Ni-Co双金属催化剂在二氧化碳重整甲烷反应中的催化活性研究

采用等体积浸渍法制备了Ni/BaTiO3、Co/BaTiO3和Ni-Co/BaTiO3催化剂,并在固定床反应装置上考察了在973~1 073 K这些催化剂对CO2重整CH4反应的催化活性,且采用程序升温还原技术对催化剂进行表征,发现与单金属催化剂相比,Ni-Co/BaTiO3双金属催化剂有更为优越的催化活性。结果表明在Ni-Co/BaTiO3催化剂中Ni和Co之间产生了一定的协同作用。同时研究了不同的制备方法对Ni-Co双金属催化剂催化活性的影响,用溶胶-凝胶法制备的催化剂具有更高的催化活性。     

钙钛矿型复合氧化物LaNiO_3的制备及其在CH_4/CO_2重整反应中的应用

采用溶胶-凝胶法制备钙钛矿型复合氧化物LaN iO3,采用XRD、TG-DTA作为表征手段,并且研究其在CH4/CO2重整反应中的应用。结果表明:经800℃焙烧,钙钛矿型复合氧化物的结构已经完全形成。在CH4/CO2重整反应中,H2/CO的比值总是小于1,这是因为存在逆水煤气反应。     

甲烷二氧化碳催化重整催化剂研究进展

甲烷二氧化碳催化重整反应由于对于环境保护与综合利用资源具有重大意义,近年来得到了研究者的广泛重视。本文参阅众多文献,概述了二氧化碳、甲烷催化重整反应的研究动态。着重介绍了催化剂活性组分的选取,载体影响和助剂作用等方面的最新进展。     

Ni-Co bimetallic catalyst for CH4 reforming with CO2

A co-precipitation method was employed to prepare Ni/Al₂O₃-ZrO₂, Co/Al₂ O₃-ZrO₂ and Ni-Co/Al₂O₃-ZrO₂ catalysts. Their properties were characterized by N₂ adsorption (BET), thermogravimetric analysis (TGA), temperature-programmed reduction (TPR), temperature-programmed desorption (CO₂-TPD), and temperature-programmed surface reaction (CH₄-TPSR and CO₂-TPSR). Ni-Co/Al₂O₃-ZrO₂ bimetallic catalyst has good performance in the reduction of active components Ni, Co and CO₂ adsorption. Compared with mono-metallic catalyst, bimetallic catalyst could provide more active sites and CO₂ adsorption sites (C + CO₂ = 2CO) for the methane-reforming reaction, and a more appropriate force formed between active components and composite support (SMSI) for the catalytic reaction. According to the CH₄-CO₂-TPSR, there were 80.9% and 81.5% higher CH₄ and CO₂ conversion over Ni-Co/Al₂O₃-ZrO₂ catalyst, and its better resistance to carbon deposition, less than 0.5% of coke after 4 h reaction, was found by TGA. The high activity and excellent anti-coking of the Ni-Co/Al₂O₃-ZrO₂ catalyst were closely related to the synergy between Ni and Co active metal, the strong metal-support interaction and the use of composite support.     

Ni含量对介孔Ni-CaO-ZrO2催化剂上CH4-CO2重整反应的影响研究

采用并流共沉淀法制备了Ni含量不同的介孔Ni-CaO-ZrO2纳米复合氧化物催化剂,研究了其在CH4-CO2重整反应中的催化性能。利用N2吸附-脱附(BET)、X射线粉末衍射(XRD)、程序升温还原(TPR)以及程序升温氧化(TPO)等手段对催化剂进行了表征。结果表明,Ni含量对催化剂的物化性质和催化性能有较大影响,低Ni含量的催化剂具备较完善的介孔结构,该种结构非常有利于Ni物种的分散及其在高温下的抗烧结能力,从而提高了催化剂的稳定性;但过低的Ni负载量会造成催化剂表面Ni活性位过少,进而影响催化剂的活性;另一方面,Ni含量过高会导致催化剂介孔结构的坍塌,Ni在反应条件下烧结严重,大尺寸的Ni颗粒会大大增加积炭的生成,从而造成催化剂失活。     

Carbon deposition and catalytic deactivation during CO2 reforming of CH4 over Co/MgO catalyst

The deactivation mechanism of Co/MgO catalyst for the reforming of methane with carbon dioxide was investigated. The conversion of CH₄ displayed a significant decrease in the initial stage caused by carbon deposition. There were two types of cokes, carbon nanotubes (CNTs) and carbon nano-onions (CNOs). The number of the CNO layers that coated on the surface of Co nanoparticles (NPs) increased rapidly in the initial reforming time, which was responsible for the deactivation of the Co/MgO catalyst. The deposition of CNOs was attributed to the oxidation of Co NPs. Therefore, the deactivation of the Co/MgO catalyst was originated from the first oxidization of the Co NPs into Co₃O₄ by O species (OH intermediate, CO₂, H₂O) during the reforming reaction, which accelerates the formation of coke that blocked the active metal, thus led to catalyst deactivation.     

Improved catalytic activity of SiC supported Ni catalysts for CO2 reforming of methane via surface functionalizations

The effect of surface functionalizations on structural and catalytic properties of SiC supported Ni catalysts for CO₂ reforming of methane has been investigated. Commercial SiC was surface functionalized to form a carbon composite (C-SiC) and an N-doped carbon composite (N-C-SiC) at the interface of SiC. Micro- and meso-pores were generated after surface functionalizations. The reforming activity followed the sequence of Ni/N-C-SiC > Ni/C-SiC > Ni/SiC, which can be rationalized by the enhanced Ni dispersion and enriched basic sites on the functionalized catalysts. The present work demonstrates surface functionalization as a simple method to improve the catalytic activity of SiC supported catalysts.     

Influence of binder on the porosity of carbon materials

The formation of porosity in carbon materials is considered. In hot-pressed materials with medium-sized grains, porosity is formed by the destruction of binder when blanks are fired to 600°C. In cold-pressed small-grain materials, shrinkage and binder destruction are responsible for the porosity. Up to 600°C, the yield of volatiles and shrinkage compensate the development of porosity, which mainly appears above 600°C. Using various binders, we may obtain carbon materials with small or large porosity. In addition, the binder affects the pore size and distribution. Methods of producing carbon materials with elevated porosity are considered, including the use of filler from a single size fraction and the use of pore-forming agents, Highly porous carbon materials are also produced from binder, with no filler. The raw materials employed are synthetic tars or mesophase pitch. The properties of carbon materials with different pore content are compared.     

Effects of promoters on catalytic activity and carbon deposition of Ni/γ‐Al2O3 catalysts in CO2 reforming of CH4

Catalytic reforming of methane with carbon dioxide was studied in a fixed‐bed reactor using unpromoted and promoted Ni/γ‐Al₂O₃ catalysts. The effects of promoters, such as alkali metal oxide (Na₂O), alkaline‐earth metal oxides (MgO, CaO) and rare‐earth metal oxides (La₂O₃, CeO₂), on the catalytic activity and stability in terms of coking resistance and coke reactivity were systematically examined. CaO‐, La₂O₃‐ and CeO₂‐promoted Ni/γ‐Al₂O₃ catalysts exhibited higher stability whereas MgO‐ and Na₂O‐promoted catalysts demonstrated lower activity and significant deactivation. Metal‐oxide promoters (Na₂O, MgO, La₂O₃, and CeO₂) suppressed the carbon deposition, primarily due to the enhanced basicities of the supports and highly reactive carbon species formed during the reaction. In contrast, CaO increased the carbon deposition; however, it promoted the carbon reactivity. © 2000 Society of Chemical Industry     

镍负载柱撑蛭石催化甲烷与二氧化碳重整制合成气

用浸渍法制备12Ni-PCVMT催化剂,考察了制备方法对其结构及甲烷干重整催化性能的影响。结果表明,在常压,750℃条件下,经过17 h在线评价后,12Ni-PCVMT催化剂具有高的反应活性和稳定性,具有较好的镍分散性、粒径分布更均匀,比表面积较大,从而具有更好的Ni抗烧结能力及抗积炭性。     

光辐照驱动CH4/CO2催化重整制合成气

以等离子体还原制备的Ni/Al2O3和Ni/MgO-Al2O3为催化剂,用氙灯模拟太阳光聚光系统进行CH4-CO2重整反应,并考察其催化性能及能量转化效率,实验结果表明,以等离子体还原并加入MgO助剂制备的Ni/MgO-Al2O3催化剂具有较好的低温催化活性,在温度为740℃时,CH4和CO2的最高转化率分别为83.6 25%.1和%,能量转化效率为41.5%,大大高于光伏法制氢效率的10.85%;XRD表征表明,等离子体还原使催化剂活性组分Ni具有良好的分散性和更小的纳米团簇结构,有利于甲烷的转化;MgO助剂的加入增强了催化剂表面的碱性,促进了CO2的吸附和解离。     

铁基氧载体化学链CO2重整CH4方法制备合成气

提出一种铁基氧载体（Fe₃O₄/FeO）化学链CO₂重整CH₄方法制备合成气。为评价该系统的性能,采用Aspen Plus软件对其进行过程模拟和热力学分析。以CH₄转化率、CO₂转化率、能源利用效率和产气氢碳比（H₂/CO）为评价指标,得到系统的优化运行条件,并研究各操作参数（包括各反应器的温度和压力、氧载体甲烷比和CO₂甲烷比）对系统性能的影响。结果表明：当系统处于优化工况时,得到CH₄转化率为97.91%、CO₂转化率为32.76%、能源利用效率为93.77%及产气氢碳比为0.93。该系统能有效利用CO₂和CH₄这两种温室气体获得较低氢碳比的合成气,利于二甲醚的高效合成。     

Improvement of Pt/ZrO2 by CeO2 for high pressure CH4/CO2 reforming

CH₄/CO₂ reforming over Pt/ZrO₂, Pt/CeO₂ and Pt/ZrO₂ with CeO₂ was investigated at 2 MPa. Pt/ZrO₂, which shows stable activity under 0.1 MPa, and Pt/CeO₂ showed gradual deactivation with time at the high pressure. The deactivation was suppressed drastically on Pt/ZrO₂ with CeO₂ prepared by different impregnation order (co-impregnation of Pt and CeO₂ on ZrO₂, and consecutive impregnation of Pt and CeO₂ on ZrO₂). The amount of coke deposition was found insignificant and similar among all the catalysts (including Pt/ZrO₂ and Pt/CeO₂). Catalytic activity after the reaction for 24 h was in agreement with Pt particle size after the reaction for same period, indicating that the difference of the catalytic stability is mainly dependent on the extent of Pt aggregation through catalyst preparation, H₂ reduction, and the CH₄/CO₂ reforming. Pt aggregation and the amount of coke deposition were least pronounced on (Pt–Ce)/ZrO₂ prepared by impregnation of CeO₂ on Pt/ZrO₂ and the catalyst showed highest stability.     

Role of support in reforming of CH4 with CO2 over Rh catalysts

The reforming of CH₄ with CO₂ over supported Rh catalysts has been studied over a range of temperatures (550–1000 K). A significant effect of the support on the catalytic activity was observed, where the order was Rh/Al₂O₃>Rh/TiO₂>Rh/SiO₂. The catalytic activity of Rh/SiO₂ was promoted markedly by physical mixing of Rh/SiO₂ with metal oxides such as Al₂O₃, TiO₂, and MgO, indicating a synergetic effect. The role of the metal oxides used as the support and the physical mixture may be ascribed to the promotion in dissociation of CO₂ on the surface of Rh, since the CH₄ + CO₂ reaction is first order in the pressure of CO₂, suggesting that CO₂ dissociation is the rate-determining step. The possible model of the synergetic effect was proposed.     

Shell煤气化制合成气与甲烷重整二氧化碳耦合研究

为了优化化工合成过程,节约资源,减排温室气体CO2,采用Aspen Plus软件,基于Gibbs自由能最小原理,对Shell煤气化制合成气与CH4、CO2耦合过程进行模拟。分析了CH4、CO2、O2三者之间的比例对于重整合成气的影响。结果表明:当CO2/CH4体积比为1.02时,O2/CH4体积比为0.1时,得到氢碳比为0.829。通过灵敏度分析了O2量和压力对反应的影响,O2量的增加,反应温度升高,有利于耦合反应的进行;压力的增加,不利于耦合反应,但是加压可以提高生产强度,因此一般都选用加压条件下进行。     

载体对镍基催化剂CH4/CO2重整反应性能的影响

采用等体积浸渍法制备了Ni/BaTiO3、Ni/Al2O3和Ni/BaTiO3-Al2O3催化剂,对催化剂进行表征,并与催化剂活性相关联.发现与单一载体催化剂相比,具有适当比例组成的Ni/BaTiO3-Al2O3催化剂有更为优越的催化性能.结果表明Ni/BaTiO3-Al2O3催化剂有较大的比表面积;复合载体在制备过程中发生了反应,所生成的BaAl2O4可以阻止γ-Al2O3的相变并极大的提高了载体的热稳定性.     

MoO3的晶型对Mo2C制备及其甲烷二氧化碳重整催化性能的影响

于不同温度(350℃、450℃、550℃和650℃)焙烧(NH4)6Mo7O24.4H2O,制得不同晶型的MoO3,以其为前驱体程序升温碳化制备了一系列的Mo2C催化剂,用于催化甲烷二氧化碳重整制合成气的反应进行活性评价。并通过热重分析、X射线衍射分析和程序升温还原等表征,讨论了MoO3的晶型与所制备的Mo2C的体相和催化剂性能的关系。结果表明,350℃和450℃焙烧(NH4)6Mo7O24.4H2O可制得较为单一的正斜方晶结构的α-MoO3,α-MoO3通过范德华力连接的层状结构有利于在程序升温碳化过程中由CH4/H2分解产生的活泼氢和活泼碳插入层间,促进了Mo2C的生成,进而催化性能较佳。     

Modification of alumina support with TiO2-P25 in CO2 reforming of CH4

Catalyst activity and stability for CO₂ reforming of CH₄ depends specifically upon the support and the active metal. A side reaction of dry reforming of methane is the decomposition to carbon that covers the Ni particles causing catalyst deactivation. Hence, an appropriate combination of Ni with support is needed to allow for long term stable operation. In this paper, CO₂ reforming of CH₄ is studied by investigating the effect of addition of TiO₂-P25 separately to γ-Al₂O₃ and α-Al₂O₃ supports used for nickel based catalyst. The reforming reactions are performed using (CO₂:CH₄) feed ratio of 1:1 and reaction temperature range of 500–800 °C. Both fresh and used catalysts are characterized by SEM and TGA techniques. It is found when α-Al₂O₃ support is modified with 20 wt% TiO₂-P25, the catalyst activity and stability is enhanced. The conversion rates of CH₄ and CO₂ without and with 20 wt% TiO₂-P25, respectively, are changed from 72.3% to 76.7% and 73.3% to 81.2%, respectively, and, most importantly, carbon formation is reduced from 28.1 to 12.8, respectively. However, when γ-Al₂O₃ support is modified with TiO₂-P25, the catalyst activity is enhanced with simultaneous increase in carbon formation.     

基于响应面分析法的CO_2-CH_4催化重整工艺优化

文中开展了对CO_2-CH_4催化重整制备合成气的工艺过程研究,以使用最广泛的负载型Ni/γ-Al_2O_3为催化剂,以CO_2的转化率和H_2/CO比为评价指标,利用单因素实验对CO_2与CH_4的转化率及产物H_2/CO的比例进行分析,得到适合F-T合成的低H_2/CO比的合成气。利用Box-Behnken响应面法对CO_2的转化率及H_2/CO比进行优化,得到双响应值下的最佳工艺条件为:CO_2/CH_4摩尔比为1.70,进料空速为8 227.78 h~(-1),反应温度为728.77℃。在双目标下,CO_2最大转化率与最小H_2/CO比分别为87.83%和0.949。在此条件下进行5次平行实验,得到CO_2转化率与H_2/CO比分别为87.89%和0.949。