二(2-氨基乙基)-(3-氨基丙基)胺的合成新方法

以二(氰基甲基)胺及丙烯腈为原料，通过亲核加成、氢化反应合成了不等臂有机多胺化合物二(2-氨基乙基)-(3-氨基丙基)胺，标题化合物及其中间产物经多种谱学手段表征确证。在优化条件下，产物的总收率为67％，含量99.5％(HPLC)。     

丁腈胶乳的加氢反应

采用水合肼/过氧化氢氧化还原体系，以硼酸为催化剂，在常压下进行丁腈胶乳的氢化反应，研究了过氧化氢加入方式，硼酸和水合肼用量，反应温度及反应时间对丁腈胶乳加氢度的影响。结果表明，过氧化氢连续滴加再附加室温条件，氢化反应效果最好。当硼酸用量为2.64mmol，水合肼用量为95.2mmol，过氧化氮用量为79.3mmol。在60℃，6h下，丁腈胶乳的加氢度可达到90%以上。     

焙烧温度对CuMgAl催化剂催化糠醇加氢制戊二醇的影响

采用共沉淀法制得物质的量比为n(Cu²⁺)∶n(Mg²⁺)∶n(Al³⁺)=10∶65∶25的CuMgAl类水滑石前体（CMA-HT），经过不同温度焙烧制得CuMgAl水滑石催化剂。通过傅里叶变换红外光谱（FTIR）、热重分析（TG）、X射线粉末衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、N₂-物理吸附、程序升温还原（H₂-TPR）、H₂-程序升温脱附（H₂-TPD）、CO₂-程序升温脱附（CO₂-TPD）和NH₃-程序升温脱附（NH₃-TPD）等对催化剂的结构进行表征，在高压反应釜中考察了CuMgAl水滑石催化剂催化糠醇（FFA）加氢制1,2-戊二醇（1,2-PeD）和1,5-戊二醇（1,5-PeD）的催化性能。研究结果表明，焙烧温度对催化剂的结构及其催化性能具有显著的影响，金属活性中心和碱性位随焙烧温度的升高先增加后减少。经600℃焙烧的CMA催化剂表面存在适宜的金属中心和碱性位，在金属位和碱性中心的协同催化下，表现出了优异的催化性能。在140℃，H₂压力为4 MPa的条件下，反应8 h，糠醇的转化率和戊二醇的收率分别达74.13%和58.36%。     

对苯二甲酸精制钯碳催化剂内扩散有效因子的估算

在高压磁力搅拌间歇反应釜中研究了粗对苯二甲酸在不同反应温度下,两种粒径的Pd/C催化剂上加氢精制反应的规律。按照该反应对于对羟基苯甲醛(4 CBA)是拟一级反应估算了催化剂的内扩散有效因子η值。本试验估算的η值与动力学研究拟合得到的η值吻合良好。     

The kinetics of CO2 hydrogenation on a Rh foil promoted by titania overlayers

Submonolayer deposits of titania on a Rh foil have been found to increase the rate of CO₂ hydrogenation. The primary product, methane, exhibits a maximum rate at a TiO _x coverage of 0.5 ML which is a factor of 15 higher than that over the clean Rh surface. The rate of ethane formation displays a maximum which is 70 times that over the unpromoted Rh foil; however, the selectivity for methane remains in excess of 99%. The apparent activation energy for methane formation and the dependence of the rate on H₂ and CO₂ partial pressure have been determined both for the bare Rh surface and the titania-promoted surface. These rate parameters show very small variations as titania is added to the Rh catalyst. The methanation of CO₂ is proposed to start with the dissociation of CO₂ into CO_(a) and O_(a), and then proceed through steps which are identical to those for the hydrogenation of CO. The increase in the rate of CO₂ hydrogenation in the presence of titania is attributed to an interaction between the adsorbed CO, released by CO₂ dissociation, and Ti³⁺ ions located at the edge of TiO _x islands covering the surface. Differences in the effects of titania promotion on the methanation of CO₂ and CO are discussed in terms of the mechanisms that have been proposed for these two reactions.     

Synergistic Catalysis of Carbon Dioxide Hydrogenation into Methanol by Yttria-Doped Ceria/γ-Alumina-Supported Copper Oxide Catalysts: Effect of Support and Dopant

Methanol synthesis from carbon dioxide hydrogenation was studied over ceria/-alumina- and yttria-doped ceria (YDC)/-alumina-supported copper oxide catalysts to seek insight into the catalysis at metal–support interfaces. It was found that, in comparison with Cu/-Al₂O₃, the Cu/CeO₂/-Al₂O₃ and Cu/YDC/-Al₂O₃ catalysts exhibited substantial enhancement in activity and selectivity toward methanol formation. The extent of enhancement was augmented by increased ceria loading on -alumina and with increased yttria doping into ceria. The enhancement is inferred to result from the synergistic effect between copper oxide and surface oxygen vacancies of ceria.     

α-蒎烯催化加氢合成顺式蒎烷的研究

本文研究了以镍系催化剂催化α－蒎烯加氢合成高选择性的顺式蒎烷。考察了反应压力、反应温度及催化剂用量等因素对产品的影响，在此基础上确定了适宜的工艺参数。在此条件下反应，α－蒎烯转化率＞99％，顺式蒎烷选择性＞95．7％。     

室温离子液体1-烷基-3-甲基咪唑硫酸甲酯的合成及电导率研究

利用硫酸二甲酯分别与N-甲基及N-丁基咪唑在室温下反应,一步合成了离子液体1-甲基-3-甲基咪唑硫酸甲酯和1-丁基-3-甲基咪唑硫酸甲酯,测定了在不同温度下离子液体的电导率.结果表明:随着温度的升高,离子液体的电导率迅速增加;同时电导率与温度的变化关系符合多项式方程和Vogel-Tammann-Fulcher(VTF)方程.     

Ni-W2C催化葡萄糖氢解制备低碳二元醇反应机理研究

采用HPLC、LC-MS、GC-MS等分析手段对不同工艺条件下Ni/W₂C催化葡萄糖加氢转化的中间产物及终产物进行定性定量分析，研究了葡萄糖加氢转化过程的反应机制和历程。研究发现：葡萄糖加氢转化过程中同时平行发生了加氢、异构和逆向羟醛缩合（氢解）三类反应；葡萄糖发生加氢反应能够得到六元醇且其不会再进一步转化，发生逆向羟醛缩合反应主要生成乙二醇（C₂产物），发生异构反应则可生成果糖，其进行逆向羟醛缩合的产物则为1,2-丙二醇和甘油（C₃产物）；高浓度葡萄糖条件下，其异构产物果糖发生脱水反应生成的5-HMF浓度过高发生聚合，进而导致结焦。根据葡萄糖加氢转化的反应网络，提出了调控反应过程中C₂产物和C₃产物分布的策略，并通过增加催化剂用量来加快果糖脱水的竞争反应速率(加氢、氢解)，进而实现了高浓度（10%，质量分数）葡萄糖的加氢转化。此外，葡萄糖加氢转化过程中存在明显的浓度效应，反应物浓度越低，越有利于发生逆向羟醛缩合反应，反之则有利于发生加氢反应。     

Lewis acidity as an explanation for oxide promotion of metals: implications of its importance and limits for catalytic reactions

Sub-monolayer quantities of metal oxides are found to influence CO hydrogenation, CO₂ hydrogenation, acetone hydrogenation, ethylene hydroformylation, ethylene hydrogenation, and ethane hydrogenolysis over Rh foils. The metal oxides investigated include AlOx, TiOx, VOx, FeOx, ZrOx, NbOx, TaOx, and WOx. Only those reactions involving the hydrogenation of C-O bonds are enhanced by the oxide overlayers. The coverage at which maximum rate enhancement occurs is approximately 0.5 ML for each oxide promoter. Titanium, niobium, and tantalum oxides are the most effective promoters. XPS measurements after reaction show that of the oxides studied titanium, niobium, and tantalum oxide overlayers are stable in the highest oxidation states. The trend in promotion effectiveness is attributed to the direct relationship between oxidation state and Lewis acidity. For the oxide promoters, bonding at the metal oxide/metal interface between the O-end of adsorbed CO and the Lewis acidic oxide is postulated to facilitate C-O bond dissociation and subsequent hydrogenation.