六亚甲基亚胺在MCM-22分子筛合成中的导向作用及分解行为研究

对以六亚甲基亚胺为模板剂合成MCM-22分子筛的方法进行了优化，并对模板剂在合成中的作用及焙烧分解行为进行了研究。结果表明，采用合适的水与硅物质的量比和晶化温度能有效降低六亚甲基亚胺用量；六亚甲基亚胺在MCM-22分子筛合成过程中起结构导向和平衡电荷的作用；在干燥焙烧过程中无气相六亚甲基亚胺外排，烟气中含氮化合物以NH₃、NO和NO₂为主。     

六亚甲基亚胺的合成进展

六亚甲基亚胺是七元杂环亚胺类化合物,是多种有机产品重要的中间体,其合成方法有己内酰胺法、己二胺法、己二醇法、己二腈法等;国内外对其合成工艺和催化剂进行了广泛研究,其中最有影响力的是日本三菱油化所开发的连续化加氢工艺和钴合金催化剂.采用己内酰胺为原料是工业上生产六亚甲基亚胺的主要方法,但是己内酰胺极易聚合,反应转化率低,而且已有的金属催化剂寿命较短,选择性不高,所以其技术关键就是选择合适的催化剂.     

江苏六亚甲基亚胺装置投产

六亚甲基亚胺生产装置日前在江苏东方化【集团投产,填补了该产品国内空白。六亚甲基亚胺是合成农药、医药、染料的中问体,由于合成日寸选择催化剂较难,世界只有少数儿套装置生产。该产品今年计划生产的全部产品已被韩国订购。江苏六亚甲基亚胺装置投产@杨宏~~     

N-Ti-MCM-22分子筛的合成及光催化性能研究

以叠氮化钠为氮源、硅溶胶为硅源、钛酸四丁酯为钛源、六亚甲基亚胺(HMI)为模板剂,按SiO2∶0.03TiO2∶(0-0.01)N∶0.03HMI∶0.035Al2O3∶0.2NaOH∶20H2O的摩尔比,采用静态水热晶化法合成了具有MWW层状结构的N-Ti-MCM-22分子筛。研究了所合成的分子筛的光催化性能,考察了催化剂的含氮量、催化剂的投加量、pH值、亚甲基蓝的初始浓度、光催化时间等因素对光催化降解亚甲蓝的影响。结果表明:N-Ti-MCM-22分子筛对亚甲基蓝的光催化降解效果较好,催化剂的投加量为1g/L、亚甲基蓝初始浓度在4mg/L、pH为中性在紫外光下的降解效果较好,脱色率及降解率分别达到了95.9%和97.8%,并采用XRD、TEM和EDS等对分子筛样品进行了表征。     

模板剂类型对ZSM-35分子筛物性的影响研究

采用环己胺及六亚甲基亚胺为模板剂,在动态水热体系中成功合成出ZSM-35分子筛。以环己胺为模板剂时,所得ZSM-35分子筛具有相对高的结晶度,其形态具有三维交错生长的特点,晶粒尺寸3~7μm。以六亚甲基亚胺为模板剂合成的ZSM-35相对结晶度略低,形态为二维片状,晶片较大的维度方向尺寸约2~8μm,短维度方向尺寸约100 nm。二维ZSM-35 BET比表面及孔容皆高于三维形态的ZSM-35;以六亚甲基亚胺为模板剂合成的ZSM-35具有更高的总酸量、较多的中强酸分布及较多的B酸中心。     

采用二元模板剂合成MCM-22分子筛的研究

以硅溶胶和偏铝酸钠分别为硅源和铝源制备MCM-22,采用动态水热法合成MCM-22分子筛,考察了以六亚甲基亚胺和哌嗪二元模板剂对合成MCM-22分子筛的影响。XRD和SEM分析表明：采用二元模板剂能够合成较纯的MCM-22分子筛,并且表面形貌基本相同。     

己内酰胺加氢制六亚甲基亚胺技术

六亚甲基亚胺是农药中间体，由己内酰胺加氢制六亚甲基亚胺的催化剂及生产工艺经259吨／年规模装置运转，己内酰胺的单程转化率390％，己内酰胺转化为六亚甲基亚胺的选择性395％，产品六亚甲基亚胺的纯度398．1％。     

Ce-MCM-22分子筛的合成与吸附性能

采用静态水热晶化法,以硅溶胶为硅源、六亚甲基亚胺(HMI)为模板剂,通过掺杂Ce合成了具有MWW层状结构的Ce-MCM-22分子筛.利用粉末X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)等方法对其进行了表征,考察了各种因素对Ce-MCM-22分子筛吸附亚甲基蓝溶液的影响,结果表明当Ce-MCM-22分子筛的投加量为0.6 g/L,亚甲基蓝浓度为2.0 mg/L,pH值为7,震荡60 min时,吸附脱色效果较好.     

新型水杨醛亚胺及其胺衍生物的合成

2,4-二叔丁基苯酚与六亚甲基四胺进行甲酰化反应,生成3,5-二叔丁基水杨醛,再与2-丙硫基乙胺发生缩合反应,合成了一种新型的水杨醛亚胺型希夫碱2-[2-(丙硫基乙基氨基)甲基]-4,6-二叔丁基苯酚,进一步用硼氢化钠还原可得其胺衍生物。产物通过核磁共振、红外光谱和元素分析进行了表征。     

六亚甲基亚胺合成研究

对ε-己内酰胺加氢制六亚甲基亚胺的工艺进行了研究,筛选了催化剂,考察了氢气流量、反应温度、反应压力以及催化剂量对反应收率的影响。实验结果表明,采用Ra-Co为催化剂,以二乙二醇二甲醚为溶剂,氢气流量0.3 m3/h,反应压力3.0 MPa,反应温度220~230℃,催化剂用量10 g时,六亚甲基亚胺的收率达到44.2%。与传统工艺相比,本研究中催化剂及溶剂可连续使用,降低了成本。     

常温合成条件对两步法制备氢氧化镁阻燃剂中试研究的影响

在自行研制的中试设备上用两步法（氢氧化钠合成法-水热反应法）制备出了氢氧化镁阻燃剂,分析了常温合成条件对制备氢氧化镁的影响.研究发现在相同的水热条件下,提高常温合成温度和降低氢氧化钠加料速率,有利于常温产物的水热改性处理,使之生成形貌规则、粒径分布均匀、分散性良好的氢氧化镁六方片状颗粒.     

Nucleation and growth history of zeolite LTA synthesized from kaolinite by two different methods

The synthesis of zeolite Linde Type A (LTA) from kaolinite by two different routes: (1) conventional hydrothermal alkaline activation and (2) alkaline fusion prior to hydrothermal reaction, as well as its nucleation and growth history, were investigated. Using the first method, co-crystallization of sodalite and cancrinite, probably via an unstable zeolite LTA intermediate, was observed during treatment of kaolinite in NaOH solutions. The addition of a SiO₂ source promoted the co-precipitation of several zeolite phases, including zeolites LTA, X and P, with traces of sodalite and cancrinite. By fusion with NaOH followed by hydrothermal reaction, kaolinite was converted into zeolite LTA. Synthesized materials appeared stable thermodynamically under the experimental conditions. The synthesis products have been characterized by X-ray diffraction, scanning electron microscopy and Fourier Transform Infrared Spectroscopy.     

水热法制备Ni/Nd2O3催化剂及其催化水合联氨制氢

采用水热合成法制备了Ni/Nd₂O₃催化剂，对其催化水合联氨制氢性能进行了考察，探讨了催化剂合成条件及催化体系中NaOH浓度对催化性能的影响，并采用XRD、XPS、TEM、TG对催化剂进行了分析表征。结果表明，当Ni/Nd=94∶6、水热条件为8h、120℃时，合成的Ni/Nd₂O₃催化剂在催化水合联氨制氢时表现出了最优的催化性能，其H₂选择性为95.9%。该催化剂中Ni的结晶度较高，Nd以Nd₂O₃的形式存在，具有促进颗粒分散、暴露活性位点、协助Ni、Nd电子转移等优点。与不加NaOH溶液的催化制氢体系相比，当NaOH的加入浓度为1.3mol/L时，催化剂催化水合联氨的制氢速率提高了约3.7倍。催化剂可维持良好的稳定性，循环使用5次后H₂选择性仍高达94.4%。     

SrSn_4P_6O_(24)粉料的合成

本研究的目的在于根据NZP[NaZr2 (PO4) 3]晶体化学特性 ,设计出一新的NZP化合物SrSn4P6 O2 4(SSP) ,为二元及多元NZP热膨胀调整提供新的单元组成 .为此 ,本研究采用固相法、共沉淀法及水热法进行了合成实验 ,并做了XRD ,SEM ,TEM及IR光谱检测 .结果表明 :3种方法都能合成SSP ,其中以共沉淀法合成的物相最纯 ,固相法合成的SSP的X射线衍射强度最大 .粉料的颗粒形貌取决于合成条件及合成方法 ,水热法在使用磷酸作矿化剂时获得了单分布形状为正六边形的颗粒 ,物相为单斜相 .使用水和氢氧化钠为矿化剂时 ,颗粒为近似方形及圆形 ,均为NZP相     

Preparation of Monodispersed Tin-Doped Indium Oxide Powders by Hydrothermal Method

This paper presents a hydrothermal method for synthesizing tin-doped indium oxide (ITO) powder. It shows that monodispersed ITO powders of diameter 70±10 nm can be readily prepared by a process using NaOH as a basic source and involving hydrothermal synthesis at 240°C in 12 h and post-calcination at 500°C. The powder size is decreased by increasing the initial indium and tin concentration ([In+Sn]_precursor) and the excess NaOH concentration ([NaOH]_excess) in the solution. The proposed technique has a significant potential for the commercial production of ITO nanopowders.     

Hydrothermal Preparation and Morphology Characteristics of Y3Fe5O12

The influences of processing parameters such as mineralizer, temperature, and nonstoichiometry on reaction product and morphology were investigated in the hydrothermal synthesis of yttrium iron garnet, Y₃Fe₅O₁₂ (YIG). A cubic YIG phase was synthesized successfully under hydrothermal conditions of 200°C and 6 h from yttrium and iron hydroxide coprecipitates obtained by adjusting the pH to 10.5 using NH₄OH. The other mineralizer, NaOH, was not effective in forming the garnet phase. Nonstoichiometric compositions utilizing excess Y content tended to increase the yield of the garnet phase, but did not affect the morphology. Different morphology characteristics were observed by changing the synthesis temperature. Isometric YIG particles disappeared at a relatively high temperature of 250°C, resulting in irregular star-shaped particles of YIG due to the preferential orientation during particle growth.     

粉煤灰合成沸石及其处理焦化废水A/O出水的试验

以NaOH作碱源,采用水热晶化法将粉煤灰转化成沸石.通过改变灼烧温度、NaOH浓度、液固比、晶化时间,考察合成条件对合成沸石阳离子交换容量的影响,并应用于焦化废水A/O出水的处理.结果表明:在灼烧温度为700℃、NaOH浓度为1 mol/L、液固比为5:1 mL/g、晶化时间为36 h条件下,合成沸石的阳离子交换容量最高为167 mmol/100g,是原粉煤灰的12.8倍,高于天然沸石的160 mmol/100 g;合成沸石处理焦化废水A/O出水的最佳条件是反应时间为1 h,沸石投加量为2g/100mL,pH值为6.0～9.0,此时NH3-N、COD去除率及出水质量浓度分别为46.7%、17.6%和62.6、197.8 mg/L,合成沸石对NH广N的吸附符合Freundlich吸附等温式.     

A comparative study of two methods for the synthesis of fly ash-based sodium and potassium type zeolites

Fly ash (FA) from the Rugeley Power Station, West Midlands (England) was used in a study on synthesis at laboratory scale of zeolitic materials under various conditions by two different routes. Zeolitic materials were synthesized from FA by hydrothermal treatment in NaOH (Na-phillipsite, hydroxysodalite, hydroxycancrinite, tobermorite, analcime and herschelite) and KOH (hydroxysodalite, zeolite Barrer-KF, K-chabazite and zeolite Linde Type F) solutions. By fusion with NaOH followed by hydrothermal reaction, FA was converted into faujasite and hydroxysodalite. No zeolitic materials were obtained by this method using KOH as alkali activator. The process of synthesis was optimised by applying a wide range of experimental conditions with a wide range of reaction temperature, time, alkali hydroxide concentration and solid/solution ratio. The efficiency FA-based zeolites (FAZs) for heavy metal and ammonium uptake from synthetic solutions at laboratory scale have been investigated by the authors, revealing that these FAZs may reach appropriate cation exchange capacities for their application in industrial wastewater treatment.     

体型化NaA分子筛的制备研究

以粉煤灰一步酸溶法提取氧化铝剩余的酸溶渣为原料制备具有一定强度的地质聚合物,经过水热反应原位转化NaA分子筛。通过研究合成过程中的硅铝比、碱量、液固比等因素对制备体型化分子筛的影响,得到了制备酸溶渣基地质聚合物原位转化NaA型分子筛的最佳条件：在二氧化硅与三氧化二铝物质的量比为1.8、氧化钠与三氧化二铝物质的量比为1.0、水与酸溶渣质量比为1.2条件下制备出地质聚合物,之后在0.5 mol/L的75 mL氢氧化钠溶液中晶化,在晶化温度为100 ℃、晶化时间为8 h条件下可以制备出晶相单一、结晶度高的NaA体型化分子筛。制备的NaA体型化分子筛具有明显的立方体形貌,颗粒分布均匀,孔径为0.685 nm,比表面积为86.75 m²/g,抗压强度为4.5 MPa。