贵金属和载体对催化剂催化脱氧裂化性能的影响

采用浸渍法制备了一系列分别负载活性组分Pt,Pd,Ru的γ-Al2O3载体催化剂和分别以固体酸γ-Al2O3,Si O2-Al2O3,USY-Al2O3为载体的Pd催化剂。通过XRD、HRTEM、H2-TPR、NH3-TPD、BET等分析表征技术和以油酸甲酯为模型化合物的反应体系,考察了贵金属及载体性质对催化剂催化加氢脱氧性能和催化裂化性能的影响。结果表明:贵金属及其粒子大小是影响催化剂催化加氢脱氧活性的主要因素;载体的酸强度、酸量是影响催化剂催化裂化性能的主要因素。同时,该性能也受比表面积和孔结构特征的影响;Pd/USY-Al2O3在系列催化剂中表现出了良好的催化加氢脱氧活性和最佳的催化裂化活性。     

La、Ba的添加对Pd/Y2O3-ZrO2催化氧化CH4性能的影响

以浸渍法制备了1.0%Pd/Y2O3-ZrO2催化剂,考察了Pd负载过程中La和Ba的添加对Pd/Y-ZrO2催化氧化CH4性能的影响,用BET、XRD、CO脉冲、TEM和H2-TPR等方法对所制备的催化剂进行表征。结果表明,La和Ba的添加降低了Pd/Y2O3-ZrO2催化剂氧化CH4的活性。催化剂中活性金属的分散度及体相PdO的还原性影响催化剂对CH4的氧化活性,La、Ba的添加降低了Pd/Y2O3-ZrO2催化剂中活性金属Pd的分散性,使Pd在高温老化后更容易团聚,同时增强了PdO与载体的相互作用,使PdO不容易被还原。     

不同载体对甲醇分解钯催化剂性能的影响

用浸渍法制备了Pd/γ-Al2O3和Pd/Ce0.65Zr0.35O22种甲醇分解催化剂。采用XRD,NH3-TPD(NH3-Temperature-Programmed Desorption),XPS及H2-TPR(H2-Temperature-Programmed-Redution)等手段对2种催化剂的结构和性能进行表征,并考察了催化剂上甲醇低温分解的活性。结果表明,Pd/Ce0.65Zr0.35O2催化剂具有较弱的表面酸性及良好的低温还原性能;XPS结果表明2种催化剂中的Pd均以氧化态形式存在,并且Pd在Ce0.65Zr0.35O2固溶体上呈高度分散状态,Pd与Ce间具有较强的相互作用。结合活性考察可知,Pd+的存在有利于甲醇的分解。Pd/Ce0.65Zr0.35O2催化剂具有高的催化活性,220℃时甲醇转化率接近100%。     

氧化铝孔结构特征对Pd基催化剂性能的影响

考察2种γ-Al2O3改性前后的孔结构参数,并以改性氧化铝为涂层基体材料制备Pd基催化剂。结果表明,改性Al2O3-02具有比表面积:134.691m2·g-1,孔容:0.5851cm3·g-1,孔径:8.6877nm,且用其制备的Pd基催化剂TWC-02的性能较优越;该催化剂经950℃煅烧后,Pd均匀分散于改性Al2O3-02表面,甚至温度≥1050℃高温条件下煅烧后Pd的分散性仍较好。氧化铝对Pd基催化剂起到结构助催化作用,起燃活性评价试验也证实改性Al2O3-02的这一优越性能。     

La改性Pd基催化剂催化甲烷氧化的抗水热性能研究

甲烷是第二大温室气体,其年度增温潜能是CO2的26～28倍。天然气车排放尾气中的主要成分为未燃烧完全的甲烷和高浓度的水(高达20%),目前已有大量研究表明水会严重影响Pd活性组分的催化活性及氧化铝载体的催化稳定性,因此如何在高含水废气中处理这些甲烷一直是天然气车后处理催化剂的研究热点。本研究采用等体积浸渍法制备了改性载体(AlLa5、AlLa10和AlLa15),并用过量浸渍法将0.5%Pd负载到改性载体Al2O3-La和未改性载体γ-Al2O3上,同时考察了La的引入比例对催化剂催化甲烷氧化中的耐水热性能影响,用N2物理吸脱附、CO脉冲吸附、XPS和XRD等方法对所制备催化剂进行表征。结果表明,La的加入明显提高催化剂在催化甲烷氧化中的耐水热性能,其中Pd/AlLa5表现出最优异的耐水热稳定性。     

高活性Pd-Fe催化剂对CO的低温氧化性能研究

用共沉淀法制得Pd-Fe催化剂,考察了煅烧温度、载体、金属担载量对CO低温催化氧化反应活性的影响。结果表明,负载在炭黑上的Pd-Fe催化剂经200℃和300℃煅烧,性能最佳,在室温下可将CO完全转化。采用透射电镜(TEM)、X射线光电子能谱(XPS)、X射线粉末衍射(XRD)和CO化学吸附表征发现,催化剂的高活性是由于Pd与Fe之间具有强相互作用,导致Pd向界面Fe3+(Fe2O3)进行电子转移,形成还原态的Fex+物种。Pd O和还原态的Fex+物种分别是吸附CO和O2的活性中心,成为CO氧化高活性的主要原因。     

Pd/γ-Al2O3催化剂上甲烷-氘化氢之间的氢氘交换性能研究

利用浸渍法制备了Pd/γ-Al2O3催化剂,采用X射线粉末衍射(XRD)、X光电子能谱(XPS)和程序升温还原(TPR)等物理化学手段对其进行了表征,并在固定床微型反应器上考察了其催化活性。实验结果表明,载体内部有Pd元素,Pd和载体γ-Al2O3发生了强相互作用。在对甲烷与氘化氢间的氢氘交换反应中,Pd/γ-Al2O3催化剂显示出较好的催化活性。     

氧化铜在γ-Al2O3载体表面的分布及其硫化性能（英文）

采用浸渍方法制备不同氧化铜含量的CuO/γ-Al2O3催化剂。使用XRD、SEM和程序控制升温还原(TPR)方法研究γ-Al2O3载体表面氧化铜的分布情况。用X射线定量分析方法得到氧化铜在γ-Al2O3中的分散阈值为0.275g/g,即0.275CuAl。当氧化铜负载量小于或大于其分散阈值时,高度分散或结晶状氧化铜将会出现在γ-Al2O3载体表面。TPR实验表明0.1CuAl和纯CuO还原温度范围分别为420-690°C和290-380°C。氧化铜与载体之间的相互作用导致0.1CuAl不易被还原。0.5CuAl呈现2个分步还原温度范围,分别为210-300°C和410-730°C,证实了γ-Al2O3载体表面高度分散和结晶状分布的氧化铜。硫化实验表明,最佳氧化铜负载量小于其分散阈值,氧化铜以亚单层形式分布在γ-Al2O3载体表面。     

镧助剂对Pd/Al_2O_3催化剂性能的影响

一氧化碳(CO)-亚硝酸甲酯(MN)气相氧化偶联合成草酸二甲酯(DMO)的反应是煤制乙二醇的关键转化步骤,现用的Pd/Al_2O_3催化剂中钯负载量高达1%。在催化剂制备过程中添加不同助剂,用催化燃烧热阻型检测系统考察其对合成反应的催化性能影响。表征分析表明,镧助剂可改善钯在载体上的分散;当La_2O_3/Al_2O_3=14 mg/g时,La_2O_3在载体表面以单层分散,制成的催化剂中钯分散性最好。性能评价结果显示,载钯量0.2%的催化剂具有较好的稳定性,在优化反应条件下,其性能甚至优于工业催化剂。     

Pd/CeCoOx催化剂上Pd组分分散性改进及其NGVs尾气净化性能

近年来,天然气汽车（NGVs）尾气净化三效催化剂的研究主要集中在具有高分散性的负载型贵金属催化剂。本文利用金属有机骨架（MOFs）模板法制备了纳米结构的CeCoOx复合氧化物作为载体,并与传统溶胶-凝胶法（SG）制备的铈钴氧化物比较,探究了贵金属Pd在两种催化剂载体上的分散状态及其对催化性能的影响。结果表明,以CeCo-MOFs材料为前驱体衍生制备的Pd/CeCoOx(M)催化剂其CO、NO、CH4三效催化性能相比溶胶-凝胶法制备的相同组成Pd/CeCoOx(SG)催化剂低了约100 ℃左右,具有更低的低温活性。以CeCo-MOFs为前驱体衍生制备的铈钴复合氧化物晶体粒子更小,晶相结构均匀,具有更大的比表面积,促进了Pd组分分散状态的提高,也丰富了催化剂的氧空位和结构缺陷,显著提高了催化剂的低温三效催化性能。利用MOFs前驱体热分解得到的复合氧化物可以作为三效催化贵金属活性组分分散的良好材料。     

GdF_3:Ce~(3+),Ln~(3+)(Ln~(3+)=Eu~(3+),Tb~(3+),Dy~(3+),Sm~(3+))纳米晶体的制备与发光性能研究

应用共沉淀法,制备共掺同一敏化剂(Ce3+)和不同激活剂(Tb3+,Eu3+,Sm3+,Dy3+)的GdF3纳米晶体。在单一波长(254nm)紫外光的激发下,掺杂不同镧系激活离子的样品能够发射出不同颜色的明亮可见发光,因而适用于多色生物标记。     

三自由度并联机构（3SPS 3SRR）的位置分析

针对一种3SPS-3SRR并联机构,运用符号法对该机构进行位置分析建模及求解。构建动、静坐标系,通过矩阵转换对机构建立约束方程,运用Sylvester消元方法进行消元得到机构单变元输入输出方程,求得机构位姿的封闭解。最后进行实例求解,得到该机构处于一般姿态的32组实数解,并使机构处于特殊位姿,将所得封闭解与预估解对比,从而验证该位置求解模型的正确性。基于符号法的3SPS-3SRR并联机构位置分析模型具有准确、高效的特点,规避了基于数值法的诸多缺点,对该机构的深入分析具有重要理论意义及实用价值。     

Phase diagrams of binary systems: AgNO3KNO3 and AgNO3 -@#@ NaNO3

AgNO₃-KNO₃ and AgNO₃-NaNO₃ phase diagrams were drawn using a simultaneous thermal analysis technique in the range 373 to 623 K. The apparatus is described briefly. Figure 1 shows a continuous solid solution in equilibrium with the liquid phase. It exhibits a eutectoid mixture (20 mol% NaNO₃) at 380.7 K. Figure 2 shows a eutectic mixture (45 mol % KNO₃) at 413 K, a eutectoid mixture (20 mol % KNO₃) at 409 K, and a continuous invariant at 404 K.     

Thermodynamic analysis of the CsNO3-KNO3-NaNo3 system

The thermodynamic properties of the CsNO₃-KNO₃-NaNO₃ system have been derived from an optimization procedure using experimental and published information concerning phase diagram and thermodynamic data for the constituent binary systems and ternary liquid phase. The results are in very close agreement with the experimental data.     

3-D or not 3-D

When developing mathematical models of physical phenomena, physical scientists have been limited to two-dimensional solutions. In some cases, those solutions may be qualitatively correct, but in many others, the solutions are far from reality. This paper presents three examples of the limitations of two-dimensional modeling :diffusion-limited electrolytic reduction of a liquidproduct from a liquid electrolyte, morphological development of a solid dendrite, and behavior of a two-phase fluid under shear.     

3

In this paper, a planning algorithm for multi-path/multi-layer circular locus is poposed. The algorithm is applied to weld the nipples on the header of boiler. Multi-path/multi-layer circular locus is planned according to three teaching points, which is lapped head-on-end to satisfy the requirement of technology. For the nipples wherever they are arranged radially or axially, even if there are errors caused by positioning and thermal deformations, providing that nipple's position and orientation relative to the teaching one can be measured, the multi-path/multi-layer circular locus can be planned without teaching any more. The algorithm has been applied in welding robot for manufacturing power station' boiler.     

BiFeO3-BaTiO3-LaFeO3三元多铁性陶瓷材料的制备及性能

采用固相法制备了1-x(0.71BiFeO3-0.29B aTiO3)-xLaFeO3 (x=0.0,0.1,0 2,0 3,0 4,0.5)三元多铁性陶瓷材料,并研究了LaFeO3含量对陶瓷物相结构、微观组织、电学性能和磁电耦合性能的影响。结果显示,所有陶瓷均为单一钙钛矿结构,但随LaFeO3含量的增加,伴随着结构相变。所得陶瓷晶粒尺寸均匀,表现出良好的微观形貌,陶瓷晶粒随LaFeO3含量的增加而明显变小。虽然LaFeO3的加入在一定程度上降低了陶瓷的介电常数,但分析发现,x=0.1时能降低陶瓷的漏导,其漏电流达到了最小值,在10-7~10-8 A/cm2数量级,并且该陶瓷的剩余极化强度Pr和磁电耦合系数αME均达到最大值,分别为0.45μC/cm2和132.21 mV/cm·Oe (120 kHz)。因此,与0.71BiFeO3-0.29BaTiO3陶瓷相比,添加少量LaFeO3可以在一定程度上增加陶瓷的铁电性和磁电耦合性能。     

Features of feathery γ structure in a near-γ TiAl alloy

This work characterizes the feathery-like structures produced in a Ti–46.8Al–1.7Cr–1.8Nb (at.%) alloy during rapid continuous cooling from the α domain. Their morphology and crystallography are described using different microscopy and orientation mapping techniques. These feathery-like structures are divided into many small domains, characterized by low-angle misorientations (rotated less than 15°) between the domains. The domains comprise multiple parallel γ lamellae and rare traces of α₂. These lamellae follow the Blackburn orientation relationship and have a {1 1 1}_γ habit plane. Two types of γ-feathery structures were identified according to their location and crystallography. The grain-boundary γ-feathery structures originate from lamellar structures that grow into a neighboring grain. Alternatively, the internal γ-feathery structures are located in the interior of prior α grains and show an average misorientation of 36° around one $〈100{〉}_{{\mathrm{\gamma }}_{\text{L}}}$ axis of the lamellar structure in which it is embedded. This paper describes these two γ-feathery structures in detail and discusses their development in light of the mechanisms available in the literature, particularly sympathetic nucleation.     

Electronic structures of semiconducting FeGa3, RuGa3, OsGa3, and RuIn3 with the CoGa3- or the FeGa3-type structure

Electronic structure of FeGa₃, RuGa₃, OsGa₃ and RuIn₃ with the crystal structures belonging to the space group of P4n2 (No. 118), which is usually referred to as the CoGa₃-type structure, and P4₂/mnm (No. 136), which is usually referred to as the FeGa₃-type structure, have been calculated using a first-principle pseudopotential method based on the density-functional theory within the local density approximation (LDA) with the generalized gradient correction. All of them have the similar band structure in that the valence band maximum occurs at or near A and the conduction band minimum occurs at a point between Z and Γ. From the total energies calculated, compounds with the FeGa₃-type structures are more stable than those with the CoGa₃-type structures. The band gaps of FeGa₃, RuGa₃, OsGa₃ and RuIn₃ with the FeGa₃-type structure are about 0.50, 0.26, 0.68, and 0.30 eV, respectively, which are wider than those with the CoGa₃-type structure. Calculated band gaps are wider than the observed gaps, which is unusual in the LDA calculation.     

PMN-PNN-PT单晶的固相法生长研究

采用两步法和埋入PMN-PT单晶为模板的等离子放电烧结（SPS）技术制备出了致密的单一钙钛矿相的PMN-PNN-PT陶瓷，随后在1200℃下退火100h来诱导晶体的生长。实验结果表明，PMN-PNN-PT单晶〈111〉方向的生长速度明显快于〈001〉方向，而〈111〉方向生长的晶体形状为V字形，这是由钙钛矿结构的生长机理决定的，钙钛矿结构晶体的生长是通过〈001〉方向的层状生长来实现的。