甲烷干重整Ni基催化剂失活及抑制失活研究进展

使用甲烷和二氧化碳为原料,通过甲烷干重整反应可以将其转化为合成气。由于此反应可以利用甲烷和二氧化碳这两种温室气体,因而近年来受到了研究人员广泛的关注。其中,反应所使用的Ni基催化剂由于其较高的活性和较低的成本得到了较为深入的研究。针对甲烷干重整Ni基催化剂,本文简要介绍了几种常用的制备方法,并指出了在反应条件下存在的活性组分Ni的烧结和积炭的生成这两个问题,还详细分析了其各自的影响因素。另外,还从使用特殊载体、添加助剂以及构造特殊结构三方面阐述了甲烷干重整Ni基催化剂的失活解决方案,并指出解决催化剂的烧结和积炭问题是当前该领域的研究重点。     

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。     

甲烷二氧化碳重整制合成气中积炭效应的数值模拟

通过建立包含动量、质量传递以及化学反应动力学方程的多物理场耦合数值模型,对以Ni为催化剂的甲烷二氧化碳重整制合成气过程中的积炭效应展开了计算。计算结果阐明了包含多孔介质催化剂段的反应通道中的速度场及压力分布,以及在通道中随气体流动以及沉积在催化剂表面的碳颗粒的浓度分布,分析了积炭对 催化剂孔隙率和渗透率的影响,并进一步讨论了甲烷浓度以及温度对积炭产生的影响,最后提出了消减积炭的方法。本文的结论对于进一步研究Ni基催化剂在CH₄-CO₂重整制合成气反应中积炭效应的消减有一定的指导意义。     

Carbon dioxide reforming of methane in kilohertz spark‐discharge plasma at atmospheric pressure

The spark‐discharge plasma, generated between tubular and rotary‐disc electrodes using a sine‐wave high voltage with 5 kHz frequency, was explored for CO₂ reforming of CH₄. Based upon the investigation on the effects of specific energy input and CO₂/CH₄ ratio, the energy costs (EC) and fuel‐production efficiencies (η) at various CO₂/CH₄ ratios (r) in the same conversion range were compared and accordingly their sequences were given: EC (r = 0.5) and EC (r = 3) are the lowest; η(r = 0.5) is the highest. Compared with other nonthermal discharge techniques, the kilohertz spark discharge exhibits low EC and high fuel‐production efficiency, especially at high total‐carbon conversions. Preliminary investigation on partial oxidation and CO₂ mixed reforming at (O₂ + CO₂)/CH₄ = 0.5 exhibited high H₂/CO ratio (nearly 2) and low total‐carbon EC (0.59–0.96 MJ/mol, 58–77% of total‐carbon conversion, and O₂/(CO₂ + O₂) = 0.8). © 2010 American Institute of Chemical Engineers AIChE J, 2011     

甲烷二氧化碳重整镍基催化剂的研究

采用浸渍法制备不同组成催化剂Ni-M/γ-Al₂O₃（M=Zr、Co、Mg、Nd）,通过固定床反应装置考察不同助剂、助剂含量和反应温度对催化剂活性的影响,并对催化剂进行X射线衍射表征。结果表明,14Ni-5Mg/γ-Al₂O₃的催化活性较好,随着反应温度的升高,甲烷转化率和CO收率均升高,反应温度升至800 ℃时,甲烷转化率达97.54%。采用共沉淀法制备载体、浸渍法制备的催化剂14Ni/MgO-Al₂O₃,在反应温度800 ℃、压力1.013 kPa、n(CO₂)∶n(CH₄)=1.2和催化剂用量0.5 g条件下,CO收率高于14Ni-5Mg/γ-Al₂O₃催化剂,但甲烷转化率略低。     

Hydrogen production via chemical looping dry reforming of methane: Process modeling and systems analysis

The present study presents and analyses a family of “chemical looping dry reforming” (CLDR) processes that produce inherently separated syngas (H₂ and CO) streams via a combination of methane cracking in a “cracker reactor” and the Boudouard reaction (i.e., conversion of the formed carbon with CO₂ to CO) in a “CO₂ reactor,” and then further maximize the H₂ yield via conversion of the produced CO via water-gas-shift. Remaining CO₂ emissions are minimized via CO₂ capture and sequestration. Four different configurations are evaluated which differ in how the heat required for the highly endothermic dry reforming reaction is supplied: (i) combustion of additional CH₄ feed (CLDR-CH₄); (ii) combustion of some of the CO produced in the CO₂ reactor (CLDR-CO); and combustion of some of the carbon produced in the cracker reactor with (iii) pure oxygen (CLDR-C-oxy); or (iv) with air (CLDR-C-air). Process models are developed to comparatively analyze the mass and energy balances of these configurations, and benchmark them against H₂-production via conventional dry reforming and steam reforming of methane. Our results show that CLDR-C-oxy is the most promising H₂-production pathway among the chemical looping and conventional technologies both in terms of chemical energy efficiency and in terms CO₂ emissions. Thus, the unique flexibility offered by the production of inherently separated syngas streams in CLDR enables overcoming the disadvantage of the strongly endothermic dry reforming reaction by combusting carbon internally in the reactor and thus achieving highly effective heat integration. Overall, the results support the technical viability and demonstrate the promise for strong process intensification of CLDR compared to conventional dry reforming and even steam reforming, the most widely used H₂-production pathway to-date.     

核壳结构在甲烷干重整中的应用

甲烷干重整可以将两种温室气体(CO₂和CH₄)转化为合成气,传统负载型催化剂存在金属烧结、碳沉积的问题,导致失活。核壳结构催化剂具有空间限域效应,能有效解决以上问题。本文根据壳的种类,将核壳结构分为SiO₂壳层、Al₂O₃壳层和其他壳层三类,并分别从制备方法、形貌结构、催化特性的角度介绍了研究现状。文中指出：氧化硅壳层的优势是制备简单,壳层易于调控,热稳定性高;Al₂O₃壳层能够提供碱性位点,增强CO₂吸附与反应;CeO₂壳层则可以提供氧空位,促进CO₂活化和积炭的气化。据此,本文展望了核壳结构在未来的几个研究方向：对壳层材料的拓展与研究;对蛋黄壳、三明治等新型核壳结构的研究;精准调节核壳结构的形态并研究构效关系;大规模制备和工业应用等。     

An efficient technique for improving methanol yield using dual CO2 feeds and dry methane reforming

Steam methane reforming (SMR)-based methanol synthesis plants utilizing a single CO₂ feed represent one of the predominant technologies for improving methanol yield and CO₂ utilization. However, SMR alone cannot achieve full CO₂ utilization, and a high water content accumulates if CO₂ is only fed into the methanol reactor. In this study, a process integrating SMR with dry methane reforming to improve the conversion of both methane and CO₂ is proposed. We also propose an innovative methanol production approach in which captured CO₂ is introduced into both the SMR process and the recycle gas of the methanol synthesis loop. This dual CO₂ feed approach aims to optimize the stoichiometric ratio of the reactants. Comparative evaluations are carried out from a techno-economic point of view, and the proposed process is demonstrated to be more efficient in terms of both methanol productivity and CO₂ utilization than the existing stand-alone natural gas-based methanol process.     

Evaluation of the economic and environmental impact of combining dry reforming with steam reforming of methane

Lately, there has been considerable interest in the development of more efficient processes to generate syngas, an intermediate in the production of fuels and chemicals, including methanol, dimethyl ether, ethylene, propylene and Fischer–Tropsch fuels. Steam methane reforming (SMR) is the most widely applied method of producing syngas from natural gas. Dry reforming of methane (DRM) is a process that uses waste carbon dioxide to produce syngas from natural gas. Dry reforming alone has not yet been implemented commercially; however, a combination of steam methane reforming and dry reforming of methane (SMR + DRM) has been used in industry for several years.     

太阳能甲烷干重整复杂反应体系的热化学储能特性

基于热力学第一和第二定律对太阳能甲烷干重整复杂反应体系的热力学特性进行建模分析,研究该体系在不同太阳光照强度时的反应器温度响应及热化学储能特性,以及副反应和各部分能量损失对整个体系能量效率的影响规律。通过平衡常数法计算反应器平衡状态时的物质组成,并进而利用热力学模型计算不同条件下入口气转化率、选择性、功效率和能量转换效率的变化规律。结果表明：进料比n(CO₂)/n(CH₄)的升高有助于提高甲烷转化率、选择性、功效率和能量转换效率;反应器温度的变化对系统热化学储能特性的影响显著,在较低温区（923～1123K）,副反应较多,且随着温度的升高副反应逐渐受到抑制,积炭减少,功效率和能量转换效率逐渐升高,并在1123K时达到峰值;温度继续升高（>1123K）,反应器辐射损失显著增加,导致功效率和能量转换效率随温度升高而降低;高温区（>1200K）,副反应受到抑制,复杂反应体系的系统效率同单一反应体系趋于一致,副反应基本对系统性能无影响。     

A review on catalyst development for conventional thermal dry reforming of methane at low temperature

Carbon dioxide (CO₂) utilization and conversion, as one of the main parts of carbon capture, utilization, and storage (CCUS), is not only considered an important way to mitigate global warming but also an attractive industrial route to produce valuable fuels and chemical feedstocks. Catalytic dry reforming of methane (DRM) is a promising technology for carbon dioxide utilization and conversion as it can produce syngas, carbon monoxide (CO), and hydrogen (H₂) for widespread industrial production processes. In most studies of the DRM reaction, a relatively high operational temperature (i.e., >700°C) has been applied since the reactivity limitation of widely used Ni-based catalysts at low temperatures and the extremely endothermic property of the DRM reaction. However, high cost and high requirement of thermal stability for catalysts have become a severe problem impeding the further commercialization of DRM technology. Decreasing the operational temperature (i.e., <700°C) is considered a promising way for further application of the DRM route to convert CO₂ and produce syngas. However, traditional Ni-based catalysts suffered from unsatisfied reactivity and severe coke formation, leading to quick deactivation at low temperatures. Developing a catalyst with excellent catalytic activity, coke resistance, and improved thermal stability is necessary for low-temperature DRM reactions. In recent years, with significant development in materials, catalyst design, and computational simulation, some synthesized catalysts have achieved considerable improvement in catalytic performance in low-temperature DRM. Hence, a review of recent development on low-temperature DRM catalysts is provided here to further guide and profoundly understand catalyst design for low-temperature DRM.     

Dry reforming of methane to synthesis gas over supported molybdenum carbide catalysts

The dry reforming of methane at elevated pressure over supported molybdenum carbide catalysts, prepared from oxide precursors using ethane TPR, has been studied. The relative stability of the catalysts is Mo₂C/Al₂O₃>Mo₂C/ZrO₂>Mo₂C/SiO₂>Mo₂C/TiO₂, and calcination of the oxide precursor for short periods was found to be beneficial to the catalyst stability. Although the support appears to play no beneficial role in the methane dry reforming reaction, the alumina-supported material was stable for long periods of time; this may be important for the production of pelletised industrial catalysts. The evidence suggests that the differences in the stabilities may be due to interaction at the precursor stage between MoO₃ and the support, while catalyst deactivation is due to oxidation of the carbide to MoO₂, which is inactive for methane dry reforming.     

Mechanistic aspects of carbon dioxide reforming of methane to synthesis gas over Ni catalysts

A study of the kinetic isotope effect (CH₄/CO₂ CD₄/CO₂) for carbon dioxide reforming of methane to synthesis gas shows that an isotope effect exists with k_{CH 4}/k_{CD 4} ratio of 1.05–1.97, depending on reaction temperature and catalyst applied. The attainment of stable performance over Ni/La₂O₃ catalyst is found to be related to the strong chemisorption of CO₂, weak chemisorption of CH₄ and slow rate of CH_x formation, and fast rate for CH_x removal by oxidation.     

Intrinsic kinetics of nickel/calcium aluminate catalyst for methane steam reforming

A new catalyst for steam reforming of methane based on nickel/calcium aluminate is prepared. The new catalyst has shown stability and high activity at low steam to methane ratios. In this paper the intrinsic rate equations are derived and parameters estimation made. The rate equations show non-monotonic dependence on steam partial pressure. The rate equations also show that the primary product is CO₂ while CO is formed via the reverse water-gas shift reaction. The mechanism proposed and the rate equations obtained indicate that it may be essential to propose specific rate models for any given catalyst rather than generalized mechanism and rate models.     

助剂MgO对甲烷二氧化碳重整Co/BaTiO3催化剂催化性能的影响

采用溶胶-凝胶法在Co/BaTiO3催化剂中引入助剂MgO,考察了其对甲烷二氧化碳重整Co/BaTiO3催化剂的催化反应性能的影响,利用X射线衍射仪(XRD)、H2程序升温还原(H2-TPR)对催化剂进行了表征,结果表明,助剂MgO使钴催化剂中的活性Co2O3组分增多,还原性和分散性能较好;在n(CO2)∶n(CH4)为1∶1、气相空速(GHSV)为12 000 h-1、反应温度为700℃的条件下,催化剂Co-MgO/BaTiO3表现出良好的催化性能,且反应初期甲烷转化率可达到94.87%,CO选择性可达85.21%,H2收率可达74.08%。     

Z型甲烷蒸汽转化催化剂用于补碳制合成甲醇合成气的研究

选择工业应用效果较好的CNYQ、Z-2和Z-3型催化剂，并补加CO₂,对在其上的甲烷水蒸汽转化制合成气催化反应过程进行了测试研究。结果表明，在适当补加CO₂、反应温度600～850 ℃下，制得的合成气适合于甲醇合成。Z型催化剂用于CH₄-H₂O-CO₂转化制合成甲醇合成气，在当前情况下可满足某些合成甲醇厂的需要。     

基于太阳能蓄热过程的甲烷二氧化碳重整研究进展

热化学储能技术因为其储能密度高、热损小、能长距离运输等优点而成为保证太阳能长久稳定供应的关键技术。本文对基于甲烷二氧化碳重整反应的太阳能热化学储热系统研究现状进行了回顾,重点讨论了甲烷重整催化剂、重整反应器以及储能系统整体的传热特性等3个方向的研究进展。指出新型高效催化剂以及反应器开发和性能测试是目前该领域的主要研究方向。发现辐射热损失、非均匀温度分布特性、辐射热流的时变波动特性,以及由此造成的能量与化学反应的不匹配限制了热化学系统能量储存效率的进一步提高,并提出催化剂的催化特性与物性/结构参数依变关系,反应器辐射吸收特性、传热传质特性和反应特性之间的相互作用机制,以及系统时变动态特性与反应物流/辐射能流的匹配关系是建立甲烷重整热化学储能系统优化设计理论亟待解决的关键问题。     

Investigating dry reforming of methane with spatial reactor profiles and particle‐resolved CFD simulations

Dry reforming of methane (DRM) over nickel in a fixed‐bed reactor of spheres was studied experimentally and with CFD simulations. Temperature and mole fraction profiles were measured in a dedicated profile reactor as function of axial coordinate. Particle‐resolved CFD simulations took into account conjugate heat transfer, surface‐to‐surface radiation, and surface reactions described by microkinetics. Energy transport of CFD simulations were verified by studying heat transfer without chemical reactions. DRM experiments could not be reproduced with the original microkinetics formulation, even with the axial temperature profile applied. A detailed analysis of the microkinetics showed that thermodynamic inconsistencies are present, which are amplified by high surface coverage of CO*. After modifying the mechanism the experiments could be reproduced. This study shows how complex interactions between local transport phenomena and local kinetics can be quantified without relying on transport correlations. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4436–4452, 2016     

流化床在甲烷临氧CO2重整反应中的作用研究

在流化床反应器中进行甲烷临氧CO₂重整制合成气反应。通过计算分析了催化剂颗粒在床层内的流化特性。对比实验表明,流化床反应器在催化剂活性、稳定性、自热过程以及催化剂积炭等方面均体现出比固定床反应器的优越性。在流化床反应器中进行的甲烷自热重整反应,甲烷的转化率接近热力学平衡值,床层温度梯度小于10 ℃, 反应20 h后,催化剂表面无积炭。