钠代草酰乙酸乙酯的合成及与苯肼的反应

以乙酸乙酯和草酸二乙酯为原料，经交叉Claisen酯缩合反应合成钠代草草酰乙酸乙酯。讨论反应时间、碱的浓度、原料配比对反应的影响。得出较佳工艺条件为：n(乙醇钠）：n（乙酸乙酯）：n(草酸二乙酯）＝1．02：1．02：1．00，乙醇钠浓度为19．5％，反应时间为4h，产率为76％。用此盐与苯肼与酸性条件下进行加成缩合反应可制得1－苯基－3－羧酸乙酯－5－吡唑啉酮。产物的结构经红外光谱分析确认。     

3-乙基-2-羟基-2-环戊烯-1-酮的合成研究

以戊二酸和草酸二乙酯为主要原料，经酯化、酯缩合、烷基化和水解脱羧4步反应合成香料化合物3－乙基－2－羟基－2－环戊烯－1－酮，产品经熔点测定和红外光谱分析证明了结构。同时初步考察并确定各步反 应的工艺条件，产物总收率为41．7％。     

CO气相催化偶联制草酸二乙酯反应中催化剂的失活与再生研究

在固定床反应器中,对一氧化碳气相催化偶联合成草酸二乙酯的反应体系进行了人为飞温,两次飞温过程分别为:反应温度从120℃飞温到400～500℃和1000～1200℃,考察飞温后催化剂的活性。对飞温失活催化剂进行再生后,测定了再生催化剂的活性。利用XPS技术对催化剂表面元素进行分析测试,发现第一次催化剂飞温失活的主要原因是催化剂活性组分Pd被氧化所致,而第二次催化剂飞温失活的主要原因是催化剂活性组分Pd被其它元素所覆盖。对第一次失活催化剂再生后,其活性可恢复至原来水平,对第二次失活催化剂再生后,其活性仅恢复到原有催化剂活性的50%。     

甲基异丙基酮和二乙基酮合成催化剂研究

研究了载钯的锆基催化剂上甲醇丁酮一步法合成甲基异丙基酮和二乙基酮的反应.由ZrOCl2.8H2O等制备的Pd-ZrO2/MnOx/ZnO催化剂对甲醇丁酮一步反应合成甲基异丙基酮和二乙基酮具有良好的催化性能.重点考察了催化剂组成对反应的影响,结果表明:钯负载量对催化剂活性和选择性影响较大;锆基载体中添加MnOx和ZnO作为助剂是必要的,可以显著提高催化剂催化活性和选择性;负载少量钾可以有效降低重组分的生成.结合反应机理分析,反应经脱氢-缩合-加氢三个步骤,催化剂中加氢脱氢活性中心和酸性活性中心的匹配程度决定了催化剂的活性和选择性,催化剂上氢溢流的能力对催化剂的活性和选择性有明显的影响.     

Synthesis and properties of manganese-doped barium titanate

An oxalate route for the production of BaTiO₃ has been modified to incorporate Mn (upto 2%) as a dopant and the reaction sequence has been studied. The resulting Mn-doped BaTiO₃ exhibits a dielectric constant with an increasing insensitivity to temperature and applied a.c. field as the Mn content is increased. These samples possess a high electrical resistivity even after treatment in hydrogen at 1100°C and are therefore suitable as dielectric for multilayer capacitors with base metal electrodes.     

Use of a pulsed column contactor as a continuous oxalate precipitation reactor

The current objective of coprecipitating uranium, and minor actinides in order to fabricate a new nuclear fuel by direct (co)precipitation for further transmutation, requires to develop specific technology in order to meet the following requirements: nuclear maintenance, criticity, and potentially high flowrates due to global coprecipitation. A new type of device designed and patented by the CEA was then tested in 2007 under inactive conditions and with uranium. The patent is for organic confinement in a pulsed column (PC). Actually, pulsed columns have been working for a long time in a nuclear environment, as they allow high capacity, sub-critical design (annular geometry) and easy high activity maintenance. The precipitation reaction between the oxalate complexing agent and a surrogate nitrate - cerium(III) or neodymium(III) alone, or coprecipitated uranium(IV) and cerium(III) - occurs within an emulsion created in the device by these two phases flowing with a counter-current chemically inert organic phase (for example tetrapropylene hydrogen—TPH) produced by the stirring action of the column pulsator. The precipitate is confined and thus does not form deposits on the vessel walls (which are also water-repellent); it flows downward by gravity and exits the column continuously into a settling tank.The results obtained for precipitation of cerium or neodymium alone in a short column of small diameter have demonstrated that high throughputs are feasible without system malfunctions. The measured particle size of the precipitates ranges from 20 to 40 μm on average, and the measured device outflow indicates that the precipitation reaction is complete. These results suggest that this laboratory design can be extrapolated to an industrial column. Moreover, a recent test campaign demonstrated that a uranium-cerium coprecipitate easily forms when the two nitrates are mixed in a pulsed column of the same size operating under very similar process conditions. Qualitatively, the coprecipitate meets the process requirements to filter, calcine and fabricate the new nuclear fuel in the downstream steps.     

碳酸二乙酯与邻苯二酚乙基化反应合成邻羟基苯乙醚

以Cr2O3/Al2O3为催化剂、碳酸二乙酯(DEC)为乙基化试剂,邻苯二酚在气相连续流动固定床反应器内进行乙基化反应合成了邻羟基苯乙醚;考察了反应温度、空速、原料配比等条件对催化剂活性的影响,同时考察了催化剂的稳定性。实验结果表明,Cr2O3负载量(质量分数)为21%的Cr2O3/Al2O3催化剂对该反应具有较好的催化活性;适宜的反应条件为:反应温度603K,重时空速1.5h-1,n(DEC)∶n(邻苯二酚)=4.0,在此条件下反应7h,邻苯二酚转化率高达100.0%,目的产物邻羟基苯乙醚的选择性最大为83.02%。升高反应温度有利于反应的进行,但反应温度过高会导致副产物的增加。催化剂的稳定性实验结果表明,在20h内催化剂的活性稳定,之后目的产物选择性逐渐降低,副产物苯环的碳烷基化产物的含量逐渐增加。     

Conventional and wet proofed CuO/Al2O3 catalysts for phenol oxidation: deactivation studies in a trickle bed reactor

A large variety of catalytic systems have been studied for the catalytic wet air oxidation of phenolic solutions. Most of them show good activity, but serious stability problems. In this contribution, stability studies were performed over CuO/Al₂O₃ conventional (CNT) and polytetrafluorethylene coated (C3T) catalysts used for the oxidation of 5 g L^?1 phenol solutions in a trickle bed reactor (140 °C and 7 atm of oxygen pressure). For the hydrophilic catalyst, phenol conversion decreased with usage due to the formation of Cu₂O and copper oxalate phases. For the wet proofed catalyst, the hydrophobic layer prevented the appearence of those phases, and conversion levels remained practically constant with reaction time. After usage, both catalysts were oxidized at 400 °C and tested for reaction: in the case of the C3T catalyst, the phenol conversion was increased over its initial level; for CNT catalyst, the phenol conversion was also increased, but initial levels were not completely restored. The deactivation mechanism of the CNT catalyst is associated with the formation of the Cu₂O and copper oxalate phases during reaction. For catalyst C3T, practically no deactivation was observed. Copyright © 2007 Society of Chemical Industry     

Composition and availability of soluble and insoluble oxalates in raw and cooked taro (Colocasia esculenta var. Schott) leaves

Taro (Colocasia esculenta var. Schott) is a major staple food crop in parts of Asia and the Pacific Islands and is grown as a minor crop in New Zealand. Soluble, insoluble and total oxalate content of young and older leaves were determined by HPLC following hot water (80 °C) and hot (80 °C) acid (0.2 mol/L HCL) extractions. Young taro leaves contained 589 ± 35.8 mg total oxalates/100 g fresh weight (FW) while older taro leaves contained (443 ± 15.0 mg total oxalates/100 g FW). Soluble oxalates were 74% of the total oxalate content of the young and old leaves.     

高纯超细SrTiO3粉料的液相合成方法

本文研究了三种高纯超细ＳｒＴｉＯ３粉料的液相合成方法：草酸盐沉淀法、过氧化物热分解法和液相直接沉淀法。通过在使用原料、制备流程、工艺条件、粉料收率及粉料性能等方面的对比得出：液相直接沉淀法具有原料便宜易得、工艺流程简单、操作方便、不需高温热分解和粉料收率高等优点，而且制得的粉料在粒度、粒度分布、颗粒形状及团聚状态等方面均优于另外两种方法制备出的粉料。