新型硫酸法C_4烷基化工艺的模拟

提出了一种新型硫酸法C4烷基化生产工艺,丁烯原料在气相状态下进入反应器,与液相异丁烷、浓硫酸混合后,部分丁烯溶于液相,在液相中进行反应;通过控制反应器的压力,部分液相吸收反应热而汽化,使反应温度基本稳定;经气液分离、酸烃分离及产品分馏后,气相丁烯、异丁烷、浓硫酸分别构成循环。采用Aspen Plus过程模拟软件对新工艺过程进行模拟计算的结果表明,在反应器进口压力0.2 MPa、压降4.5 k Pa的条件下,反应器进出口温度均在7.2℃左右,可通过调节反应器压力实现温度的控制;反应器进口液相中烷烯质量比为145∶1,可减少副反应的发生;与传统硫酸法C4烷基化工艺相比,新工艺耗电量可降低30%。     

Single‐step synthesis of a radically polymerizable 1,1′‐bi‐2‐naphthol derivative for asymmetric catalysis

A new polymerizable 1,1′‐bi‐2‐naphthol derivative for polymer‐supported catalytic asymmetric synthesis is presented. The synthesis is conducted within a single reaction step, which is a major advantage over other approaches presented in the literature. The ligand‐bearing polymer is prepared through copolymerization with N‐isopropylacrylamide. Preliminary experiments on the utility in catalytic asymmetric alkylation reactions reveal the accessibility and activity of the polymer‐attached catalysts. The stereoselectivity of the reaction is found to be somewhat lower than for reactions performed in the presence of free 1,1′‐bi‐2‐naphthol, and thus requires further optimization. The enantiomeric excess of the reaction products was determined via ¹H NMR spectroscopy after chiral derivatization with (R)‐α‐methylbenzyl isocyanate. © 2015 Society of Chemical Industry     

无硼体系MCM-22分子筛的合成

以哌啶(PI)为模板剂,在不添加晶化助剂下,采用动态水热晶化法合成MCM-22分子筛,考察了晶化时间、PI和Si O2、OH-和Si O2、Si O2和Al2O3的物质的量之比等对晶化产物的影响,结果表明,PI和Si O2,OH-和Si O2,Si O2和Al2O3的物质的量之比为0.50~0.70,0.09~0.10和30~40,晶化时间48~72 h的条件下,能较好地合成MCM-22分子筛。在苯与乙烯液相烷基化制乙苯反应中,以哌啶为模板剂与采用六亚甲基亚胺为模板剂合成的MCM-22分子筛的催化性能相当。     

原料中正丁烷组分对烷基化装置设计的影响

烷基化装置原料中的正丁烷组分作为烷基化反应的惰性组分,在装置设计中并不是我们重点关注的对象;但其在原料中浓度的高低,会影响烷基化油产品的收率和产品质量,同时对装置分馏部分设计有着较大的影响,通过对原料中正丁烷组分含量的分析,有助于我们在前期设计阶段更准确的估算装置分馏系统的设备规格及装置消耗。     

CPVC的不稳定性分析

选取国内外4种CPVC样品,利用GPC、NMR和酚烷基化等方法分别对CPVC的相对分子质量及分子质量分布、分子链序列结构、不稳定氯原子含量进行测试和分析,在此基础上对CPVC样品的热性能和加工性能进行了评价。     

Design,Synthesis, and Biological Evaluation of Shikonin and Alkannin Derivatives as Potential Anticancer Agents via a Prodrug Approach

To minimize the cytotoxicity of shikonin and alkannin that arises through the generation of reactive oxygen species (ROS) and alkylation of the naphthazarin ring, two series of novel core‐scaffold‐modified shikonin and alkannin derivatives were designed. These derivatives, which differ in their configurational and positional isomerism (R‐, S‐, and 2‐ and 6‐isomers) were synthesized in high enantiomeric excess (>99 % ee). The selectivity of the dimethylated derivatives was significantly higher than the parent shikonin in vitro, but some side effects were still observed in vivo. Surprisingly, the dimethylated diacetyl derivatives with poor anticancer activity in vitro showed tumor‐inhibiting effects similar to paclitaxel without any toxicity in vivo. The anticancer activity of these derivatives is in agreement with their low ROS generation and alkylating capacity, emphasizing their potential as prodrugs. This strategy provides means to address the nonspecific cytotoxicity of naphthazarin analogues toward normal cells.     

国产硫酸法烷基化精制系统中脱酸技术开发与应用

烷基化油是国Ⅵ汽油质量升级的关键调和组分,在国内市场的需求量和产能不断扩大的情形下,如何提高烷基化产品的质量和生产过程的清洁是烷基化发展的重点方向。本文综述了硫酸法烷基化反应流出物处理技术现状,简述了STARCTCO工艺中传统酸洗、碱洗、水洗湿式处理技术流程,并重点介绍了纤维强化聚结分离技术在国产SINOALKY工艺中的工程开发及成功应用。基于实验研究和侧线试验,在国产硫酸法烷基化反应流出物处理领域开发出多级精细聚结干式处理技术。精制系统中干式脱酸技术的开发与应用显著降低了能耗和相关环境污染,提高了装置的环保性,有助于我国烷基化技术的绿色低碳发展。     

Insights into the confinement effect on isobutane alkylation with C4 olefin catalyzed by zeolite catalyst: A combined theoretical and experimental study

Elucidating the confinement effect harbours tremendous significance for isobutane alkylation with C₄ olefin. Herein, the confinement effect over zeolite catalysts was elucidated by combining DFT calculations, experiments (using the novel Beta zeolite exposing only external surfaces (Beta-E) and conventional Beta-I zeolite with both external and internal surfaces) and multi-techniques (e.g., TGA-DTG, HRTEM, SEM and XRD). It is found that the main active sites for C₄ alkylation reaction are located on internal surface rather than external surface. On the external surface, the hydride transfer reaction does not occur because the H-shared intermediate cannot be formed without the confinement effect. Moreover, the external surface has stronger selectivity for C₄ olefin adsorption than isobutane, leading to enhanced oligomerization reactions. Therefore, the suitable micropore with confinement effect is essential for zeolite-catalyzed C₄ alkylation. The atomic-scale insights of this work are of great referential importance to the design of highly effective zeolite catalyst.     

异丙醇和苯液相烷基化反应制备异丙苯

研究MWW结构的有机硅微孔沸石催化剂在苯和异丙醇液相烷基化反应中的性能,考察反应温度、反应压力和空速等对催化剂催化性能的影响。结果表明,反应温度低于150℃时,催化剂活性和稳定性较差,主要反应为烷基化反应及异丙醇的分子内脱水和分子间脱水反应,反应产物为异丙苯、丙烯和异丙醚。反应温度高于170℃时,催化剂活性和稳定性良好,异丙醇接近完全转化,主要反应为烷基化反应,主要产物为异丙苯和多异丙苯。随着原料空速的增大,异丙醇转化率和异丙苯选择性降低,异丙醚和丙烯选择性增大。反应压力(1.5~2.5)MPa时,反应为液相烷基化过程,反应压力的变化对催化剂催化性能影响较小。     

聚萘二甲酸乙二酯的生产和应用

综述了聚萘二甲酸乙二酯(PEN)及其原料2,6-二甲基萘(2,6-DMN)的生产工艺,对比分析了2,6-DMN的各种分离和提纯技术,并介绍了PEN的主要用途及发展前景。生产PEN的2,6-DMN的纯度必须达到98.0%,2,6-DMN的合成、分离与提纯是制约PEN生产的瓶颈。采用络合结晶法及乳化结晶法分离和提纯2,6-DMN的工艺较简单,产品收率及纯度均较高,工业化可能性较大。随着环保要求的提高,可再生或可重复使用的PEN制品必将受到重视。因此,国内应加大这方面的科研力度,以实现PEN在国内的工业化生产。