Hydrogen production by steam reforming of liquefied natural gas (LNG) over mesoporous nickel–alumina xerogel catalysts prepared by a single-step carbon-templating sol–gel method

A series of mesoporous nickel–alumina xerogel catalysts (denoted as CNAX) were prepared by a single-step carbon-templating sol–gel method using different amount of carbon template (X), and they were applied to the hydrogen production by steam reforming of liquefied natural gas (LNG). Textural properties of CNAX catalysts were improved with increasing the amount of carbon template. CNAX catalysts exhibited diffraction peaks corresponding to nickel aluminate phase, while CNA18 and CNA24 catalysts showed additional bulk nickel oxide phase. From TPR measurements, it was revealed that the interaction between nickel species and alumina in the CNAX catalysts became weakened with increasing the amount of carbon template. Crystallite size of metallic nickel in the reduced CNAX catalysts showed a volcano-shaped trend with respect to the amount of carbon template. In the steam reforming of LNG, CNAX (X = 0, 6, 12, and 18) catalysts exhibited a stable catalytic performance during the reaction, while CNA24 catalyst showed a significant catalyst deactivation. Crystallite size of metallic nickel served as an important factor determining the catalytic performance in the steam reforming of LNG. Initial LNG conversion and initial hydrogen yield increased with decreasing crystallite size of metallic nickel of the catalysts. Among the catalysts tested, CNA12 catalyst with the smallest crystallite size of metallic nickel showed the best catalytic performance.     

Dehydrogenation of Propane on Pt or PtSn Catalysts with Al2O3 or SBA-15 Support

Dehydrogenation of propane on Pt or PtSn catalyst over Al2O3 or SBA-15 support was investigated. The catalysts were characterized by CO-pulse chemisorption, thermogravimetry, temperature-programmed-red...     

Highly active Pt decorated Pd/C nanocatalysts for oxygen reduction reaction

This article describes findings of the correlation between the atomic scale surface structure and the electrocatalytic performance of nanoengineered Pt-Pd/C catalysts for oxygen reduction reaction (ORR), aiming at providing a new fundamental insight into the role of the detailed atomic decorated structure of the catalysts in fuel cell reactions. Carbon-supported Pt decorated Pd nanoparticles (donated as Pt-Pd/C), with Pt coverage close to a monolayer, were prepared from a simple galvanic replacement reaction between Pd/C particles and PtCl₄^2? at room temperature. The decorated architecture was confirmed by extensive microstructural characterization techniques, including TEM, XRD, XPS, HAADF-STEM, ICP and HS-LEIS. The catalysts were also examined for their intrinsic kinetic activities towards oxygen reduction reaction. The results have shown that the Pt-Pd/C catalysts are highly active towards molecular oxygen electrocatalytic reduction. These findings have profound implications to the design and nanoengineering of decorated surfaces of catalysts for oxygen reduction reaction.     

Heavy paraffin dehydrogenation and hydrogenation of nitrobenzene to aniline: Effects of operating conditions

Auto-thermal heat exchanger configurations are recognized as a novel concept in process intensification. In the current study, the influence of operating conditions in a novel coupling reactor with radial-flow pattern is investigated for heavy paraffin dehydrogenation process. Catalytic hydrogenation of nitrobenzene to aniline takes place in the exothermic side and supplies the necessary heat for the endothermic dehydrogenation of heavy paraffin reaction. The performance of the reactor is numerically investigated for various key operating variables, such as inlet molar flow rates of exothermic and endothermic streams, number of subsections, and exothermic side angle. The reactor performance is analyzed based on temperature, olefin production rate, and nitrobenzene conversion.     

加氢催化剂RSDS-21/RSDS-22的器外再生和重生及应用

介绍中化弘润石油化工有限公司600 kt/a催化汽油加氢装置加氢催化剂RSDS-21,RSDS-22首次进行反应器外再生、重生及工业应用情况。经过器外烧炭再生及重生后,RSDS-21中碳质量分数由4.21%下降至0.52%,硫质量分数由5.60%下降至0.51%;RSDS-22中碳质量分数由4.90%下降至0.55%,硫质量分数由5.20%下降至0.84%,重生后催化剂颗粒完整。各项开工数据表明,经过硫化处理后,催化剂活性恢复较好,基本达到装置初次开工时催化剂活性水平,各项产品指标达到国标要求。反应在低温状态下进行,有利于降低产品汽油辛烷值损失,延长催化剂使用寿命。此次催化剂再生、重生效果较好,达到生产要求。     

Graft copolymers from commercial chlorinated polypropylene via Cu(0)‐mediated atom transfer radical polymerization

Commercially available chlorinated polypropylene has been used as a macroinitiator for the Cu(0)‐mediated atom transfer radical polymerization of methyl methacrylate and tert‐butyl acrylate to obtain well‐defined graft copolymers. The relatively narrow molecular weight distribution in the graft copolymers and linear kinetic plots indicated the controlled nature of the copolymerization reactions. Both Fourier transform infrared and ¹H NMR studies confirmed that the graft reactions had taken place successfully. After graft copolymer formation, tert‐butyl groups of poly(tert‐butyl acrylate) side chains were completely converted into poly(acrylic acid) chains to afford corresponding amphiphilic graft copolymers. © 2016 Society of Chemical Industry     

Innovative electrodes for direct methanol fuel cells based on carbon nanofibers and bimetallic PtAu nanocatalysts

Direct methanol fuel cells are very promising power sources, but the easy poisoning of the platinum anode electrocatalyst by CO-like reaction intermediates, restricts their industrial application and commercialization. The development of Pt-based alloys or bimetallic catalysts, in which the second metal acts as Pt poisoning inhibitor, is one of the main promising solutions to this problem. In this work we have combined the use of unconventional methods to deposit the catalyst nanoparticles with unconventional carbon supports. Innovative electrodes made of platelet carbon nanofibers, directly grown on graphite paper, as substrate for electrodeposited platinum and gold bimetallic nanoparticles, have been developed. These electrodes allow having a single layer with both the diffusive and catalytic function, and a considerable decrease of noble metals amount (about five times), with consequent large cost reduction. Moreover, the replacement of the conventional ink deposition methods with electrodeposition for platinum and gold dispersion, considerably increases the catalytic activity. The electrocatalytic performance results were encouraging. Gold allows increasing the catalyst poisoning tolerance and then the electrode long term stability. The innovative electrodes show a performance improvement up to three times compared to a commercial carbon substrate electrode (Vulcan XC-72R) with ink-spray deposited PtRu nanoparticles as catalyst.     

聚烯烃弹性体技术进展

聚烯烃弹性体为一类新型乙烯与高级α-烯烃共聚物，由于应用茂金属催化技术且分子结构中引入大量高级α-烯烃共聚单体并保留一定聚乙烯结晶相而兼备可塑性和弹性，具有良好的机械性能、加工性能和热性能。聚烯烃弹性体主要生产商有Exxon公司、Dow化学公司、Mitsui公司和LG公司，均采用溶液法聚合工艺及茂金属催化技术，其中,以Dow化学公司的Insite聚合工艺与CGC茂金属催化技术为代表，限定几何构型（CGC）催化剂为桥联单茂结构催化剂，其自身结构变化对催化性能影响较大，改变桥基团、Cp环上的烷基取代基和配位基团均可得到不同结构和性能的催化剂。Exxon公司采用Exxpol茂金属催化剂开发Exact塑性体［密度(0.860~0.915) g·cm^-3］，包括乙烯-辛烯共聚物、乙烯-己烯共聚物和乙烯-丁烯共聚物;采用同种催化技术，溶液法生产丙烯基弹性体，商品名为Vitamaxx。2003年，日本Mitsui公司-三井弹性体新加坡公司100 kt·a-1的乙丙橡胶弹性体装置投产，装置采用茂金属催化技术和独有的溶液法聚合工艺，商品名为Tafmer［密度(0.862~0.905) g·cm^-3］。韩国LG公司将独特的茂金属催化剂与溶液法聚合工艺相结合，生产聚烯烃弹性体［密度(0.865~0.903) g·cm^-3］，商品名为LUCENE。我国目前没有聚烯烃弹性体生产企业，开展过一些高共聚性能茂金属催化剂的研发，应用于聚烯烃弹性体技术开发。     

双（三环己基膦）氯化钯的合成及其结构表征

以氯亚钯酸钠与三环己基膦为原料，在乙醇介质中合成双（三环己基膦）氯化钯，该合成过程简单、绿色环保和对设备要求低。采用元素分析、红外光谱以及核磁共振磷谱等表征合成样品的组成与结构,结果表明，在三环己基膦与氯亚钯酸钠物质的量比大于2.4和反应温度70 ℃条件下，双（三环己基膦）氯化钯收率达99.6%，且纯度较高。