Cu/Zn比对微波辐射老化制备CuO/ZnO/Al2O3催化剂结构和活性的影响

在微波辐射条件下, 对共沉淀法制备合成甲醇CuO/ZnO/Al₂O₃催化剂前驱体的母液进行老化, 通过改变Cu/Zn比, 研究了微波辐射对催化剂性能的影响, 并结合XRD, FTIR, DTG, H₂-TPR, XPS等表征手段, 探讨了微波辐射对前驱体物相组成及催化剂微观结构的影响. 结果表明: 在微波辐射老化条件下, Cu/Zn比对催化剂前驱体物相组成影响较大, 微波辐射有利于绿铜锌矿(Cu, Zn)₅(CO₃)₂(OH)₆晶相选择生成. 当Cu/Zn比为2.0时, 前驱体中含有较多的绿铜锌矿物相, 且结晶较好, 焙烧后形成的催化剂中CuO-ZnO协同作用较强, CuO分散性好, 导致H₂还原温度低, 在浆态床合成甲醇过程中表现出良好的催化活性和稳定性, 甲醇时空收率(STY)达到309.0 g•kg^－1•h^－1, 失活率仅为0.11%/d, 远优于常规水浴加热制备的催化剂.     

Structure and Thiophene Hydrodesulfurization Activity of MoS2/Al2O3 Catalysts

It was found that, in MoS₂/Al₂O₃ catalysts prepared by exfoliation, the structure of MoS₂ is strongly distorted. The catalytic activities of these catalysts and traditionally prepared catalysts toward the hydrodesulfurization of thiophene were compared. It was established that the stacking dimension of MoS₂ in the catalysts prepared by exfoliation was 200 Å, whereas it was 20 Å in a standard catalyst. It was demonstrated that, although the number of molybdenum atoms in the edge plane per gram of MoS₂ in the catalysts prepared by exfoliation was 10 times smaller than that in the standard catalyst, the activity of these catalysts was close to the activity of the standard catalyst. On this basis, it was suggested that the hydrodesulfurization of thiophene can occur on the basal plane of MoS₂ that has a defect-free structure with a distorted environment of molybdenum.     

Physical and Chemical Properties and Activity of Fe–Co–Cu Oxide Catalysts in Oxidation of CO

We have studied the physical and chemical properties and activity of Fe–Co–Cu oxide catalysts in oxidation of CO. We have shown that the high activity of these catalysts is promoted by formation of the Cu₂(OH)₃NO₃ structure, which is modified by hematite clusters. The presence of OH groups is favorable for the formation of active sites for CO oxidation on the surface of the oxide catalysts.     

Aromatization ofn-butane over Ni-ZSM-5 and Cu-ZSM-5 zeolite catalysts prepared by using Ni and Cu impregnated silica, fiber

The reaction ofn-butane aromatization was carried out over Ni-ZSM-5 and Cu-ZSM-5 zeolite catalysts prepared by using Ni and Cu impregnated silica fiber during the process of ZSM-5 zeolite synthesis. The catalysts prepared were characterized by X-ray powder diffraction, nitrogen adsorption and X-ray fluorescency. The acidic properties of the catalysts were investigated by temperature-programmed desorption of ammonia using a mass spectrometer equipped with a QTMD detector. The effect of catalyst pretreatment, reaction temperature, and time on stream on the reaction ofn-butane to aromatic hydrocarbons were investigated. The modification of ZSM-5 by Ni and Cu increased the selectivity to aromatic hydrocarbons. The state of Ni and Cu and their stabilization in the ZSM-5 structure was highly influenced by the mode of catalyst pretreatments.     

Methane to Liquid Hydrocarbons over Tungsten-ZSM-5 and Tungsten Loaded Cu/ZSM-5 Catalysts

Metal containing ZSM-5 can produce higher hydrocarbons in methane oxidation. Many researchers have studied the applicability of HZSM-5 and modify ZSM-5 for methane conversion to liquid hydrocarbons, but their research results still lead to low conversion, low selectivity and low heat resistance. The modified HZSM-5, by loading with tungsten (W), could enhance its heat resistant performance, and the high reaction temperature (800℃) did not lead to a loss of the W component by sublimation. The loading of HZSM-5 with tungsten and copper (Cu) resulted in an increment in the methane conversion as well as CO2 and C5 selectivities. In contrast, CO, C2-3 and H2O selectivities were reduced. The process of converting methane to liquid hydrocarbons (C5 ) was dependent on the metal surface area and the acidity of the zeolite. High methane conversion and C5 selectivity, and low H2O selectivity are obtained over W/3.0Cu/HZSM.     

醋酸仲丁酯加氢反应中Cu/B/Ca/Al_2O_3催化剂的失活及再生

Cu/B/Ca/Al2O3催化剂在长达1 118 h的催化醋酸仲丁酯加氢反应中出现了明显的失活.经过对比分析反应前、后和再生催化剂的组成、形貌和结构,发现金属铜粒子在长时间反应后无明显聚集,醋酸仲丁酯加氢反应中部分氧化钙向醋酸钙转变而引起催化剂结构的改变以及有机物种在催化剂表面的沉积是其失活的根本原因.失活后的催化剂经过350℃空气焙烧再生能够有效消除表面沉积的醋酸钙和有机物种,基本恢复催化剂的结构及其催化醋酸仲丁酯加氢反应的性能.     

Cu含量对以水滑石为前驱体的Cu/Co/Mn/Al催化剂高级醇合成性能的影响

A series of Cu/Co/Mn/Al catalysts derived from hydrotalcite precursors with different Cu/Co molar ratios (0, 0.1, 0.5, 1.0, and 2.0) were prepared and used for the synthesis of higher alcohols from syngas. N₂ physical adsorption desorption, inductively coupled plasma atomic emission spectrometry (ICP-AES), X-ray diffraction (XRD), scanning electron microscopy (SEM), hydrogen temperature-programmed reduction (H₂-TPR), thermogravimetry (TG), and high-resolution transmission electron microscopy (HRTEM) techniques were employed to investigate the physical and chemical properties of the Cu/Co/Mn/Al catalysts. The results show that the optimum Cu content can increase specific surface area, improve reducibility, and form regular layered structure to provide more uniform distribution of active sites, thereby enhancing catalytic activity and alcohol selectivity. When the Cu/Co molar ratio was 0.5, the yield of alcohol and the alcohol selectivity reached the maximum values of 0.071 g·g^-1·h^-1 and 35.9%, respectively.     

Pd-Mo-K/Al2O3催化剂的结构及合成醇性能

采用 XRD、EXAFS 技术研究了不同Pd含量的 Pd-Mo-K/Al2O3 催化剂结构,并关联其合成低碳混合醇性能。结果表明,在氧化态 Mo-K/Al2O3 催化剂体系中添加 Pd后,“K-Mo”物相晶粒变小,分散度提高,说明钯可能和钾钼物种发生了较强的相互作用。经硫化还原处理后,发生了氧硫交换,钼主要以MoS2物种形式存在,其粒度随着Pd含量的增加而明显减小。尺寸的显著变化可能导致MoS2与载体作用形式的改变,从而影响CO加氢催化反应的性能。在硫化态催化剂中,Pd的添加不仅能提高CO加氢合成醇的收率和选择性,而且有利于改善产物的分布。基于以上结果,认为“K-Mo”作用物种和Pd物种均为合成醇的催化活性组份,它们间的相互协同作用使催化剂性能得到显著改善。     

季鏻盐型三相相转移催化剂的制备及其化学结构与相转移催化活性的关系

 使用两种 ω-氯代酰氯 (氯乙酰氯与氯丁酰氯) 对交联聚苯乙烯微球 (CPS) 进行 Friedel-Crafts 酰基化反应,使用 1,4-二氯甲氧基丁烷对 CPS 微球进行氯甲基化反应, 分别将可交换的氯引入 CPS 微球表面, 制备了化学改性的 CPS 微球. 然后使用三苯基膦对改性微球进行季鏻化反应, 制备了间隔臂 (spacer arm) 长度不同的三种季鏻 (QP) 盐型三相相转移催化剂 QP-CPS. 考察了主要反应条件对制备过程的影响, 并以氯化苄与乙酸钠合成乙酸苄酯的反应体系作为三相相转移催化的模型体系, 初步考察了 QP-CPS 的相转移催化活性,探索了催化剂结构与相转移催化活性的关系. 结果表明, 季鏻盐的化学稳定性较差,在制备过程中需控制反应时间与温度, 且宜选用极性较高的溶剂. 季鏻盐型三相相转移催化剂 QP-CPS 对乙酸苄酯的合成具有较高的催化活性, 在液-固-液之间可有效地实现反应物种乙酸根的转移. 与季铵盐 (QN) 型三相相转移催化剂 QN-CPS 相比, 季鏻盐型三相相转移催化剂 QP-CPS 具有更高的相转移催化活性. 间隔臂越长, QP-CPS 的相转移催化活性越高, QP-CPS 的亲水和亲油性能对相转移催化活性也有很大的影响.     

含Bi、Mg的硅酸铜催化剂的制备及其催化性能

以硝酸铋、硅酸钠和MgO-SiO₂复合微球为原料,分别采用共沉淀法和浸渍-沉淀法制备了含Bi、Mg的硅酸铜催化剂，其结构经SEM，低温N₂吸附-脱附、XRD和XPS表征。研究了催化剂在甲醛乙炔化合成1,4-丁炔二醇反应中的催化性能。结果表明：采用共沉淀法制备的催化剂具有高比表面积、孔径和孔体积，炔化反应活性高，1,4-丁炔二醇选择性大于96%。催化剂表面的活性组分主要为无定形硅酸铜，分散度与稳定性较好，活性组分Cu和Bi不易流失。     

CuO-MnO2/Al2O3 催化臭氧化催化剂的制备、结构表征及性能

采用浸渍法,以Al2O3为载体制备了氧化铜和二氧化锰复合的双组分负载型金属催化臭氧化催化剂.以松花江水的UV254去除率作为催化剂活性指标,通过正交试验,确定了催化剂的最佳制备条件.实验结果表明,催化剂的最佳制备条件如下:浸渍5h,活性组元体积比为3:1,于90℃干燥2h,于200℃焙烧3h.采用扫描电镜对催化剂的结构进行了表征;通过TG-DTA测试分析了催化剂热分解过程的反应速率、热效应和物质变化过程;运用XPS分析了催化剂表面元素的组成、元素相对含量和元素价态.     

甲醇合成催化剂Cu—Mn／Al2O3中锰的助催化作用

甲醇合成催化剂Ｃｕ－Ｍｎ／Ａｌ２Ｏ３中锰的助催化作用李基涛张伟德高利珍（厦门大学化学系物理化学研究所厦门３６１００５）林建毅陈华毅Ｋ．Ｌ．Ｔａｎ（国立新加坡大学物理系０５１１）关键词甲醇合成Ｍｎ的助催化作用活性表面态铜催化剂分类号Ｏ６４３．３２甲醇是...     

氧化铈对Pd催化剂氧化活性和热稳定性的影响

氧化铈对Pd催化剂氧化活性和热稳定性的影响;钯催化剂;催化氧化     

Highly active copper catalysts for steam reforming of methanol. Catalysts derived from Cu/Zn/Al alloys

-Hydrogen transfer from -phenylethyl hydroperoxide (HROOH) to excited anthraquinone, acetophenone and benzophenone occurs only in the polar aprotic acetonitrile. At the same time, the triplet of duroquinone abstracts -hydrogen both in polar and non-polar solvents. The rate constant of the latter reaction decreases with increasing solvent polarity.     

Formation of Nanosized Catalysts Based on Palladium Phosphine Complexes and the Nature of Their Activity

Findings on the formation and features of nanosized particles based on palladium complexes, which are active in hydrogenation catalysis, are summarized. Depending on the nature of a reducing agent, nanosized particles formed by the reduction of palladium(II) phosphine complexes are either metallic nuclei stabilized by organophosphorus ligands or associates of polynuclear phosphido or phosphinideno palladium complexes whose surface contains immobilized Pd(0) clusters. The ensembles of the Pd(0) atoms are active in hydrogenation.     

P对Cu/Al2O3催化剂结构及其催化甘油氢解反应性能的影响

采用分步浸渍法制备了P改性的Cu/Al2O3催化剂,利用N2吸附-脱附、X射线衍射、红外光谱、紫外-可见光谱、H2程序升温还原、NH3程序升温脱附和N2O解离吸附等方法对催化剂进行了表征,考察了P含量及浸渍次序对催化剂结构及其催化甘油氢解反应性能的影响.结果表明,先浸渍P再浸渍Cu时,所制Cu/Al2O3催化剂酸性较高,同时还促进了Cu的分散.随P含量的增加,催化剂的酸量及Cu分散度提高,并且Cu与P物种的相互作用增强;然而,P含量较高时会覆盖Cu,使暴露的Cu表面降低.先浸渍Cu后浸渍P时,尽管也提高了相应催化剂的酸性,但对Cu分散的影响不大,并且还会覆盖Cu使暴露的Cu表面明显降低.先浸渍P明显提高了Cu/Al2O3上甘油氢解反应性能.在220oC,3MPa,质量空速2h?1以及H2/甘油摩尔比20的条件下,当P含量由0增加至6%时,甘油转化率从17.1%升至95.0%,1,2-丙二醇选择性从83.7%升至97.2%.这可归因于催化剂酸性的提高及Cu与P间的相互作用.     

Reversible Nature of Coke Formation on Mo/ZSM‐5 Methane Dehydroaromatization Catalysts

Non‐oxidative dehydroaromatization of methane over Mo/ZSM‐5 zeolite catalysts is a promising reaction for the direct conversion of abundant natural gas into liquid aromatics. Rapid coking deactivation hinders the practical implementation of this technology. Herein, we show that catalyst productivity can be improved by nearly an order of magnitude by raising the reaction pressure to 15 bar. The beneficial effect of pressure was found for different Mo/ZSM‐5 catalysts and a wide range of reaction temperatures and space velocities. High‐pressure operando X‐ray absorption spectroscopy demonstrated that the structure of the active Mo‐phase was not affected by operation at elevated pressure. Isotope labeling experiments, supported by mass‐spectrometry and ¹³C nuclear magnetic resonance spectroscopy, indicated the reversible nature of coke formation. The improved performance can be attributed to faster coke hydrogenation at increased pressure, overall resulting in a lower coke selectivity and better utilization of the zeolite micropore space.     

Hydrocarbon specificity in the selective catalytic reduction of NOx over Cu-ZSM-5 and Co-ZSM-5 catalysts

Transformation of surface nitrates under CH₄ (CH₄+O₂) was found to ensure steady-state activity of Co-ZSM-5 in the selective catalytic reduction of nitrogen oxides by methane (CH₄-SCR). For Cu-ZSM-5, such species are mainly converted into NO. Relaxation of the coordination sphere due to oxygen and NO adsorption, stability of C,N-containing intermediates and activation routes of hydrocarbons (methane, propane) were analyzed as factors determining catalytic properties of Cu and Co cations.     

超声辐照下化学沉积法制备Cu/Al2O3复合粉体材料

声化学是利用超声波的空化效应产生局部高温高压等极端物理条件加速化学反应或改变化学反应途径的一门新学科．Ｃｕ／Ａｌ２Ｏ３复合粉末材料是一种近年来倍受关注的新型金属／非金属复合粉末材料．本文报道了超声在化学沉积法制备Ｃｕ／Ａｌ２Ｏ３复合粉末材料中的应用,...