稀土改性镍催化剂对CO2甲烷化反应的影响

以稀土为助剂 ,金属镍为活性组份 ,研究了不同稀土对镍催化剂的改性作用 ,同时用活性比表面、H2 -TPD、CO2 - TPD及 XPS等方法对催化剂进行了表征。结果表明 ,稀土对镍催化剂的 CO2 甲烷化活性有明显的促进作用 ,其中以稀土 Sm的改善效果最好 ;海泡石和 Sm既能增大镍催化剂的活性比表面积 ,又能提高 H2 和 CO2 的吸附量 ,同时降低反应的活化能 ,增大镍上的电子云密度。     

The influence of Metal Dusting on gas reactions

Gas composition analysis measurements have been performed in the outlet gas stream of a laboratory metal dusting test furnace in order to study the influence of metal dusting on gas reactions. This analysis has shown that carbon deposition is associated with metal dusting, i.e. the material most severely attacked by metal dusting, catalyses the formation of carbon to the largest extent. Also, metal dusting has not been seen to influence the methanation reactions. A kinetic model has been used to interpret the obtained data with respect to the catalytic activity of several high temperature materials showing that the catalytic activity of the material can vary by orders of magnitude for different reactions.     

SMAI法制备的Ni-Ag/SiO_2双金属催化剂的催化性质

应用溶剂化金属原子浸渍（ＳＭＡＩ）法和普通浸渍（ＣＩ）法制备了金属含量相同的ＳｉＯ２负载Ｎｉ－Ａｇ双金属催化剂。研究了这些催化剂在甲苯和二丙酮醇加氢以及ＣＯ２甲烷化反应中的催化性质。结果表明，与组成相同的普通浸渍法催化剂相比，在所有这些反应中ＳＭＡＩ法催化剂都显示出较高的催化活性。这是因为ＳＭＡＩ法催化剂具有较高的分散度和还原性（零价金属百分比）     

The role of oxygen vacancies in the CO2 methanation employing Ni/ZrO2 doped with Ca

The Ni/ZrO₂ catalyst doped with Ca and Ni/ZrO₂ were employed in the CO₂ methanation, a reaction which will possibly be used for storing intermittent energy in the future. The catalysts were characterized by X-ray photoelectron spectroscopy (XPS, reduction in situ), X-ray diffraction (XRD, reduction in situ and Rietveld refinement), electron paramagnetic resonance (EPR), temperature-programmed surface reaction, cyclohexane dehydrogenation model reaction, temperature-programmed desorption of CO₂ and chemical analysis. The catalytic behavior of these catalysts in the CO₂ methanation was analyzed employing a conventional catalytic test. Adding Ca to Ni/ZrO₂, the metallic surface area did not change whereas the CO₂ consumption rate almost tripled. The XRD, XPS and EPR analyses showed that Ca⁺² but also some Ni²⁺ are on the ZrO₂ surface lattice of the Ni/CaZrO₂ catalyst. These cations form pairs which are composed of oxygen vacancies and coordinatively unsaturated sites (cus). By increasing the number of these pairs, the CO₂ methanation rate increases. Moreover, the number of active sites of the CO₂ methanation rate limiting step (CO and/or formate species decomposition, rls) is enhanced as well, showing that the rls occurs on the vacancies-cus sites pairs.     

The influence of CO,CO2 and H2O on selective CO methanation over Ni(Cl)/CeO2 catalyst: On the way to formic acid derived CO-free hydrogen

For the first time the influence of CO, CO₂ and H₂O content on the performance of chlorinated NiCeO₂ catalyst in selective or preferential CO methanation was studied systematically. It was shown that the rate of CO methanation over Ni(Cl)/CeO₂ increases with the increasing H₂ concentration, is independent of CO₂ concentration and decreases with increasing CO and H₂O concentrations; the rate of CO₂ methanation is weakly sensitive to H₂ and CO₂ concentrations and decreases with increasing CO and H₂O concentrations. High catalyst selectivity was attributed to Ni surface blockage by strongly adsorbed CO molecules and ceria surface blockage by Cl, which both inhibit CO₂ hydrogenation.For the first time, selective CO methanation over Ni(Cl)/CeO₂ was studied for deep CO removal from formic acid derived hydrogen-rich gases characterized by high CO₂ (40–50 vol%), low CO (30–1000 ppm) content and trace amounts of water. Composite Ni(Cl)/CeO₂-η-Al₂O₃/FeCrAl wire mesh catalyst was demonstrated to be effective for this process at temperatures of 180–220°С, selectivity 30–70%, WHSV up to 200 L (STP)/(g∙h). The catalyst provides high process productivity, low pressure drop, uniform temperature distribution, and appears highly promising for the development of a compact CO cleanup reactor. Selective CO methanation was concluded to be a convenient way to CO-free hydrogen produced by formic acid decomposition.     

煤制天然气展望

阐述了天然气资源短缺的现实与开发煤制天然气的可行性,简介了煤制天然气的技术途径与经济可行性,指出合理的天然气生产布局及其开发的必要性,建议加强对直接甲烷化、甲烷化催化剂及多联产产业的开发力度。     

电转气地质储能技术的经济性分析

电转气(power-to-gas)是一项将电能转化为高能量密度可燃气体的化学储能技术,该技术与地质储能相结合,有望满足未来大容量储能需求,并成为未来有效储能技术选择之一.电转气地质储能技术中涉及电离制氢、甲烷化、二氧化碳(CO2)地质储存、人工合成甲烷(CH4)地质储存4个阶段.由于电转气地质储能技术发展处于初步阶段,...     

全自热非等压醇烷化净化新工艺替换铜洗净化技改小结

介绍了山东肥城化肥厂利用原有的 10 0 0mm及 80 0mm氨合成装置 ,采用先进的全自热高压醇烷化净化新工艺代替铜洗净化工艺的技术改造及运行情况     

添加稀土氧化物对甲烷化催化剂中镍分散度的影响

本文对稀土氧化物的助剂作用做了进一步研究，对添加１４种稀土氧化物的催化剂进行了活性表面积、ＣＯ吸附ＩＲ谱、表观活化能的测定及ＡＥＳ表面微区分析。结果表明，添加稀土氧化物助剂，提高了镍的分散度，使镍更富集于表面，增加了反应的活性中心数目，反应活化能没有降低，具有结构效应，但不同稀土元素的作用不同。这可能与稀土元素本身的性质有关。     

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.