SAPO-34分子筛晶化过程的MAS NMR研究

用MAS NMR方法研究了SAPO-34分子筛的晶化过程.发现硅进入骨架有两种方式,在晶核形成过程中,硅直接参与反应,与磷和铝同时进入骨架;在晶化过程的后期,部分硅原子取代了骨架中的磷原子或磷铝原子对进入骨架,从而形成了SAPO-34分子筛的多种硅铝结构.     

原位漫反射红外光谱研究SAPO-34分子筛的吸附性能

采用漫反射红外光谱原位考察了298－773K范围H2O，NH3和NO在SAPO－34分子筛上的吸附行为结果表明，SAPO－34对水的吸附是可逆的，对NH3和NO的吸附则是不可逆的。吸附水在623K完全脱附，脱水后的分子筛在3625－3600cm^-1出现表征桥式羟基（Si-OH-Al）的特征峰。发现SAPO－34对NH3和NO均有良好的吸附－催化活性。吸附NH3后，桥式羟基消失，位于3135，3032和1399cm^-1处在423K时出现三个吸收峰，在673K达最大，且峰高分别是SAPO－34骨架峰高的3.9,1.7和6.7倍；吸附NO后，在室温下位于1364cm^-1也观测到一强而尖锐的峰，其强度与骨架峰强度相当。对这些峰进行归属表明，吸附NH3和NO后产生了新的物种NO3^-。     

不同模板剂合成SAPO-34分子筛的表征与热分解过程研究

采用XRD、SEM、FT IR、TG DTA等表征手段 ,对分别以正磷酸、拟薄水铝石和硅溶胶为磷源、铝源和硅源 ,用五种模板剂合成的SAPO 34分子筛进行了表征 .不同模板剂合成的SAPO 34分子筛在晶粒粒度分布上有相当大的差异 .通过TEAOH Et3 N或者TEAOH Morpholine复合模板剂法可以有效地调节晶粒粒度 .不同模板剂合成的SAPO 34分子筛的红外骨架振动相似 ;而模板剂分子与分子筛骨架的作用方式有区别 .模板剂种类对SAPO 34分子筛骨架热稳定性没有影响 ,但对其热分解的行为有影响     

沸石分子筛/泡沫铝复合吸附材料-水非平衡吸附制冷特性分析

基于线性驱动力(LDF)非平衡吸附模型,计算了不同吸附层厚度、不同循环周期沸石分子筛/泡沫铝复合吸附剂-水的基本循环吸附制冷性能.结果表明非平衡吸附对于循环性能有很大影响.同时通过和沸石分子筛-水系统比较,由于复合吸附材料的强化传热作用,在循环周期较短时,具有更高的COP、单位吸附剂质量制冷功率以及单位吸附床质量制冷功率.     

吸附式制冷的动态特性分析

以非平衡吸附模型为基础,计算了加热流体温度变化时,系统的性能系数COP以及单位质量吸附剂制冷功率SCP随时间的变化,结果表明加热流体温度变化对系统COP和SCP值有很大影响,并且影响相对滞后于加热流体温度的变化.计算结果也表明对于两吸附床的吸附式制冷系统,在稳定运行时,由于吸附床温度、吸附量不断变化、循环周期较长及封闭期影响,其瞬时性能也是不稳定的,如果采用三床交替循环,则可有效改善其瞬时性能的稳定性.     

活性炭-甲醇吸附制冰机的循环特性分析

所研究的吸附式制冰机以块状活性炭和甲醇为工质对,采用烟气加热。研究表明,对于本系统,双床循环较为合 适;双床循环中回热回质过程可以有效的改善吸附床的工作性能以及系统的热力完善度,并能将系统的制冷功率提高7％ 到11％。在循环时间为50 min时,回热回质条件下制冷功率为2 kw左右,可以实现每小时制冰15 kg左右。     

沸石分子筛/泡沫铝复合吸附剂及其吸附制冷性能

本文提出了一种强化传热传质的沸石分子筛／泡沫铝复合吸附剂及其制备方法,用HotDisk热物性测量仪测量了其导热系数为2．89 W／mK。基于平衡吸附对其吸附制冷的性能进行了理论计算,并与沸石分子筛-水吸附制冷系统性能进行了比较。结果表明虽然由于金属铝的热容影响,使系统COP下降,但制冷功率有大幅提高。     

吸附制冷系统吸附床设计及导热性能研究

吸附式制冷是一种适合于太阳能、生物质能等低品位能源驱动的节能环保型制冷技术。以活性炭-甲醇工质对为研究对象,设计了一种带有分散到吸附剂中的矩形支管、刺孔膜片式吸附质管的壳管式吸附床,定性研究了扩散通量和扩散传质系数之间的关系及其传质特性;同时,通过分析吸附床的导热性能,进行了吸附质管制作材料(不锈钢、铝合金、铁皮)的导热性能测定试验。试验表明,铝合金材质(膨胀系数较大)的导热性能较好,可以作为吸附质管制作材料的最佳材质,有助于为促进吸附质的传质扩散、优化吸附床的结构设计及改进生产工艺等提供理论参考。     

基于平行流扁管吸附式制冷系统性能实验研究

设计了一种新型平行流铝扁管吸附床结构,搭建了吸附式制冷实验台。通过实验研究不同运行参数下的吸附式制冷系统性能差异,比较不同热源和冷源温度、换热流体流量下吸附式制冷系统COP的变化。结果表明,当冷、热源温度为10℃和60℃,换热流体流量为0.26 kg/s时,新型吸附式制冷系统COP达到最大值0.35。当冷源温度在20℃附近时,增大热源温度可有效提高吸附式制冷系统COP,并且换热流体流量越大,增加的幅度越明显;当换热流体流量在0.13~0.26 kg/s范围内时,系统COP随着冷源温度的增大剧烈下降,并且换热流体流量越小,下降趋势越显著;当热源温度在55~60℃范围内时,COP随着换热流体温度的增大明显增大,并且冷源温度越高,COP增大的趋势越明显。     

热管式吸附床制冷性能的实验研究

利用高效热管作为吸附床的传热部件,有效地提高了船用柴油机废气的热量回收。本文将热管式吸附床与传统的壳管式吸附床进行了性能对比。同时,选择氯化钙-氨作为吸附工质对,通过实验测定解吸、吸附过程的变化情况。本文的研究结果表明,采用热管式吸附床使得初始解吸和吸附速率有明显提高,从而有效缩短解吸和吸附周期,并能有效提高系统的SCP和COP。     

A solid-state NMR study of the formation of molecular sieve SAPO-34

This work examined the formation of a catalytically important microporous material, SAPO-34, in the presence of HF under hydrothermal synthesis conditions. The local environments of P, Al, F and Si atoms in several solid phases obtained at different stages of crystallization were characterized by several solid-state NMR techniques including ³¹P, ²⁷Al, ¹⁹F and ²⁹Si MAS, ²⁷Al triple-quantum MAS, ³¹P{²⁷Al} transfer of populations in double-resonance, ²⁷Al{³¹P} rotational-echo double-resonance (REDOR), ²⁷Al→³¹P heteronuclear correlation spectroscopy, ³¹P{¹⁹F} and ²⁷Al{¹⁹F} REDOR as well as ¹H→³¹P cross polarization. The NMR results provide the new insights into the formation of SAPO-34.     

炭分子筛吸附分离甲烷/氮混合物研究进展

高效浓缩甲烷/氮气混合气中的甲烷是合理利用煤层气、油田气和垃圾填埋气等资源时面临的重要技术难题之一。甲烷与氮气分子存在着微小的、但可操作的动力学直径差异。文中分析了以炭分子筛作为吸附剂,采用变压吸附分离技术分离甲烷/氮气的可行性,对炭分子筛的吸附分离机理、国内外的研究进展以及混合气在炭分子筛吸附床上的吸附动力学模型进行了探讨,并指出了在这一技术应用方面的一些不足。     

Ultrasonic pretreatment for hydrothermal synthesis of SAPO-34 nanocrystals

Synthesis of SAPO-34 nanocrystals which has been recently considered as a challenging task was successfully performed by sonochemical method using TEAOH as structure directing agent (SDA). The products were characterized by XRD, SEM, EDX, BET and TGA. The average crystal size of the final product prepared sonochemically is 50 nm that is much smaller than that of synthesized under hydrothermal condition and the morphology of the crystals changes from uniform spherical nanoparticles to spherical aggregates of cube type SAPO-34 crystals respectively. In the case of sample synthesized sonochemically with aid of hydrothermal condition, the surface area is significantly upper than that of obtained by the conventional static hydrothermal technology with almost the same crystallinity. SAPO-34 framework synthesized by just ultrasonic treatment is unstable and a significant part of SAPO-34 nanocrystals is transformed to the dense phase of AlPO₄ structure, i.e., Cristobalite. Contrary to hydrothermal method that at least 24 h of the synthesis time is required to obtain fully crystalline SAPO-34, sonochemical-assisted hydrothermal synthesis of samples leads to form fully crystalline SAPO-34 crystals taking only 1.5 h. In a sonochemical process, a huge density of energy for crystallization is provided by the collapse of bubbles which formed by ultrasonic waves. The fact that small SONO-SAPO-34 crystals could be prepared by the sonochemical method suggests a high nucleation density in the early stages of synthesis and slow crystal growth after nucleation.     

Stability and textural properties of cobalt incorporated MCM-48 mesoporous molecular sieve

Transition metal cobalt incorporated MCM-48 mesoporous molecular sieves (CoMCM-48) with different Co contents were synthesized hydrothermally at 120 °C for 24 h by directly adding fluoride ions to the initial gel. The resulting materials were characterized by means of XRD, TEM, FT-IR, UV-vis, TPR and N₂ physical adsorption, respectively. The effect of various factors, such as the Si/Co molar ratio, calcination temperature and hydrothermal treatment time, on the crystalline structure and textural properties of CoMCM-48 was investigated in detail. The results show that the CoMCM-48 mesoporous materials with high specific surface area were successfully synthesized. A small amount substitution of Co for Si in MCM-48 did not significantly change the textural properties while the higher cobalt incorporated leads to decrease of the surface area and deterioration of structural regularity. Furthermore, the resulting CoMCM-48 still retained the cubic mesoporous framework even after calcination at 800 °C for 4 h or hydrothermal treatment at 100 °C for 24 h.     

Effect of the thermal and hydrothermal treatment on textural properties of Zr-MCM-41 mesoporous molecular sieve

Zr-containing mesoporous molecular sieves were synthesized by hydrothermal method using cetyltrimethyl ammonium bromide as a template and sodium silicate and zirconium sulfate as raw materials. The structure and morphology of the synthesized samples were characterized via various physicochemical methods, including X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, solid state nuclear magnetic resonance (²⁹Si MAS-NMR) techniques, thermal gravimetric-differential scanning calorimeter (TG-DSC) and N₂ physical adsorption, respectively. The effect of the different initial ZrO₂:SiO₂ molar ratio, the different thermal treatment temperature and the different hydrothermal treatment time on textural property was investigated. The experimental results reveal that the as synthesized samples possess a typical mesoporous structure of MCM-41. On the other hand, the specific surface area and pore volume of the synthesized Zr-MCM-41 mesoporous molecular sieve decrease with the increase of the amount of zirconium incorporated in the starting material, the rise of thermal treatment temperature and the prolonging of hydrothermal treatment time, the mesoporous ordering becomes poor. Also, when the molar ratio of ZrO₂:SiO₂ in the starting material is 0.1, the mesoporous structure of the Zr-MCM-41 mesoporous molecular sieve still retains after calcination at 750 °C for 3 h or hydrothermal treatment at 100 °C for 6 d, and have specific surface areas of 423.9 and 563.9 m²/g, respectively.     

CH_4/N_2混合气体在CMS上的低温吸附分离实验研究

将煤层气液化后运往终端市场是一种十分有效的利用方式。与常规天然气不同,抽放煤层气含氮量高,采用有效的方式实现CH4/N2分离是煤层气液化流程中重要的环节。吸附分离是提高煤层气中甲烷浓度的可行方法。为了与低温液化过程紧密结合,探讨在低温下实现CH4/N2吸附分离的可行性,文中对CH4/N2在碳分子筛(CMS)上的低温分离特性进行了实验研究,并与常温下的实验结果进行了对比。实验结果表明,低温下CH4/N2吸附分离的特性与常温下有明显差别。     

Theoretical study on adsorption properties of methyl methacrylate and its molecular chain within metal‐organic frameworks

Utilizing metal‐organic frameworks (MOFs) as a “polymerization container” is a very effective method to prepare oriented and therefore birefringent polymer materials. In particular, the adsorption of polymer monomers and molecular chains within MOFs has a profound impact on the orientation of polymer chains. In this work, a theoretical study on the adsorption properties of methyl methacrylate (MMA) and its molecular chain within MOFs has been conducted by employing a combination of molecular dynamics, density functional theory, and Monte Carlo method, where 2 MOFs, [Zn₂(1,4‐benzenedicarboxylate)₂triethylenediamine]_n and [Zn₂(4,4′‐biphenyldicarboxylate)₂triethylenediamine]_n, were chosen. The corresponding number and degree of orientation of adsorbed molecules in these 2 MOFs were obtained from the simulations. The calculation results revealed 3 factors that affect the adsorption and orientation of MMA monomers in MOF pore channels. First, as the walls of the MOF pores are polar surfaces and consist of metal ions and organic ligands, the electrostatic interaction between the MOF channels and polar MMA molecules promotes the adsorption and orientation of the MMA monomers within the pore channel. Second, the electrostatic interactions between monomers can reduce the intermolecular gaps, which similarly assist in their orientation. Last, the relative sizes of the MOF pores and the monomers are also relevant. When the sizes of the MOF channels and monomers are similar, the molecular chains show a higher degree of orientation. The results and the findings of this work could provide predictive methods for selecting polymeric monomers or MOFs that may be ideal for the control of polymer chain orientation.     

固体吸附式制冷系统性能的实验研究

搭建了吸附系统性能实验装置和吸附式制冷实验台,将活性炭与铝屑混合配置作为研究对象。实验表明:当活性炭与铝屑的混合比例为10:7时,该混合吸附剂吸附率最大;解吸温度从82℃升到96℃时,蒸发温度与解吸温度成负相关,当解吸温度为96℃时,蒸发温度最小为14.2℃;解吸温度从82℃升到96℃时,系统COP与解吸温度成正相关,当解吸温度为96℃时,系统COP最大为0.212。