酯交换法合成碳酸甲乙酯催化剂的研究进展

碳酸甲乙酯（EMC）是一种环境友好型的不对称碳酸酯，因其独特的结构性质被广泛用作溶剂或有机合成中间体，特别是随着锂离子电池的迅猛发展，其作为电池电解液主要成分市场需求量急增。文中简单介绍了光气法、氧化羰化法和酯交换法合成碳酸甲乙酯的研究进展。重点针对最具发展前景的酯交换法合成EMC工艺路线中所用催化剂进行了综述；讨论和分析了该路线所用催化剂的类型、结构、性质及性能，并对当前研究中存在的问题进行了归纳和分析总结。最后本文分析并展望了酯交换法合成EMC催化剂的研究方向及新型合成工艺发展趋势，提出研发经济、高效、稳定且制备工艺简单的非均相催化剂，并与反应精馏技术耦合是今后的主要发展趋势，期望为EMC的高效合成提供参考和借鉴。     

Combination of nuclear magnetic resonance spectroscopy and nonlinear methods to analyze the copolymerization of phosphonic acid derivatives

We demonstrate in this study that the combination of modern inline monitoring methods [here: inline nuclear magnetic resonance (NMR)] with simulations gains more exact and profound kinetic results than previously used methods like linearization without that combination. The ¹H-NMR spectroscopic data (more than 100 data points) are used to construct the copolymerization diagram. The reactivity ratios are obtained applying the van Herks nonlinear least square method. The examination of the radical copolymerization of 2-hydroxyethyl methacrylate (HEMA) with (2-{[2-(ethoxycarbonyl)prop-2-en-1-yl]oxy}ethyl) phosphonic acid (ECPPA) as important adhesive monomer used in dentistry yields reactivity ratios of r_HEMA = 1.83; r_ECPPA = 0.42. The copolymerization diagram reflects nonideal, non-azeotropic copolymerization. The sequence distribution of the obtained by Monte Carlo simulation indicates the generation of statistical copolymers. As an important finding, it is demonstrated that the repeating units responsible for etching and adhesion are arranged over the whole polymer chain, which is necessary to achieve proper functionality. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48256.     

Effect of the presence of ethyl lauroyl arginate on the technological properties of edible fish gelatin films

Physical, chemical and antimicrobial properties of fish gelatin films with different concentrations of ethyl lauroyl arginate (LAE) were studied. Optical properties of film-forming solution did not vary with increased LAE content. However, pH and surface tension increased. The incorporation of LAE into the formulation increased moisture and solubility of the films. In addition, the presence of LAE affected mechanical properties, making films stronger and more flexible; it had no effect on water vapour permeability. Finally, films with LAE significantly increased antimicrobial properties against Listeria innocua, Shewanella putrefaciens and Pseudomonas fluorescens, but not against Aeromonas hydrophila. These antimicrobial films could be used as an alternative technology for extending shelf-life of fresh fish products.     

甲乙酮装置剩余丁烯的循环利用

对甲乙酮装置剩余丁烯的循环利用进行了研究,采用聚结器脱水-净化的方法,脱除了剩余丁烯中的仲丁醇、仲丁醚、甲乙酮和水分等杂质,使得剩余丁烯得到了循环使用,满足了水合工段的进料要求,同时提高了甲乙酮的产品质量。     

聚能式逆流超声强化制备脂肪酸乙酯工艺研究

以大豆油脱臭馏出物为原料,通过聚能式逆流超声强化与乙醇反应制备脂肪酸乙酯。分析醇油体积比、反应温度、超声功率、催化剂用量和反应时间对脂肪酸乙酯转化率、得率、含量和生物柴油转化率的影响。通过正交实验优化得到:脂肪酸乙酯转化率最优工艺条件为醇油体积比20∶1,反应温度35℃,超声功率300 W,催化剂用量1.6%,反应时间30 min;脂肪酸乙酯得率最优工艺条件为醇油体积比30∶1,反应温度40℃,超声功率600 W,催化剂用量1%,反应时间30 min;脂肪酸乙酯含量最优工艺条件为醇油体积比20∶1,反应温度40℃,超声功率600 W,催化剂用量1%,反应时间60 min;生物柴油转化率最优工艺条件为醇油体积比25∶1,反应温度35℃,超声功率500 W,催化剂用量1%,反应时间30 min。     

Comparison of co-current and counter-current flow in a bifunctional reactor containing ammonia synthesis and 2-butanol dehydrogenation to MEK

In this study, a multi-tubular thermally coupled packed bed reactor in which simultaneous production of ammonia and methyl ethyl ketone (MEK) takes place is simulated. The simulation results are presented in two co-current and counter-current flow modes. Based on this new configuration, the released heat from the ammonia synthesis reaction as an extremely exothermic reaction in the inner tube is employed to supply the required heat for the endothermic 2-butanol dehydrogenation reaction in the outer tube. On the other hand, MEK and hydrogen are produced by the dehydrogenation reaction of 2-butanol in the endothermic side, and the produced hydrogen is used to supply a part of the ammonia synthesis feed in the exothermic side. Thus, 30.72% and 31.88% of the required hydrogen for the ammonia synthesis are provided by the dehydrogenation reaction in the co-current and counter-current configurations, respectively. Also, according to the thermal coupling, the required cooler and furnace for the ammonia synthesis and 2-butanol dehydrogenation conventional plants are eliminated, respectively. As a result, operational costs, energy consumption and furnace emissions are considerably decreased. Finally, a sensitivity analysis and optimization are applied to study the effect of the main process parameters variation on the system performance and obtain the minimum hydrogen make-up flow rate, respectively.     

超声微波耦合制备P(AM-DMC-BA)及其污泥脱水研究

以丙烯酰胺(AM)为主单体、甲基丙烯酰氧乙基三甲基氯化铵(DMC)为阳离子单体、丙烯酸丁酯(BA)为疏水单体,偶氮二异丁脒盐酸盐(V-50)为引发剂,通过微波和超声耦合技术合成新型高效阳离子共聚物絮凝剂P(AM-DMC-BA)。考察了原料对P(AM-DMC-BA)特性黏度及转化率的影响,P(AM-DMC-BA)对其进行了表征,并用于污泥脱水实验。结果表明,当单体AM、DMC、BA的质量分数分别为22.5%、7.5%、1%,引发剂V-50的质量分数为2%,尿素的质量分数为1.2%,聚合体系pH为3.5,制得的P(AM-DMC-BA)的特性黏度及转化率最高。当共聚物投加量为45 mg/L、污泥溶液pH为7时,其对污泥有较好的脱水性能,且具有良好的pH抗性。     

负载型Co基双功能催化剂上戊酸酯生物燃料的制备

采用浸渍法制备了HZSM-5、HY、Hβ以及MCM-22四种载体上负载Co的催化剂,在高压反应釜中,开展了以乙酰丙酸乙酯为原料一步法加氢脱氧合成戊酸乙酯以及戊酸生物燃料的研究。采用XRD、XPS、TEM、FT-IR、NH₃-TPD、H₂-TPR、py-FTIR、ICP-AES等对催化剂进行表征。结果表明,10Co/HZSM-5催化剂由于Co在HZSM-5上分布均匀,并且B酸酸性、总酸量以及还原性能最优,在保持较高的反应性能的同时,提高了产物的选择性,具有较高的催化性能。进一步对反应温度、反应压力等进行优化,在反应温度为240℃、压力为3 MPa、反应3 h时,以正辛烷作溶剂,催化剂表现出较高的催化性能,乙酰丙酸乙酯的转化率达到100%,戊酸酯和戊酸的总收率可达90%。