电解二聚法生产己二腈工艺流程模拟与优化

在丙烯腈电解制己二腈工艺的基础上,研究开发己二腈分离流程。使用PROⅡ模拟软件对电解液中己二腈的分离提纯工艺进行了模拟优化。考察了理论塔板数、回流比、冷凝温度和压力等因素对同系物分离塔的影响,得到了最佳工艺条件,在此条件下可获得质量分数为99.5%的己二腈,模拟计算结果与实验结果基本相符。     

镍基催化加氢合成氨基己腈

以Ni/K_2O-La_2O_3-Al_2O_3为催化剂,采用固定床反应器,系统地考察了反应温度、氢气空速、己二腈液时空速和进料速率等对己二腈选择加氢生成6-氨基己腈的影响。结果表明,随着反应温度的升高,己二腈加氢转化率先增加后降低,6-氨基己腈选择性逐步下降;其中提高氢气空速、降低己二腈液时空速和进料速率(氢腈物质的量之比不变),均有利于提高己二腈转化率,但6-氨基己腈选择性下降。以乙醇为溶剂,在常压,温度180℃,氢气空速3 600 h~(-1),己二腈液时空速0.24 h~(-1),己二腈的乙醇溶液流速5 mL/h(氢腈物质的量之比为86)的条件下,催化性能较好,反应40 h后趋于稳定,己二腈的转化率基本维持在50%～55%,6-氨基己腈的选择性为80%左右。     

电解法生产己二腈回收腈类模拟与优化

在丙烯腈电解制己二腈工艺的基础上,研究开发腈类分离流程.使用PROⅡ模拟软件对从电解液中回收丙腈和丙烯腈工艺进行了模拟优化,考察了理论塔板数、进料位置、回流比和冷凝温度对分离效果的影响,得到了适宜的操作工艺条件,模拟结果可用于指导工业设计.     

骨架镍催化剂在腈类加氢中的应用

介绍3种类型骨架镍催化剂在己二腈加氢中的应用,并对加氢结果进行比较。结果表明,3种类型骨架镍催化剂均可以实现己二腈加氢,己二腈转化率和己二胺选择性较高。同时对其他二腈如2-甲基戊二腈和丁二腈进行加氢研究,进一步表明骨架镍在腈类加氢中具有独特优势。     

己内酰胺制备氨基己腈工艺过程中杂质的测定

采用全二维气相色谱-质谱联用仪(GC×GC-MS)对己内酰胺氨化制备氨基己腈的反应液进行分析,得知己内酰胺制备氨基己腈反应液中含有环己亚胺、5-己烯腈、2-亚甲基-4-戊烯腈、氰基-1-环戊烯等副产物。当调整工艺路线和催化剂配方时,己内酰胺制备氨基己腈的副产物成分会随之变化。多次实验表明,副产物环己亚胺、5-己烯腈是己内酰胺制备氨基己腈反应中的主要副产物,为后续精馏得到纯度为99.9%的氨基己腈提供了依据。     

己二腈部分加氢合成氨基己腈镍基催化剂的研究

考察了MgO.K_2O和La_2O_3助剂对己二腈部分加氢合成氨基己腈负载型镍基催化剂的影响,并考察了反应温度、反应压力、反应物浓度及催化剂与己二腈质量比对催化剂反应性能的影响.结果表明.所研制的负载型镍基催化剂具有较好的活性和选择性.在氢分压2.6MPa,氨分压1.8MPa,反应温度377K和催化剂与己二腈质量比为0.140.16的条件下,己二腈转化率和氨基己腈选择性分别可达70%左右和78%左右。     

多胺混合物分离提纯工艺研究

对己二腈催化加氢生产己二胺过程中的产物二次分离后产生的多胺混合物（工业残液）进行了分离提纯工艺研究。根据多胺混合物中各组分的物化性质的差异,确定了减压精馏和冷却结晶相结合的工艺路线,并通过试验确定了适宜的工艺条件。在此条件下分离得到丁二胺、环己二胺和己二胺单体,摩尔分数可达：0.75、0.91和0.91,收率分别为：95.5%、87%和80%。     

抓紧时机发展我国己二腈工业

分析了发展我国己二腈工业的市场条件和原料条件,提出要抓住时机加快发展我国己二腈工业,同时还对我国己二腈工业的建设地点、工艺路线选择和投资合作方式提出了建议.     

已二腈常压液相氢化合成已二胺

己二腈催化氢化反应一般需在压力下进行,关于已二腈的常压氢化反应还研究得很少。泊莱奥白拉任斯基等曾经研究了已二腈常压液相氢化反应,以钯-活性炭和少量的二氧化铂的混合物做催化剂,反应在强酸介质中进行,以防止仲胺的生成。已二胺产率一般可以达到70～80%。阿尔布卓夫等利用阮来镍催化剂进行己二腈常压氯化反应,发现主要产物为ω-氨基己腈,产率93%。村桥和泷泽在饱包和氨的甲醇溶液中,以镍、氧化铝或阮来镍做催化剂,进行了己二腈常压氢化反应,得到的主要产物是ω-氨基已腈,产率52～57%。此外,拉捷尔(W.A.Lazier)还研究了在镍催化剂上己二腈的常压气相氢化反应,反应温度为150～350℃,虽有过量氨存在,但反应的主要产物却是环己亚胺。     

高纯2-甲基-3-丁烯腈连续精馏过程的模拟与分析

针对2-甲基-3-丁烯腈及顺式-2-戊烯腈为主的同系物连续精馏过程中,同系物减压分离塔操作条件优化困难等特点,在深入分析高纯2-甲基-3-丁烯腈减压精馏工艺流程的基础上,通过灵敏度分析和水力学分析等并结合物性分析,以合适的热力学模型对同系物减压精馏塔进行稳态模拟与分析,考察塔板数、进料位置、塔顶采出流率和进料流率的摩尔比、摩尔回流比、塔内压力等对分离过程的影响,优化工艺参数,最终得到2-甲基-3-丁烯腈、顺式-2-戊烯腈的质量分数分别达到97.05%、96.57%。模拟结果与试验结果相差不大,为该工艺的实际开发提供了重要的理论依据。     

由丁二烯合成己二腈及己二胺的技术发展现状

工业生产中己二胺基本由己二腈（AND）加氢还原来制备,后者主要由丁二烯为原料生产。根据合成路线的不同,具有工业价值的由丁二烯合成己二腈和/或己二胺的方法可划分为4种：丁二烯直接催化氢氰化法合成ADN,丁二烯氯化-金属氰化法合成ADN,羧酸、氨热脱水法合成ADN及HMDA,丁二烯经己二醛合成HMDA。本文将论述上述合成方法的技术要点和涉及的化学反应机理,并对各个方法进行比较。     

Highly efficient synthesis of 5‐cyanovaleramide by Rhodococcus ruber CGMCC3090 resting cells

BACKGROUND: The chemo‐selective biocatalytic hydrolysis of nitriles presents a valuable alternative to chemical hydrolysis, a procedure in which harsh conditions are applied. In this study, Rhodococcus ruber CGMCC3090 is used for 5‐cyanovaleramide (5‐CVAM) production by means of adiponitrile (ADN) hydration. Several parameters that affect the biocatalyzation process are investigated. RESULTS: The effective production of 5‐CVAM from ADN with good regioselectivity was successfully achieved using the resting cells of Rhodococcus ruber CGMCC3090. The reaction parameters for 5‐CVAM production were investigated during the experiment, and it was found that resting cells were effective in converting ADN at high concentrations (up to 2.0 mol L^?1) and the hydration reaction was slightly inhibited by different concentrations of 5‐CVAM. After 100 min of incubation, more than 99.2% of the added adiponitrile was converted to 5‐CVAM when the cell concentration was 1.05 g dry cell weight (DCW) L^?1. CONCLUSION: The study provides a facile and feasible way of achieving high 5‐CVAM production levels while maintaining high purity of the product obtained. Copyright © 2012 Society of Chemical Industry     

Liquid phase hydrogenation of adiponitrile over directly reduced Ni/SiO2 catalyst

Liquid phase hydrogenation of adiponitrile (ADN) to 6-aminocapronitrile (ACN) and hexamethylenediamine (HMD) was investigated on Ni/SiO₂ catalysts prepared under different conditions. In this reaction, the highly reactive imine intermediate forms condensation byproducts by reacting with the primary amine products (ACN and HMD). A highly dispersed Ni/SiO₂ catalyst prepared by the direct reduction of Ni(NO₃)₂/SiO₂ was found to suppress the condensation reactions by promoting the hydrogenation of adsorbed imine, and it gave excellent hydrogenation activity and primary amine selectivity. Addition of NaOH increased the primary amine selectivity to 79% at the ADN conversion of 86%.     

Ion Chromatographic Analysis of Ammonium Dinitramide–Oxidizer for Propellant and Pyrotechnic Applications

Analysis of ammonium dinitramide (ADN), the advance rocket propellant oxidizer, in pure form as well as in mixtures was carried out by ion chromatography (IC). The purity of ammonium dinitramide was directly determined by estimating the dinitramide ions and indirectly by estimating the impurities. Both methods gave results comparable with those determined by Differential Scanning Calorimetry and UV spectroscopy. The chemical composition of ADN in mixtures containing nitrate, chromate, chlorate, perchlorate, and thiocyanate ions was quantitatively estimated in the same solution without any interferences or prior separation of analyte ions. The newly developed ion chromatographic methods for the analysis of ADN are simple and fast with good accuracy and precision when compared to other analytical techniques. The IC methods are found to be highly suitable for quality control analysis of ADN containing compositions and for the online process monitoring of the formation of ADN in the reaction mixture.     

己二腈生产技术现状及市场趋势分析

主要介绍了己二腈的用途和生产工艺路线,详细介绍了己二腈原料市场的产能现状及需求趋势,分析了国内发展己二腈工业化生产装置的重要意义,提出了己二腈技术重点研究的发展方向。     

己二腈的生产现状及市场分析

对己二腈的几种主要生产工艺进行了评述,包括丙烯腈电解二聚法、己二酸催化氨化法、丁二烯法和己二酰胺降解水解法。对己二腈的需求和市场情况进行了分析。     

High flash point electrolyte for use in lithium-ion batteries

The high flash point solvent adiponitrile (ADN) was investigated as co-solvent with ethylene carbonate (EC) for use as lithium-ion battery electrolyte. The flash point of this solvent mixture was more than 110 °C higher than that of conventional electrolyte solutions involving volatile linear carbonate components, such as diethyl carbonate (DEC) or dimethyl carbonate (DMC). The electrolyte based on EC:ADN (1:1 wt) with lithium tetrafluoroborate (LiBF₄) displayed a conductivity of 2.6 mS cm⁻¹ and no aluminum corrosion. In addition, it showed higher anodic stability on a Pt electrode than the standard electrolyte 1 M lithium hexafluorophosphate (LiPF₆) in EC:DEC (3:7 wt). Graphite/Li half cells using this electrolyte showed excellent rate capability up to 5C and good cycling stability (more than 98% capacity retention after 50 cycles at 1C). Additionally, the electrolyte was investigated in NCM/Li half cells. The cells were able to reach a capacity of 104 mAh g⁻¹ at 5C and capacity retention of more than 97% after 50 cycles. These results show that an electrolyte with a considerably increased flash point with respect to common electrolyte systems comprising linear carbonates, could be realized without any negative effects on the electrochemical performance in Li-half cells.