用CO_2吸附法分析分子筛的孔结构

以NaA,NaY和NaZSM-5分子筛为研究对象,以CO2为吸附质,通过吸附数据测定,研究分子筛材料微孔结构的吸附表征方法.计算了NaA、NaY和NaZSM-5分子筛的微孔孔容,其中基于D-A方程的微孔孔容值与文献值一致.根据CO2吸附数据分析了3种分子筛的孔径分布.发现对于含有球形孔结构的NaA,NaY分子筛和NaA+NaY混合物,HK(Horvath-Kawazoe)球形模型(HKsphere)能够很好地描述其孔径分布,而HK柱状模型(HKcylinder)能够很好地表征具有柱状孔道结构的NaZSM-5分子筛.单一的HK方法不能表征同时含有柱状孔和球形孔的NaA+NaZSM-5混合物,使用HKcylinder只能得到混合物材料中柱状孔的分布情况,而使用HKsphere只能得到球形孔的分布情况.     

活性炭吸附CO2与其微孔体积的关系

对五种活性炭样品进行液氮温度下的N2吸附、碘吸附测定和冰点下的CO2吸附表征。结果表明,碘吸附值测定法和基于N2吸附等温线的BET方程、D-R方程,孔结构参数都不能正确反映活性炭对CO2的吸附特性;由CO2吸附等温线得到的D A模型参数也不适合分析活性炭吸附CO2特性;CO2吸附等温线的密度泛函理论（DFT）分析结果表明,CO2在活性炭上的吸附发生在极微孔内,DFT分析的微孔孔容与吸附等温线反映的吸附性能完全一致。因此,根据CO2吸附等温线的DFT模型是准确反映活性炭吸附CO2特性的表征分析方法。     

A型沸石/活性炭复合材料的制备及甲烷/氮气吸附分离性能

以沥青和煤矸石为原料,经炭化、活化后获得型体活性炭材料(AC),并在此基础上进行水热晶化,研究晶化时间对复合材料中4A沸石的形成、孔结构和甲烷、氮气吸附性能的影响。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、77 K下的氮气吸附-脱附以及273 K下的CO_2吸附等温线对样品进行表征,结果表明水热晶化后,复合材料中的硅铝形成立方结构的4A沸石,出现了0.45~0.6 nm的微孔,微孔孔容增加,并伴有少量的中孔和大孔。复合材料在298 K下的甲烷(CH_4)和氮气(N_2)吸附等温线的结果表明,晶化时间6 h的复合材料AC-2的甲烷吸附量被提高至10.8 m L/g,并保持较高的CH4/N2平衡分离比(3.7)。     

氢在沸石上的吸附行为

应用基于Ono-Kondo格子理论得到的通用吸附等温方程, 通过分析氢在不同温度下, 在沸石NaX、CaA、NaA和ZSM-5上的吸附数据, 确定了氢的最大单层吸附容量. 并引入维里吸附方程, 由第二维里吸附系数和圆柱孔的Lennard-Jones(12-6)势模型计算了氢与沸石微孔壁面的作用势. 结果表明, 通用吸附等温方程可较好地描述氢在沸石上的超临界吸附行为, 拟合所得的氢在沸石上的最大单层吸附容量与吸附剂相关, 而与吸附温度无关. 圆柱孔作用势模型计算所得的氢分子在沸石上的吸附作用势与吸附热相近. 氢分子间的作用力表现为吸引力.     

源自密胺基多孔聚合物的富氮微孔炭及选择性吸附CO_2

以间苯二甲醛和三聚氰胺为原料,通过Schiff碱缩合反应合成了密胺基多孔聚合物(POP),经高温炭化后得到富氮微孔炭(NMC).利用N2吸脱附和傅里叶变换红外(FTIR)光谱表征了POP和炭化后产物NMC的结构和组成,与POP相比,NMC的官能团数量减少,比表面积和微孔孔容大幅增加.元素分析表明NMC含氮量高达12.5%(w).采用体积法测定了CO2、CH4和N2在NMC上的单组分吸附平衡等温线,NMC展示出良好的CO2吸附性能,298 K、100 kPa下CO2平衡吸附量可达2.34 mmol·g-1.双位Langmuir(DSL)模型和单位Langmuir(SSL)模型分别较好地描述了CO2、CH4和N2在NMC上的吸附平衡数据,在此基础上,应用理想吸附溶液理论(IAST)预测了双组分混合气在NMC上的吸附等温线,结果表明NMC对CO2-N2和CO2-CH4有非常高的CO2吸附选择性,分别为144.9和12.8.     

CXN天然沸石的研究Ⅱ.吸附性质

采用N2,NH3,CO2,乙烯,丙烯,水,甲醇,乙醇,丙醇等作为吸附剂,研究了由我国CXN天然沸石改性制得的H-STI和Na-STI沸石的吸附性质,H-STI和Na-STI沸石的BET表面积及微孔孔体积约为420m2/g和0.20m3/g.根据NH3和CO2在H-STI沸石上的吸附等温线计算得到它们的吸附热分别为44.8和26.5kJ/mol.乙烯,丙烯,甲醇,乙醇,丙醇等在Na-STI沸石上的吸附等温线表明该沸石对有机分子的吸附具有链长选择性.在低分压下水相对于甲醇的吸附量表明沸石具有一定的疏水性质.     

氩吸附法研究多级孔分子筛的孔结构

采用不同方法分别制备了双介孔分子筛、介微孔分子筛及介孔沸石材料,利用氩吸附法并结合XRD技术表征了多级孔分子筛的孔结构。探讨了适用于多级孔分子筛的孔径分布计算方法,揭示了不同类型吸附等温线与孔径分布、孔型及孔容等之间的关系。研究表明,对于多级孔分子筛、微孔和介孔的孔径分布分别用SF法和BJH法计算较适宜,全孔分析可用NLDFT法计算。通过对TS-1介孔沸石的孔结构分析发现, TPAOH 在改性制备介孔TS-1的过程中起到了生成介孔及促进二次晶化的双重作用。     

氢气在A和X型沸石上超临界吸附的格子密度函数模型

采用基于三维Ono-Kondo方程的格子密度函数理论(LDFT)模型模拟了氢气在A和X型微孔沸石上的超临界吸附等温线. 根据沸石孔的尺寸和形状, LDFT模型将氢分子在孔中的吸附位分布近似为简单立方、面心立方和体心立方的团簇结构. 模拟结果表明, LDFT模型可有效地用于描述氢气在A和X型沸石上的单层或多层超临界吸附行为. 模拟所得的吸附等温线与实验测定结果吻合. 特别是, LDFT模型中的氢-沸石作用势能参数的准确性得到了Lennard-Jones(12-6)势能方法的有效验证. 因此, LDFT模型被用于预测了更宽温度和压力范围内氢气在X沸石上的超临界吸附.     

亚硝胺在小微孔沸石上的“嵌入式”吸附探讨

通过结构计算分析了大体积的六亚甲基亚硝胺（NHMI）和N’-亚硝基去甲烟碱（NNN）在小微孔沸石上各种可能的吸附方式,结合实验事实推断出它们以－N－N=O官能团嵌入沸石孔道进行吸附的几率最大.这种“嵌入式”吸附方式是小微孔沸石得以吸附、分离那些体积远远大于其孔径的毒物分子的重要原因,可用以拓宽沸石在生态环境保护中的应用.     

微孔/介孔复合分子筛的合成及其对CO2的吸附性能

采用两步晶化法将合成的沸石前驱液(S)或沸石固体粉末(P)经不同浓度(c)的NaOH处理后, 分别以表面活性剂十六烷基三甲基溴化铵(CTAB)软模板或介孔炭(Meso-C)硬模板为导向剂, 自组装合成S-β-MCM41(c)、P-β-MCM41(c)、P-ZSM-MCM41(c)、P-ZSM-C系列微孔/介孔复合分子筛. 考察了沸石分子筛种类、碱处理液浓度以及介孔模板剂对合成复合分子筛结构与性能的影响. X射线衍射(XRD)、透射电子显微镜(TEM)和氮气吸附-脱附表征结果表明产物具有微孔/介孔多级孔结构. 该材料对CO₂的吸附能力比纯微孔或介孔材料均有明显提高, 其中P-ZSM-MCM41(2)的CO₂吸附容量最大可达1.51 mmol·g^-1, 为ZSM-5沸石吸附量的两倍多.     

亚硝胺在沸石催化剂上的程序升温表面反应

 采用程序升温表面反应技术研究了二甲基亚硝胺,吡咯烷亚硝胺和环六亚甲基亚硝胺在NaY,NaZSM－5和HZSM－5等沸石及MCM－41中孔分子筛上的脱附及分解．结果表明,沸石对亚硝胺有独特的吸附和催化分解作用．同时,研究了沸石孔结构及表面酸性对亚硝胺分解反应的影响．     

Gibbs ensemble Monte Carlo simulation of supercritical CO2 adsorption on NaA and NaX zeolites

Adsorption of supercritical carbon dioxide on two kinds of zeolites with identical chemical composition but different pore structure (NaA and NaX) was studied using the Gibbs ensemble Monte Carlo simulation. The model frameworks for the two zeolites with SiAl ratio being unity have been chosen as the solid structures in the simulation. The adsorption behaviors of supercritical CO2 on the NaA and NaX zeolites, based on the adsorption isotherms and isosteric heats of adsorption, were discussed in detail and were compared with the available experimental results. A good agreement between the simulated and experimental results is obtained for both the adsorbed amount and the bulk phase density. The intermediate configurational snapshots and the radial distribution functions between zeolite and adsorbed CO2 molecules were collected in order to investigate the preferable adsorption locations and the confined structure behavior of CO2. The structure behaviors of the adsorbed CO2 molecules show various performances, as compared with the bulk phase, due to the confined effect in the zeolite pores.     

氢在A、X及ZSM-5型沸石上的高压物理吸附

The hydrogen adsorption properties and uptake capacities of the A, X and ZSM-5 types of zeolites were investigated at temperatures of 77, 195 and 293 K and pressures up to 7MPa, using a conventional volumetric adsorption apparatus. All hydrogen adsorption isotherms were basically type I, but the maximum in isotherm,a unique feature of supercritical adsorption, was observed at high pressures of 2-5 MPa at 77 K. The isosteric heats of adsorption were determined from the isotherms and the factors that influence their variations were discussed. Different types of zeolites exhibited remarkably different hydrogen uptake, based on both the framework structure and the nature of the cations present. The highest gravimetric storage capacity of 2.55wt% was obtained for NaX-type zeolite at 4 MPa and 77 K. In CaA, NaX and ZSM-5 types of zeolites,hydrogen uptakes were proportional to the specific surface areas, which were associated with the available void volumes of the zeolites. A threshold in hydrogen adsorption observed in NaA and KA was attributed to a pore blocking effect by large cations in KA. A ratio of the kinetic diameter of adsorbate to the effective opening diameter of zeolite was used to judge the blocking effect for physisorption.     

The effects of polymer chain rigidification, zeolite pore size and pore blockage on polyethersulfone (PES)-zeolite A mixed matrix membranes

The polyethersulfone (PES)-zeolite 3A, 4A and 5A mixed matrix membranes (MMMs) were fabricated with a modified solution-casting procedure at high temperatures close to the glass transition temperatures (T_g) of polymer materials. The effects of membrane preparation methodology, zeolite loading and pore size of zeolite on the gas separation performance of these mixed matrix membranes were studied. SEM results show the interface between polymer and zeolite in MMMs experiencing natural cooling is better (i.e., less defective) than that in MMMs experiencing immediate quenching. The increment of glass transition temperature (T_g) of MMMs with zeolite loading confirms the polymer chain rigidification induced by zeolite. The experimental results indicate that a higher zeolite loading results in a decrease in gas permeability and an increase in gas pair selectivity. The unmodified Maxwell model fails to correctly predict the permeability decrease induced by polymer chain rigidification near the zeolite surface and the partial pore blockage of zeolites by the polymer chains. A new modified Maxwell model is therefore proposed. It takes the combined effects of chain rigidification and partial pore blockage of zeolites into calculation. The new model shows much consistent permeability and selectivity predication with experimental data. Surprisingly, an increase in zeolite pore size from 3 to 5 Å generally not only increase gas permeability, but also gas pair selectivity. The O₂/N₂ selectivity of PES-zeolite 3A and PES-zeolite 4A membranes is very similar, while the O₂/N₂ selectivity of PES-zeolite 5A membranes is much higher. This implies the blockage may narrow a part of zeolite 5A pores to approximately 4 Å, which can discriminate the gas pair of O₂ and N₂, and narrow a part of zeolites 3A and 4A pores to smaller sizes. It is concluded that the partial pore blockage of zeolites by the polymer chains has equivalent or more influence on the separation properties of mixed matrix membranes compared with that of the polymer chain rigidification.     

Unconventional, highly selective CO2 adsorption in zeolite SSZ-13

Low-pressure adsorption of carbon dioxide and nitrogen was studied in both acidic and copper-exchanged forms of SSZ-13, a zeolite containing an 8-ring window. Under ideal conditions for industrial separations of CO(2) from N(2), the ideal adsorbed solution theory selectivity is >70 in each compound. For low gas coverage, the isosteric heat of adsorption for CO(2) was found to be 33.1 and 34.0 kJ/mol for Cu- and H-SSZ-13, respectively. From in situ neutron powder diffraction measurements, we ascribe the CO(2) over N(2) selectivity to differences in binding sites for the two gases, where the primary CO(2) binding site is located in the center of the 8-membered-ring pore window. This CO(2) binding mode, which has important implications for use of zeolites in separations, has not been observed before and is rationalized and discussed relative to the high selectivity for CO(2) over N(2) in SSZ-13 and other zeolites containing 8-ring windows.     

多级孔NaX分子筛的合成及CO2吸附性能

采用两步晶化和氨基酸辅助的协同合成策略, 制备了具有高产率(89%)和高结晶度(微孔体积为0.30 cm ³/g)的多级孔NaX分子筛. 利用X射线粉末衍射、 扫描电子显微镜、 透射电子显微镜和氮气吸附等技术, 考察了两步晶化和氨基酸加入量对NaX分子筛的形貌、 相对结晶度和产率的影响. 实验结果表明, 两步晶化有利于多级孔结构的产生, 氨基酸的引入有助于提高分子筛相对结晶度和产率. 与传统方法合成的NaX分子筛相比, 该合成策略制备的多级孔NaX分子筛展现出更优异的CO₂吸附性能, 在273 K和100 kPa条件下, 其CO₂吸附量达到154.2 cm ³/g, 而传统NaX分子筛的CO₂吸附量为147.6 cm ³/g. 该合成策略为绿色且高效制备高质量的多级孔分子筛提供了新思路.     

凹凸棒土粘结剂对13X分子筛吸附性能的促进作用

以凹凸棒土为粘结剂制备了13X分子筛吸附剂.研究了其孔结构、表面电性和对水、CO2和N2分子的吸附性能,并与高岭土为粘结剂的同类吸附剂进行了比较.结果表明,凹凸棒土发达的孔隙结构、大的比表面和表面负电性质有利于其吸附容量的改善,而13X/凹凸棒土中丰富的中孔促进了其对CO2的吸附速率.另外由CO2吸附热力学分析可知,CO2在13X/凹凸棒土上具有较低的吸附热,结果将有利于其在吸附剂上的脱附.     

Separation of gas mixtures using a range of zeolite membranes: a molecular-dynamics study

Gas separation efficiencies of three zeolite membranes (Faujasite, MFI, and Chabazite) have been examined using the method of molecular dynamics. Our investigation has allowed us to study the effects of pore size and structure, state conditions, and compositions on the permeation of two binary gas mixtures, O(2)N(2) and CO(2)N(2). We have found that for the mixture components with similar sizes and adsorption characteristics, such as O(2)N(2), small-pore zeolites are not suited for separations, and this result is explicable at the molecular level. For mixture components with differing adsorption behavior, such as CO(2)N(2), separation is mainly governed by adsorption and small-pore zeolites separate such gases quite efficiently. When selective adsorption takes place, we have found that, for species with low adsorption, the permeation rate is low, even if the diffusion rate is quite high. Our results further indicate that loading (adsorption) dominates the separation of gas mixtures in small-pore zeolites, such as MFI and Chabazite. For larger-pore zeolites such as Faujasite, diffusion rates do have some effect on gas mixture separation, although adsorption continues to be important. Finally, our simulations using existing intermolecular potential models have replicated all known experimental results for these systems. This shows that molecular simulations could serve as a useful screening tool to determine the suitability of a membrane for potential separation applications.