丙烯腈装置回收塔内聚合物生成原因的分析

针对丙烯腈生产过程中回收塔内聚合物堵塞降液管造成回收塔运行周期短的问题,通过对丙烯腈回收塔内各组分分布的模拟计算,直观显示了回收塔内各组分的浓度分布,发现了回收塔的聚合段与丙烯醛的富集段相吻合的现象,初步得出了回收塔内局部聚合的原因;通过对塔内聚合物的特性分析和评判,进一步证实了“回收塔内局部聚合严重是由于在聚合段丙烯醛聚集引起”这一现象;根据模拟计算结果和实际运行经验,提出了预防聚合物堵塞降液管的措施,并进行了部分生产验证,为丙烯腈生产企业延长装置运行周期提供了理论指导。     

由乙腈一步法制备乙酸丁酯的研究

以丁醇和制备丙烯腈的副产物乙腈为原料 ,采用一步法合成了乙酸丁酯。通过正交实验得到了影响反应的 4种因素。确定了最佳的工艺条件为 :催化剂的量为样品质量的 40 % ;n(CH3CN)∶ n(C4 H9OH) =1∶ 1 .0 5 ;反应温度为 1 0 5℃ ;反应时间为 8h。在此反应条件下 ,乙酸丁酯的收率为 88.8% ,纯度可达 99.5 %。并用气相色谱及红外光谱对产品的纯度进行了表征     

p,V, T and derived thermodynamic data for toluene,trichloromethane, dichloromethane,acetonitrile, aniline,and n-dodecane

Experimentally determined p,V,T data are reported for toluene, trichloromethane, dichloromethane, acetonitrile, aniline, and n-dodecane at 278, 288, 298, 313, and 323 K, except for dichloromethane, for which the highest temperature was 298 K. At each temperature, measurements were done at pressures up to about 280 MPa or (for aniline and n-dodecane) at a lower pressure slightly below the freezing pressure at the temperature of measurement. Values of the isobaric expansivity isothermal compressibility and (for toluene, trichloromethane, dichloromethane, and acetonitrile) internal pressure, derived from the p,V,T data, are presented.     

高沸点溶剂法合成原乙酸三甲酯

对低沸点溶剂法制备原乙酸三甲酯工艺进行了改进，比较了煤油、2-乙基己醇、氯苯、异佛尔酮、邻苯二甲酸二丁酯、乙二醇二丁醚等高沸点溶剂对反应的影响，筛选出最优高沸点溶剂煤油：研究了新反应体系的醇解pH值、溶剂的循环使用次数对反应的影响及溶剂循环损耗率，结果表明，醇解的最佳pH值为5．6；随着溶剂循环次数增加，原乙酸三甲酯收率从83．6％(1次)逐渐下降到76．7％(16次)；溶剂次平均损耗率4．6％。实现了直接蒸馏产品，溶剂循环使用的新工艺。避免了旧工艺先蒸溶剂，后蒸产品，产品大量分解，收率低等缺点。     

4-甲氧基苯乙腈的又一种合成法

以4-羟基苯乙酰胺为原料,经甲基化和脱水两步反应合成了4-甲氧基苯乙腈,总收率76.5%。     

FT-IR characterization of carbenium ions,intermediates in hydrocarbon reactions on H-ZSM-5 zeolites

A series of N-alkylacetonitrilium ions were characterized by IR spectroscopy on an activated H-ZSM-5 sample pretreated by CD₃CN with various adsorbed olefins. Two kinds of(CN) band were evidenced according to whether the carbenium ion is secondary (2387 cm^–1) or tertiary (2376 cm^–1). The method is able to detect the isomerization intermediates of cyclohexene into methyl-cyclopentene.     

Regulating the Water Molecular in the Solvation Structure for Stable Zinc Metal Batteries

Rechargeable aqueous zinc batteries are promising energy storage devices because of their low cost, high safety, and high energy density. However, their performance is plagued by the unsatisfied cyclability due to the dendrite growth and hydrogen evolution reaction (HER) at the Zn anode. Herein, it is demonstrated that the concentrated hybrid aqueous/non-aqueous ZnCl₂ electrolytes constitute a peculiar chemical environment for not only the Zn-ions but also water molecules. The high concentration of chloride ions substitutes the H₂O molecular in the solvation structure of Zn²⁺, while the acetonitrile further interacts with H₂O to decrease its activity. The hybrid electrolytes both inhibit the dendrite formation and HER, enabling an ultrahigh average Coulombic efficiency of 99.9% in the Zn||Cu half-cell and a highly reversible Zn plating/stripping with a low overpotential of 21 mV. Using this hybrid electrolyte, the Zn||polytriphenylamine (PTPAn) full cell deliveres a high discharge capacity of 110 mAh g⁻¹, a high power density of 9200 W kg⁻¹ at 100 °C and maintains 85% of the capacity for over 6000 cycles at 10 °C. This study provides a deep understanding between the solvation structure and columbic efficiency of Zn anode, thus inspiring the development for stable Zn batteries.     

Isolation and identification of (3-methoxyphenyl)acetonitrile as a phytotoxin from meadowfoam (Limnanthes alba) seedmeal

Ethyl ether, ethanol, and water extracts of meadowfoam (Limnanthes alba Hartweg ex. Benth.) seedmeal were prepared and bioassayed against velvetleaf (Abutilon theophrasti Medicus) and wheat (Triticum aestivum L. Cardinal). Both the ethyl ether and ethanol fractions, but not the water extract, inhibited velvetleaf and wheat radicle elongation. Fractionation of the extracts indicated that (3-methoxyphenyl)acetonitrile (3-MPAN) was the active compound from both extracts, comprising >97% of the active ethanol fraction. 3-Methoxybenzyl isothiocyanate, which had been previously shown to be the major breakdown product of glucolimnanthin, the majorL. alba glucosinolate, was not detected in either extract. Radicle elongation of velvetleaf and wheat were inhibited by 3-MPAN with I₅₀ (the concentration required to inhibit growth by 50%) values of approximately 4 × 10^–4 M (velvetleaf) and 7×10^–4 M (wheat).Mention of firms or products does not imply endorsement by the U.S. Department of Agriculture over other firms or products not mentioned.     

2—氨基—4—甲氧基—6—甲基均三嗪的合成

着重介绍了2-氨基-4-甲氧基-6-甲基均三嗪的合成方法。     

用酸性乙腈-硫酸铜体系从辉铜矿中浸出铜

研究了用酸性乙腈-硫酸铜体系从辉铜矿中提取铜。试验结果表明，当温度为53～54℃、盐酸体积分数为10％、乙腈体积分数为60％、Cu(Ⅱ)的量稍大于矿样中的含铜量时，仅需2h，铜浸出率可达95％。