Methanol dehydrogenation in the liquid phase with Ru/active carbon catalyst

In contrast to the gas-phase reaction, the liquid-phase reaction of methanol with Ru/C catalyst scarcely gave methane. Product distribution strongly depended on reaction conditions even under atmospheric pressure.     

铁系无铬(NBC-1)型高温变换催化剂 Ⅳ.吸附性能及CO变换反应机理的研究

通过程序升温脱附（ＴＰＤ）、程序升温表面反应（ＴＰＳＲ）及脉冲反应（ＰＳＲ）等化学物理技术,综合分析研究了铁系无铬（ＮＢＣ－１）型ＣＯ高温变换催化剂的吸附性能及化学反应特性。研究表明,ＮＢＣ－１型催化剂对Ｈ２Ｏ具有很强的吸附能力,不易吸附ＣＯ及ＣＯ２,该催化剂上水煤气变换反应的机理为氧化－还原（ｒｅｄｏｘ）反应机理     

Contrasted effect of CO on the metal‐catalyzed cycloisomerization of O‐tethered enynes derived from monoterpenes

The CO‐bubbling effect in cycloisomerization reactions of enynes derived from monoterpenes has been studied using PtCl₂, [Rh₂Cl₂(CO)₄] and AuCl₃ as catalytic systems. All the precursors are efficient catalysts for the cycloisomerization of O‐tethered enynes. The reaction proceeds through exo‐dig and endo‐dig pathways, which are consistent with the exclusive coordination of the alkyne triple bond to the metal center. The CO ligand not only increases the reaction rates but also induces significant variations in the two reaction pathways. Notably, this effect is also strongly dependent on the nature of the starting enyne. Copyright © 2011 John Wiley & Sons, Ltd.     

Tungstophosphoric acid nanoparticles supported on polyamic acid: A mild and recoverable heterogeneous catalyst for the selective synthesis of mono and bulky bis(1,8-dioxooctahydroxanthene)s under solvent-free conditions

A series of 1,8-dioxooctahydroxanthene derivatives and some crowded bis(1,8-dioxooctahdroxanthene) were selectively synthesized using tungstophosphoric acid nanoparticles supported on polyamic acid (TPA/PAA) as a new catalyst in solvent-free conditions. The high purity products were isolated and catalyst was easily separated in simple work-up and was recycled several times without loss of reactivity under the described reaction conditions. The reaction is characterized by short reaction time, high efficiency and environmentally friendly reaction conditions.     

Development of high performance Cu/ZnO-based catalysts for methanol synthesis and the water-gas shift reaction

Our groups studies on Cu/ZnO-based catalysts for methanol synthesis via hydrogenation of CO₂ and for the water-gas shift reaction are reviewed. Effects of ZnO contained in supported Cu-based catalysts on their activities for several reactions were investigated. The addition of ZnO to Cu-based catalyst supported on Al₂O₃, ZrO₂ or SiO₂ improved its specific activity for methanol synthesis and the reverse water-gas shift reaction, but did not improve its specific activity for methanol steam reforming and the water-gas shift reaction. Methanol synthesis from CO₂ and H₂ over Cu/ZnO-based catalysts was extensively studied under a joint research project between National Institute for Resources and Environment (NIRE; one of the former research institutes reorganized to AIST) and Research Institute of Innovative Technology for the Earth (RITE). It was suggested that methanol should be produced via the hydrogenation of CO₂, but not via the hydrogenation of CO, and that H₂O produced along with methanol should greatly suppress methanol synthesis. The Cu/ZnO-based multicomponent catalysts such as Cu/ZnO/ZrO₂/Al₂O₃ and Cu/ZnO/ZrO₂/Al₂O₃/Ga₂O₃ were highly active for methanol synthesis from CO₂ and H₂. The addition of a small amount of colloidal silica to the multicomponent catalysts greatly improved their long-term stability during methanol synthesis from CO₂ and H₂. The purity of the crude methanol produced in a bench plant was 99.9 wt% and higher than that of the crude methanol from a commercial methanol synthesis from syngas. The water-gas shift reaction over Cu/ZnO-based catalysts was also studied. The activity of Cu/ZnO/ZrO₂/Al₂O₃ catalyst for the water-gas shift reaction at 523 K was less affected by the pre-treatments such as calcination and treatment in H₂ at high temperatures than that of the Cu/ZnO/Al₂O₃ catalyst. Accordingly, the Cu/ZnO/ZrO₂/Al₂O₃ catalyst was considered to be more suitable for practical use for the water-gas shift reaction. The Cu/ZnO/ZrO₂/Al₂O₃ catalyst was also highly active for the water-gas shift reaction at 673 K. Furthermore, a two-stage reaction system composed of the first reaction zone for the water-gas shift reaction at 673 K and the second reaction zone for the reaction at 523 K was found to be more efficient than a one-stage reaction system. The addition of a small amount of colloidal silica to a Cu/ZnO-based catalyst greatly improved its long-term stability in the water-gas shift reaction in a similar manner as in methanol synthesis from CO₂ and H₂.     

Four-component coupling reactions of silylacetylenes, allyl carbonates, and trimethylsilyl azide catalyzed by a Pd(0)-Cu(I) bimetallic catalyst. Fully substituted triazole synthesis from seemingly internal alkynes

Fully substituted triazoles were synthesized via the four-component coupling reaction of unactivated silylacetylenes, two equivalents of allyl carbonates, and trimethylsilyl azide in the presence of a Pd(0)-Cu(I) bimetallic catalyst. Various trisubstituted 1,2,3-triazoles were obtained in good yields. The reaction most probably proceeds through the [3+2] cycloaddition reaction between the alkynylcopper species and azide followed by the cross-coupling reaction between the vinylcopper intermediate and π-allylpalladium complex.     

Effective tri-metallic TiO2 supported catalyst for hydrocarbon production from carbon dioxide

The current socio-economic issues with concerns on environmental quality and global warming are attributed to high concentrations of atmospheric carbon dioxide due to extensive usage of fossil fuels. Thus, over the last two decades, comprehensive work has been reported on carbon capture and storage and catalytic conversion of carbon dioxide to hydrocarbons. Among these, the reactions with hydrocarbons to form value-added products have been in focus. In this work, an attempt was made to identify the feasibility of the reaction: carbon dioxide and steam to form hydrocarbons of fuel value. After reviewing the literature on the development of various catalysts and their mechanism, a multi-metallic catalyst supported by TiO₂ Nano-needles was explored. The reaction mechanism is expected to proceed with activated CO₂ complex and hydroxyl groups over the metal oxide catalyst. Current reported work on CO₂ and Hydrogen proceeds with activated CO₂ and protons over the catalyst. The characterization techniques mainly XPS, XRD, TGA, FESEM-EDAX, FTIR, and NMR were used to analyze the catalyst activity and to confirm the products formed. The reaction is found to yield methanol and oxygen only. However, the conversion is found to be 0.4% - 3.8% in the temperature range 350°C to 550°C. The reaction of CO₂ with hydroxyl groups from water vapor can be effective as an alternative to the reaction with protons from hydrogen.     

碳化镍钼催化剂的制备及其甲烷干气重整活性(英文)

Nickel molybdenum carbide catalysts were prepared and their activities in the CO2 reforming of methane at a low CO2/CH4 reactant ratio were investigated using a microreactor at atmospheric pressure and at 973 K.The effect of the catalyst preparation method and the Ni/Mo ratio on the increase in catalyst life and the promotion of catalytic activity were investigated using N2 adsorption,X-ray diffraction, temperature-programmed carburization,temperature-programmed reaction,and a reforming reaction.The 25Ni75Mo catalyst that was carburized at 813 K exhibited the highest hydrogen formation ability and gave the least carbon deposition.The incomplete carburization of the Mo oxide species in the catalyst that was carburized at a lower temperature gradually gave a more active carburized species.The NiMoOxCy in the catalyst was more active in hydrogen formation during the dry reforming of methane whileβ-Mo2C andη-Mo3C2 were less active.     

乙炔羰基化反应催化剂:由均相到多相

基于非石油路线制备的乙炔小分子,其羰基化反应可制备大量高附值化学品,在CO排放的环境治理以及化学品应用方面有着十分重要的意义.本文主要概述了乙炔羰基化反应的催化剂由均相到多相的研究进展,总结了乙炔单/双羰基化催化剂种类及添加剂对反应活性的影响.基于反应机理分析提出调控结构敏感性因素(尺寸效应及形貌效应)制备高效催化剂的...     

Oxidation of ethylbenzene to styrene oxide in the presence of cellulose‐supported Pd magnetic nanoparticles

Palladium and Fe₃O₄ nanoparticles were deposited on N‐(2‐aminoethyl)acetamide‐functionalized cellulose for use in a catalytic reaction. The catalyst was characterized using Fourier transform infrared spectroscopy, thermogravimetric analysis, X‐ray diffraction, energy‐dispersive X‐ray analysis and transmission electron microscopy, and applied in the oxidation reaction of ethylbenzene at 100 °C using H₂O₂. Styrene oxide was obtained as the sole product of the oxidation reaction during 24 h. This reaction has some advantages such as one‐pot transformation of ethylbenzene to styrene oxide, high yield, excellent selectivity and magnetically recoverable catalyst. Also, the recovered catalyst could be used in the oxidation reaction four times without decrease in yield. Copyright © 2016 John Wiley & Sons, Ltd.     

Measurement of heterogeneously catalyzed gas reactions by DSC

Gas reactions, catalyzed by solid catalysts, can be measured by DSC. In the experimental set-up an open sample pan with catalyst (powder or pellet) is placed on the sample side of the DSC sensor. The reactive gas mixture flows through the cell and reacts on the catalyst surface. The heat effect, caused by this reaction, results into a DSC signal.The calibration procedure is described for quantitative evaluation of the DSC measurements. For illustration four different reaction systems are discussed.     

硅胶固载化－Lewis酸催化剂的研究

以硅胶为基质用γ－ＧＯＰＳ偶联后，接枝邻位氨基吡啶，间位、对位酰氨基吡啶三种配体后，与ＦｅＣｌ３或ＳｎＣｌ４饱和溶液络合，合成固载化的Ｌｅｗｉｓ酸催化剂，并以此类催化剂进行缩醛缩酮及酯化反应，获得良好效果．且催化剂可重复使用多次不失效，证实此类催化剂络合效应是好的     

氟喹诺酮作为钯催化Heck反应有效配体的研究

研究了氟喹诺酮作为钯催化Heck反应的有效配体. 碘苯、溴苯和其它芳基卤衍生物与丙烯酸丁酯、苯乙烯等取代乙烯类化合物在钯和氟喹诺酮的催化下发生Heck反应. 讨论了配体、催化剂用量、碱和溶剂对Heck反应产率的影响. 该反应的最优化条件是: 钯源为Pd(OAc)2 (0.1 mol%), 诺氟沙星作为配体(0.2 mol%), K2CO3作为碱, DMA作为溶剂, 取代碘苯及溴苯和它们的衍生物与丙烯酸丁酯、苯乙烯等乙烯基化合物的反应均可以得到高收率的目标偶联产物.     

合成气直接转化制取芳烃研究进展（英文）

芳烃类化合物是石化行业重要的基础原料.非石油基碳资源经合成气直接转化制取芳烃具有重要的应用前景,但该过程仍存在着芳烃收率低以及催化剂稳定性差等难题.近年来相关工作取得重要进展,研究人员尝试通过高效催化剂的设计和操作条件的优化以获得更好的催化反应性能.本综述首先对该过程进行了热力学分析,并根据催化剂体系对相关研究成果进行分类总结,主要包括改性FT催化剂和复合催化剂.然后,对各类催化剂体系的反应性能特点和机理进行了深入探讨.改性FT催化剂常采用添加助剂或引入分子筛载体的方法调变反应中间体在传统FT催化剂上的反应路径,以促进芳烃的生成.但是,该过程倾向于生成链烃而致使芳烃选择性受到限制,而且容易形成积炭,催化剂稳定性差.复合催化剂可分为氧化物-分子筛和FT-分子筛催化剂,合成气首先在氧化物或者FT催化剂上生成某些亚稳态中间物种,随后扩散至分子筛孔道内经芳构化转化为芳烃.对于氧化物-分子筛复合催化剂,CO在氧化物上活化并生成醇类(主要是甲醇),随后在分子筛上进行C-C偶联、环化、芳构,生成芳烃.在该串联反应中,由于中间产物的不断转化,不仅使CO加氢反应的平衡右移,提升转化率,而且增加了芳烃的收率与反应的稳定性.另外,该过程CH4产物的选择性极低.对于FT-分子筛复合催化剂,合成气首先在高温FT催化剂上生成低碳烃类,然后转移至分子筛孔道内进行芳构化,该方法可以获得较高的CO转化率但芳烃选择性仍比较低.文章还详细描述了针对不同过程的反应器设计,包括单反应器和双反应器.在单反应器中可装填改性FT催化剂或物理混合的复合催化剂.对于复合催化剂,存在两种活性组分的优化反应条件不一致以及混合方式影响反应活性和产物分布等问题.因此,探索更佳的反应工艺条件对于实现合成气直接转化制芳烃的工业应用具有重要意义.双反应器则是将复合催化剂的两种功能组分分开装填,使分步过程分别在各自最佳反应条件下进行,从而避免了不匹配的问题.最后,该综述展望了合成气直接转化制芳烃过程存在的挑战和应用前景,为更好地设计催化剂、构建反应路径和优化工艺条件提供指导.     

PVP-Pd催化剂六氯苯加氢脱氯中两种氢源的贡献

近年来,随着环境问题的日益突出,含卤有机化合物作为一类主要的环境污染物,其加氢脱卤反应的研究越来越多地受到人们的关注.     

一种新的高分子Lewis酸催化剂的制备及其催化活性的研究

本文研究了高分子催化剂CPVC-FeCl_3在酯化、酯交换、缩醛或缩酮的合成及呐 重排反应中的应用。本催化剂具有操作简便、无腐蚀性,催化剂易从反应混合物中分离、并能重复使用等优点。     

乙酸异戊酯的合成

以乙酸和异戊醇作为原料,利用SnCl4催化作用下的酯化反应合成了乙酸异戊酯;研究了反应时间、酸醇的物质的量之比、催化剂用量、带水剂用量等因素对产物收率的影响,并确定了优化反应条件.结果表明,优化反应条件为:反应时间60min,酸醇物质的量之比1∶0.8(乙酸5.76mL),催化剂用量0.35g,带水剂用量10mL.在优化反应条件下,产物收率最高可达86.3%.     

负载Fe2O3的Zr基钙钛矿催化剂对逆水煤气反应的影响

采用固相反应法制备了钙钛矿结构的BaZr_0.9Y_0.1O₃,并用BaZr_0.9Y_0.1O₃作为载体负载Fe₂O₃,通过X射线衍射分析（XRD）、扫描电子显微镜（SEM）观察负载型催化剂的晶相结构和微观形貌,同时考察了制备的催化剂的逆水煤气反应催化活性。结果表明,BaZr_0.9Y_0.1O₃粉体1200℃煅烧5h时,负载型催化剂具有较好的催化活性;BaZr_0.9Y_0.1O₃对逆水煤气反应有一定的催化作用,负载少量的Fe₂O₃催化剂可以明显促进CO₂还原,在空速为1.13h^-1,温度为650℃时,CO收率可以达到31%;催化剂经过长时间运行催化效果良好,制备的催化剂活性较稳定。     

Deactivation studies of nano-structured iron catalyst in Fischer-Tropsch synthesis

A nano-structured iron catalyst for syngas conversion to hydrocarbons in Fischer-Tropsch synthesis (FTS) was prepared by micro-emulsion method. Compositions of bulk iron phase and phase transformations of carbonaceous species during catalyst deactivation in FTS reaction were characterized by temperature-programmed surface reaction with hydrogen (TPSR-H2), and XRD techniques. Many carbonaceous species on surface and bulk of the nano-structured iron catalysts were completely identified by combined TPSR-H2 and XRD spectra and which were compared with those recorded on conventional co-precipitated iron catalyst. The results reveal that the catalyst deactivation results from the formation of inactive carbide phases and surface carbonaceous species like graphite, and it will be increased when the particle size of iron oxides was reduced in FTS iron catalyst.     

Catalytic synthesis of C-alkylimidazoles over platinum-alumina catalysts

The synthesis of C-alkylimidazoles from 1,2-diamines and carboxylic acids over bifunctional platinum—alumina catalysts has been studied. It has been shown that this method is effective for the synthesis of 2-alkyl and 2,4-dialkylimidazoles including imidazoles with long-chain alkyls. The effect of the reaction temperature, space velocity of the flow of the raw materials, and dilution by hydrogen on the yield of product has been examined for the example of the synthesis of 2-methylimidazole from ethylenediamine and acetic acid, and the stability of the catalyst in continuous reaction cycles with intermediate oxidative regeneration has been studied. The composition of the accompanying products has been established and a mechanism proposed for their formation.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 932–940, April, 1992.