己二腈合成工艺路线研究进展

己二腈作为一种重要的有机化工原料,工业上主要用于加氢合成己二胺,进而用于生产尼龙66的单体。目前己二腈的合成技术主要被巴斯夫、英威达、旭化成、首诺等国外公司垄断。己二腈的工业合成方法主要包括丁二烯氢氰化法、丙烯腈电解二聚法、己二酸氨化脱水法等。本文对合成己二腈的已工业化的工艺和尚处于实验研究阶段的工艺进行了归纳整理。     

己二腈的市场前景和生产技术

概述了己二腈产能现状、市场前景及生产技术,重点介绍了丙烯腈电解二聚法和丁二烯直接氰化法,对比了两条路线,结果表明,目前丁二烯直接氰化法更具优势。简要介绍了国内生产技术的研究现状,指出己二腈国产化的重要性和紧迫性。     

英威达重启兴建上海尼龙66聚合物项目

英威达公司日前表示,公司当前正在推进在中国上海新建一家尼龙-6,6中间体和聚合物工厂的计划。该工厂将使用公司拥有专利的丁二烯基技术生产己二胺（HMD）和己二腈（ADN）以及不同种类的专用化学品和尼龙-6,6聚合物。     

英威达中国上海尼龙66聚合物项目“复苏”

<正>据悉,英威达公司2011年表示,公司当前正在推进先前宣布的在中国上海新建一家尼龙66中间体和聚合物工厂的计划。该工厂将使用公司拥有专利的丁二烯基技术生产己二胺(HMD)和己二腈(ADN)以及不同种类的     

己二腈生产工艺综述

介绍了四种传统的己二腈生产工艺技术及特点，指出丁二烯直接氰化法的研发与大规模丁二烯氰化装置的建设对中国己二腈工业的具有重要意义。     

英威达中国上海尼龙-6，6聚合物项目“复苏”

据悉,英威达公司日前表示,公司当前正在推进先前宣布的在中国上海新建一家尼龙-6,6中间体和聚合物工厂的计划。该工厂将使用公司拥有专利的丁二烯基技术生产己二胺（HMD）和己二腈（ADN）以及不同种类的专用化学品和尼龙-6,6聚合物。     

上海英威达建设世界级的己二腈／己二胺项目

该项目位于上海市化学工业区C4-2地块,采用英威达专有技术生产尼龙6,6中间体己二腈及己二胺,产品规模为己二胺（HMD）20万吨／年,己二腈（ADN）30万吨／年。项目总投资56亿元,建设周期2008年-2009年。     

己二胺的生产工艺与应用

己二胺是生产尼龙-66的主要原材料。己二胺生产方法主要有己二腈法、己二醇法、己内酰胺法、己二酸法、丁二烯法等。主要介绍了目前己二胺合成工业化、大型化常用的生产工艺,从己二胺催化加氢的反应机理及Raney-Ni催化剂的应用角度出发,为改进现有生产工艺及优化、更新催化剂配方起到重要的指导作用。     

Ni-Fe/CaO催化己二腈部分加氢制备6-氨基己腈

与传统工艺相比，丁二烯氢氰化法制备己内酰胺具有绿色、经济、环境友好等特点，其中己二腈（ADN）部分加氢制备6-氨基己腈（ACN）是该工艺的核心步骤。该文以尿素为沉淀剂，采用沉积沉淀法制备了Ni/CaO和Ni-Fe/CaO催化剂，并将其应用于ADN部分加氢制备ACN。XRD结果表明，Fe掺杂后的催化剂生成了FeNi3合金相；TEM结果表明，Fe掺杂后金属Ni变得更加分散。考察了反应温度、反应压力对ADN加氢性能的影响，实验结果表明，在80 ℃、4 MPa、催化剂用量为0.1 g的温和条件下反应2h，ADN转化率为87.5%，ACN选择性为74.4%，失活后的催化剂经过氢气还原后能够重复使用。     

己二腈生产技术的研究进展

己二腈是工业上合成尼龙66的重要的中间体,目前世界上主流的合成路线主要有两种：丙烯腈电解二聚法与丁二烯直接氢氰化法。本文着重对这两种工艺路线的技术特点与化学反应原理做了详细的介绍,并对两种工艺做了比较。结果表明丙烯腈电解二聚法优点在于工艺过程简单,但其电解费用和丙烯腈价格限制了该工艺的发展,丁二烯直接氢氰化法虽然采用剧毒且易挥发的氰化氢为生产原料,且在催化剂的制备、回收与再生方面技术难度高,但是在能耗、原料成本、产能方面,丁二烯法相比丙烯腈电解二聚法更有优势,具有更好的市场竞争力,是我国己二腈生产技术中优先发展的方向。     

Analysis of ADN,Its Precursor and Possible By‐Products Using Ion Chromatography

In the last years ammonium dinitramide (ADN) appeared to be a promising new oxidator and a possible substitute for ammonium nitrate (AN) and especially for the chlorinated oxidizer ammonium perchlorate. Among other main advantages of ADN are to be mentioned the higher energy input combined with a reduced pressure in application. Furthermore, ADN shows no phase transitions like AN. For evaluating the purity of the synthesized and/or treated or aged pure or formulated ADN, the estimated ammonium nitrate content was taken into account. AN is known to be as well a by‐product of the ADN synthesis as a possible decomposition product of ADN. Thermally treated ADN decomposes mainly to N₂O, H₂O, NO₂ and AN which further reacts to N₂O and NH₃. Determining the nitrate contents assuming the rest being intact ADN must not lead to correct values especially in cases where ADN was treated/handled at higher temperatures in open systems. Concerning the technical scale synthesis of ADN, the precursor ammonium nitrourethane (ANU) must be eliminated in a quick but sufficient way needing a suitable analysis method for detecting nitrourethane besides nitrate and ADN. The objective of this work was to develop a suitable ion chromatographic method for the direct analysis of the anions concerned. Different ion exchanger phases were tested with organic and/or inorganic eluants. The ionic strength and flow rate of the eluant was improved to get an acceptable resolution for nitrite and nitrate combined with a short run time for the whole analysis. Detection was realized by electrical conductivity or UV absorption whereby the measurement wavelengths were optimized in order to get a small signal‐to‐noise ratio and simultaneously a suitable sensitivity especially for NO₃⁻ and nitrourethane. Under improved conditions (Ion Pac 11, 1 ml/min NaOH, 300 mmol), limits of detection (LOD) of 0.05 to 0.01 ppm were realized for NO₃⁻ and NO₂⁻, respectively, measured at 214 nm. Using 220 nm as detection wavelength resulted in a LOD of about 0.3 ppm for nitrate. Using a wavelength between 210 and 220 nm results in a LOD for ANU of about 1 ppm. The linearity range for the analysis of DN⁻ (285 nm) was found to be very broad (up to 700 ppm). All anions can be analyzed in one run taking maximally 30 minutes.     

混酸法合成ADN的分离纯化工艺研究

二硝酰胺铵（ADN）是一种高能高燃速和不含氯元素的新型氧化剂,混酸法合成ADN时会生成大量的无机盐副产物,采用活性炭吸附的方法可以对ADN进行有效的分离纯化。对活性炭的种类、吸附溶剂的种类、解吸溶剂的种类、吸附浓度、吸附方式进行了研究,并确定了较佳的工艺条件,制备了质量分数达99．5％以上的ADN。     

Optimization of Potassium Dinitramide Preparation

The synthesis of potassium dinitramide (KDN), an intermediate in the ammonium dinitramide (ADN) synthesis, was optimized to reduce the costs of the ADN synthesis in order to facilitate competitiveness of this oxidizer with ammonium perchlorate (AP). The optimal conditions for the synthesis of KDN like feedstock molar ratio, nitration time, and temperature were determined. KDN was obtained in ca. 48 % yield. The modifications introduced allowed to reduce feedstock consumption and energy intensity of the process.     

Combustion of Propellants with Ammonium Dinitramide

This paper reports a series of experiments involving ammonium dinitramide (ADN), a new energetic oxidizer of potential use in composite solid propellants. The experiments include (a) self‐deflagration of pressed pellets of ADN; (b) combustion of sandwiches with ADN laminae on both sides of a binder lamina that is either “pure” or filled with particulate oxidizer and other additives; and, (c) combustion of propellants with a bimodal oxidizer size distribution, wherein, combustion of coarse ADN and fine AP (ammonium perchlorate) and vice versa were used, in addition to mixtures of coarse ADN and AP, fine ADN and AP, and all‐ADN or all‐AP formulations.     

负载型Zn(OAc)2催化合成1,6-六亚甲基二氨基甲酸甲酯

采用等体积浸渍法制备了一系列不同载体负载Zn(OAc)_2催化剂,用于1,6-己二胺(HDA)与碳酸二甲酯(DMC)反应制备1,6-六亚甲基二氨基甲酸甲酯(HDC)。通过X射线粉末衍射(XRD),N_2物理吸附(BET),NH_3程序升温脱附(NH_3-TPD),热重分析(TG-DTG),傅里叶变换红外光谱(FTIR)和X射线光电子能谱(XPS)对催化剂进行了表征,结果表明,硅胶负载Zn(OAc)_2催化剂上Si—O—Zn键的形成有利于DMC的活化,表面酸性位促进了碱性HDA的活化,从而使其具有最佳催化活性。在反应温度80℃、反应时间6 h、DMC/HDA摩尔比2∶1、催化剂用量n〔Zn(OAc)_2〕∶n(HDA)=0.02∶1的条件下,HDA转化率为96.0%,HDC收率可达68.5%,催化剂具有良好的稳定性,循环利用5次后活性无明显下降。     

Mechanical Properties of Smokeless Composite Rocket Propellants Based on Prilled Ammonium Dinitramide

Ammonium dinitramide (ADN) is a high performance solid oxidizer of interest for use in high impulse and smokeless composite rocket propellant formulations. While rocket propellants based on ADN may be both efficient, clean burning, and environmentally benign, ADN suffers from several notable disadvantages such as pronounced hygroscopicity, significant impact and friction sensitivity, moderate thermal instability, and numerous compatibility issues. Prilled ADN is now a commercially available and convenient product that addresses some of these disadvantages by lowering the specific surface area and thereby improving handling, processing, and stability. In this work, we report the preparation, friction and impact sensitivity and mechanical properties of several smokeless propellant formulations based on prilled ADN and isocyanate cured and plasticized glycidyl azide polymer (GAP) or polycaprolactone‐polyether. We found such propellants to have very poor mechanical properties in unmodified form and to display somewhat unreliable curing. However, by incorporation of octogen (HMX) and a neutral polymeric bonding agent (NPBA), the mechanical properties of such smokeless formulations were significantly improved. Impact and friction sensitivities of these propellants compare satisfactorily with conventional propellants based on ammonium perchlorate (AP) and inert binder systems.     

二硝酰胺铵防吸湿技术研究进展

二硝酰胺铵(ADN)的吸湿性是影响其广泛应用的一个主要原因.从ADN的吸湿原因、吸湿机理、防止吸湿方法几方面介绍了ADN防吸湿技术的研究进展,并指出了我国今后ADN防吸湿技术的发展方向.     

分子筛催化C_9芳烃脱烷基的研究

将Bi、Ni、Mo、Pt分别负载在氢型ZSM-5、MOR、Y分子筛上,以异丙苯为模型化合物对分子筛催化加氢脱烷基性能进行评价,考察了不同金属的活性和分子筛结构。结果表明,不同分子筛载体上,不同金属脱烷基活性大小次序为:Pt>Mo>Ni>Bi;分子筛的孔结构可限制产物的形成,从而影响烷基转移反应和脱烷基反应二者的活性。此外,酸强度和密度的分布与金属同样重要,它们之间的平衡协同作用对催化剂的活性有着至关重要的作用。     

Helicase‐Dependent Isothermal Amplification of DNA and RNA by Using Self‐Avoiding Molecular Recognition Systems

Assays that detect DNA or RNA (xNA) are highly sensitive, as small amounts of xNA can be amplified by PCR. Unfortunately, PCR is inconvenient in low‐resource environments, and requires equipment and power that might not be available in these environments. Isothermal procedures, which avoid thermal cycling, are often confounded by primer dimers, off‐target priming, and other artifacts. Here, we show how a “self avoiding molecular recognition system” (SAMRS) eliminates these artifacts and gives clean amplicons in a helicase‐dependent isothermal amplification (SAMRS‐HDA). We also show that incorporating SAMRS into the 3′‐ends of primers facilitates the design and screening of primers for HDA assays. Finally, we show that SAMRS‐HDA can be twofold multiplexed, difficult to achieve with HDA using standard primers. Thus, SAMRS‐HDA is a more versatile approach than standard HDA, with a broader applicability for xNA‐targeted diagnostics and research.     

Blue fluorescent conductive poly(9,10‐di(1‐naphthalenyl)‐2‐vinylanthracene) homopolymer and its highly soluble copolymers with styrene or 9‐vinylcarbazole

A new blue fluorescent monomer, 9,10‐di(1‐naphthalenyl)‐2‐vinylanthracene, was designed and synthesized in good yield. Its homopolymer poly(9,10‐di(1‐naphthalenyl)‐2‐vinylanthracene) (P(ADN)) and soluble conductive vinyl copolymers poly[(9,10‐di(1‐naphthalenyl)‐2‐vinylanthracene)‐co‐styrene] (P(ADN‐co‐S)) and poly[(9,10‐di(1‐naphthalenyl)‐2‐vinylanthracene)‐co‐(9‐vinylcarbazole)] (P(ADN‐co‐VK)) were synthesized using free radical solution polymerization. All the polymers showed high glass transition mid‐point temperatures (203 to 237 °C) and good thermal stabilities. The photoluminescence emission of the copolymers was similar to that of P(ADN) (with two maxima at 423 and 442 nm). The lifetimes of P(ADN‐co‐S) (6.82 to 7.91 ns) were all slightly less than that of P(ADN) (8.40 ns). The lifetime of P(ADN‐co‐VK) increased from 7.8 to 8.8 ns with an increase in VK content. The fluorescence quantum yields of P(ADN‐co‐S) showed an overall increasing tendency from 0.42 to 0.58. The quantum efficiencies of P(ADN‐co‐VK) decreased from 0.36 to 0.19 with an increase of VK fraction. With increasing S/VK content, the highest occupied molecular orbital of P(ADN‐co‐S)/P(ADN‐co‐VK) ranged from ?5.58 to ?5.73 eV, which was similar to that of P(ADN) (?5.71 eV). The band gaps of P(ADN‐co‐S) and P(ADN‐co‐VK) were about 2.97 eV, which were equal to that of P(ADN), and smaller than that of 2‐methyl‐9,10‐di(1‐naphthalenyl)anthracene (MADN) (3.04 eV) and poly(9‐vinylcarbazole) (3.54 eV). Preliminary electroluminescence results were obtained for a homojunction device with the configuration ITO/MoO₃ (20 nm)/P(ADN)/LiF (1 nm)/Al (100 nm), which achieved only 30–50 cd m^?2, due to P(ADN) having a low mobility of 4.7 × 10^?8 cm² V^?1 s^?1 compared to that of its model compound MADN of 6.5 × 10^?4 cm² V^?1 s^?1. © 2013 Society of Chemical Industry