分子筛生产工艺中的节能新技术——固相转化法的创新和应用

本文主要介绍了固相法合成沸石分子筛的合成机理及演绎发展历程;其中的干粉法（固相原位转化法）及湿胶法（超高浓度体系法）两种固相法节能新技术在合成MOR、ZSM-5等沸石分子筛生产过程中的应用情况,并简要阐述了这两种创新方法的本质及其特殊的工艺特点;并讨论了其在未来生产中的发展趋势。     

原位固相转化法合成ZSM-35沸石

在原位固相转化体系下成功合成了ZSM-35沸石。利用XRD、IR和SEM等手段表征了物理化学特性,并探讨了碱度对晶化过程及晶体形貌的影响。酸碱浸泡试验及耐热测试均表明,该体系下合成的ZSM-35沸石具有良好的耐酸、耐碱性和优良的热稳定性。     

以煤基工业废料为原料固相法合成小粒径圆形A型沸石分子筛

首次以煤基工业废料为原料为固相法（H2O和Na2O的摩尔比低于0．9），合成了具有圆形晶粒形貌的小晶粒（1um)A型沸石分子筛，其各项质量指标符合行业标准，并对合成的条件及机理进行讨论，提供了固相转化机理在低硅类沸石合成领域的实验佐证，并为大宗煤工业废渣的综合治理及深层次开发利用提供基础性数据。     

固相法合成W-ZSM-5分子筛

通过固相法原位合成了W-ZSM-5分子筛, XRD和红外表征结果表明,部分钨同晶取代硅进入ZSM-5骨架,未进入骨架的钨高度分散在ZSM-5表面。产品晶粒形貌规则,具有较高的比表面积,经过焙烧脱模板剂后仍然保持较高的结晶度。NH3-TPD结果表明,合成的W-ZSM-5总酸量低于Al-ZSM-5。微反结果表明,硅与钨物质的量比45的W-ZSM-5微反活性与硅与铝物质的量比120的Al-ZSM-5的微反活性接近。     

基于固相转化机理合成五元环沸石的新技术

A novel technology of preparing zeoliltes based on solid-solid mass transformation mechanism is developed for the first time. By employing this technology, three different types of highly crystallized pentasil zeolites,ZSM-35 (FER-type), Silicalite-l(MFI-type) and Mordenite(MOR-type), are successfully synthesized in the solid system. In terms of commercial production, the technology‘could simplify synthesis procedure and make the continuous production of zeolites possible, so as to improve the productivity. Additionally, it is environmentally friendly because the crystallization occurs in solid phase where there exists no pollution caused by waste liquid. Therefore, this technique provides us with a new indusr, rial process for the clean and continuous production of zeolites.The characteristics in synthesis chemistry and the crystallization mechanism involved in the technology are also discussed.     

固相法硫酸钾生产工艺及技术经济评价

简要介绍固相法生产硫酸钾的生产工艺和技术特点,并对该方法进行技术经济评价。采用该方法生产硫酸钾,投入产出比高,产品质量好,副产品市场前景广阔,符合国家当前资源综合利用和化肥发展的产业政策。     

固相法合成大茴香醛

本文探讨了用甲氧基苯甲酰肼与聚苯乙烯磺酰氯反应生成N—酰基—N′—聚苯乙烯磺酰肼,该肼被Na_2CO_3分解,能够制备出较高收率的大茴香醛。     

由尿素固相法合成三聚氰酸的研究

本文报道了尿素在熔融状态下缩合合成三聚氰酸,产率稳定在70～74％,纯度≥98.5％。同时对粗产物的三种纯化方法做了对比试验,得出用硫酸溶液回流精制是可取的方法。     

研磨法运用于固相有机合成中的新进展

研磨方法在固相有机合成中的应用研究近二三十年来发展非常迅速,它比传统的有机合成方法更方便和易于操作,在研磨条件下许多传统的反应可以在较温和的条件下进行,或者提高收率、或者缩短反应时间,甚至可以引起某些在传统条件下不能进行的反应。本文主要综述了近年来研磨法应用于固相有机合成中的一些新进展。     

Efficient and novel method for surface oxidation of polypropylene in the solid phase using microwave irradiation

The oxidation of polypropylene in the solid phase in the presence of potassium permanganate was carried out using microwave irradiation. The oxidation was achieved at time intervals of 20, 40, 60, and 90 s. According to the data available from FTIR spectroscopy, the vinylic and carbonyl groups are observed on the polymer surface. It is noteworthy that by using this method of oxidation we have saved energy and time and also less pollution has been entered into the environment by minimum oxidant consumption with maximum efficiency. © 20001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1317–1323, 2001     

固相法合成ZIF-8的表征和催化性能研究

以二甲基咪唑为有机配体,ZnO为Zn源,采用固相法制备了系列沸石咪唑酯骨架结构材料ZIF-8(S),并用XRD、FTIR、N_2吸附、SEM等手段进行了表征。主要考察了固相法制备ZIF-8的合成条件,并与常规溶剂法合成的ZIF-8(MeOH)进行了比较研究。结果表明,采用固相法可成功制备出高结晶度纯相的ZIF-8,且所制备的ZIF-8(S)与在甲醇体系中合成的ZIF-8(MeOH)相比,结晶度高,晶体粒度大,但由于其较小的外表面积,在丙二腈与苯甲醛的Knoevenagel缩合反应中的催化活性相对较低,对简单高效、环境友好的固相合成法制备ZIF-8的性能与应用研究具有重要意义。     

Investigating the solid phase synthesis of lanthanum chromite

Conclusions We studied the kinetics of solid phase synthesis of lanthanum chromite and solid solutions based on it in the system La₂O₃-Cr₂O₃-CaO-O₂.A relationship was obtained between the degree of conversion in the system and the synthesis temperature, the exposure time, and the CaO concentration. The synthesis of pure LaCrO₃ from oxides is quantitatively complete at 1695 K and with an exposure time of 2 h. The presence in the original mixture of CaCO₃ leads to the formation, in addition to LaCrO₃, of the compound -Ca(CrO₂)₂, and then with increase in the synthesis time to 10 h, at 1695 K, to the formation of solid solutions of the type La_1–xCa_xCrO₃ (x0.25). We determined the constants for the crystal lattices for the synthesized solid solutions.The technological parameters determined for the solid-phase synthesis can be used in work on the preparation of resistor elements made of lanthanum chromite.Translated from Ogneupory, No. 3, pp. 9–12, March, 1990.     

The role of amines in the synthesis of zeolites by water-organic vapor phase transport

A number of articles have been published to illustrate the role of amines for the synthesis of zeolites and porosils. Some of the results are contradictory on the role of amines. In this study, the roles of amines are investigated by water-organic vapor-phase transport method. This method is attractive because the dilution effects by mother liquid can be avoided and the composition of the synthesized zeolite is equivalent to that of the parent gel. Thus, the relation between the gel and amine can be explained clearly. In the zeolite synthesis, the templating effect of amine is less plausible, whereas the molecules with higher dipole moment and appropriate dimension such as propylamine have higher effectiveness. The protonated amines cannot work as active cations independently but amines activate the inactive cations (organic and alkali) in the gel by means of reinforcement of the pH level in the gel.     

固相合成胸腺五肽的分离与纯化

胸腺五肽(TP5)是一种很有发展前景的药物,具有胸腺素的全部生理功能。固相合成法是胸腺五肽生产的主流技术,目前,对固相合成的五肽一般采用反相色谱技术纯化,但效率低、成本高,仅限于小规模制备。实验采用离子交换法纯化,并进行了方案优化,发现在pH4 4醋酸盐缓冲液平衡、盐梯度洗脱条件下纯化TP5,一步分离纯度可达98 23%。该法可以满足大规模制备的要求,且成本很低。     

The role of the support in solid phase peptide synthesis

The effect of the polymer-support on the kinetics and coupling efficiency of amino acid condensations is described. Changes in the degree of swelling of the support network during peptide synthesis are also evaluated. The advantages of the solid phase method in particularly difficult amino acid sequences are highlighted. Finally, the question of site isolation and its relationship to polystyrene chain flexibility is discussed.     

低热固相合成碱式碳酸钠铝纳米晶及其数据挖掘

对合成碱式碳酸钠铝的新方法进行了研究,以聚乙二醇-400（PEG-400）为模板,硫酸铝为铝源,用低热固相反应一步法成功合成得到碱式碳酸钠铝.基于均匀设计实验方案以及数据挖掘技术的应用,在数据挖掘成果的指导下进行了实验.XRD表征的结果表明,用最优工艺条件合成得到的产物为4.9 nm的NaAl(OH)₂CO₃,故同时优化控制了碱式碳酸钠铝的组成及粒度,从而得到比较纯净的碱式碳酸钠铝纳米晶体.     

固态离子交换制备Cu(Ⅰ)分子筛研究进展

固态离子交换是将金属离子引入分子筛结构中一种十分简单而有效的方法,它克服了溶液离子交换存在的诸多不利因素。本文介绍了固态离子交换制备Cu(Ⅰ)型分子筛的反应原理、制备条件的影响以及不同结构Cu(Ⅰ)型分子筛的应用。鉴于微波场中离子运动速率显著加快的特点,提出采用微波加热可以显著提高固态离子交换反应速率,对于提高Cu+离子交换度,消除残留CuCl的影响,获得高性能的Cu(Ⅰ)Y催化剂具有重要的应用价值。