C02，CH4在全硅MFI型沸石中吸附的分子模拟

采用巨正则蒙特卡洛（GCMC）分子模拟方法研究了CO2,CH4分子在全硅MFI型沸石中的吸附行为,计算得到了纯组分和两组分的混合物在不同温度时的吸附等温线;分析了全硅MFI型沸石对混合组分的选择性吸附;模拟还得到了COz,CHt分子在全硅MFI型沸石中的吸附位。     

苯分子在Y沸石中跳跃扩散机制的动力学Monte Carlo模拟

利用动力学Monte Carlo （KMC）模拟方法计算了苯在Y沸石中扩散的自扩散系数,并考察了3种不同W-W位间跳跃扩散机制下的自扩散系数及其对温度和浓度的依赖关系.实验测量结果表明,苯在Y沸石中的长程运动主要是经S_Ⅱ-W-S_Ⅱ笼间的跳跃,基本不发生W-W之间的跳跃.相应得到的自扩散系数对温度的依赖关系较接近实验值;自扩散系数浓度依赖变化趋势为：先随覆盖量的增加而减小,到覆盖量大于S位的饱和覆盖量（每个超笼中4个分子）后,则随覆盖量增加先增后减,但也不会大于零覆盖量时扩散系数值,该情形与考虑W-W之间跳跃时完全不同.此外,模拟结果表明,使用正确的跳跃机制是KMC方法能正确模拟客体分子在沸石内扩散行为的关键.     

C3/MRC液化流程中原料气成分及制冷剂组分匹配

针对两种代表性原料天然气No.1和No.2,利用Aspen HYSYS流程模拟软件对C3/MRC天然气液化流程进行了动态模拟,考虑了混合制冷剂高低压变化、混合制冷剂组分改变,通过模拟研究获得了混合制冷剂各个组分N₂、CH₄、C₂H₆及C₃H₈在制冷系统中的不同作用,同时获得了制冷剂组分与混合制冷剂高低压以及原料天然气c_p-T之间的依赖关系,全面动态地展示了制冷剂各组分在C3/MRC流程中的影响和作用。在此基础上,又对比了原料天然气No.1和No.2在不同混合制冷剂高低压下C3/MRC流程的能耗指标。研究结果表明：原料天然气的c_p-T关系是决定整个C3/MRC流程能耗高低的关键因素,而混合制冷剂的组分或高低压的选择则对系统能耗影响较弱。混合制冷剂的组成及其高低压力的选择应根据原料天然气的c_p-T关系进行合理选取,以确保流程设计更为合理。     

多孔氧化铝中气体的有效扩散系数

在两种氧化铝中 ,分别采用C₂H₄ 、Ar和CO₂ 进行了两组分和三组分的Wicke -Kallenbach定态扩散实验 .由尘气模型和Stefan -Maxwell方程建立起的扩散通量方程 ,对实验结果加以处理 ,得到了两组分扩散的有效扩散系数及三组分扩散的虚拟两组分有效扩散系数 .同时 ,针对过渡区扩散推出了等温下两组分扩散的有效扩散系数为常数应满足的基本条件 ,所得结论和实验结果相吻合 .而对三组分扩散中的虚拟两组分有效扩散系数不能按照常数处理 .此外 ,无论是两组分或三组分扩散 ,对每一种氧化铝而言 ,有着相近的曲折因子 ,从而证实了曲折因子是与多孔介质结构密切相关的参数     

在多孔α-Al2O3陶瓷管上合成 ZSM-35型沸石膜

分别以吡咯烷和正丁胺为模板剂,在多孔α-Al₂O₃陶瓷管（3～5 μm）外表面上原位直接合成出ZSM-35型沸石膜,XRD、SEM对沸石膜进行表征和单组分气体H₂、N₂ 和C₃H₈的渗透性能测试表明：所合成出的沸石膜表面连续完整,晶粒之间互锁生长,沸石膜的厚度约为12～18 μm,具有典型的ZSM-35沸石结构,不同的模板剂对沸石膜的表面形态影响较大;经不同焙烧温度处理的沸石膜, 随着处理温度增高, 沸石膜表面晶粒的排列沿(h 0 0)取向性明显增强;所合成的沸石膜在室温下单组分气体H₂、N₂和C₃H₈渗透率达到10^-6数量级,H₂/N₂ 和H₂/C₃H₈理想分离因数均超过Knudsen扩散.     

CO_2,CH_4在全硅MFI型沸石中吸附的分子模拟

采用巨正则蒙特卡洛(GCMC)分子模拟方法研究了CO2,CH4分子在全硅MFI型沸石中的吸附行为,计算得到了纯组分和两组分的混合物在不同温度时的吸附等温线;分析了全硅MFI型沸石对混合组分的选择性吸附;模拟还得到了CO2,CH4分子在全硅MFI型沸石中的吸附位。     

D4/APAEDMS本体开环共聚反应的Monte Carlo模拟

Monte Carlo方法模拟八甲基环四硅氧烷与N-β-氨乙基-γ-氨丙基甲基二甲氧基硅烷（D₄/APAEDMS）的本体开环共聚动力学.在兼顾模拟精度与计算经济性基础上,模拟过程采用自由体积理论简化处理扩散效应并与本征反应动力学耦合.本征动力学常数通过模拟主要共聚基元反应得到,基于优化的动力学常数通过模拟从分子水平揭示：（1）D₄/APAEDMS本体开环共聚存在总活性基团的“稳态”行为;（2）D₄/APAEDMS本体开环共聚反应过程的重均分子量与数均分子量以及分子量分布系数存在“突变”特性.     

CH4和CO2在活性炭微球内扩散系数的测定

活性炭微球是一种储存及净化天然气的新型碳材料.采用高精度的重力分析仪(IGA-003, HIDEN)对天然气主要成分CH₄和CO₂杂质在活性炭微球材料内的扩散性质进行了研究.运用Fick扩散模型关联得到了CH₄及CO₂在活性炭微球内的扩散系数.研究结果表明,CH₄与CO₂在活性炭微球内的扩散属于晶体扩散,二者的扩散系数处于10^-13m²·s^-1数量级上.同时,CH₄与CO₂在介孔活性炭微球内的扩散速率均随着温度的增加而增加,随着体系平衡压力的增加而减小,而且CH₄的扩散速率要略大于CO₂的扩散速率.研究结果可用于活性炭微球吸附剂应用中传质性质的计算.     

烟气气相组分及Ca(OH)_2对KMnO_4氧化NO的影响机理

在固定床反应器中考察了KMnO₄氧化烟气中NO的过程,分析了烟气组分H₂O、O₂及SO₂对NO氧化过程的影响规律,得到了Ca（OH）₂对KMnO₄氧化NO的影响机理。实验结果表明,H₂O是KMnO₄氧化NO的必要条件;在含H₂O条件下,O₂可以提高NO氧化率。SO₂与氧化剂反应生成无水钾镁钒类复盐K₂Mn₂（SO₄）₃对NO氧化具有负面作用;Ca（OH）₂的加入提高了氧化剂表面的固体碱度从而促进氧化过程进行;通过添加Ca（OH）₂可以降低SO₂对NO氧化过程的负面影响。根据气体成分和产物分析可知,KMnO₄在钙基吸收剂表面氧化烟气中NO的机理可能是KMnO₄以离子态将吸附在氧化剂表面的NO和SO₂氧化为NO₂和SO₃,生成的NO₂、SO₃再传递到氧化位临近的碱性位被吸收。     

烟气气相组分及Ca（OH）2对KMnO4氧化NO的影响机理

在固定床反应器中考察了KMnO₄氧化烟气中NO的过程,分析了烟气组分H₂O、O₂及SO₂对NO氧化过程的影响规律,得到了Ca（OH）₂对KMnO₄氧化NO的影响机理。实验结果表明,H₂O是KMnO₄氧化NO的必要条件;在含H₂O条件下,O₂可以提高NO氧化率。SO₂与氧化剂反应生成无水钾镁钒类复盐K₂Mn₂（SO₄）₃对NO氧化具有负面作用;Ca（OH）₂的加入提高了氧化剂表面的固体碱度从而促进氧化过程进行;通过添加Ca（OH）₂可以降低SO₂对NO氧化过程的负面影响。根据气体成分和产物分析可知,KMnO₄在钙基吸收剂表面氧化烟气中NO的机理可能是KMnO₄以离子态将吸附在氧化剂表面的NO和SO₂氧化为NO₂和SO₃,生成的NO₂、SO₃再传递到氧化位临近的碱性位被吸收。     

Tuning the framework polarity in MFI membranes by deboronation: Effect on mass transport

The polarity of a zeolite is an important parameter determining the transport and separation properties in zeolite packed beds and membranes. This study focuses on the systematic variation of the zeolite polarity for membrane applications by varying the amount of silanol groups within the framework of the MFI zeolite by deboronation and consecutive heat treatment from 9 to 4 silanol groups per unit cell. The decrease in the number of silanol groups after heat treatment is confirmed by diffuse reflection infrared Fourier transform (DRIFT) and ²⁹Si Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR). The permeation of pure water through the modified silicalite membranes is insensitive to the number of silanol groups, attributed to a decreased adsorption compensated by an increased diffusivity. The ethanol selectivity in water/ethanol mixtures shows an increase with decreasing amount of silanol groups. Residual boron in the zeolite may react with ethanol and decrease its adsorption capacity. A reduction in flux through the debronated MFI membranes was not observed after ethanol/water permeation.     

Adsorption of 2,4,6‐Trinitrotoluene on MFI Zeolite

2,4,6‐Trinitrotoluene (TNT) was adsorbed onto all silica MFI zeolite. These TNT doped zeolite samples were examined using Fourier Transform Infrared Spectroscopy (FTIR) and X‐ray Diffraction (XRD). Results indicate that, using FTIR with an Attenuated Total Reflection (ATR) accessory, mass loading percentages as low as 2.5 mass percent TNT in zeolite are detectable. It was also observed that adsorption of TNT onto MFI did not suppress the IR absorbing vibrations of TNT. TNT doped zeolite samples were washed, using vacuum aspiration, with water and acetone, both of which stripped the TNT from the zeolite samples, indicating that the adsorption of TNT onto MFI zeolite is a physisorption, rather than chemisorption, phenomenon. Finally, a lack of strain‐induced peak broadening from XRD studies indicate that TNT does not enter the zeolitic pore structure, rather, it is adsorbed onto the zeolite surface.     

在不同构型分子筛催化剂中吸附和扩散的分子模拟

基于巨正则蒙特卡洛和分子动力学,对NH₃-SCR反应体系中吸附质分子（NO与NH₃）在不同拓扑结构沸石分子筛（LTL、FER、LEV、BEA、MOR、FAU、CHA和MFI）上的吸附和扩散特性进行系统研究。结果表明,对于全硅分子筛而言,其分子筛的拓扑结构影响NO与NH3在分子筛上的吸附,综合吸附量及吸附作用能发现,MFI和LEV分子筛对NO具有较优的吸附特性;MFI和BEA分子筛对NH₃ 具有较优的吸附特性。研究了Si与Al物质的量比对BEA分子筛吸附性能影响,结果表明,随着Si与Al物质的量比降低,分子筛自由体积逐渐增加,进而有助于分子筛催化剂对NO和NH₃的吸附。采用分子动力学模拟计算NO与NH₃在不同构型全硅分子筛上的扩散系数,发现具有三维直通道且孔径较大的分子筛催化剂有利于NO和NH₃在其孔道内部的扩散,MFI虽然具备三维孔道结构,但由于存在Z型交叉通道,一定程度阻碍了反应物分子的扩散。     

Diffusion of hydrocarbon mixtures in MFI zeolite: Influence of intersection blocking

Branched and cyclic hydrocarbons such as iso-butane, 2-methylpentane, 3-methylpentane, 2,2-dimethyl-butane and benzene are preferentially adsorbed at the intersections of the channels of MFI zeolite; they serve as bottlenecks for molecular traffic in mixtures with linear C1–C6 alkanes. Molecular dynamics simulations show that as the loadings of tardier iC4, 2MP, 3MP, 22DMB, and Bz is progressively increased to four molecules per unit cell the diffusivity of the more mobile linear alkane reduces nearly to zero. The reduction in the n-alkane diffusivity is quantitatively similar irrespective of the branched/cyclic hydrocarbon.     

ZrO2 和Al2O3支撑的MFI 型沸石分子筛膜:支撑体材料对膜性能的影响

采用水热合成法，以纯SiO2为源物质，在介孔Y2O3掺杂的ZrO2(YZ)及大孔α-Al2O3支撑体上制备出高质量的MFI型沸石分子筛膜，通过H2／n-C4H10气体混合物的渗透分离和p-xylene的蒸发研究了不同支撑体上MFI型沸石分子筛膜分离性能，在较低温度范围，YZ支撑的MFI型沸石分子筛膜中n-C4H10的渗透率比Al2O3支撑的膜高很多，最大n-C4H10与H2的分离率达到500，Al2O3支撑的膜中py-xylene的蒸发流量随时间下降很快，而YZ支撑的膜中的蒸发流量则变化缓慢，用XRD对膜的晶体结构进行分析，通过多种温度下热处理不同支撑体上的膜样品研究了其热稳定性与支持体材料的关系，YZ支撑的MFI型沸石分子筛膜的MFI结构在1000摄氏度后仍能保持，而Al2O3支撑的膜950摄氏度时已完全转变为石英相，研究结果表明，YZ支撑的MFI型沸石分子筛膜比Al2O3支撑的膜表现出更好的厌不性，热稳定性以及抗阻塞性。     

Alkylation of benzene by benzyl chloride over H-ZSM-5 zeolite with its framework Al completely or partially substituted by Fe or Ga

Liquid-phase benzylation of benzene by benzyl chloride to diphenylmethane over H-ZSM-5, H-gallosilicate(MFI), H-galloaluminosilicate(MFI), H-ferrosilicate(MFI) and H-ferroaluminosilicate(MFI) zeolites at 80°C has been investigated. A complete or partial substitution of Al in H-ZSM-5 zeolite by Fe or Ga results in a drastic increase in the catalytic activity of the zeolite in the benzylation process. The redox function of the zeolite is relatively more important than its acid function in the benzylation process.     

Atomistic simulations for adsorption and separation of flue gas in MFI zeolite and MFI/MCM-41 micro/mesoporous composite

Adsorption of pure CO₂ and N₂ and separation of CO₂/N₂ mixture in MFI zeolite and MFI/MCM-41 micro/mesoporous composite have been studied by using atomistic simulations. Fully atomistic models of MFI and MFI/MCM-41 are constructed and characterized. A bimodal pore size distribution is observed in MFI/MCM-41 from simulated small- and broad-angle X-ray diffraction patterns. The density of MFI/MCM-41 is lower than MFI, while its free volume and specific surface area are greater than MFI due to the presence of mesopores. CO₂ is preferentially adsorbed than N₂, and thus, the loading and isosteric heat of CO₂ are greater than N₂ in both MFI and MFI/MCM-41. CO₂ isotherm in MFI/MCM-41 is similar to that in MFI at low pressures, but resembles that in MCM-41 at high pressures. N₂ shows similar amount of loading in MFI, MCM-41 and MFI/MCM-41. The selectivity of CO₂ over N₂ in the three adsorbents decreases in the order of MFI>MFI/MCM-41>MCM-41. With increasing pressure, the selectivity increases in MFI and MFI/MCM-41, but decreases in MCM-41. The self-diffusivity of CO₂ and N₂ in MFI decreases as loading increases, while in MFI/MCM-41, it first increases and then drops.     

Effect of clinoptilolite filler on the physical and mechanical properties of polypropylene

This study aims to investigate the mechanical and physical properties of polypropylene (PP) filled by natural zeolite. For this purpose, a natural zeolite (at 1–6 wt% filler loadings) with two different particle sizes was used. Two different kinds of silane coupling agents (3‐aminopropyltriethoxysilane, GAPTES and 3‐glycidoxypropyltrimethoxysilane, GPTMS) at three different volume ratios were used to improve the zeolite compatibility with PP and to improve the mechanical properties of composites. Fillers and PP were compounded with a twin screw extruder, and the composites were moulded with injection moulding press. The samples were subjected to mechanical tests (i.e., impact and tensile tests) and physical tests (i.e., hardness, density, and melt flow index, MFI). The physical test results showed that the levels of hardness and density of both unmodified and modified zeolite‐filled PP composites were higher compared with neat PP. The MFI values of composites were decreased by increasing zeolite loading level. Composites including GAPTES modified zeolite showed improved yield strength, impact strength and stiffness compared with composites filled with unmodified zeolite particles. POLYM. COMPOS. 34:1396–1403, 2013. © 2013 Society of Plastics Engineers