Study on Pd-Pb/CaCO3 Catalyst for Selective Hydrogenation of Acetylenic Link in Hydrocarbon

多数脂肪族天然产物，都含有一个或多个碳碳双键，这些双键的构型往往对其生理活性起了决定性的作用。炔烃催化半氢化生成顺式烯烃作为有机合成中重要的一步反应，能同时引起官能团和立体化学的异构，长期以来备受关注。尽管经历了50多年的考验，Lindlar催化剂以其高效和实用，在有机合成上，依然是炔烃半氢化构筑Z-烯烃的最常用方法。本文的创新点在于：（1）用正交试验研究了喹啉、催化剂、温度等因素对炔键选择加氢的影响，方差分析及显著性检验结果表明喹啉添加量与催化剂用量之间的配比对炔烃氢化反应的选择性有重大影响，并利用二元表和二元图得到了优化的反应条件：即催化剂120mg，喹啉100mg，苯乙炔1.2g，温度2...Most aliphatic natural products contain one or more di- or trisubsitituted double bonds, often present in the 1, 3-diene or 1, 3-enyne, with a specific double bond geometry being a requirement for biological activity. Cis-selective semi-hydrogenation of alkynes is receiving on-going attention as an important step in organic synthesis to induce functionality and stereochemistry simultaneously. Desp...学位：理学硕士院系专业：化学化工学院化学系_物理化学(含化学物理)学号：20022506

Improvement on Pd-Pb/CaCO_3 catalyst for selective hydrogenation of acetylenic linkage in hydrocarbons

利用XRD和SEM研究了EDTA、草酸等助剂对沉淀CaCO3显微结构的影响,结果表明,CaCO3晶型及形貌随助剂不同而变化,甚至同一助剂不同添加量亦会导致其晶相的显著差异。XRD分析表明,在草酸存在下,沉积物为单一的方解石相,该晶型的CaCO3对Pd Pb/CaCO3催化剂呈现明显的模板效应。不同还原方法的尝试说明,水合肼是一种好的还原剂。TEM研究表明,在适宜条件下对催化剂老化处理,表面金属钯颗粒发生聚并,并且由此带来部分氢化选择性的较大提高。Influences of additives (PVA, oxalic acid, EDTA, ZnCl_2) on microstructure of precipitated calcium carbonate (CaCO_3) were investigated using SEM and XRD. The results indicated that crystal form and shape of CaCO_3 vary with both type and quantity of the additives. XRD results showed that the deposit crystallized in calcite in the presence of oxalic acid,which exhibited distinct template effect in Pd-Pb/CaCO_3 system. The test results of different reduction methods showed that hydrazine hydrate was a good reducing agent. TEM images showed that palladium particles on the catalyst surface agglomerated after appropriate aging treatment and thus improved partial hydrogenation selectivity of the catalyst

Methane Combustion over PdO Crystallite Manipulated by Support Template

通过对PdO活性组分在单斜与四方型氧化锆载体上的热化学性质和催化活性进行比较性的研究显示,单斜型ZrO2的表面原子能够满足与PdO的结构适应性匹配条件,它可以通过界面原子的取向附生作用对表面PdO物种聚集形态进行调控,从而促进PdO组分在单位载体表面上的分散.此外,升降温循环过程的DTG分析还表明,单斜载体模板在反复的氧化还原循环中逐渐将结晶型PdO加工成取向附生型PdO,不断改善PdO物种的氧迁移性质,促进了热还原钯物种在高温区的氧化再生.这两种载体效应有效地抑制了甲烷燃烧反应在高温区的活性振荡,增加了燃烧的稳定性与催化剂的反应耐受性.四方ZrO2晶相在载体内的掺杂将导致上述的载体效应受到明显抑制.A comparative investigation on the thermochemical and catalytic properties of palladium oxide crystallite supported on monoclinic or tetragonal-doped zirconia, demonstrated that by sharing the interfacial atoms with monoclinic zirconia, PdO crystallite aggregates at the aid of this epitaxy on the support template to acquire better dispersion. Moreover, tracking the heating-cooling cycles in air atmosphere, DTG analysis illustrated that the crystallized PdO gradually transforms into the epitaxial PdO species on the monoclinic zirconia and the improved mobility of oxygen in lattices promotes the oxidative regeneration of PdO at high temperature thereby. Combining the above two superiorities on aggregation forms of PdO, the template of monoclinic zirconia inhibits the high temperature deactivation of catalysts for methane combustion, mean- while, increases the stability of combustion reaction and the sustainability of catalysts. However, the doping of tetragonal zirconia into monoclinic support muffles those advantages prominently.国家基础研究重点发展规划(No.G1999022400);; 国家自然科学基金(No.20203014)资助项目

Methane combustion over PdO crystallite manipulated by support template

A comparative investigation on the thermochemical and catalytic properties of palladium oxide crystallite supported on monoclinic or tetragonal-doped zirconia, demonstrated that by sharing the interfacial atoms with monoclinic zirconia, PdO crystallite aggregates at the aid of this epitaxy on the support template to acquire better dispersion. Moreover, tracking the heating-cooling cycles in air atmosphere, DTG analysis illustrated that the crystallized PdO gradually transforms into the epitaxial PdO species on the monochnic zirconia and the improved mobility of oxygen in lattices promotes the oxidative regeneration of PdO at high temperature thereby. Combining the above two superiorities on aggregation forms of NO, the template of monoclinic zirconia inhibits the high temperature deactivation of catalysts for methane combustion, meanwhile, increases the stability of combustion reaction and the sustainability of catalysts. However, the doping of tetragonal zirconia into monoclinic support muffles those advantages prominently

载体对甲烷催化部分氧化制合成气的影响

运用固定床流动反应装置、ＴＰＲ和ＸＲＤ等手段考察了载体的晶相组成、比表面和孔结构等性质对Ｎｉ基催化剂在甲烷部分氧化制合成气中反应性能的影响。结果表明，热稳定性好、导热好的惰性材料如（Ｃａ）ＭｇＡｌ２Ｏ４等是甲烷部分氧化制合成气理想的催化剂载体。载体必须具有适当的比表面和孔结构，以利于反应物分子在催化剂表面吸附并与活性中心充分接触，同时也有利于产物分子脱附并离开催化剂表面，防止副反应（积碳反应和燃烧反应）的发生，及时把反应热移走，避免热点产生使催化剂失活。另外还发现，具有不同比表面和孔结构的催化剂具有不同的最佳空

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通讯作者：李长贵 E-mail：[email protected] 作者简介：赵慧（1980-），女，助理研究员 主要从事病毒疫苗质量控制工作目的 应用假病毒中和法建立检测血清HPV16/18中和抗体滴度检测方法并进行验证。方法 分别采用不同批次假病毒以及不同代次细胞对不同滴度的HPV16/18阳性血清进行多次平行检测，考察这些因素对检验结果的影响；同时通过对抗HPV16/18双价阳性血清、抗HPV16单价阳性血清和抗HPV18单价阳性血清的检测进一步评估中和抗体检测法的准确性、特异性及重复性。结果 不同批次假病毒和不同代次细胞对检验结果的影响均在四倍范围内，此外该检测法的准确性、特异性、重复性均在可接受标准范围之内。结论建立的假病毒法可满足中和抗体效价检测的要求，可用于评价疫苗的免疫效果。国家高技术研究发展计划（2012AA02A402）；国际科技合作项目 (2010DFB30100

Study on Pd-Pb/CaCO_3 Catalyst for Selective Hydrogenation of Acetylenic Link in Hydrocarbon

用正交试验研究了喹啉、催化剂、温度等因素对炔键选择加氢的影响,方差分析及显著性检验结果表明喹啉添加量与催化剂用量之间的配比对炔烃氢化反应的选择性有重大影响,并利用二元表和二元图得到了优化的反应条件.不同还原方法的尝试说明水合肼也是一种好的还原剂.两种浸渍方法的对比表明,用双浸渍法制备的钯催化剂选择加氢性能整体优于常规浸渍法制备的催化剂,当浸渍比为1 1时选择性最好,并对该现象进行了讨论.Influence of quinoline,catalyst,temperature and so on,on selective hydrogenation of acetylenic link was investigated with orthogonal test method.The results of analysis of variance and test of significance indicate that,mixing different doses of quinoline and catalyst do cause obvious difference in hydrogenation selectivity of alkynes.Then the optimal reaction condition is established by bipartite graph.The trial of different reductive methods explains that hydrazine hydrate is also a kind of good reducing agent.Comparison of the double impregnation method (DI) with the conventional impregnation method (CI) shows that the properties of the catalyst prepared by DI method are better than those prepared by CI method.Ensuing improvement of semihydrogenation selectivity was found and discussed

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