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Data-driven future for nanofiltration: Escaping linearity 数据驱动的纳滤未来:逃避线性
Q1 ENGINEERING, CHEMICAL Pub Date : 2023-05-01 DOI: 10.1016/j.memlet.2023.100040
Gergo Ignacz, Aron K. Beke, Gyorgy Szekely

Compared with traditional membrane separation methods such as distillation and chromatography, nanofiltration (NF) affords decreased waste generation and energy consumption. Despite the multiple advantages of NF and materials available for NF membranes, the industrial applicability of this process requires improvement. To address these challenges, we propose four important pillars for the future of membrane materials and process development. These four pillars are digitalization, structure–property analysis, miniaturization, and automation. We fill gaps in the development of NF membranes and processes by fostering the most promising contemporary technologies, e.g., the integration of process analytical technologies and the development of a parallel artificial nanofiltration permeability assay (PANPA) or large online databases. Moreover, we propose the extensive use of density functional theory-aided structure–property relationship methods to understand solute transport process at a molecular level. Realizing an inverse design would allow researchers and industrial scientists to develop custom membranes for specific applications using optimized properties.

与传统的膜分离方法(如蒸馏和色谱)相比,纳滤(NF)减少了废物的产生和能耗。尽管NF和可用于NF膜的材料具有多种优点,但该工艺的工业适用性需要改进。为了应对这些挑战,我们为膜材料和工艺发展的未来提出了四个重要支柱。这四大支柱是数字化、结构-性能分析、小型化和自动化。我们通过培养最有前途的当代技术来填补纳滤膜和工艺开发方面的空白,例如工艺分析技术的集成和并行人工纳滤渗透性测定(PANPA)或大型在线数据库的开发。此外,我们建议广泛使用密度泛函理论辅助的结构-性质关系方法来理解分子水平上的溶质传输过程。实现逆向设计将使研究人员和工业科学家能够利用优化的性能为特定应用开发定制膜。
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引用次数: 3
On the balance between albumin loss and removal of middle molecules in dialyzers 透析器中白蛋白损失与中间分子去除的平衡
Q1 ENGINEERING, CHEMICAL Pub Date : 2023-05-01 DOI: 10.1016/j.memlet.2023.100044
Franziska Hagemann , John Linkhorst , Hannah Roth , Matthias Wessling

Tuning the pore size distribution of hemodialysis membranes is essential for the membrane’s selectivity and significantly affects the quality of the dialysis treatment. Tailoring the membrane’s molecular weight cut-off appropriately balances the removal of middle-molecular-weight uremic toxins while avoiding albumin loss. This undesirable albumin loss is a potential side effect and concern for clinical use when aiming at increased removal of middle molecular weight molecules (middle molecules). It is hypothesized that control of the position of a narrow pore size distribution allows middle molecule removal while simultaneously counteracting the unwanted albumin loss. This study presents a comprehensive ex-vivo methodology and novel data on the balance of the clearance of middle molecules and albumin loss at different blood and dialysate flow rates using novel dialyzers. The outcomes hold significance for dialysis therapy, while the insights acquired have broader implications for the selectivity of ultrafiltration membranes.

The Theranova dialyzer shows the largest clearance for small-middle molecules. Phylther stands out with higher removal of the middle molecule YKL-40 than the other dialyzers but exhibits a significant albumin loss. Theranova demonstrates the best compromise between low albumin loss and good clearances of middle molecules.

调节血液透析膜的孔径分布对膜的选择性至关重要,并显著影响透析治疗的质量。定制膜的分子量截止值可以适当平衡中等分子量尿毒症毒素的去除,同时避免白蛋白损失。当旨在增加中等分子量分子(中间分子)的去除时,这种不希望的白蛋白损失是临床使用的潜在副作用和关注点。假设控制窄孔径分布的位置允许去除中间分子,同时抵消不需要的白蛋白损失。这项研究提供了一种全面的离体方法和新的数据,用于使用新型透析器在不同血液和透析液流速下平衡中间分子的清除和白蛋白损失。这些结果对透析治疗具有重要意义,而获得的见解对超滤膜的选择性具有更广泛的意义。Theranova透析器显示出对中小分子的最大清除率。Phylther比其他透析器对中间分子YKL-40的去除率更高,但表现出显著的白蛋白损失。Theranova证明了低白蛋白损失和中间分子良好清除之间的最佳折衷。
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引用次数: 1
Catalytic effect of trifluoroacetic acid on the CO2 transport properties of organic-inorganic hybrid silica membranes 三氟乙酸对有机-无机杂化二氧化硅膜CO2输运性能的催化作用
Q1 ENGINEERING, CHEMICAL Pub Date : 2023-05-01 DOI: 10.1016/j.memlet.2023.100047
Ikram Rana, Hiroki Nagasawa, Toshinori Tsuru, Masakoto Kanezashi

Developing silica membranes that are highly selective for CO2 has always been a challenge due to the small sizes of the pores and less amount of CO2 philic sites in a typical silica network structure. Herein, we describe the fabrication of silica (tetraethoxysilane) membranes functionalized with 3-aminopropyltriethoxysilyl (APTES) and trifluoroacetic acid (TFA). An interaction generated among primary (NH2) amines and TFA was identified, which was then also revealed by the reversible nature of CO2 adsorption/desorption — an opposite trend from observations when using another catalyst (HCl). The resultant TEOS-APTES (TFA) membranes demonstrated CO2 permeance of 3.8 × 10−7 mol m  2 1 Pa−1 and CO2/N2 selectivity of 35 at 50 ⁰C via the effect of surface diffusion. This is attributed to the increased microporosity and structural variations affected by TFA, which enhanced molecular sieving and controls the CO2-philic sites (-NHCOCF3) via interaction with amines. This novel approach would be effective for the energy-efficient fabrication of highly CO2-permeable membranes.

开发对CO2具有高度选择性的二氧化硅膜一直是一个挑战,因为在典型的二氧化硅网络结构中,孔的尺寸较小,亲CO2位点的数量较少。在此,我们描述了用3-氨基丙基三乙氧基硅烷(APTES)和三氟乙酸(TFA)功能化的二氧化硅(四乙氧基硅烷)膜的制备。发现了伯(NH2)胺和TFA之间产生的相互作用,随后CO2吸附/解吸的可逆性质也揭示了这一点——这与使用另一种催化剂(HCl)时的观察结果相反。所得的TEOS-APTES(TFA)膜在50℃时表现出3.8×10−7 mol m−2 s−1 Pa−1的CO2渗透性和35的CO2/N2选择性⁰C通过表面扩散的作用。这归因于TFA影响的微孔性增加和结构变化,TFA通过与胺的相互作用增强了分子筛分并控制了亲CO2位点(-NHCOCF3)。这种新方法对于高效制造高CO2渗透膜是有效的。
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引用次数: 0
Dual-phase ionic-conducting membranes: Pressure dependence of gas permeation flux 双相离子导电膜:气体渗透通量的压力依赖性
Q1 ENGINEERING, CHEMICAL Pub Date : 2023-05-01 DOI: 10.1016/j.memlet.2023.100041
Jerry Y.S. Lin, Oscar Ovalle-Encinia

Pressure dependence of gas permeation flux for dual-phase ionic-conducting membranes is critical to the design and operation of separation or reaction processes using these membranes. However, literature on dual-phase membranes has mainly focused on temperature, rather than pressure dependence of gas permeation flux. This paper presents a theoretical approach for the development of the pressure dependence of gas permeation flux for dual-phase membranes, demonstrated with CO2 permeation for samarium-doped-ceria (SDC)/molten-carbonate (MC) dual-phase membranes. The paper presents a model showing that gas permeation through dual-phase ionic-conducting membranes is controlled not only by the intrinsic ion (or electronic) conductivity of the materials for each phase, but also by the geometric factor defined as the ratio of the volume to tortuosity of each phase. These geometric factors for both phases are determined by the topological structure of each phase. Dual-phase membranes of the same materials can have very different pressure-dependent flux equations depending on the topological structure dictated by synthesis method and conditions. CO2 permeation through SDC-MC membranes made of SDC with low porosity is controlled by carbonate conduction in the molten carbonate phase, leading to logarithmic CO2 pressure-dependent flux equation. CO2 permeation through SDC-MC membrane of SDC with intermediate porosity is controlled by oxygen ionic conduction in the SDC phase, and the CO2 permeation flux shows power-law dependence on CO2 pressures. The validity of the model is confirmed by comparison of the modeling results with experimental CO2 permeation data for SDC-MC membranes. This work provides a direction for developing pressure-dependent gas permeation flux equations for various dual-phase ionic-conducting membranes.

双相离子导电膜的气体渗透通量的压力依赖性对于使用这些膜的分离或反应过程的设计和操作至关重要。然而,关于双相膜的文献主要关注气体渗透通量的温度依赖性,而不是压力依赖性。本文提出了一种发展双相膜气体渗透通量压力依赖性的理论方法,并以掺钐二氧化铈(SDC)/熔融碳酸盐(MC)双相膜的CO2渗透为例进行了验证。本文提出了一个模型,表明气体通过双相离子导电膜的渗透不仅受各相材料的固有离子(或电子)电导率的控制,还受定义为各相体积与曲折度之比的几何因子的控制。两个相的这些几何因子由每个相的拓扑结构决定。根据合成方法和条件所规定的拓扑结构,相同材料的双相膜可能具有非常不同的压力相关通量方程。CO2通过由低孔隙率SDC制成的SDC-MC膜的渗透由熔融碳酸盐相中的碳酸盐传导控制,从而产生对数CO2压力相关通量方程。具有中等孔隙率的SDC通过SDC-MC膜的CO2渗透受SDC相中氧离子传导的控制,并且CO2渗透通量显示出对CO2压力的幂律依赖性。通过将建模结果与SDC-MC膜的实验CO2渗透数据进行比较,证实了该模型的有效性。这项工作为开发各种双相离子导电膜的压力相关气体渗透通量方程提供了方向。
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引用次数: 0
Can machine learning methods guide gas separation membranes fabrication? 机器学习方法能否指导气体分离膜的制作?
Q1 ENGINEERING, CHEMICAL Pub Date : 2022-11-01 DOI: 10.1016/j.memlet.2022.100033
Arash Tayyebi , Ali S. Alshami , Xue Yu , Edward Kolodka

Transforming a vast array of candidate materials into membranes with suitable morphologies and improved molecular separation performance is an arduous and costly endeavor for membrane scientists. With the advancement made in artificial intelligence and machine-learning in recent years, it is timely to ask: can machine learning methods guide gas separation membranes Fabrication? The answer is “YES”, and this article explains the justifications for this answer by systematically reviewing and analyzing the up-to-date research efforts in the field. This work aimed to explore the potential of ML algorithms as an effective and cost-saving tool in guiding the experimental process of developing the next generation polymeric membranes, and in addressing the critical needs in the field. Findings demonstrate that training Heteropolymers instead of Homopolymers, synthesizing novel polymers by an inverse design approach, and using reliable datasets that are created under the same conditions, are the most crucial factors to achieve the design intent. A path from A to Z for anyone who intends to use ML algorithms in the membranes’ synthesis process is offered. The article concludes with a brief discussion on future development prospects and open issues that are yet to be addressed for ML‐driven polymeric‐based membranes design and optimization.

将大量候选材料转化为具有合适形态和改进分子分离性能的膜对膜科学家来说是一项艰巨而昂贵的努力。随着近年来人工智能和机器学习的进步,机器学习方法能否指导气体分离膜的制造是一个及时的问题。答案是肯定的,本文通过系统地回顾和分析该领域最新的研究成果来解释这一答案的理由。这项工作旨在探索机器学习算法的潜力,作为一种有效和节省成本的工具,指导开发下一代聚合物膜的实验过程,并解决该领域的关键需求。研究结果表明,训练异聚物而不是均聚物,通过反设计方法合成新型聚合物,以及使用在相同条件下创建的可靠数据集,是实现设计意图的最关键因素。为任何打算在膜合成过程中使用ML算法的人提供了从A到Z的路径。文章最后简要讨论了未来的发展前景和尚未解决的ML驱动聚合物基膜设计和优化的开放性问题。
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引用次数: 12
Designing triple-layer superhydrophobic/hydrophobic/hydrophilic nanofibrous membrane via electrohydrodynamic technique for enhanced anti-fouling and anti-wetting in wastewater treatment by membrane distillation 利用电水动力学技术设计超疏水/疏水/亲水三层纳米纤维膜,增强膜蒸馏处理废水的防污防湿能力
Q1 ENGINEERING, CHEMICAL Pub Date : 2022-11-01 DOI: 10.1016/j.memlet.2022.100030
Xiao-Qiong Wu , Xing Wu , Hui-Wen Huo , Quan-Bao Zhao , Yu-Ming Zheng , Zongli Xie

Developing high-performance membranes for membrane distillation (MD) to treat highly saline industrial wastewater is of great significance. In this work, a superhydrophobic/hydrophobic/hydrophilic triple-layer membrane combining an electrosprayed superhydrophobic top layer, an electrospun hydrophobic nanofibrous intermediate layer and a hydrophilic microporous membrane substrate was fabricated by using electrohydrodynamic techniques. The top superhydrophobic surface possesses a unique surface morphology composing of hydrophobic SiO2-polymer microbeads with nanoscaled protrusions and interconnected thin nanofibers, which contributed to the enhanced water flux for desalination in direct contact MD. By tuning the concentrations of hydrophobic SiO2 nanoparticles and polyvinylidene fluoride-co-hexafluoropropylene for electrospraying the top layer, the triple-layer membrane showed both enhanced anti-fouling and anti-wetting properties due to the reduced liquid-solid contact area and stable Cassie-Baxter state. The triple-layer membrane exhibited stable MD performances when using real seawater and industrial flue gas desulfurization wastewater as the feed solutions, while no obvious fouling and wetting being observed even at 60% water recovery. This study provides an effective approach for fabricating a high-performance triple-layer superhydrophobic/hydrophobic/hydrophilic membrane for potential practical MD applications for industrial wastewater treatment.

开发膜蒸馏(MD)处理高盐工业废水的高性能膜具有重要意义。利用电流体动力学技术,制备了由电喷涂超疏水顶层、电纺疏水纳米纤维中间层和亲水微孔膜基板组成的超疏水/疏水/亲水三层膜。顶部超疏水表面具有独特的表面形貌,由具有纳米级突起的疏水SiO2-聚合物微珠和相互连接的薄纳米纤维组成,这有助于提高直接接触MD海水淡化的水通量。通过调节疏水SiO2纳米颗粒和聚偏氟乙烯-共六氟丙烯的浓度,对顶层进行电喷涂,由于减少了液固接触面积和稳定的Cassie-Baxter状态,三层膜具有增强的抗污和抗湿性能。三层膜在以真实海水和工业烟气脱硫废水为进料溶液时表现出稳定的MD性能,即使在60%的回收率下也没有出现明显的污垢和润湿现象。该研究为制备高性能三层超疏水/疏水/亲水性膜提供了有效途径,具有潜在的工业废水处理实际应用前景。
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引用次数: 6
Creation of water-permeation pathways with matrix-polymer functionalized carbon nanotubes in polymeric membranes for pervaporation desalination 基质聚合物功能化碳纳米管在渗透蒸发脱盐聚合物膜上的水渗透途径的建立
Q1 ENGINEERING, CHEMICAL Pub Date : 2022-11-01 DOI: 10.1016/j.memlet.2022.100027
Cheng Tseng, Ying-Ling Liu

Membrane-based pervaporation desalination is an effective process for freshwater resource and treatments on waste brines. Both water permeation fluxes and salt rejection are concerned for the membrane-based desalination. In this work an effective approach to increase the water permeation fluxes of the pervaporation desalination membranes has been demonstrated through utilization of matrix-polymer functionalized carbon nanotubes in creation of water permeation pathways in the membranes. With poly(vinyl alcohol) (PVA) as the matrix polymer for membrane fabrication, a small amount of PVA-functionalized CNTs (0.06 wt%) effectively increases the water permeation fluxes of the PVA membranes from 1,630 to 6,140 gm−2h−1 (feeding solution: 3.5 wt% NaCl(aq) at 25 °C) without sacrifice of salt rejection, corresponding to a 3.77-times of increase in water permeation flux. The membrane is also workable on concentrated salt aqueous solution (15 wt% NaCl(aq)). The approach has the potential to be employed to other polymer membranes for pervaporation separation.

膜渗透蒸发脱盐是一种有效的淡水资源化和废盐水处理技术。膜法脱盐既要考虑渗透通量,又要考虑排盐率。在本研究中,利用基质聚合物功能化碳纳米管在渗透蒸发脱盐膜中建立水渗透通道,有效地提高了渗透蒸发脱盐膜的水渗透通量。以聚乙烯醇(PVA)为基质聚合物制备膜时,少量PVA功能化CNTs (0.06 wt%)可有效地将PVA膜的水通量从1,630 gm−2h−1提高到6,140 gm−2h−1(进料溶液:3.5 wt% NaCl(aq), 25°C),而不牺牲盐的析出,相当于水通量增加了3.77倍。该膜也适用于浓盐水溶液(15 wt% NaCl(aq))。该方法具有应用于其他聚合物膜渗透汽化分离的潜力。
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引用次数: 6
Are commercial polyamide seawater and brackish water membranes effectively charged? 商用聚酰胺海水膜和微咸水膜是否有效带电?
Q1 ENGINEERING, CHEMICAL Pub Date : 2022-11-01 DOI: 10.1016/j.memlet.2022.100032
Bastiaan Blankert, Kees Theo Huisman, Fernan David Martinez, Johannes Simon Vrouwenvelder, Cristian Picioreanu

New developments in modeling solute transport in reverse osmosis (RO) membranes are based on the mechanistic description of solution friction and electromigration. In these models, the membrane charge significantly impacts the separation that occurs in the membrane through Donnan partitioning. One implication of membrane charge is that the salt permeability strongly depends on the ion concentration in the feedwater. In this study, we experimentally evaluate the effect of salinity, varied over almost two orders of magnitude (ca. 10–650mM), on four commercially available polyamide seawater RO and brackish water RO membranes. We found no significant effect of feed concentration on observed salt permeability, while the membrane performance closely resembled the specification by the manufacturers. We also demonstrate that a minor leak in the membrane provides a plausible alternative explanation to trend between concentration and salt permeability reported in other studies. The standard solution diffusion model provides a satisfactory description of our data for the membranes and feedwater conditions that we tested.

模拟溶质在反渗透(RO)膜中的运移的新进展是基于溶液摩擦和电迁移的机理描述。在这些模型中,膜电荷显著影响通过Donnan分配发生在膜上的分离。膜电荷的一个含义是,盐的渗透性很大程度上取决于给水中的离子浓度。在本研究中,我们通过实验评估了盐度变化近两个数量级(约10-650mM)对四种市售聚酰胺海水反渗透膜和微咸水反渗透膜的影响。我们发现饲料浓度对观察到的盐渗透性没有显著影响,而膜的性能与制造商的规格非常接近。我们还证明,膜上的微小泄漏为其他研究报告的浓度和盐渗透率之间的趋势提供了一种合理的替代解释。标准溶液扩散模型对我们测试的膜和给水条件的数据提供了令人满意的描述。
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引用次数: 5
Global optimization for accurate and efficient parameter estimation in nanofiltration 纳滤中精确高效参数估计的全局优化
Q1 ENGINEERING, CHEMICAL Pub Date : 2022-11-01 DOI: 10.1016/j.memlet.2022.100034
Danyal Rehman , John H. Lienhard

One of the most well-established frameworks for modeling multicomponent transport in nanofiltration (NF) is the Donnan-Steric Pore Model with Dielectric Exclusion (DSPM-DE). Conventional DSPM-DE characterizes transport across NF membranes through four governing membrane parameters: (1) pore radius; (2) effective membrane thickness; (3) membrane charge density; and (4) the dielectric constant inside the membrane pores. The process for quantifying these parameters is typically sequential. First, neutral solute experiments are performed to determine pore radius and effective membrane thickness. Next, charged species experiments are conducted, and the data is used to regress out the remaining parameters. The resulting regressions are often performed using local search algorithms that can struggle to provide low residuals with robust fits. In addition, this two-step approach tends to: (1) require a substantial number of charged and uncharged solute experiments; and (2) introduce assumed relationships between pore size and water flux, such as the Hagen-Poiseuille equation, which may not be representative of transport through complex pore networks. To address these issues, we propose the use of metaheuristic global optimization techniques supplemented with gradient-free local search and maximum likelihood estimation to simultaneously regress all four membrane parameters directly from charged species experiments. We validate our approach against eight independent datasets across diverse input salinities, compositions, and membranes.

模拟纳滤(NF)中多组分输运的最完善的框架之一是具有介电排斥的Donnan-Steric孔模型(DSPM-DE)。传统的DSPM-DE通过四个控制膜参数来表征NF膜上的转运:(1)孔半径;(2)有效膜厚;(3)膜电荷密度;(4)膜孔内介电常数。量化这些参数的过程通常是顺序的。首先,进行中性溶质实验来确定孔隙半径和有效膜厚度。接下来,进行带电物质实验,并利用数据回归出剩余参数。所得到的回归通常使用局部搜索算法来执行,这些算法很难提供具有鲁棒拟合的低残差。此外,这种两步法往往:(1)需要大量的带电和不带电溶质实验;(2)引入孔隙大小与水通量之间的假设关系,如Hagen-Poiseuille方程,该方程可能不能代表通过复杂孔隙网络的输运。为了解决这些问题,我们建议使用元启发式全局优化技术,辅以无梯度局部搜索和最大似然估计,同时直接从带电物质实验中回归所有四个膜参数。我们针对不同输入盐度、成分和膜的8个独立数据集验证了我们的方法。
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引用次数: 5
Scaling electrospray based additive manufacturing of polyamide membranes 聚酰胺膜的电喷雾增材制造
Q1 ENGINEERING, CHEMICAL Pub Date : 2022-11-01 DOI: 10.1016/j.memlet.2022.100035
Mayur Ostwal , Edward Wazer , Marianne Pemberton , Jeffrey R. McCutcheon

Additive manufacturing based on electrospray printing has been demonstrated to fabricate polyamide membranes with separation properties similar to commercial membranes while also offering exceptional control of membrane thickness and roughness. In this work, we report on the scalability of the electrospray process to produce membrane leaves that are 10 times the area of membranes fabricated in literature through electrospray printing. The large membrane leaves exhibited salt rejection of >90% (at 2000 ppm feed salt concentration) and ∼0.7 LMH/bar flux, which is comparable to smaller printed membranes using the same process.

基于电喷涂印刷的增材制造已经被证明可以制造出具有与商业膜相似的分离特性的聚酰胺膜,同时也提供了对膜厚度和粗糙度的卓越控制。在这项工作中,我们报告了电喷雾工艺的可扩展性,可以生产出比文献中通过电喷雾印刷制造的膜面积大10倍的膜叶。大膜叶片的盐去除率为>90%(在饲料盐浓度为2000 ppm时),通量为~ 0.7 LMH/bar,与使用相同工艺的较小印刷膜相当。
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引用次数: 1
期刊
Journal of Membrane Science Letters
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