CeO2-Al2O3复合载体负载Ni基催化剂催化COx共甲烷化性能

通过浸渍沉淀法分别制备Ni/Al₂O₃、Ni/CeO₂和Ni/CeO₂-Al₂O₃催化剂,并对其分别进行不同CO/CO₂比例下COx共甲烷化性能评价。发现Ni/Al₂O₃催化剂催化CO转化为CH4的能力明显高于Ni/CeO₂,而催化CO₂甲烷化的性能则相反。采用Ni/CeO₂-Al₂O₃催化剂,可以在提高CO转化率的同时而不降低CO₂转化率。结合BET、XRD、TPR、TPD和原位红外等各种表征手段,发现CeO₂掺杂虽然降低了催化剂的比表面积和金属Ni的分散度,但却可明显提高其吸附活化CO₂的能力,这主要是由于具有较高含量氧空位的CeO₂的掺杂可以提高载体表面碱性位,促使共甲烷过程中CO_...     

ZrO2-Al2O3复合氧化物对负载Ni基催化剂合成甲烷的性能影响

采用并流沉淀法制备了不同配比的ZrO2-Al2O3复合氧化物,并通过浸渍法制备了10% Ni/ZrO2-Al2O3催化剂,考察了复合氧化物载体的水热稳定性及ZrO2与Al2O3的配比对合成气制甲烷Ni基催化剂性能的影响。研究结果表明：ZrO2的添加能在一定程度上抑制Al2O3的水解反应,这可能是ZrO2与Al2O3形成固溶体所致。随着ZrO2含量增加,复合氧化物载体的水热稳定性先降低后升高,当ZrO2与Al2O3质量比为0.24时,载体的水热稳定性最好。不同配比的ZrO2-Al2O3复合氧化物负载Ni基催化剂的稳定性与载体的水热稳定性变化是一致的,说明载体的抗水热能力增强,催化剂结构更稳定,催化剂的活性稳定性相应增加。     

负载Ni催化剂表面Ni的形态及其甲烷化活性研究

采用浸渍法制备了具有不同Ni负载量的NiO/γ-Al2O3催化剂,经过不同温度下的焙烧处理后得到一系列共9个催化剂样品。借助X射线光电子能谱分析比较Ni负载量和焙烧处理温度对Ni在催化剂载体表面存在的形态。结果表明,对于Ni负载量为10%的样品,Ni离子会在催化剂表面以八面体配位的镍和表面尖晶石NiAl2O4的形态存在,随着焙烧温度的提高,以表面尖晶石NiAl2O4形式存在的Ni的比例也增加;当Ni负载量达到20%以上,以NiO形态存在的Ni会更多的出现在催化剂表面,而提高焙烧温度不利于NiO的存在。CO甲烷化微反评价的结果显示,表面富集NiO的催化剂具有更好的甲烷化催化活性。     

ZrO2添加对MoO3/Al2O3催化剂耐硫甲烷化性能的影响

采用共沉淀法制备了ZrO₂-Al₂O₃复合载体,并进一步制备了MoO₃/ZrO₂-Al₂O₃催化剂,考察了不同ZrO₂质量分数对催化剂结构及其耐硫甲烷化性能的影响。利用N₂物理吸附、X射线衍射、H₂程序升温还原和透射电子显微镜等手段对催化剂的结构进行了表征。结果表明,MoO₃/ZrO₂-Al₂O₃中ZrO₂的添加可以明显削弱MoO₃与载体间的相互作用,促进Mo物种的还原,适量ZrO₂的存在还有助于提高催化剂的比表面积,改善Mo活性相的分散性,使催化剂表现出优异的耐硫甲烷化活性。     

不同载体负载的Mo基甲烷化催化剂

研究γ-Al₂O₃、CeO₂和ZrO₂负载的Mo基催化剂性质及其甲烷化性能。采用N2物理吸附、H₂程序升温还原、X射线衍射和透射电镜对催化剂进行表征,使用固定床,在550 ℃、3 MPa、5 000 h^-1、V(H₂)∶V（CO）=1.0且含有H2S的合成气中对催化剂甲烷化性能进行测试。结果表明,3种载体中,Mo在ZrO₂载体上分散度最高,甲烷化反应中Mo/ZrO₂催化剂活性最高; CeO₂负载的Mo相抗烧结能力最强,甲烷化反应中Mo/CeO₂催化剂稳定性最好。     

负载型Ni基CO甲烷化催化剂研究进展

负载型Ni基催化剂是应用于CO甲烷化反应的重要催化剂,其金属分散度、活性位结构和化学组成是决定催化剂活性与稳定性的关键因素。综述了金属Ni活性中心结构、载体与助剂对负载型Ni基催化剂甲烷化反应活性和稳定性的影响,在提高催化剂活性的基础上,为开发低成本的负载型Ni基催化剂具有重要意义。     

ZrO2-Al2O3复合载体对镍基催化剂甲烷化性能的影响

采用分步浸渍法制备了不同ZrO2载量的Ni/ZrO2-Al2O3催化剂,利用N2物理吸附、X射线衍射(XRD)、H2程序升温还原(H2-TPR)、H2程序升温脱附(H2-TPD)、程序升温氧化(TPO)等手段对催化剂的结构进行表征,并考察了其在低H2/CO比(H2/CO约为1)下CO甲烷化的催化性能。结果表明,ZrO2助剂可削弱NiO与载体Al2O3间的相互作用,抑制镍铝尖晶石的生成。适量ZrO2的引入有助于提高活性组分Ni的还原度和分散度,对催化剂的甲烷化性能有促进作用。通过分析反应后催化剂上的积炭性质,发现ZrO2的加入能有效地抑制低活性碳物种的生成,提高催化剂的抗积炭能力,从而改善催化剂的稳定性。     

浸渍溶液对Ni/Al_2O_3催化剂CO甲烷化性能的影响

通过浸渍法制备Ni/Al_2O_3催化剂,研究不同浸渍溶液(水、无水乙醇、N,N-二甲基甲酰胺)对催化剂的结构和甲烷化反应性能的影响。采用X射线衍射、氮气吸附脱附、紫外-可见光漫反射光谱、氢气程序升温还原、扫描电子显微镜等分析方法对催化剂的结构和形貌进行表征。结果表明,以DMF作为浸渍溶剂制备的催化剂(Ni/Al_2O_3-D)具有较小的镍颗粒尺寸和强的金属-载体作用力,在CO甲烷化反应中表现出更好的低温活性、高甲烷选择性和高温稳定性。     

CO_2 methanation over TiO_2–Al_2O_3 binary oxides supported Ru catalysts

TiO_2 modified Al_2O_3 binary oxide was prepared by a wet-impregnation method and used as the support for ruthenium catalyst. The catalytic performance of Ru/TiO_2–Al_2O_3catalyst in CO_2 methanation reaction was investigated. Compared with Ru/Al_2O_3 catalyst, the Ru/TiO_2–Al_2O_3catalytic system exhibited a much higher activity in CO_2 methanation reaction. The reaction rate over Ru/TiO_2–Al_2O_3 was 0.59 mol CO_2·(g Ru)1·h-1, 3.1 times higher than that on Ru/Al_2O_3[0.19 mol CO_2·(gRu)-1·h-1]. The effect of TiO_2 content and TiO_2–Al_2O_3calcination temperature on catalytic performance was addressed. The corresponding structures of each catalyst were characterized by means of H_2-TPR, XRD, and TEM. Results indicated that the averaged particle size of the Ru on TiO_2–Al_2O_3support is 2.8 nm, smaller than that on Al_2O_3 support of 4.3 nm. Therefore, we conclude that the improved activity over Ru/TiO_2–Al_2O_3catalyst is originated from the smaller particle size of ruthenium resulting from a strong interaction between Ru and the rutile-TiO_2 support, which hindered the aggregation of Ru nanoparticles.     

Steady-state methanation kinetics over a Ni/Al2O3 catalyst

Extensive kinetic data for the methanation reaction over a Ni/Al₂O₃ catalyst were obtained in a specially designed gradientless reactor operating at steady state. The reactor pressure was 101.3 kPa, and three temperatures were used, namely, 503, 513 and 523 K. The following three-parameter phenomenological model based on a proposed Langmuir-Hinshelwood mechanism adequately describes the data: r = L² K₃ K₄^0.5 k₅ P^0.5H₂ Pco/ [1 + K₃ (k₅ / k₆)Pco + K₄^0.5 P^0.5H₂ ]² With dissociative adsorption of hydrogen and hydrogen-assisted dissociation of adsorbed carbon monoxide, the postulated mari is the CH surface group, and the rds is the hydrogenation of the surface CH group.     

Kinetics of the methanation of carbon dioxide over a supported Ni-La2O3 catalyst

The kinetics of the methanation of carbon dioxide was investigated using an alumina supported Ni-La₂O₂ catalyst in a differential and integral reactor. In the differential reactor the molar ratio of H₂ to CO₂ was varied from 0.6 to 30. In the integral reactor the rates were measured with up to 90% conversion. Both reactor tests were carried out at temperatures between 513 and 593 K. The experimental results were described by a Langmuir-Hinshelwood type equation. The kinetics can be explained by assuming equilibrium of dissociative carbon dioxide and hydrogen adsorption, and assuming hydrogenation of surface carbon as the rate determining step.     

生物质合成气甲烷化机理及催化体系研究进展

天然气的供需矛盾促使人们寻找新的天然气资源,其中利用生物质合成天然气（Bio-SNG）的替代技术受到了全世界的关注。在整个工艺过程中,生物质合成气制取甲烷是关键技术,而甲烷化催化剂是其核心要素。简述了近年来生物质合成气甲烷化机理及其催化体系的研究进展,重点讨论了合成气中CO甲烷化、CO₂甲烷化反应机理,以及甲烷化催化剂中活性金属、助剂和载体对CO甲烷化、CO₂甲烷化以及CO与CO₂共存条件下甲烷化反应性能的影响,分析了目前仍存在的主要问题,并指出了进一步研究的发展方向。     

二氧化碳甲烷化催化剂的研究进展

CO₂催化加氢甲烷化反应是温室气体CO₂资源化利用的有效途径之一。本文回顾了CO₂催化加氢甲烷化催化剂的研究现状, 其中Ni基催化剂是研究最为广泛的CO₂甲烷化催化剂。重点介绍了Al₂O₃、SiO₂和La₂O₃载体及CeO₂和La₂O₃助剂等对Ni基催化剂CO₂甲烷化性能的影响, 阐述了载体的结构、电子性能、化学性能和助剂等对Ni基催化剂CO₂甲烷化性能的影响。结合几种非Ni基CO₂甲烷化催化剂的对比研究发现, 具有有序介孔结构的Co基催化剂也表现出了优越的CO₂甲烷化性能。由此表明, 催化剂新颖的结构也是影响CO₂甲烷化性能的重要因素, 通过催化剂结构、组成等的调变, 能实现CO₂低温高效甲烷化, 为CO₂甲烷化工业化进程奠定基础。     

Selective methanation of CO over supported Ru catalysts

The catalytic performance of supported ruthenium catalysts for the selective methanation of CO in the presence of excess CO₂ has been investigated with respect to the loading (0.5–5.0 wt.%) and mean crystallite size (1.3–13.6 nm) of the metallic phase as well as with respect to the nature of the support (Al₂O₃, TiO₂, YSZ, CeO₂ and SiO₂). Experiments were conducted in the temperature range of 170–470 °C using a feed composition consisting of 1%CO, 50% H₂ 15% CO₂ and 0–30% H₂O (balance He). It has been found that, for all catalysts investigated, conversion of CO₂ is completely suppressed until conversion of CO reaches its maximum value. Selectivity toward methane, which is typically higher than 70%, increases with increasing temperature and becomes 100% when the CO₂ methanation reaction is initiated. Increasing metal loading results in a significant shift of the CO conversion curve toward lower temperatures, where the undesired reverse water–gas shift reaction becomes less significant. Results of kinetic measurements show that CO/CO₂ hydrogenation reactions over Ru catalysts are structure sensitive, i.e., the reaction rate per surface metal atom (turnover frequency, TOF) depends on metal crystallite size. In particular, for Ru/TiO₂ catalysts, TOFs of both CO (at 215 °C) and CO₂ (at 330 °C) increase by a factor of 40 and 25, respectively, with increasing mean crystallite size of Ru from 2.1 to 4.5 nm, which is accompanied by an increase of selectivity to methane. Qualitatively similar results were obtained from Ru catalysts supported on Al₂O₃. Experiments conducted with the use of Ru catalyst of the same metal loading (5 wt.%) and comparable crystallite size show that the nature of the metal oxide support affects significantly catalytic performance. In particular, the turnover frequency of CO is 1–2 orders of magnitude higher when Ru is supported on TiO₂, compared to YSZ or SiO₂, whereas CeO₂- and Al₂O₃-supported catalysts exhibit intermediate performance. Optimal results were obtained over the 5%Ru/TiO₂ catalyst, which is able to completely and selectively convert CO at temperatures around 230 °C. Addition of water vapor in the feed does not affect CO hydrogenation but shifts the CO₂ conversion curve toward higher temperatures, thereby further improving the performance of this catalyst for the title reaction. In addition, long-term stability tests conducted under realistic reaction conditions show that the 5%Ru/TiO₂ catalyst is very stable and, therefore, is a promising candidate for use in the selective methanation of CO for fuel cell applications.     

Influence of the support on CO2 methanation over Ru catalysts: an FT-IR study

The hydrogenation of CO₂ to methane has been investigated over Ru catalysts supported on zeolite (H-ZSM-5) and on silica. Supported Ru catalysts were very active for the hydrogenation of CO₂. Ru/ZSM-5 was more selective to methane than Ru/SiO₂. On the basis of FT-IR spectra of CO and CO₂ adsorbed on the catalysts, it has been suggested that this behaviour can be related to a higher positive polarization of ruthenium on the zeolite. This leads to a weaker Ru–CO bond on the H-ZSM-5-supported sample with a corresponding increase of the hydrogen surface coverage that favours the transformation of the intermediate CO to methane. This revised version was published online in July 2006 with corrections to the Cover Date.