Pure-silica MFI zeolite membrane by cooperative templating approach for ethanol-water separation

Pure-silica MFI zeolite membrane composed of intergrown four prism crystals was fabricated by using tetrabutylammonium (TBA⁺) and tetraethylammonium (TEA⁺) as cooperating templates and the induced function of MFI seeds under synthesis solution with molar composition of 1TEOS:0.2TBAOH:0.2TEABr:180H₂O. The ethanol/water separation factor was 64 with a flux of 1.40 kg m⁻² hr⁻¹ for 5 wt% ethanol/water mixture at 60°C. In contrast, single TBAOH and TEAOH template led to formation of uncontinuous MEL and MFI membrane respectively, without ethanol-selectivity. The behavior of quaternary ammonium (TBA⁺ and TEA⁺) varied in different system: (a) In “TBA⁺+ TEA⁺” system, TBA⁺ and TEA⁺ were incorporated into MFI zeolite channel simultaneously; (b) In “TPA⁺+ M⁺” system (M = TEA or TBA), either TEA⁺ or TBA⁺ could not be occluded into channel, however, appropriate amount of TBA⁺ could accelerate membrane crystallization, meanwhile increase in TEA⁺ slowed down crystallization rate of MFI membrane. This work extends the alternative preparation approaches of ethanol perm-selective MFI membrane.     

b轴取向MFI分子筛膜的制备及应用研究进展

分子筛膜是一种新型的无机膜,具有孔道结构规整、化学和热稳定性好、机械强度高、抗污染性能好、易于改性等优点。b轴取向MFI分子筛膜因可以缩短传质路径、降低传质阻力、提高扩散效率,在膜分离和膜反应器领域有着广泛的应用前景,受到国内外学者的普遍关注。综述了b轴取向分子筛膜的制备方法及应用研究进展。详细介绍了原位水热合成法、二次生长法、微波辅助合成法、无凝胶法、固相转化法及纳米片法等。二次生长法可以控制分子筛膜的微观结构,且受载体表面性质的影响较小;微波辅助法可以缩短结晶时间,降低能耗,对工业化生产具有重要意义;无凝胶法具有制备工艺简单、环境友好等优点。在上述方法的基础上,将纳米片作为晶种可以降低膜厚。最后,展望了b轴取向MFI分子筛膜的发展前景,在制备b轴取向连续无缺陷MFI分子筛膜方面仍面临许多挑战,包括提高膜的机械强度和长期运行稳定性、实现粗糙或弯曲以及大尺寸载体表面取向膜层的制备等。     

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.     

含氟体系中MFI型分子筛膜的制备及其乙醇/水分离性能

以氟化铵为矿化剂、四丙基溴化铵为模板剂,在负载晶种的钇稳定氧化锆(YSZ)中空纤维支撑体表面合成了MFI型分子筛膜,并用于乙醇/水的分离;系统考察了氟硅比(n_NH4F/n_SiO2)、合成时间等条件对膜分离性能的影响,在n_NH4F/n_SiO2为0.8、合成时间为8 h下合成出高性能膜,其通量达8.2 kg·m^-2·h^-1、乙醇/水分离因子为47;同时研究了MFI型分子筛膜在乙醇/水体系中的分离稳定性,揭示出该方法所合成膜表面无Si-OH,从而避免了Si-OH与乙醇反应而带来膜分离性能的下降.     

On-stream modification of MFI zeolite membranes for enhancing hydrogen separation at high temperature

-Alumina-supported MFI zeolite membranes were modified by on-stream catalytic thermal cracking of methyldiethoxysilane (MDES) molecules inside the zeolitic channels during the separation of H₂/CO₂ gas mixture at 450 °C and atmospheric pressure. The MDES vapor was carried by the H₂/CO₂ feed gas and the effect of modification was monitored continuously through online analysis of the permeate stream. The modified membrane exhibited a significant increase in H₂ selectivity over CO₂ with a moderate decrease in H₂ permeance. At 450 °C, the modified MFI membrane obtained a H₂/CO₂ permselectivity of 17.5 with H₂ single gas permeance of 1.86 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ as compared to a permselectivity of 2.78 and permeance of 2.75 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ for the membrane before modification. The modified membrane also showed good performance and stability in separation of H₂/CO₂ gas mixture containing up to 28.4% water vapor at 450 °C and atmospheric pressure.     

Effect of substrate curvature on microstructure and gas permeability of hollow fiber MFI zeolite membranes

Literature data show that gas permeability of MFI zeolite membrane varies depending on the geometry of supports. The present work investigates the effects of the surface curvature of substrates on the microstructure and the gas permeation property of supported zeolite membranes. MFI zeolite membranes were grown on porous alumina hollow fibers with different diameters (surface curvature) by the secondary growth method. Single gas permeation and H₂/CO₂ binary gas separation from 25 to 300 were conducted to study the membrane quality. The zeolite membranes on supports of larger surface curvature have higher permeability and lower selectivity due to the presence of more inter‐crystalline gaps in the zeolite layer formed during the template removal step. The effects of the support surface curvature (and geometry) on zeolite membrane microstructure and gas permeation characteristics are semi‐quantitatively analyzed by a transport model considering both structural change and gas diffusion in micropores. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3419–3428, 2018     

TMCS修饰MFI分子筛膜的制备及乙醇/水分离稳定性的研究

采用三甲基氯硅烷（TMCS）作为修饰源对MFI分子筛膜进行表面改性,系统考察了TMCS浓度以及修饰时间对于MFI分子筛膜在分离乙醇/水混合物时的性能影响。SEM、XRD、²⁹Si NMR、FT-IR、接触角实验及分离实验结果表明,TMCS可以与硅羟基反应,嫁接分子筛膜表面,在消除膜表面硅缺陷的同时提高膜的疏水性及膜分离性能的稳定性。随着TMCS浓度以及反应时间的增加,修饰后MFI分子筛膜的通量及分离因子略有下降,但稳定性增强。在TMCS的浓度为0.4%（质量）,修饰时间为2 h时,所得到的膜具有最佳渗透汽化分离性能,并可在60℃下分离5%（质量）乙醇/水混合物时保持良好的稳定性。在连续90 h渗透汽化分离过程中,其渗透通量稳定在1.61 kg·m^-2·h^-1 左右,分离因子保持在20以上。     

Permeation properties of hydrogen and water vapor through porous silica membranes at high temperatures

Silica and cobalt‐doped silica membranes that showed a high permeance of 1.8 × 10^?7 mol m^?2 s^?1 Pa^?1 and a H₂/N₂ permeance ratio of ～730, with excellent hydrothermal stability under steam pressure of 300 kPa, were successfully prepared. The permeation mechanism of gas molecules, focusing particularly on hydrogen and water vapor, was investigated in the 300–500°C range and is discussed based on the activation energy of permeation and the selectivity of gaseous molecules. The activation energy of H₂ permeation correlated well with the permeance ratio of He/H₂ for porous silica membranes prepared by sol–gel processing, chemical vapor deposition (CVD), and vitreous glasses, indicating that similar amorphous silica network structures were formed. The permeance ratios of H₂/H₂O were found to range from 5 to 40, that is, hydrogen (kinetic diameter: 0.289 nm) was always more permeable than water (0.265 nm). © 2010 American Institute of Chemical Engineers AIChE J, 2011     

A novel carbonized polydopamine (C‐PDA) adsorbent with high CO2 adsorption capacity and water vapor resistance

Novel carbonized polydopamine adsorbents (C‐PDAs) with high surface area, high CO₂ adsorption capacity and superior moisture resistance performance were prepared by one‐step synthesis method using polydopamine as carbon precursor at different KOH/C ratios, and then characterized. CO₂ and water vapor adsorption performances of C‐PDAs were examined separately by static adsorption and fixed‐bed experiments. Results showed that BET area and pore volume of C‐PDA‐4 were up to 3342 m²/g and 2.01 cm³/g, respectively. Its CO₂ adsorption capacity reached up to 30.5 mmol/g at 25 bar, much higher than many other adsorbents including metal‐organic frameworks (MOFs). C‐PDAs prepared with high KOH/C ratios had low surface element concentrations of O and N resulting in low surface hydrophilic property. H₂O(g) isotherm of C‐PDA was much lower than those on Mg‐MOF‐74, Cu‐BTC, and MIL‐101(Cr). Fixed‐bed experiments showed that co‐presence of water vapor in feed stream with 30% RH had negligible impact on CO₂ working capacity of C‐PDA. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3730–3738, 2016     

酸性气体分离膜的研究现状及进展

当前,气体分离膜是一种环保绿色的分离技术,本文概括了目前用于去除CO2的商业膜材料(醋酸纤维素、聚酰亚胺和含氟聚合物),对不同膜的物理化学性质,气体渗透特性等进行了介绍。     

面向工业过程碳减排的分子筛膜技术研究进展

我国工业过程碳排放占比高达70%,实施节能增效、替代燃料、CO₂捕集等是实现工业过程碳减排的重要路径。高效膜分离技术已成为过程工业节能减排和环境治理的共性支撑技术。本文围绕碳减排目标,结合本文作者课题组在分子筛膜领域的相关工作,重点论述分子筛膜分离技术在有机溶剂脱水、清洁能源生产、CO₂分离和反应过程强化等领域的研究进展。基于本文作者课题组十余年的有机溶剂脱水产业化工作,提出降低膜装备投资的中空纤维分子筛膜技术路线、强化分子筛膜应用技术研究是实现大规模工业应用的关键。分子筛膜在工业气体分离领域仍属空白,加强高硅/全硅分子筛膜的制备及其在复杂组成气体的分离应用研究,对推动分子筛膜气体分离的实际应用至关重要。     

Interactions of Ta2O5 with water vapor at elevated temperatures

Tantalum pentoxide (Ta₂O₅) and its solid solution phases are candidate coatings for components to be used in combustion environments. Thus, it is important to understand the response of Ta₂O₅ to high‐temperature water vapor, a product of combustion. Thermogravimetric methods are used to examine the oxide in reactant streams of controlled water vapor contents at 1250°C‐1450°C. The observed weight loss indicates a reaction of the general form ½ Ta₂O₅(s) + x H₂O(g)=TaO_y(OH)_x(g). Methodical variation in the water vapor pressure suggests the products are a mix of TaO(OH)₃(g) and Ta(OH)₅(g). Evidence of TaO(OH)₃(g) was observed with a sampling mass spectrometer. The measured hydroxide and oxyhyroxide vapor fluxes from Ta₂O₅ are compared with calculated vapor fluxes from SiO₂ and Al₂O₃. Ta₂O₅ exhibits fluxes similar to those from SiO₂ due to gaseous metal hydroxide formation.     

Gas permeation and separation properties of polyimide/ZSM‐5 zeolite composite membranes containing liquid sulfolane

The preparation, characterization, and gas permeation properties of novel composite membranes containing polyimide (PI), liquid sulfolane (SF), and zeolite (ZSM‐5) were investigated to address the interface defects between the PI and the zeolite. The free‐standing composite membranes were prepared by the solvent casting method. The gas permeability of the PI+ZSM‐5 membrane was higher than that of PI, whereas its gas selectivity was significantly reduced, suggesting that these results are attributed to the interface defects. The CO₂ selectivity of PI+ZSM‐5+SF was higher than those of the PI+ZSM‐5 membranes because of the introduction of liquid SF into the interface defects. Furthermore, liquid SF enhanced the CO₂/H₂ selectivity near the recent upper bound. Therefore, the use of liquid SF could be an effective approach to preventing interface defects and increasing the CO₂ selectivity, particularly for CO₂/H₂. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

The adsorption of water vapor on super absorbent product at low temperatures and low mass

The adsorption isotherms of water vapor on super absorbent product have the same form of type III isotherm at ambient temperature with the hysteresis phenomena. For temperatures lower than ambient, the isotherms become deformed because of the chains effect. The polymer is characterized by a multilayer adsorption, which occurs before a full‐course is complete. During adsorption reactions, the polymer undergoes rearrangement polymeric network, which results from a cooperative diffusion of the water molecules and from a chain spacing followed by an expansion of the polymeric network. Three types of water molecules adsorbed on polymer were identified: strongly dependent water, adsorbed water, and the water only trapped between the macromolecular chains. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1450–1456, 2006     

沸石的改性处理及吸附性能研究

介绍了沸石改性的方法,讨论了影响沸石吸附性能的因素.实验表明,在废水温度为25℃,pH为6,Cd2 的初始质量浓度为50 mg/L,吸附剂的用量为20g/L,吸附时间为120 min的条件下,改性沸石对镉离子的去除率达到99.12%.     

Langmuir-Blodgett法制备高H2选择性取向ZSM-5分子筛分离膜

利用Langmuir-Blodgett（LB）技术首先在多孔氧化铝载体表面有序组装了单层b-轴取向Silicalite-1分子筛晶种层,再采用二次生长法,以溴化六丙双铵（dimer-TPABr）为结构导向剂配制二次生长合成液,在175℃反应48h制备了高度b-轴取向ZSM-5（Si/Al=120）分子筛膜。扫描电镜（SEM）表征显示ZSM-5分子筛膜致密连续且厚度约为2.6μm。X射线衍射（XRD）表征结果显示,膜的b-轴晶体优先取向值高达0.858。气体分离性能测试结果显示,制备的ZSM-5分子筛膜在高温焙烧脱除有机模板剂过程中会产生缺陷。经硅烷试剂四甲氧基硅烷（TMOS）对缺陷修复后,ZSM-5分子筛膜表现出高的H₂选择性分离性能,H₂/CO₂分离因子高达68 （T=25℃,p=0.1MPa）,对应的H₂渗透速率为1.36×10^-8mol/(m²·s·Pa)。     

Catalytic activity of Co,Mo and CoMo supported on NaY zeolite: hydrodesulfurization of gas oil at high pressure

Three series of Co/NaY, Mo/NaY and CoMo/NaY zeolite catalysts with variable metal content, prepared by a conventional impregnation method, were characterized by XRD, IR spectroscopy (oxide state) and acidity measurements (sulfide state), and tested in hydrodesulfurization (HDS) of gas oil at high pressure in the temperature range 275–350°C. The combined results of surface area, XRD and IR showed that in the catalysts with high metal loading a small loss in crystallinity and a partial blockage of the zeolite supercages were produced by Mo oxide species. The number of acid sites, which was lower for the Co/NaY than for the Mo/NaY catalysts, increased with increasing Co or Mo loading, but the strength of the acid sites was stronger for the Co/NaY series. HDS specific activities of the Co/NaY and Mo/NaY monometallic catalysts reached a maximum at very low loadings of Co ( 0.10 at. nm^–2) or Mo ( 0.16 at. nm^–2) by the double action of the metal sulfide species and the strong acid sites generated on the zeolite by the Co or Mo incorporation. In the binary CoMo/NaY catalysts, the synergy between Co and Mo species was significant for high Mo contents only.     

Influence of novel surface modifying macromolecules and coagulation media on the gas permeation properties of different polymeric gas separation membranes

Integrally skinned asymmetric membranes for the separation of O₂ and N₂ were fabricated by the phase inversion technique from polysulfone, polyetherimide, and polyimide. Two types of surface modifying macromolecules (SMMs) including hydrophilic SMM (LSMM) and charged SMM (cSMM) were synthesized and blended with the casting solution to modify the membrane surface. The cast film was then immersed in the first coagulant alcohol (methanol, ethanol, or isopropanol) for a predetermined period, before being immersed in the second coagulant (water). The SMMs used in these experiments were laboratory synthesized by the two‐step process of polyurethane prepolymer synthesis and end capping, before being characterized by differential scanning calorimetry. Their molecular structure was determined from the molecular weight obtained by gel permeation chromatography. The membranes were characterized by contact angle measurement and O₂ and N₂ gas permeation performance. Attempts were made to interpret the gas permeation data by delayed demixing affected by solubility parameters of polymer, solvent, and nonsolvent. Furthermore, the permeation performance of cSMM membranes was interpreted by the solvation of the charged sulfonate groups present in cSMM. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Separation of CO2 and CH4 on CaX zeolite for use in Landfill gas separation

In this study, adsorption separation of main components of landfill gas, methane (CH₄) and carbon dioxide (CO₂) was carried out. Henry's law constants, limiting heat of adsorption values, pure and binary isotherms for CO₂ and CH₄ were determined for CaX zeolite adsorbent. Pure isotherm data were compared to those for NaX zeolite from previous studies. The CO₂ adsorption capacity of CaX was greater than that of NaX; however, NaX's separation factor was higher. The heat of adsorption for CO₂ for CaX was higher than those for NaX. © 2013 Canadian Society for Chemical Engineering     

The influence of metal oxides on the separation properties of hybrid alginate membranes

ABSTRACT

Alginate membranes filled with different metal oxide particles were prepared and the influence of the presence of different amounts of Fe₃O₄, ZnO, and Ag₂O particles on ethanol and water permeation was discussed. Ethanol and water vapour permeation rates were determined using the measuring cell method, and the mass transport coefficients were evaluated. It was found that the highest transport parameters were obtained for membranes with the highest metal oxide content. Furthermore, the highest flux, equal 8.49 kg·m^?2·h^?1, was obtained for the alginate membrane filled with 15 wt% of silver oxide particles, while the greatest selectivity coefficients were noted for membranes containing magnetite. In this case, for the alginate membrane with 15 wt% of magnetite content, the selectivity coefficient reached the best value of 108.15.