LiNO_3改性ZSM-5分子筛催化乳酸制丙烯酸的失活行为研究

采用X射线粉末衍射(XRD)、傅里叶变换红外光谱(FT-IR)、热重-差示扫描量热分析(TG-DSC)、X射线光电子能谱(XPS)对新鲜和再生Li-ZSM-5催化剂在乳酸脱水制丙烯酸反应中的失活原因进行了研究.结果表明,催化剂失活主要是因为乙醛和丙烯酸在酸性位点结焦生成酮类或醛类积碳前驱体、低聚烃类和高聚烃类积碳,导致活性位减少而失活.催化剂经焙烧再生,若碳物种不能脱除干净,将导致积碳速率增加,活性位减少的速度加快,稳定性降低.     

焦脱镁叶绿酸-a甲酯的E-环格氏反应及其脱氧衍生物的合成

以焦脱镁叶绿酸-a甲酯及其3-甲酰甲基为起始原料,通过与直链烷基溴化镁或者环烷基溴化镁进行格氏反应,将131-位羰基转化为烷羟基,经脱水在E-环形成环外碳碳双键,完成单(双)烷亚甲基取代的131-脱氧焦脱镁叶绿酸衍生物的合成,并且讨论了格氏反应的立体化学.所合成的新化合物均经UV,IR,1H NMR及元素分析证明其结构.     

芳香聚酰亚胺气体分离膜

芳香聚酰亚胺一直在电子、复合材料及粘接剂等领域广泛地应用。最近,聚酰亚胺膜已用于气体的分离过程。这是因为芳香聚酰亚胺是具有高玻璃化温度的玻璃态聚合物,它对小分子比大分子有更大的选择透过性,高选择性是与玻璃态聚合物的僵硬主链,对不同尺寸的分子提供筛分作用相连系的。新开发的芳香聚酰亚胺膜是用联苯四甲酸二酐与芳香二胺缩聚制备的聚酰亚胺溶液制造的。这种中空纤维状的膜是由一个多孔结构支撑的一个很薄的外表面组成的。它可通过聚合物溶液采用干——湿法过程纺丝而成,经溶剂交换干燥,外层的致密部分由计算可知厚度低于0.1μm。它对H_2与CO、CH_4.N_2及其它气体的分离有高度的选择性。由于它具有聚酰亚胺特有的耐高温性能,所以可以在很广的气体加工条件下使用。这种膜对水蒸气有很高的透过性,因而也可用于有机蒸气的脱水,或空气干燥。此膜对水蒸气的透过速度为乙醇的100～200倍。30%的乙醇水溶液,经一次膜分离,浓度可提高到99%。空气干燥系统可产出达到-50℃露点的空气。     

Dehydration Reaction of Manganese(II) Oxalate Dihydrate in the Solid State New Method in the Study of Non-isothermal Kinetics

A new method was proposed for determining the most probable mechanism function of a solid phase reaction. According to Coats-Redfern's integral equation E_β→0 was calculated by extrapolating β to zero using a series of TG curves with different heating rates. Similarly, E_α→0 was calculated according to Ozawa's equation. The most probable mechanism function of the solid phase dehydration of manganese(II) oxalate dihydrate was confirmed to be G(α)=(1-α)^1/2 by comparing E_α→0 with E_β→0. This revised version was published online in July 2006 with corrections to the Cover Date.     

氧化硅掺杂对硫酸化氧化锆酸性中心浓度和强度的提高

用氧化硅掺杂硫酸化氧化锆可以增强硫酸化氧化锆的酸性. 以413～453 K下甲醇液相脱水为模型反应考察了改进催化剂的性能. 结果表明,在掺杂和未掺杂氧化硅的硫酸化氧化锆催化剂上甲醇均相继脱水生成二甲醚和乙烯. 在掺杂了氧化硅的催化剂上还有一定量的丙烯生成,而未掺杂氧化硅的催化剂上则没有丙烯生成.     

食品接触用再生塑料的非有意添加物和鉴别技术研究进展

随着塑料废弃物导致的环境污染加重,塑料的回收利用备受关注。食品接触用再生塑料逐渐成为关注的重点,再生塑料中非有意添加物的安全性是将其用作食品接触材料的关键所在。为了避免不合规的再生塑料流入食品接触材料市场,危害消费者的健康安全,再生塑料的鉴别技术显得非常重要。该文首先对再生塑料中非有意添加物的研究进行总结,并重点概述了国内外对原生和再生塑料的鉴别技术,如质谱技术、光谱技术和热分析技术;近年来化学计量学方法也逐渐被用于再生塑料鉴别领域,提高了再生塑料的鉴别效率和准确率。     

A Thermal and Structural Study On Lanthanum Hexacyanocobaltate(III) Pentahydrate, La[Co(CN)6]⋅5H2O

Thermal and structural changes of lanthanum hexacyanocobaltate(III) pentahydrate, La[Co(CN)₆]⋅5H₂O were investigated by means of thermal analysis, visible electronic spectra, IR, powder X-ray diffraction, EXAFS and TG-MS. The dehydration of La[Co(CN)₆]⋅5H₂O proceeded reversibly through three steps and steps corresponded to the losses of H₂O, 3H₂O and H₂O, and the enthalpy changes for these steps were 51.3, 211.0 and 38.7 kJ mol⁻¹, respectively. After the dehydration, the colour of the anhydride changed from white to blue around 290°C and an abrupt mass loss occurred at 350°C. The colour change seems to be attributable to the change of coordination geometry around the Co ions from an octahedral structure to a tetrahedral one. LnCoO₃ was obtained as a final product by heating the sample to 1000°C. This revised version was published online in August 2006 with corrections to the Cover Date.     

Study of Acidity of Aerogels ZrO2-SO42− by Isopropanol Dehydration Reaction, Surface Potential and X-Ray Photoelectron Spectroscopy

Sulphated zirconia aerogels, with definite atomic ratio S/Zr and hydrolysis ratio (H = H₂O/Zr) were prepared by the autoclave method. The addition of sulphate ions causes a decrease of the cristallinity of zirconia. XPS results show the O1s photoelectronpeak which could be decomposed in two components for the reticular oxygen of the zirconia framework and for oxygen attributed to the OH groups and/or sulphates groups, and the S2p photopeak characteristic of sulphates species. The Kelvin probe shows that the value of pure zirconia is around 200 mV. This value grows up to 1200 mV for sulphate doped catalysts. The modification of the work function is probably due to the charge transfer from the zirconium to an oxygen species, responsible for the increase of Lewis acidity. The catalysts prepared with hydrolysis ratio of H = 4 exhibit higher activities in the isopropanol dehydration reaction than those with H = 2 in the temperature range 373 K–423 K.     

Lewis acid promoted dehydration of amides to nitriles catalyzed by [PSiP]-pincer iron hydrides

The dehydration of primary amides to their corresponding nitriles using four [PSiP]-pincer hydrido iron complexes 1–4 [(2-Ph₂PC₆H₄)₂MeSiFe(H)(PMe₃)₂ ( 1 ), (2-Ph₂PC₆H₄)₂HSiFe(H)(PMe₃)₂ ( 2 ), (2-(iPr)₂PC₆H₄)₂HSiFe(H)(PMe₃)₂ ( 3 ) and (2-(iPr)₂PC₆H₄)₂MeSiFe(H)(PMe₃)₂ ( 4 )] as catalysts in the presence of (EtO)₃SiH as dehydrating reagent was explored in the good to excellent yields. It was proved for the first time that Lewis acid could significantly promote this catalytic system under milder reaction conditions than other Lewis acid-promoted system, such as shorter reaction time or lower reaction temperature. This is also the first example that dehydration of primary amides to nitriles was catalyzed by silyl hydrido iron complexes bearing [PSiP]-pincer ligands with Lewis acid as additive. This catalytic system has good tolerance for many substituents. Among the four iron hydrides 1 is the best catalyst. The effects of substituents of the [PSiP]-pincer ligands on the catalytic activity of the iron hydrides were discussed. A catalytic reaction mechanism was proposed. Complex 4 is a new iron complex and was fully characterized. The molecular structure of 4 was determined by single crystal X-ray diffraction.     

Recent advances in sodium alginate-based membranes for dehydration of aqueous ethanol through pervaporation

Sodium alginate (SA) is a progressive material for membrane fabrication. The technological development of SA-based membranes has made a significant contribution to the separation techniques, especially in aqueous organic solutions. The outstanding performance of SA is attributed to its outstanding structural flexibility and hydrophilicity. In view of structural characteristics, SA membranes have immense utilization in the pervaporation separation of organics. Among various organics, dehydration of aqueous ethanol is employed as a standard to check the success of pervaporation (PV) membrane. Because ethanol and water have comparable molecular sizes, thus difficult to extract water from aqueous ethanol mixtures than it is for other organics. A literature survey shows that wide-ranging data are available on the PV performance of SA and its modified membranes. In this context, the present review addresses the recent advances made in SA membranes for enhanced ethanol dehydration performance during the last decade. Available data since 2010 has been compiled for grafted, crosslinked, blend, mixed matrix, and composite hybrid sodium alginate membranes in terms of separation factor, permeation flux, and pervaporation separation index PSI. The data are assessed with reference to the effect of feed composition, membrane selectivity, flux, and swelling behavior.