Krypton‐xenon separation properties of SAPO‐34 zeolite materials and membranes

Separation of the radioisotope ⁸⁵Kr from ¹³⁶Xe is an important target during used nuclear fuel recycling. We report a detailed study on the Kr and Xe adsorption, diffusion, and membrane permeation properties of the silicoaluminophosphate zeolite SAPO‐34. Adsorption and diffusion measurements on SAPO‐34 crystals indicate their potential for use in Kr‐Xe separation membranes, but also highlight competing effects of adsorption and diffusion selectivity. SAPO‐34 membranes are synthesized on α?alumina disk and tubular substrates via steam assisted conversion seeding and hydrothermal growth, and are characterized in detail. Membrane transport measurements reveal that SAPO‐34 membranes can separate Kr from Xe by molecular sieving, with Kr permeabilities around 50 Barrer and mixture selectivity of 25–30 for Kr at ambient or slight sub‐ambient conditions. The membrane transport characteristics are modeled by the Maxwell‐Stefan equations, whose predictions are in very good agreement with experiment and confirm the minimal competing effects of adsorption and diffusion. © 2016 American Institute of Chemical Engineers AIChE J, 63: 761–769, 2017     

Effects of Difference in Ionic Radii on Chemical Ordering in Mixed‐Cation Silicate Glasses: Insights from Solid‐State 17O and 7Li NMR of Li–Ba Silicate Glasses

Understanding of the extent of cation disorder and its effect on the properties in glasses and melts is among the fundamental puzzles in glass sciences, materials sciences, physical chemistry, and geochemistry. Particularly, the nature of chemical ordering in mixed‐cation silicate glasses is not fully understood. The Li–Ba silicate glass with significant difference in the ionic radii of network‐modifying cations (~0.59 Å) is an ideal system for revealing unknown details of the effect of network modifiers on the extent of mixing and their contribution to the cation mobility. These glasses also find potential application as energy and battery materials. Here, we report the detailed atomic environments and the extent of cation mixing in Li–Ba silicate glasses with varying X_BaO [BaO/(Li₂O + BaO)] using high‐resolution solid‐state nuclear magnetic resonance (NMR) spectroscopy. The first ¹⁷O MAS and 3QMAS NMR spectra for Li–Ba silicate glasses reveal the well‐resolved peaks due to bridging oxygen (Si–O–Si) and those of the nonbridging oxygens including Li–O–Si and mixed {Li, Ba}–O–Si. The fraction of Li–O–Si decreases with an increase in X_BaO and is less than that predicted by a random Li–Ba distribution. The result demonstrates a nonrandom distribution of Li⁺ and Ba⁺ around NBOs characterized by a prevalence of the dissimilar Li–Ba pair. Considering the previously reported experimental results on chemical ordering in other mixed‐cation silicate glasses, the current results reveal a hierarchy in the degree of chemical order that increases with an increase in difference in ionic radius of the cation in the glasses [e.g., K–Mg (~0.66 Å) ≈Ba–Mg (~0.63 Å) ≈Li–Ba (~0.59 Å) > Na–Ba (~0.33 Å) > Na–Ca (~0.02 Å)]. The ⁷Li MAS NMR spectra of the Li–Ba silicate glasses show that the peak maximum increases with increasing X_BaO, suggesting that the average Li coordination number and thus Li–O distance decrease slightly with increasing X_BaO, potentially leading to an increased activation energy barrier for Li diffusion. Current experimental results confirm that the degree of chemical ordering due to a large difference in ionic radii controls the transport properties of the mixed‐cation silicate glasses.     

Fabrication of Homogenous Polymer‐Zeolite Nanocomposites as Mixed‐Matrix Membranes for Gas Separation

Interfacial void‐free mixed‐matrix membranes (MMMs) of polyimide (PI)/zeolite were developed using 13X and Linde type A nano‐zeolites and tested for gas separation purposes. Fabrication of a void‐free polymer‐zeolite interface was verified by the decreasing permeability developed by the MMMs for the examined gases, in comparison to the pure PI membrane. The molecular sieving effect introduced by zeolite 13X improved the CO₂/N₂ and CO₂/CH₄ selectivity of the MMMs. Separation tests indicated that the manufactured nanocomposite membrane with 30 % loading of 13X had the highest permselectivity for the gas pairs CO₂/CH₄ and CO₂/N₂ at the three examined feed pressures of 4, 8 and 12 atm.     

制纯氧分子筛

变压吸附(Press Swing Adsorption,PSA)制纯氧具有很好的工业应用前景,但氩气和氧气在制氧分子筛上的吸附选择性接近于1,因而不能分离,不能通过一步PSA制备出纯度高于95%的氧气。氩气和氧气在银离子交换沸石分子筛上的吸附选择性大于1,有可能成为制纯氧分子筛,但目前其选择性还不能满足工业分离的要求。本文介绍了银离子交换沸石分子筛在制纯氧领域的研究进展,并探讨了制纯氧分子筛的研究展望。     

Various Techniques for Preparation of Thin‐Film Composite Mixed‐Matrix Membranes for CO2 Separation

The application of thin‐film composite mixed‐matrix membranes (TFC‐MMMs) for gas separation is widely considered as an efficient separation technology. The principal methods for the preparation of TFC‐MMMs are dip‐coating, phase inversion, and interfacial polymerization comprising different types of support layers. These methods influence the CO₂ permeation over the selective and support layers. A comprehensive review is provided for capturing new details of progress achieved in developing TFC‐MMMs with detailed performance of gas separation in the previous few years. Various preparation techniques of TFC‐MMMs and their effect on the gas separation performance of the prepared membranes are described.     

基于双回流变压吸附工艺的空气分离模拟及分析

双回流变压吸附是一种在吸附塔中间位置进料,塔顶和塔底分别采用轻、重组分回流的变压吸附过程,能够同时生产两种高纯度、高回收率的产品气。以实验室自主合成的LiLSX分子筛为吸附剂,利用Aspen Adsorption模拟软件,对进料组成为78%N₂/21%O₂/1%Ar的实际空气进行了两塔双回流变压吸附的模拟研究。模拟结果表明：当原料气为78%N₂/21%O₂/1%Ar,吸附压力为2 bar(1 bar=10⁵ Pa),解吸压力为0.3 bar,进料量为0.4 m³/h,轻组分回流流量为0.095 L/min,重组分回流流量为5.22 L/min时,能够得到体积分数为95.67%的O₂和体积分数为98.25%的N₂,回收率分别为94.60%和99.91%。并且进一步探究了进料位置、吸附时间、轻组分回流流量、重组分产品气流量等因素对O₂和N₂两种产品气纯度和回收率的影响。     

Fabrication of mixed‐matrix membranes with MOF‐derived porous carbon for CO2 separation

Mixed‐matrix membranes (MMMs) have shown great advantages but still face some challenges, such as the trade‐off between permeability and selectivity, stability, and the lack of efficient ways to enhance them simultaneously. Here, the fabrication of MMMs with metal‐organic frameworks derived porous carbons (MOF‐PCs) as fillers which exhibit selective‐facilitating CO₂ transport passage originating from interactions between fillers and CO₂ is showed. With the aid of the developed multicalcination method, MOF‐PCs with variable N‐contents were prepared and incorporated into PPO‐PEG matrix for the first time to prepare MMMs, which show excellent separation performance for CO₂/CH₄ mixture with a tunable separation performance by combining different N‐contents and surface areas of MOF‐PCs. Moreover, the developed MMMs have hydrothermal and chemical stability. This work not only presents a series of MMMs with both good separation properties and stability, it also provides useful information for guiding the fabrication of high performance MMMs for practical application. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3400–3409, 2018     

A new cation‐modified Al‐polyacrylamide flocculant for solid–liquid separation in waste drilling fluid

A new cation‐modified Al‐polyacrylamide (CAPAM) flocculant was prepared by the in situ polymerization of acrylamide (AM) and (2‐methacryloyloxyethyl) trimethyl ammonium chloride (DMC) with Al(OH)₃ sol. The optimum preparation conditions were obtained by a one‐factor experimental design: as the amount of AlCl₃ was fixed at 0.025 mol, the polymerization time, polymerization temperature, n(AM) : n(AlCl₃), n(DMC) : n(AlCl₃), and n(K₂S₂O₈) : n(AM) were 4 h, 70°C, 8, 0.9, and 1.82 × 10^?3, respectively. The CAPAM was characterized by thermogravimetric analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, and transmission electron microscopy. The solid–liquid separation performance of the CAPAM was evaluated in terms of water content. The CAPAM showed better flocculation performance than cationic polyacrylamide and polyaluminum sulfate at a fixed concentration of 0.3% in waste drilling fluid and tended to perform well in alkaline solution. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41641.     

Dynamic modeling and collocation‐based model reduction of cryogenic air separation units

High purity distillation columns and multi‐stream heat exchangers (MSHXs) are critical units in cryogenic air separation plants. This article focuses on modeling approaches for the primary section of a super‐staged argon plant. A full‐order stage‐wise model for distillation columns in air separation units (ASUs) that considers key process phenomena is presented, followed by a reduced‐order model using a collocation approach. The extent of model reduction that can be achieved without losing significant prediction accuracy is demonstrated. A novel moving boundary model is proposed to handle MSHXs with phase change. Simulation results demonstrate the capability of the proposed model for tracking the phase change occurrence along the length of the heat exchanger. Dynamic simulation studies of the integrated plant show that the thermal integration between the feed and product streams captured in the primary heat exchanger is critical to accurately capture the behavior of ASUs. © 2016 American Institute of Chemical Engineers AIChE J, 62: 1602–1615, 2016     

Actual air separation through poly(aniline‐co‐toluidine)/ethylcellulose blend thin‐film composite membranes

Several multilayer thin‐film composite membranes were fabricated of ethylcellulose (EC) and poly(aniline‐co‐ortho‐toluidine) or poly(ortho‐toluidine) blend as selective thin films and three ultrafiltration membranes with a 10‐ to 45‐nm pore size and 100‐ to 200‐μm thickness as porous supports. The relationships between the actual air‐separation performance through the composite membranes and layer number, composition, casting solution concentration of the thin selective film are discussed. The oxygen‐enriched air (OEA) flux through the composite membranes increases steadily with increasing operational temperature and pressure. The oxygen concentration enriched by the composite membranes appears to decrease with operating temperature, but increases with operating pressure. The actual air‐separation property through the composite membranes seems to remain nearly constant for at least 320 days. The respective highest OEA flux, oxygen flux, and oxygen concentration, respectively, were found to be 4.78 × 10⁻⁵ cm³ (STP)/s · cm², 2.2 × 10⁻⁵ cm³ (STP)/s · cm², and 46% across EC/poly(o‐toluidine) (80/20) blend monolayer thin‐film composite membranes in a single step at 20°C and 650 kPa operating pressure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 458–463, 2000     

Production of argon free oxygen by adsorptive air separation on Ag‐ETS‐10

The purification of different components of air, such as oxygen, nitrogen, and argon, is an important industrial process. Pressure swing adsorption (PSA) is surpassing the traditional cryogenic distillation for many air separation applications, because of its lower energy consumption. Unfortunately, the oxygen product purity in an industrial PSA process is typically limited to 95% due to the presence of argon which always shows the same adsorption equilibrium properties as oxygen on most molecular sieves. Recent work investigating the adsorption of nitrogen, oxygen and argon on the surface of silver‐exchanged Engelhard Titanosilicate‐10 (ETS‐10), indicates that this molecular sieve is promising as an adsorbent capable of producing high‐purity oxygen. High‐purity oxygen (99.7+%) was generated using a bed of Ag‐ETS‐10 granules to separate air (78% N₂, 21% O₂, 1% Ar) at 25°C and 100 kPa, with an O₂ recovery rate greater than 30%. © 2012 American Institute of Chemical Engineers AIChE J, 59: 982–987, 2013     

Design of a two‐step pulsed pressure‐swing adsorption‐based oxygen concentrator

A two‐step pulsed pressure‐swing adsorption (PPSA) process has been modeled to assess the extent to which an oxygen concentrator might be miniaturized for medical applications. The process consists of a single bed of packed adsorbent particles that is alternately pressurized and depressurized at the feed end. An enriched oxygen product is withdrawn at ambient pressure from the product end when the bed is pressurized at the feed end. The product end remains closed during depressurization. The model development addresses the manner in which axial dispersion enters into the describing equations and the formulation of proper boundary conditions, both of which have not been handled rigorously in some prior modeling studies. The describing equations are solved using COMSOL® Multiphysics software. The effect on the performance of the adsorption time, desorption time, bed length, particle diameter, and imposed pressure drop across the bed have been investigated. An interesting novel result is that for a chosen particle size, bed length, and applied pressure drop, there is an optimum combination of adsorption and desorption times that maximizes the product purity. The results suggest that there are operating windows for both 5A and partially Ag‐exchanged Li‐substituted 13X zeolite adsorbents wherein the product oxygen purity is greater than 90%. At a given product flow rate within this operating window, the extent of miniaturization is limited by the (maximum) cycling frequency that is practically achievable. Sizing of an oxygen concentrator for personal medical applications is also discussed. A principal conclusion is that a compact oxygen concentrator capable of producing a highly oxygen‐enriched product is possible using commercially available adsorbents and implementable operating conditions. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Testing for Cointegration with Temporally Aggregated and Mixed‐Frequency Time Series

We examine the effects of mixed sampling frequencies and temporal aggregation on the size of commonly used tests for cointegration, and we find that these effects may be severe. Matching sampling schemes of all series generally reduces size distortion, and the nominal size is obtained asymptotically only when all series are skip sampled in the same way – for example, end‐of‐period sampling. We propose and analyse mixed‐frequency versions of the cointegration tests in order to control the size when some high‐frequency data are available. Otherwise, when no high‐frequency data are available, we discuss controlling size using bootstrapped critical values. We test stock prices and dividends for cointegration as an empirical demonstration.     

Design and fabrication of non‐noble metal catalyst‐based air‐cathodes for metal‐air battery

In this paper, cost‐effective non‐noble metal catalyst‐based air‐cathodes are designed, developed, and fabricated for a metal‐air battery, particularly in a non‐toxic neutral solution environment (sodium chloride). The air‐cathode and its fabrication method comprise two gas diffusion layers (GDLs) bonded on to each side of the current collector (nickel mesh) by a rolling method, and a catalyst layer bonded on one GDL by a spraying method. The GDL paste consists of carbon powder and hydrophobic chemicals, and the catalyst layer contains non‐noble metal catalyst, carbon powder, and hydrophilic chemicals. Several characterization techniques such as DTA/TG thermal analysis, electrochemical impedance spectroscopy, linear sweep voltammetry, and their associated theories are used to understand the properties and performance of the developed air‐cathodes. The advantages of the current method of forming the air‐cathode can decrease the internal electronic resistance and gas flow restriction of the system, and therefore increase air permeability as well as water transportation to the reaction sites. By using such an integrated structure of an air diffusion cathode, the cost‐effectiveness in terms of materials and manufacturing compared to the commercial air‐cathode, and the overall fabrication procedure is achieved, and the method can be easily transferred into a continuous industrial manufacturing process.     

Hydrogen Purification Using Polybenzimidazole Mixed‐Matrix Membranes with Stabilized Palladium Nanoparticles

Palladium (Pd) nanoparticles stabilized by polyethylene glycol were incorporated into polybenzimidazole (PBI) to form a mixed‐matrix membrane (MMM) for hydrogen (H₂) purification. Energy dispersive X‐ray results confirmed the existence of Pd nanoparticles in the PBI matrix. These dense membranes showed a homogeneously dispersed morphology in scanning electron microscope images that proves the excellent interphase affinity between PBI matrix and Pd nanoparticles. Unlike Pd membranes, the PBI(Pd) MMMs interact with H₂ starting from a low temperature as indicated in temperature‐programmed reduction analysis. At elevated operating temperature, the PBI(Pd) MMM exhibited a higher selectivity compared to the neat PBI membrane. The PBI(Pd) MMM also surpassed the Robeson plot which represents the permeability/selectivity trade‐off.     

高镁锂比盐湖镁锂分离与锂提取技术研究进展

随着锂离子电池在电动汽车、便携式电子设备、电动工具及电网储能中的用量持续增加,锂资源需求量快速增长。我国盐湖集中分布在青藏高原地区,青海盐湖普遍具有高镁锂比、低锂含量的特征。高镁锂比盐湖提锂是世界性难题。本文综述了高镁锂比盐湖卤水镁锂分离与锂提取技术的最新研究进展,包括萃取法、吸附法、反应/分离耦合技术、膜法和电化学法。从各技术原理、特点、性能等方面分析了各方法特征和适用性。在现有技术中,吸附法更适合高镁锂比卤水;萃取法可用于锂浓度较低的卤水;新发展的反应/分离耦合技术能实现高效提锂与镁锂资源综合利用;以纳滤、电渗析、双极膜为代表的膜法具有能耗较低和模块化的优点;电化学法具有装置简单的优势,但仍需进一步优化系统。我国盐湖锂资源提取需提高总收率,提升提锂后资源综合利用程度,发展锂产品高值化、多元化利用途径,加强盐湖提锂的工程化技术研究,突破并掌握核心技术与装备,实现盐湖资源高效、综合、可持续利用的目标。     

Deactivation kinetics of a HZSM‐5 zeolite catalyst treated with alkali for the transformation of bio‐ethanol into hydrocarbons

The kinetics of deactivation by coke of a HZSM‐5 zeolite catalyst in the transformation of bioethanol into hydrocarbons has been studied. To attenuate deactivation, the following treatments have been carried out: (i) the zeolite has been subjected to a treatment with alkali to reduce the acid strength of the sites and (ii) it has subsequently been agglomerated into a macro and meso‐porous matrix of bentonite and alumina. The experimental study has been conducted in a fixed bed reactor under the following conditions: temperature, between 300 and 400°C; pressure, 1 atm; space‐time, up to 1.53 (g of catalyst) h (g of ethanol)^?1; particle size of the catalyst, between 0.3 and 0.6 mm; feed flowrate, 0.16 cm³ min^?1 of ethanol+water and 30 cm³ (NC) min^?1 of N₂; water content in the feed, up to 75 wt %; time on stream, up to 31 h. The expression for deactivation kinetics is dependent on the concentration of hydrocarbons and water in the reaction medium (which attenuates the deactivation) and, together with the kinetics at zero time on stream, allows the calculation of the evolution with time on stream of the yields and distribution of products (ethylene, propylene and butenes, C₁‐C₃ paraffins, and C₄‐C₁₂). By increasing the temperature in the 300–400°C range the role of ethylene on coke deposition is more significant than that of the other hydrocarbons (propylene, butenes and C₄‐C₁₂), which contribute to a greater extent to the formation of coke at 300°C. © 2011 American Institute of Chemical Engineers AIChE J, 58: 526–537, 2012.     

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.