碳酸二甲酯市场现状及技术进展

目前,全球碳酸二甲酯(DMC)的产量约为12万t/a。生产方法有光气法、酯交换法、甲醇氧化羰基法和二氧化碳-甲醇直接合成法。我国DMC产量不足3万t/a,主要采用酯交换法和甲醇液相氧化羰基法。DMC可作为羰基化试剂代替剧毒物质光气用于合成聚碳酸酯、异氰酸酯、杀虫剂西维因等,用作甲基化试剂代替致癌物硫酸二甲酯合成苯甲醚。     

Interaction of methane with surfaces of silica,aluminas and HZSM-5 zeolite. A comparative FT-IR study

Infrared investigations on the interaction of methane with silica, aluminas (, and ) and HZSM-5 zeolite have been carried out. At low temperature (173 K), methane adsorption was observed over these oxides and HZSM-5 zeolite. Our findings featured that the infrared inactive ₁ band (2917 cm^–1) of a gaseous methane molecule became active and shifted to lower frequencies (2900 and 2890 cm^–1) when it adsorbed on the surfaces of these adsorbents. Our results also demonstrate that hydroxyl groups played a very important role in methane adsorption over the acidic oxides and the HZSM-5 zeolite. When interaction between the hydroxyl groups and methane took place, the band shift of the hydroxyl groups varied with different oxides. The strength of the interaction decreased according to the following sequence, Si-OH-Al>Al-OH>Si-OH, which is in accordance with the order of their acidities. At higher temperatures, methane interacted quite differently with various oxides and HZSM-5 zeolite. It has been observed that the hydroxyl groups of silica, -alumina and HZSM-5 zeolite could exchange with CD₄ at temperatures higher than 773K, while those on -alumina could exchange at a temperature as low as 573 K. Another interesting observation was the formation of formate species over Al₂O₃ (both and ) at temperatures higher than 473 K. The formate species would decompose to CO₂, or produce carbonate at much higher temperatures. Formation of formate species was not observed over silica and HZSM-5 under similar conditions, -Al₂O₃ did not adsorb or react with methane in any case.     

强碱树脂在木糖应用中存在的问题及解决方法

木糖是一种在化工、食品等领域有着广泛用途的五碳糖,工业生产是用稀强酸将玉米芯中含有的大量多缩戊糖分解为单个的木糖分子,然后通过离子交换除盐、脱色,精制提取,但在强碱离子交换柱中,木糖分子容易被部分催化异构转化为阿拉伯糖,使得木糖纯度下降,结晶困难。考察了强碱树脂再生浓度、淋洗终点pH值、交换温度以及流速对木糖分子异构的影响,得出最佳的交换工艺条件:再生剂浓度为2%、淋洗终点pH值为7.5、交换温度20℃,流速为1BV/h。     

A modified NRCS-CN method for eliminating abrupt runoff changes induced by the categorical antecedent moisture conditions

The popular Natural Resources Conservation Service Curve Number (NRCS-CN) (earlier known as Soil Conservation Service Curve Number (SCS-CN) method of rainfall-runoff modeling has often faced the criticism of exhibiting quantum jumps in runoff computations because of the sudden jumps appearing in CN-values derived from NEH-4 tables for three antecedent moisture conditions (AMC), viz., AMC-I, AMC-II, and AMC-III valid for dry, normal, and wet conditions, respectively. The variability of antecedent soil moisture within an AMC category is responsible for the abrupt jump and other deficiencies in the CN method for runoff estimation. This paper suggests a novel procedure to account for the antecedent moisture (M), preventing quantum jumps and eliminating deficiencies in determination of CN and, in turn, estimation of direct runoff. Its validity was verified utilizing the observed rainfall (P)-runoff (Q) events from 36 US watersheds, four sub-catchments of the Godavari basin, and small agricultural plots at Roorkee, India. The performance of the proposed model (M5) for runoff prediction was compared with the existing NRCS-CN (M1), Mishra and Singh (2002) (M2), Singh et al. (2015) (M3), and Verma et al. (2021) (M4) model using various performance indices. Using the CNs derived from observed events, model M5 was seen to have performed better than M1-M4 in terms of Nash Sutcliffe Efficiency (NSE), Root Mean Square Error (RMSE), and Percent Bias (PBIAS) for the data of US watersheds, and CN-P correlation improved as the coefficient of determination (R²) enhanced. Similarly, using the RS & GIS-based CNs on natural watersheds of the Godavari basin and considering AMC-I, the performance of M5 was again better than M1-M4 in terms of RMSE, Mean Bias Error (mBIAS), Mean Absolute Error (MAE), and Normalized-Nash Sutcliffe Efficiency (NNSE). Interestingly, there existed a significant (p < 0.05) relationship between the in-situ water content (w) measured for the experimental plots of Roorkee and the model input variable antecedent moisture (M), offering a physical touch to the conceptual model.     

CO2在全氟羧酸离子交换膜内促进传质特性的研究

本文以全氟羧酸离子交换膜为支撑体、乙二胺(EDA)为活性络合剂、制备促进传质膜。在常用的工业条件下,测定了纯CO_2以及CO_2/N_2二元混合物在该膜内的渗透通量。实测结果表明,此膜对CO_2的促进因子可达13.8,而对CO_2/N_2的分离因子高达316。本文假设促进传质过程的控制步骤为气体在膜相的扩散,据此导出了相应的机理模型,该模型与实测结果吻合良好。     

2,6-二(三氟甲基)吡啶的合成研究

以2,6-二氯吡啶为原料,制得2,6-二溴吡啶(收率79%)或2,6-二碘吡啶(收率56%),再分别与三氟乙酸钾反应,均可得标题化合物,收率28%~53%。该合成路线的优点是原料易得,反应条件温和,收率较高。     

From clay- to organoclay-film modified electrodes: tuning charge selectivity in ion exchange voltammetry

The surface of two natural smectite-type clay samples was chemically modified by covalent grafting of amine groups, by reaction with γ-aminopropyltriethoxysilane, which were easily protonated in HCl medium. Multisweep cyclic voltammograms of clay-film modified glassy carbon electrodes made of either the raw clays or the propylammonium-functionalized samples exposed to Ru(NH₃)₆³⁺ or Fe(CN)₆³⁻ electroactive probes were obtained. The results indicated a permselective behavior of these clay and organoclay-films based on either favorable or unfavorable electrostatic interactions. The cation-exchanging raw clay film modified electrodes exhibited accumulation properties for Ru(NH₃)₆³⁺ species while rejecting Fe(CN)₆³⁻, whereas the anion-exchanging organoclay coatings acted as a barrier against Ru(NH₃)₆³⁺ while increasing dramatically the concentration of Fe(CN)₆³⁻ species at the electrode surface. Strong binding of the probe to the organoclays resulted in a potential shift of ca. 0.1 V of the voltammetric signals characteristic of the Fe(CN)₆^3−/4− couple in the anodic direction. Their good preconcentration efficiency at low analyte concentration highlighted their interest for electroanalytical applications.     

On the catalytic C-H activation of some silicon dioxide overlayers on thin metal film systems — An observation on the isokinetic effect

Kinetic data on the exchange reaction betwee hexane and deuterium have recently been reported by Maier and coworkers [1]. The reaction was catalysed by a series of platinum or rhodium systems, some of which had the property that the upper surface was shielded by a silica overlayer. The data are reinterpreted to indicate an isokinetic temperature of 580 K. This observation indicates that all the catalysts behave in a similar manner, which means that the exchange reaction does not require a free metal surface.     

粒碱生产装置小结

介绍了气流式烧碱造粒的基本原理、特点和生产中易出现的问题及解决方法。