格子理论预测氢在碳吸附剂微孔内的过剩吸附

基于Dubinin势论的修正型D-A方程,需用实验数据定义Ps,使其适用性不受到限制,而引入基于格子理论的Ono-Kondo方程,以预测超临界高压氢气在碳狭缝微孔内的过剩吸附.预测了77～298 K温度时,氢在碳吸附剂微孔内的对比过剩吸附量,并与AX-21活性碳的氢吸附实验结果、GCMC分子模拟结果作了比较.结果表明,该方程能反映出超临界流体吸附等温线的特点,并能很好地预测氢气在活性碳微孔内的吸附趋势.     

超级活性炭的制备及其储氢性能初步研究

以高硫焦为原料,通过L9(34)正交设计,制备出一系列超高比表面积活性炭.系统地测定了氢在93K～293K、0MPa～7MPa范围内,在SBET为3886m2/g的超级活性炭上的一组吸附等温线.实验结果表明 ,吸附等温线具有Ⅰ-型等温线特征且储氢效果良好,其中在293K/5MPa、93K/6MP a的条件下,储氢质量分数分别达1.9W/%、9.8W/ %.一定条件下的等量吸附线研究表明,氢在超级活性炭上的等量吸附热较小,且主要集中在4.8kJ*mol-1～6.5kJ·     

微型变压吸附制氧机吸附剂的选择

吸附剂的选择是变压吸附制氧技术中的重要环节.采用静态吸附的方法测量了3种沸石分子筛在298 K、308 K和318 K时对N2和O2的平衡吸附量并绘出了相应的吸附等温线.结合3种吸附剂的特性参数以及其对N2和O2的吸附量,分析了影响沸石分子筛对N2和O2的吸附量的因素.以Langmuir吸附方程以及实验数据,计算出了这...     

ZSM-5沸石在空调应用中的吸附脱附性能研究

针对固体吸附式制冷在空调领域的应用,建立了一套采用ZSM-5沸石-水作为吸附工质对的实验研究系统,对其吸附脱附性能进行了实验研究,得到了吸附脱附性能曲线。比较了不同吸附床温度以及吸附床有无保温情况下,ZSM-5沸石分子筛对水的吸附情况:低温情况对水蒸气的吸附量随吸附时间明显增加,但吸附率逐渐变慢;床温升高,吸附剂达到吸附平衡所需时间缩短,平衡吸附量则有所降低。     

聚氨酯/沸石杂化材料的制备及性能

首次提出聚氨酯／沸石型有机-无机杂化的新模式，并选用表面富合活泼羟基且合有微孔直径大于0．7nm的沸石分子筛，制备出聚氨酯／沸石分子筛新型杂化材料。结果表明，其性能远优于纯聚氨酯的性能，与聚氨酯／有机蒙脱土纳米复合材料的力学性能和耐热性能相近，但耐溶剂性能和回弹性能优于前者。XRD分析表明分子筛在杂化材料中保持原状，FT—IR证实TDI能够与沸石分子筛表面的硅羟基进行接枝反应。     

饱和ATP为原料合成多级孔ZSM-5沸石分子筛的制备与表征

研究以饱和ATP吸附材料为合成沸石分子筛的硅源,采用双模板法,用四丙基氢氧化铵(TPAOH)为微孔模板剂和十六烷基三甲基溴化烷(CTAB)为介孔模板剂直接合成多级孔ZSM-5沸石分子筛,通过XRD、SE M、比表面积及孔径分析仪进行N_2吸附-脱附等手段对多级孔ZSM-5沸石分子筛表征测试分析。结果表明:饱和ATP吸附材料在180℃下,水热提纯12 h获得硅源,再加入TPAOH和CTAB进行初始凝胶反应,后移入水热反应釜中,控温180℃,水热晶化反应15 h,即得多级孔ZSM-5沸石分子筛。     

液相硅沉积改性HZSM-5分子筛的择形吸附分离性能研究

以聚硅氧烷作为改性剂,通过液相硅沉积表面修饰对HZSM-5分子筛吸附剂进行了择形功能化改性,采用X射线衍射(XRD)、NH3-TPD、比表面积与孔径分析和热重分析(TGA)等手段对改性前后的吸附剂进行了表征。分别采用液相吸附法和气相吸附法研究了ZSM-5择形分子筛对于对二甲苯(pX)和间二甲苯(mX)混合物的择形吸附分离效果,考察了硅沉积改性程度、液相吸附及气相吸附工艺条件对硅沉积修饰分子筛Si/ZSM-5择形吸附分离性能的影响。研究结果表明,分子筛吸附剂中介孔体积随着硅沉积改性次数增加而减少,而微孔体积改变较小,但4次硅改性后的分子筛吸附剂的晶体结构未发生明显变化。同时,随着硅沉积改性次数的增加,分子筛吸附剂的吸附量减小,而吸附剂的择形吸附分离系数βpX/mX增大;另一方面,气相热解吸得到的pX/mX选择性高于液相解吸法,并且二氯甲烷作为液相解析剂的pX/mX择形选择性高于甲苯和环己烷解析剂。吸附重量动态分析测试结果表明,Si/ZSM-5(0)、Si/ZSM-5(2)和Si/ZSM-5(4)的平均吸附容量分别为102.1,82.12和71.84mg/g,pXmX二甲苯混合物的扩散速率随着硅沉积改性程度的增加而明显减小。     

高比表面积PAN-ACF的吸附与孔结构解析

以KOH为活化剂制备了比表面积大于2000m^2/g的高比表面积PAN基活性炭毡（ACF）,以液氦为吸附介质在77．4K测试PAN－ACF吸附等温线,并对其孔结构进行了表征。采用BET法计算比表面积,t-plot法,Horvath-Kawazoe,Dubinin-Radushkevich方程以及密度函数理论（DFT0表征孔结构。研究表明即使比表面积超过3000m^2/g时,PAN－ACF的孔分布仍然很窄,并且含有大量的分子筛型孔,以金子克美等人提出多段吸附机理为依据,采用DR方程对PAN－ACF三段吸附过程所对应的E^0,x进行了计算。结果认为低压段的负偏离在一定程度上是由于吸附较强的微孔与表面官能团共同作用的结果,并非完全由于活化扩散引起,以上分析方法的表征结果具有较好的一致性,为PAN－ACF的吸附性能与孔结构提供了准确的信息。     

载铂多级孔ZSM-5分子筛用于邻二甲苯的“吸附-催化燃烧”循环脱除

首先利用F127作为软模板, 采用蒸汽辅助晶化法合成出具有一定介孔结构的多级孔ZSM-5分子筛, 然后采用等体积浸渍法负载铂, 成功制备了载铂的多级孔ZSM-5分子筛催化剂。利用X射线衍射(XRD)、氮气吸附等温线(N₂ isotherm)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)对制备的催化剂进行了表征, 并将催化剂用于邻二甲苯的吸附和催化燃烧反应, 最后考察了催化剂“吸附-催化燃烧”循环脱除邻二甲苯的性能。结果表明, 与传统ZSM-5分子筛相比, 多级孔ZSM-5分子筛结晶度略有下降, 但是介孔度和孔体积明显提升。介孔结构与微孔结构并存, 极大提升了多级孔ZSM-5分子筛对邻二甲苯的吸附能力, 其饱和吸附量达到了传统ZSM-5分子筛的约8倍。此外, 介孔结构的存在提高了铂的分散度, 使得载铂多级孔ZSM-5分子筛具有最佳的催化燃烧邻二甲苯性能, 三次“吸附-催化燃烧”循环使用后的吸附容量依然基本保持不变, 并且在催化燃烧过程中无二次污染物生成, 具有较高的吸附容量和循环使用稳定性。     

壳聚糖/沸石分子筛复合吸附颗粒的制备与性能

采用实验室自制壳聚糖/沸石分子筛复合吸附颗粒用于处理水中NH₄+-N和NO₃--N,通过优化工艺条件确定最佳壳聚糖/沸石分子筛复合吸附颗粒制备方法,并利用SEM、比表面积（BET）、FTIR和XPS分析壳聚糖/沸石分子筛复合吸附颗粒表面物化特性。结果表明:壳聚糖/沸石分子筛复合吸附颗粒最佳制备条件为:乙酸浓度为4vol%,壳聚糖浓度为7 g/L,振荡时间为10 h,振荡温度为30℃。制得的壳聚糖/沸石分子筛复合吸附颗粒对NH₄+-N和NO₃--N的吸附量分别达到0.636 mg/g和1.952 mg/g,去除率分别为81.60%和40.28%。壳聚糖/沸石分子筛复合吸附颗粒表面形貌呈现较多凸起和微孔,比表面积为391.52 m2/g。FTIR分析结果表明,壳聚糖特征官能团-NH₂和-CH₃已负载于沸石分子筛的基本骨架中。XPS分析结果表明,元素O1s在壳聚糖与沸石分子筛的连接过程中起主要作用,该研究成果可为北方严寒地区净水厂的提标改造提供理论依据。      

Quantum Effects on Hydrogen Isotopes Adsorption in Nanopores

We have investigated the applicability of simulations and theoretical techniques for exploring the selectivities of hydrogen isotopes. We have simulated the adsorption isotherms of H₂ in an idealized carbon slit pore at 77 K by using the grand canonical Monte Carlo simulations with the Feynman-Hibbs effective potential (FH-GCMC) and the rigorous path integral method (PI-GCMC), and we obtained good agreement between the isotherms from both simulations. This suggests that FH-GCMC, which uses the approximative Feynman-Hibbs treatment, is as useful as PI-GCMC for exploring H₂ adsorption at 77 K. Moreover, we show that the ideal adsorption solution theory (IAST) can predict the selectivity of D₂ over H₂ in the interstices of single-wall carbon nanotube (SWNT) bundles at 77 K (below 0.1 MPa) very well by comparing the obtained results with the mixture adsorption FH-GCMC simulations. This indicates that IAST is also applicable to the estimation of the selectivity of D₂ over H₂ at moderate pressures and at 77 K from experimental single-component adsorption isotherms. We also demonstrate that the FH-GCMC simulation can reproduce the experimental adsorption isotherms of H₂ and D₂ in aluminophosphate AlPO₄-5 at 77 K. Finally, we analyze the selectivity of D₂ over H₂ by IAST with the experimental single-component adsorption isotherms of H₂ and D₂ at 77 K for a variety of adsorbents: AlPO₄-5, activated carbon fibers (ACFs), HiPco SWNT, and SWNHs. The selectivities predicted by the experimental adsorption data based on the results from the FH-GCMC simulations are presented and discussed.     

Solubility of Water in Supercritical Carbon Dioxide

A new experimental circulation facility is developed to investigate the solubility of liquids in supercritical fluids at a pressure of up to 35 MPa and temperatures from 293 to 423 K. The solubility of water in supercritical carbon dioxide is experimentally investigated on the 313 and 323 K isotherms in the pressure range from 8 to 20 MPa. Empirical parameters of intermolecular interaction are obtained in the Soave approximation, which enables one to describe the solubility with an error that does not exceed the experimental error.     

Zeolite heat pump — adsorption of methanol in synthetic zeolites 13X, 4A and 5A

The adsorption isotherms for methanol adsorption in synthetic zeolites 13X, 4A and 5A were measured gravimetrically at various temperatures. The model of Langmuir and the potential theory were used for correlating the equilibrium data. The monolayer capacity was calculated using these two models. A small deviation at elevated temperatures was observed. The differential heat of adsorption was measured calorimetrically for all three zeolites. The isosteric heat of adsorption was calculated for zeolite 13X using measured equilibrium data. The log p, 1/T equilibrium diagram for zeolite 13X was computed using the Langmuir equation.     

Adsorption equilibrium of hydrogen on graphene sheets and activated carbon

For obtaining the technical data to evaluate the performance of hydrogen storage by adsorption on graphene sheets (GS), analysis of adsorption equilibrium of hydrogen on the GS and the activated carbon were carried out based on the hydrogen adsorption data covering a wide temperature range. The GS and SAC-02 activated carbon, which respectively had a specific surface area about 300 m²/g and 2074 m²/g, were selected as adsorbents. Six adsorption isotherms of excess amounts of high purity hydrogen were measured at temperature from 77.15 K to 293.15 K and pressure up to 6 MPa. Parameters of Langmuir, Langmuir–Freundlich and Toth equations were set by non-linear fit against adsorption data, predicting accuracy of the equations was then evaluated by the accumulated relative errors between experimental data and those from the equations under different pressure regions. Absolute adsorption amounts determined by the modified equation were used to calculate the isosteric heat of adsorption.It shows that both adsorption isotherms of hydrogen on the GS and the activated carbon have the features of Type I, but the trend of isotherms varying over the pressure is different within the lower temperature region. Results from Langmuir equation have the largest error. Toth equation can much accurately predict the adsorption data with an overall accumulated relative error less than 4%. The value of the isosteric heat of hydrogen adsorption on the GS is about 5.06–6.37 kJ/mol, which is much higher than 4.05–5.52 kJ/mol for hydrogen on the SAC-02 activated carbon under the whole experimental condition. It reveals that interaction between hydrogen molecules and the graphene layer is stronger than that of hydrogen and carbon surface, and Toth equation could be appropriate to analyzing adsorption equilibrium for hydrogen on carbon based adsorbents.     

Adsorption of Hydrogen in Graphitic Slit Pores

Molecular simulations of adsorption isotherms for hydrogen on graphite and graphitic slit pores are presented. The simulations employ the path integral isomorphism of Feynman to rigorously account for the quantum nature of the adsorbate. The isosteric heat of adsorption of para-hydrogen on planar graphite is computed from several different solid–fluid potential models and compared with experiment. The adsorption isotherm for hydrogen on the graphite basal plane was computed at 20 K and compared with experiment. Agreement with experiment is very good. Adsorption isotherms for hydrogen in slit pores of two different pore widths are computed at 20 K and compared with results from classical simulations. Quantum and classical isotherms exhibit qualitatively different behavior.     

Nitrogen‐Containing Microporous Conjugated Polymers via Carbazole‐Based Oxidative Coupling Polymerization: Preparation,Porosity, and Gas Uptake

Facile preparation of microporous conjugated polycarbazoles via carbazole‐based oxidative coupling polymerization is reported. The process to form the polymer network has cost‐effective advantages such as using a cheap catalyst, mild reaction conditions, and requiring a single monomer. Because no other functional groups such as halo groups, boric acid, and alkyne are required for coupling polymerization, properties derived from monomers are likely to be fully retained and structures of final polymers are easier to characterize. A series of microporous conjugated polycarbazoles ( CPOP‐2–7 ) with permanent porosity are synthesized using versatile carbazolyl‐bearing 2D and 3D conjugated core structures with non‐planar rigid conformation as building units. The Brunauer–Emmett–Teller specific surface area values for these porous materials vary between 510 and 1430 m² g^?1. The dominant pore sizes of the polymers based on the different building blocks are located between 0.59 and 0.66 nm. Gas (H₂ and CO₂) adsorption isotherms show that CPOP‐7 exhibits the best uptake capacity for hydrogen (1.51 wt% at 1.0 bar and 77 K) and carbon dioxide (13.2 wt% at 1.0 bar and 273 K) among the obtained polymers. Furthermore, its high CH₄/N₂ and CO₂/N₂ adsorption selectivity gives polymer CPOP‐7 potential application in gas separation.     

ZSM-5分子筛膜/多孔SiSiC陶瓷复合孔结构微反应器的制备

以生物形态多孔SiSiC陶瓷为载体,采用原位水热法在多孔陶瓷微孔道内壁形成了一层2～5μm厚的b轴取向生长的ZSM－5分子筛膜. 利用XRD、SEM EDX、BET分析对复合材料的相组成、微观结构和比表面积进行了表征,研究了水热晶化时间、载体预处理对原位合成分子筛膜的影响. 结果表明,随晶化时间从5h增加到15h,从不连续的单层膜演变到～5μm厚的b轴取向的连续致密多层膜,该膜层是由粒径在1μm左右的ZSM-5分子筛颗粒堆积交联而成. 载体表面Si-OH浓度越高,分子筛膜和载体的结合力越强,但是较难控制分子筛膜的定向生长. ZSM-5/SiSiC复合孔结构材料的微孔体积为0.015cm3/g,BET面积为42.8m2/g,而相应的分子筛负载量为8.6%.     

Removal of ammonium from aqueous solutions with volcanic tuff

This paper presents kinetic and equilibrium data concerning ammonium ion uptake from aqueous solutions using Romanian volcanic tuff. The influence of contact time, pH, ammonium concentration, presence of other cations and anion species is discussed. Equilibrium isotherms adequately fit the Langmuir and Freundlich models. The results showed a contact time of 3h to be sufficient to reach equilibrium and pH of 7 to be the optimum value. Adsorption capacities of 19 mg NH(4)(+)/g were obtained in multicomponent solutions (containing NH(4)(+), Zn(2+), Cd(2+), Ca(2+), Na(2+)). The presence of Zn and Cd at low concentrations did not decrease the ammonium adsorption capacity. Comparison of Romanian volcanic tuff with synthetic zeolites used for ammonium removal (5A, 13X and ZSM-5) was carried out. The removal efficiciency of ammonium by volcanic tuff were similar to those of zeolites 5A and 13X at low initial ammonium concentration, and much higher than those of zeolite ZSM-5.     

Investigation of the catalytic wet peroxide oxidation of phenol over different types of Cu/ZSM-5 catalyst

In this work oxidation of phenol with hydrogen peroxide on Cu/ZSM-5 catalysts was studied. The catalysts samples were prepared by two different methods: by ionic exchange from the protonic form of commercial ZSM-5 zeolite, and by direct hydrothermal synthesis. Characterization of the catalysts extends to X-ray diffraction (XRD), while the adsorption techniques were used for the measurement of the specific surface area. The catalytic tests were carried out in a stainless steel Parr reactor in batch operation mode at the atmospheric pressure and the temperature range from 50 to 80 degrees C. The mass ratio of the active metal component on the zeolite was in the range of 1.62-3.24 wt.%. for catalyst prepared by direct hydrothermal synthesis and 2.23-3.52 wt.% for catalyst prepared by ion exchange method. The initial concentration of phenol and hydrogen peroxide was 0.01 and 0.1 mol dm(-3), respectively. The influence of different methods of Cu/ZSM-5 preparation on their catalytic performance was monitored in terms of phenol conversion and degree of metal leached into aqueous solution.     

ZSM-5分子筛介孔的构筑

在微孔结构的ZSM-5沸石分子筛中构筑介孔,可以有效地解决ZSM-5分子筛在催化反应过程中的扩散传质和催化剂失活问题.重点阐述了在初始的合成体系中加入炭黑、介孔碳、表面活性剂等作为模板剂来构筑含介孔结构的ZSM-5和利用碱液或酸液对已合成的微孔的ZSM-5进行后处理来构筑介孔,并对含有介孔结构的ZSM-5的性质和相关的应用做了评价和展望.