业反应器模拟

甲烷水蒸气重整工艺是现阶段最主要的工业制氢技术,催化剂颗粒形状和反应器操作条件是影响重整反应器性能和产物组成的重要因素。首先从颗粒尺度研究催化剂形状对甲烷水蒸气重整反应的影响,在不同的反应温度和压力下,计算并比较了球形、柱形和环形催化剂的效率因子,其大小顺序为:柱形 < 球形 < 环形。其次,将反应器床层的质量、热量和动量传递与环形催化剂颗粒的扩散-反应方程相结合,建立了用于描述甲烷水蒸气重整工业反应器的一维轴向数学模型。计算并分析了反应器进口温度和压力对反应器床层的温度和压力分布、催化剂效率因子以及甲烷转化率和各组分浓度分布的影响,确定了适宜的工业反应器进口温度和压力,分别为773 K和3 MPa。     

甲烷二氧化碳催化重整制合成气研究进展

催化剂研究是实现甲烷二氧化碳重整制合成气工业化的关键。对近年来甲烷二氧化碳重整制合成气的催化剂研究进行综述。介绍了贵金属催化剂、非贵金属催化剂及碳化物催化剂在甲烷二氧化碳重整反应中的应用及反应机理,并对催化剂体系研究方向进行展望。     

典型碳氢化合物水蒸气重整制氢研究进展

  烃水蒸气重整是目前获取氢能源的重要方法之一,而甲烷、汽油和柴油作为典型烃类原料可满足于不同规模氢能源的需求。本文重点从催化剂、反应工艺和反应机理及动力学三个方面对甲烷、汽油和柴油蒸汽重整制氢进行介绍和评述。指出甲烷重整制氢镍基催化剂的改性和反应器设计以及反应条件的优化是其必然的发展趋势,汽油和柴油重整制氢催化剂未来设计必须具备高抗硫性和抗积炭性。此外,需加强甲烷、汽油和柴油蒸气重整制氢的机理和动力学研究。     

介微孔分子筛催化剂在甲烷重整反应中的研究进展

针对甲烷重整制氢技术,重点论述了ZSM-5、SBA-15和MCM-41分子筛催化剂不同的制备方法和采用金属粒子对催化剂进行修饰等手段对各种甲烷重整制氢反应的作用规律;在改进分子筛结构方面,尤其是针对甲烷水蒸汽反应的难点提出了相应建议。     

甲烷与二氧化碳催化重整制取合成气的研究进展

综述了甲烷与二氧化碳催化重整制取合成气的最新研究进展,比较了不同类型的催化剂在重整反应过程中的性能差异,分析了催化剂的积炭过程和重整反应机理,对非常规供能方式进行了阐述,指出了甲烷与二氧化碳催化重整制取合成气的研究方向。     

纳米Ni/MgO焙烧温度对甲烷二氧化碳重整反应的影响

甲烷二氧化碳重整反应一直以来都是人们研究的热点问题,本文对甲烷二氧化碳重整反应的催化剂Ni/MgO的焙烧温度进行了研究,使催化剂Ni/MgO得到了适宜的焙烧温度为700~800℃,并在甲烷二氧化碳重整反应中表现出良好的活性和稳定性。     

甲烷与二氧化碳重整制合成气Ni与Co基催化剂的研究进展

综述了助剂、载体与催化剂制备方法对Ni基催化剂、Co基催化剂、Ni-Co基催化剂上甲烷与二氧化碳重整制合成气催化性能的影响,以及甲烷与二氧化碳重整催化反应机理的研究,展望了催化剂未来的发展方向。     

天然气转化制备合成气研究进展

综述了目前转化利用天然气制备合成气的主要方法,包括甲烷水蒸气重整、甲烷部分氧化、甲烷二氧化碳重整、甲烷水蒸气重整与部分氧化耦合反应、甲烷部分氧化与二氧化碳重整耦合反应、甲烷水蒸气重整与二氧化碳重整耦合反应以及甲烷的三重整反应,重点介绍了前3种典型反应所用的催化剂,最后提出将这3种典型反应耦合使用,并辅以晶格氧工艺、等离子体技术、微波技术是未来甲烷转化制备合成气的发展趋势。     

甲烷间接转化制合成气的研究进展

综述了4种甲烷间接转化制合成气的方法,包括甲烷水蒸气重整、甲烷催化部分氧化、甲烷二氧化碳重整、甲烷的CO2-O2联合重整。从生产工艺和催化剂角度剖析了每种方法的优缺点,并对甲烷的CO2-O2联合重整发展方向进行了展望。     

Catalytic Dry Reforming of Methane on Ruthenium-Doped Ceria and Ruthenium Supported on Ceria

Two types of Ru–ceria catalysts were investigated, one prepared by combustion to create an atomically doped metal oxide, and the other, prepared by impregnation, as supported Ru oxide. They have different physical properties (as measured by X-ray photoelectron spectroscopy, X-ray diffraction, and Infrared spectra of adsorbed CO) but identical catalytic activity for dry reforming of methane. We show that the catalyst for dry reforming is partially reduced using XPS and IR spectroscopy. Furthermore, transient oxidation reaction spectroscopy with oxygen pulses confirms partial reduction of the catalyst is necessary for dry reforming activity.     

生物油催化重整制氢研究进展

随着各国新能源行业的兴起,氢能成为最具发展潜力的可再生能源。利用生物油进行催化重整是一种优良、高效的制氢方法,同时拓宽了生物油高值化利用的途径。本文对近年来该领域内的相关研究进行综述,重点介绍了原料对重整反应的影响（不同来源生物油及其模化物）、催化剂特性对重整反应的影响（负载贵金属与非贵金属）以及操作条件对重整反应的影响,对新兴的微波催化重整技术进行了简要介绍,并针对目前该领域所面临的困难提出了一些展望及发展方向,为生物油催化重整制氢提供重要理论依据。     

Formselektives Reformieren an zeolithhaltigen Reformierkatalysatoren

Use of bifunctional Pt/Al₂O₃ catalysts in catalytic reforming units significantly improved production. During the past four decades the power of such catalyst systems has been continuously increased by the introduction of various catalyst modifications. Use of reforming catalysts containing zeolites permits combination of shape selectivity with the conventional reforming reaction. Here, the suitability of an erionite containing catalyst for the reforming processes is demonstrated. Gasolines produced with zeolite catalysts are characterised by high values of octane numbers and low content of carinogenic benzene.     

生物油水蒸气催化重整制氢研究进展

氢气作为重要的清洁能源和化工原料,目前主要来源于化石燃料,而生物质经快速热解制得生物油用于水蒸气催化重整制氢被认为是一种高效、环保、经济的可再生能源制氢途径。本文首先综述了近年来生物油水蒸气催化重整制氢相关反应原料;然后重点讨论了生物油水蒸气催化重整反应催化剂研究近况;总结了生物油水蒸气重整反应机理与动力学分析;最后列举了重整反应器等方面的研究进展。相比于生物油,生物油模型化合物因结构简单、转化率与氢气收率高,得到广泛研究;以Ni为代表的活性金属组分催化活性高,金属间协同作用强;不同类型的载体可增强催化剂的稳定性,碱性载体还可吸收CO₂、提高催化剂抗积炭、防烧结等方面的性能;不同结构的反应器在性能方面表现各异,主要以固定床反应器为主。研制高活性、稳定性强的催化剂,提高重整反应的循环稳定性,并总结最符合动力学规律的反应机理,以及研发高效的反应器是今后生物油水蒸气催化重整制氢研究的重点。     

Ni Catalysts Supported on Mesoporous Nanocrystalline Magnesium Silicate in Dry and Steam Reforming Reactions

Mesoporous nanocrystalline MgSiO₃ with high surface area was synthesized by a hydrothermal method and employed as support in dry and steam reforming of methane. Ni/MgSiO₃ catalysts were prepared by an impregnation method and characterized by different techniques. N₂ adsorption analysis indicated that addition of nickel shifted the pore size distributions to smaller sizes. Temperature‐programmed reduction analysis revealed that a higher nickel loading enhanced the reducibility of the catalyst. The catalytic performance was improved with increasing the nickel content. The Ni/MgSiO₃ catalyst exhibited high stability in dry reforming but methane conversion declined with time‐on‐stream in the steam reforming reaction. Temperature‐programmed oxidation profiles of spent catalysts indicated that the high amount of carbon deposited on the catalyst surface in dry and steam reforming was assigned to whisker‐type carbon.     

Thermal sintering studies of an autothermal reforming catalyst

This paper describes a novel approach to life studies on catalysts used in non-isothermal reactors, using a single long-term experiment. Temperature dependence of catalyst aging is determined by comparing the activity reduction of portions of the catalyst from different sections of the reactor, subjected to different temperatures. Time dependence is determined by fitting the drift in catalyst temperatures to a time-dependent reaction rate via a thermodynamic reactor model. Experimentally, a monolithic autothermal reforming catalyst was subjected to thermally accelerated aging under reforming conditions in an adiabatic laboratory mini-flow reactor for 1000 h. Methane was used as the fuel. The axial temperature profile of the catalyst was monitored using thermocouples placed at various locations along the catalyst. A gradual change in temperature profile, with increasing temperatures due to decreasing steam-reforming activity, was observed. The aged monolith was cut up into short pieces centered on the thermocouple locations. The pieces, each aged at a different temperature due to its location, were tested individually for activity. The reduced activities were correlated with the aging temperature to obtain the temperature dependence of thermal sintering rates. A generalized power-law equation (GPLE) model for sintering was fit to the activity data. A plug flow reactor (PFR) model describing the reaction was built and the sintering kinetics were incorporated. The PFR model was used to predict changes in catalyst performance due to sintering under normal operating conditions. Thermal sintering deactivation for this catalyst was found to be within acceptable limits for commercial applications.     

Hydrogen Production by Steam Reforming of Liquefied Natural Gas Over Mesoporous Ni-Al2O3 Composite Catalyst Prepared by a Single-step Non-ionic Surfactant-templating Method

A mesoporous Ni-Al₂O₃ composite catalyst (Ni-A-NS) was prepared by a single-step non-ionic surfactant-templating method for use in hydrogen production by steam reforming of liquefied natural gas (LNG). For comparison, a nickel catalyst supported on mesoporous alumina (Ni/A-NS) was also prepared by an impregnation method. The effect of physicochemical properties on the performance of Ni-A-NS catalyst in the steam reforming of LNG was investigated. Ni-A-NS catalyst retained superior textural properties compared to Ni/A-NS catalyst. Nickel oxide species were highly dispersed on the surface of both Ni/A-NS and Ni-A-NS catalysts through the formation of surface nickel aluminate phase. Although both Ni/A-NS and Ni-A-NS catalysts exhibited a stable catalytic performance, Ni-A-NS catalyst showed a better catalytic performance than Ni/A-NS catalyst in the steam reforming of LNG. High nickel surface area and high nickel dispersion of Ni-A-NS catalyst played an important role in enhancing the dehydrogenation reaction of hydrocarbon species and the gasification reaction of adsorbed carbon species in the steam reforming of LNG. High reducibility of Ni-A-NS catalyst was also responsible for its high catalytic performance.     

CH4CO2催化重整制合成气的研究进展

综述了CH₄CO₂催化重整制合成气的研究进展，分析讨论了催化剂的研究状况、反应机理、动力学、催化剂失活特性和非常规供能方式在催化重整反应中的应用等。结果表明，CO₂催化重整过程开发成功的关键是有效抑制催化剂积炭失活。     

Catalytic application of metallic iron from the dyeing sludge ash for benzene steam reforming reaction in tar emitted from biomass gasification

Because it is the most promising method for reforming tar in a gasification system, a catalytic steam reforming reaction of tar using a dyeing sludge ash catalyst that contains mostly iron oxide has been modeled using benzene to investigate whether a steam reforming catalyst produced from waste is viable. The catalytic activity of the ash catalyst is similar to that of the commercially available iron-chrome-based catalyst for the same equivalent total amount of Fe₂O₃. The activity over the ash catalyst has been examined in terms of the weight hour space velocity (WHSV) and the reaction temperature to develop a model for the reaction kinetics. Using a power law model, the reaction order coefficients of the benzene and steam were estimated to be 0.43 and 0, respectively. The activation energy required for the ash catalyst was approximately 187.6 kJ mol^?1. In addition, the reductive properties of the iron oxide in the ash catalyst were also examined via XRD and H₂-TPR analyses.