Water/Oil Biphasic Hydroformylation of Higher Olefins over a TPPTS-Rh/SiO2 Catalyst

A novel TPPTS-Rh/SiO2 catalyst, prepared by directly modifying a heterogeneous highsurface-area Rh/SiO2 catalyst with water-soluble TPPTS ligands, could decrease the resistance of mass transfer in water/oil biphasic media for the hydroformylation of higher olefins. The catalytic performance for hydroformylation on this biphasic TPPTS-Rh/SiO2 catalyst system was higher than those of the traditional biphasic HRhCO(TPPTS)3 systems, owing to the chemical bonds between the highly dispersed Rh metal particles and the TPPTS ligands. The catalyst system is applicable for hydroformylation of higher olefins such as 1-dodecene.     

PAA/PVA SIPN高吸水性树脂的制备及性能研究

采用水溶液法合成了聚丙烯酸-聚乙烯醇(PAA-PVA)半互传网络型高吸水性树脂,其工艺条件的优化结果为:丙烯酸(AA)与PVA质量比为10∶0.5,AA中和度为80%,加入AA单体质量0.14%的引发剂和0.025%的交联剂,产物吸水率为530g/g,吸盐水率达63g/g。并采用红外光谱法表征了半互穿网络结构的形成。     

罗丹明B-Mo(V)-SCN~--PVA体系荧光熄灭法测痕量钼

在聚乙烯醇存在下,用罗丹明B-Mo(V)-SCN~-荧光熄灭法测Mo,能消除过量的SCN-对罗丹明B的熄灭作用。加入聚乙烯醇后体系的荧光熄灭倍数比未加入时大14倍。此法灵敏度高、稳定性好、操作简便,检测下限0.12ng/ml Mo.可用于测水和头发中的钼。     

Donor-acceptor properties, catalytic activity, and negative charge exoemission from the alumina surface modified with lithium cations

Donor-acceptor properties of alumina modified with lithium cations were studied by ESR of paramagnetic complexes of adsorbed anthraquinone. The results were compared with the data on negative ion emission (exoemission) accompanying the decomposition of isopropyl alcohol in the adsorption layer. The data on the activity measured by the pulse microcatalytic technique in isopropyl alcohol decomposition are discussed. Small additives of lithium were found to promote catalytic activity of the samples. The role of acid and basic sites in isopropyl alcohol decomposition was discussed. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 616–621, April, 2006.     

酯化交联聚乙烯醇膜用于渗透气化法分离EtoH／H2O的研究

合成了一系列磷酸和二元羧酸酯化交联改性的聚乙烯醇(PVA)膜,研究了它们用于水-乙醇混合液的渗透气化分离规律。磷酸改性的PVA膜具有较大的通量,当料液浓度为50%时,通量可达1200g/m~2·hr.,分离系数α_(H_2O/EtOH)=10。丙二酸改性PVA膜在料液浓度为50%时,通量可达800g/m~2·hr.,且α_(H_2O/EtOH)=18。并作了这两种膜的通量和分离系数随料液浓度的变化曲线。草酸交联的PVA膜具有较高的分离系数,但通量很小。求出了水、乙醇及总的表现渗透活化能。     

Development and application of an integrated system for monitoring ethanol content of fuels

An automated flow injection analysis (FIA) system for quantifying ethanol was developed using alcohol oxidase, horseradish peroxidase, 4-aminophenazone, and phenol. A colorimetric detection method was developed using two different methods of analysis, with free and immobilized enzymes. The system with free enzymes permitted analysis of standard ethanol solution in a range of 0.05–1.0 g of ethanol/L without external dilution, a sampling frequency of 15 analyses/h, and relative SD of 3.5%. A new system was designed consisting of a microreactor with a 0.91-mL internal volume filled with alcohol oxidase immobilized on glass beads and an addition of free peroxidase, adapted in an FIA line, for continued reuse. This integrated biosensor-FIA system is being used for quality control of biofuels, gasohol, and hydrated ethanol. The FIA system integrated with the microreactor showed a calibration curve in the range of 0.05–1.5 g of ethanol/L, and good results were obtained compared with the ethanol content measured by high-performance liquid chromatography and gas chromatography standard methods.     

超声波辅助Ru-B非晶态合金常压催化肉桂醛加氢制备肉桂醇

采用KBH₄化学还原法制备了超细Ru-B非晶态合金催化剂。Ru-B催化剂在肉桂醇液相常压加氢中显示出较高的肉桂醇选择性。在加氢过程中使用超声辐射能大大提高反应速率而肉桂醇的选择性几乎保持不变。加氢速率随着超声频率或超声时间的增加而增加。通过XRD、XPS、TEM、BET和ICP等各种表征手段，简要研究了超声辐射对Ru-B催化剂结构和电子特征的影响。同时，还讨论了超声对肉桂醛选择性加氢制肉桂醇催化性能的促进作用。     

离子液体中用Heck反应合成2-取代萘烯丙醇化合物

利用Heck反应, 在离子液体、金属钯或镍、碱和膦配体反应体系中, 由卤代萘与烯丙醇反应, 制得了高收率和高选择性的2-取代萘烯丙醇化合物. 该方法原料便宜易得、操作简单、反应体系可循环使用. 并讨论了醋酸镍替代醋酸钯、不同膦配体、溶剂及碱对反应转化率的影响. 通过核磁共振、红外光谱、质谱和元素分析对产物的结构进行了表征.