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Scaling on Surface of MA-41P Anion-Exchange Membrane in Concentration Chamber of Electrodialyzer during Processing Dilute Stratal Water Imitates 电渗析浓缩室MA-41P阴离子交换膜处理稀层水模拟物时表面结垢
IF 1.6 Q4 CHEMISTRY, PHYSICAL Pub Date : 2022-10-11 DOI: 10.1134/S2517751622050031
D. Yu. Butylskii, V. A. Troitskiy, A. S. Skudarnova, M. V. Sharafan

The results of the study of the oscillations in the chronopotentiograms during scaling on the surface of an MA-41P anion-exchange membrane facing the concentration chamber of an electrodialyzer during the processing of dilute stratal water similar in composition to natural brines incidentally produced in the gas and oil fields of the Angara–Lena basin are presented. If Mg2+ ions are present in the solution, porous Mg(OH)2 is predominantly formed on the surface of an MA-41P membrane despite the excess Ca2+ content and sufficient amount of ({text{HCO}}_{3}^{ - }) in the solution. In the absence of Mg2+ ions in the solution, CaCO3 precipitates on the surface of the membrane. During scaling, an increase in the amplitude and period of the oscillation of the potential drop ∆φ from 5 mV and on average 5–10 s (due to the development of equilibrium electroconvection) up to 50 mV and 430 s, respectively, is recorded in the chronopotentiograms of MA-41P membrane. It is established that the amplitude and period of oscillations of the potential drop as well as the pH values of the concentrate can serve as a signal for taking actions to flush and regenerate ion-exchange membranes during the electrodialysis processing of dilute solutions of stratal water.

本文介绍了在安加拉-莱拿盆地油气田附带产生的与天然盐水成分相似的稀地层水处理过程中,MA-41P阴离子交换膜面对电渗析浓缩室表面结垢时计时电位振荡的研究结果。当溶液中存在Mg2+离子时,尽管溶液中Ca2+含量超标,({text{HCO}}_{3}^{ - })含量充足,但多孔Mg(OH)2主要在MA-41P膜表面形成。当溶液中没有Mg2+离子时,CaCO3在膜表面析出。在定标过程中,MA-41P膜的计时电位图记录到电位下降∆φ的振荡幅度和周期分别从5 mV和平均5 - 10 s(由于平衡电对流的发展)增加到50 mV和430 s。建立了电渗析处理地层水稀溶液时,电位降振荡幅度和周期以及浓缩液的pH值可作为采取冲洗和再生离子交换膜行动的信号。
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引用次数: 2
Preparation and Investigation of Anion Exchange Membranes Modified with Sulfonated Polyaniline 磺化聚苯胺改性阴离子交换膜的制备与研究
IF 1.6 Q4 CHEMISTRY, PHYSICAL Pub Date : 2022-10-11 DOI: 10.1134/S2517751622050079
N. V. Loza, K. A. Taran, K. A. Kutenko

Based on the analysis of the results of sorption experiments and the study of the influence of the oxidant nature at different stages of the preparation of composites, a method has been developed for modifying anion exchange membranes with sulfonated polyaniline by in situ oxidative polymerization of 2-aminobenzenesulfonic acid. The formation of the modifier in the membranes has been proven by analyzing the ATR IR spectra of the samples. The study of the physicochemical and transport properties of composite membranes has shown that the synthesis of the modifier leads to a significant decrease in the exchange capacity from 3.41 to 1.65 mmol/gdry for the MA-40 membrane and from 0.87 to 0.21 mmol/gdry for MA-41. In this case, the electrical conductivity of the composite based on the MA-40 membrane increases by 2 to 3 times in sodium chloride solutions and that of the composite based on the MA-41 membrane decreases by a factor of 1.5–2. The current–voltage characteristics of the composite membranes were found to have asymmetry, which confirms the gradient character of the modifier distribution.

在对吸附实验结果进行分析的基础上,研究了复合材料制备不同阶段氧化性质对改性阴离子交换膜的影响,提出了用2-氨基苯磺酸原位氧化聚合磺化聚苯胺改性阴离子交换膜的方法。通过分析样品的ATR - IR光谱,证实了改性剂在膜中的形成。对复合膜的物理化学和传输性能的研究表明,改性剂的合成使MA-40膜的交换容量从3.41降低到1.65 mmol/gdry, MA-41膜的交换容量从0.87降低到0.21 mmol/gdry。在这种情况下,基于MA-40膜的复合材料在氯化钠溶液中的电导率提高了2 ~ 3倍,而基于MA-41膜的复合材料的电导率降低了1.5-2倍。复合膜的电流-电压特性具有不对称性,证实了改性剂分布的梯度特性。
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引用次数: 0
MF-4SC Membranes Modified with Carboxylated Carbon Nanotubes for Potentiometric Determination of Alanine, Valine, and Phenylalanine in Alkaline Solutions 羧化碳纳米管修饰MF-4SC膜用于碱性溶液中丙氨酸、缬氨酸和苯丙氨酸的电位测定
IF 1.6 Q4 CHEMISTRY, PHYSICAL Pub Date : 2022-08-14 DOI: 10.1134/S2517751622040072
A. V. Parshina, E. Yu. Safronova, T. S. Kolganova, V. A. Kuleshova, O. V. Bobreshova

Perfluorosulfonic acid membranes MF-4SC containing 0.5–1.0 wt % carbon nanotubes with carboxyl groups on the surface have been manufactured. On their basis, multisensory systems have been developed for the simultaneous determination of amino acids (the total concentration of their anionic and zwitterionic forms) and K+ cations in aqueous solutions at pH 8–10 in the concentration range from 1.0 × 10–4 to 5.0 × 10–2 M. The relative error in the determination of alanine (5–15%), valine (0.3–10%), and phenylalanine (0.7–5%) is comparable with that for K+ cations (1.4–11%). Differences in the cross sensitivity of sensors based on the pristine and modified membranes, necessary for their use in multisensory systems, are achieved due to changes in the microstructure of membranes and the appearance of new reaction centers that affect the conditions of non-exchange sorption of aliphatic and aromatic amino acids in different ways.

制备了含0.5-1.0 wt %碳纳米管表面羧基的全氟磺酸膜MF-4SC。在此基础上,建立了在pH为8 ~ 10,浓度范围为1.0 × 10-4 ~ 5.0 × 10-2 m的水溶液中同时测定氨基酸(阴离子和两性离子形式的总浓度)和K+阳离子的多感官系统。测定丙氨酸(5 ~ 15%)、缬氨酸(0.3 ~ 10%)和苯丙氨酸(0.7 ~ 5%)的相对误差与测定K+阳离子(1.4 ~ 11%)的相对误差相当。基于原始膜和修饰膜的传感器的交叉灵敏度差异是多感觉系统中使用所必需的,这是由于膜微观结构的变化和新反应中心的出现,以不同的方式影响脂肪族和芳香氨基酸的非交换吸附条件。
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引用次数: 0
Experimental Determination of the Effect of Temperature on the Gas Transport Characteristics of Polymeric Gas Separation Fibers Based on Polysulfone 温度对聚砜基聚合物气体分离纤维输运特性影响的实验研究
IF 1.6 Q4 CHEMISTRY, PHYSICAL Pub Date : 2022-08-14 DOI: 10.1134/S2517751622040096
K. A. Smorodin, A. A. Atlaskin, D. M. Zarubin, A. N. Petukhov, S. S. Kryuchkov, A. N. Petukhova, M. E. Atlaskina, A. N. Stepakova, A. N. Markov, I. V. Vorotyntsev

A study of the effect of temperature in a wide range (from 258.15 up to 293.15 K) on the gas transport characteristics of asymmetric polymeric gas separation fibers based on polysulfone for the components of a CO2–N2 binary gas mixture with various compositions is carried out. Within the framework of the work, the values of the permeability, diffusion, and solubility coefficients of pure gases in the temperature range of interest as well as the values of the permeability coefficient of the components of a CO2–N2 binary gas mixture are determined using gas chromatographic analysis of the permeate flow. It is demonstrated in this work that the process of separation the most effectively occurs at room temperature in the case of a low concentration of carbon dioxide (up to 15 mol %) in the binary mixture. It is experimentally shown that the separation process is the most effective at a low temperature (273.15 K) in the rest of the range of concentrations of CO2. Further decrease in temperature does not make the process of separation of the mixture more effective throughout the entire considered range of concentrations of carbon dioxide.

研究了不同温度范围(258.15 ~ 293.15 K)对不同组分CO2-N2二元气体混合物中聚砜基非对称聚合物气体分离纤维输运特性的影响。在这项工作的框架内,在感兴趣的温度范围内,纯气体的渗透性、扩散系数和溶解度系数的值,以及二氧化碳- n2二元气体混合物组分的渗透性系数的值,都是使用渗透流动的气相色谱分析来确定的。在这项工作中证明,在室温下,在二元混合物中二氧化碳浓度低(高达15 mol %)的情况下,分离过程最有效。实验结果表明,在其余CO2浓度范围内,低温(273.15 K)的分离效果最好。在整个考虑的二氧化碳浓度范围内,温度的进一步降低并不能使混合物的分离过程更有效。
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引用次数: 0
Polymer Electrolyte for Lithium Metal Batteries Based on Nafion and N,N-Dimethylacetamide 基于Nafion和N,N-二甲基乙酰胺的锂金属电池聚合物电解质
IF 1.6 Q4 CHEMISTRY, PHYSICAL Pub Date : 2022-08-14 DOI: 10.1134/S2517751622040102
D. Yu. Voropaeva, A. B. Yaroslavtsev

Lithium metal batteries are a promising replacement for lithium-ion batteries due to their ability to achieve high energy densities. A significant issue of this type of battery is dendrite growth through the separator, which makes these batteries unsafe and limits their commercial application. In this work, a single-ion conducting polymer electrolyte based on a cation-exchange membrane Nafion solvated by a ternary mixture of ethylene carbonate/dimethyl carbonate/N,N-dimethylacetamide has been obtained. It has an ionic conductivity of 1.8 mS cm–1 at 25°C and an electrochemical stability window of 4.1 V. It has been shown that the symmetrical Li/Li cell operates stably at a current density of 0.1 mA cm–2 for >350 h.

锂金属电池是锂离子电池的一个很有前途的替代品,因为它们能够实现高能量密度。这种类型的电池的一个重要问题是树突通过隔板生长,这使得这些电池不安全,并限制了它们的商业应用。本文以阳离子交换膜Nafion为基础,用碳酸乙烯/碳酸二甲酯/N,N-二甲基乙酰胺三元混合物溶剂化制备了单离子导电聚合物电解质。在25℃时离子电导率为1.8 mS cm-1,电化学稳定窗口为4.1 V。结果表明,对称锂/锂电池在0.1 mA cm-2的电流密度下稳定工作350小时。
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引用次数: 1
Effect of Sulfonation Conditions on Properties of Ion-Conducting Membranes Based on Polystyrene Grafted on Gamma-Irradiated Polyvinylidene Fluoride Films 磺化条件对γ辐照聚偏氟乙烯膜接枝聚苯乙烯离子导电膜性能的影响
IF 1.6 Q4 CHEMISTRY, PHYSICAL Pub Date : 2022-08-14 DOI: 10.1134/S2517751622040035
D. V. Golubenko, V. R. Malakhova, P. A. Yurova, M. V. Evsiunina, I. A. Stenina

The process of heterogeneous sulfonation of a radiation-grafted copolymer of polystyrene and polyvinylidene fluoride depending on the reaction time and the type of sulfonating agent (chlorosulfonic acid or its equimolar mixture with acetic acid) has been studied. The water uptake, ion-exchange capacity, and ionic conductivity of the prepared membranes have been characterized. In addition, composition and morphology of materials at different synthesis stages have been analyzed by FTIR, 1Н NMR, and EPR spectroscopies, elemental analysis, and scanning electron microscopy combined with energy dispersive X-ray microanalysis. The ionic conductivity of the prepared materials exceeds that of Nafion®212 membranes. In addition, the mechanical properties and hydrogen gas permeability of the membrane with the highest ionic conductivity (52 mS/cm at 80°C in contact with water) are better than those of the Nafion®212 membrane.

研究了聚苯乙烯-聚偏氟乙烯辐射接枝共聚物的非均相磺化反应过程,该过程取决于反应时间和磺化剂类型(氯磺酸或其与乙酸的等摩尔混合物)。对所制备膜的吸水性、离子交换能力和离子电导率进行了表征。此外,通过FTIR、1Н NMR、EPR谱、元素分析、扫描电镜结合能量色散x射线显微分析,分析了材料在不同合成阶段的组成和形貌。制备的材料的离子电导率超过了Nafion®212膜。此外,离子电导率最高的膜(在80°C与水接触时为52 mS/cm)的机械性能和氢气渗透性优于Nafion®212膜。
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引用次数: 2
Evaporation–Extraction Membrane Process for the Extraction of Lithium from Salt Lakes 蒸发-萃取膜法从盐湖中提取锂
IF 1.6 Q4 CHEMISTRY, PHYSICAL Pub Date : 2022-08-14 DOI: 10.1134/S2517751622040059
D. O. Kalmykov, S. V. Makaev, G. S. Golubev, A. V. Volkov

In this paper, the process of film distillation with a porous condensing surface (FD-PCS) is studied as applied to the tasks of concentration of lithium-containing solutions. Concentration of solutions is a part of a three-stage lithium extraction cycle that includes softening of the brine by the precipitation of Ca2+/Mg2+ cations with sodium carbonate (calculated in PHREEQC) followed by an integrated system consisting of a membrane distillation unit and a crystallizer (deposition of NaCl) and membrane extraction (extraction of Li+). The productivity flows of the film distillation module are investigated (4.15–7.49 kg m−2 h−1 at the temperatures of heating of the evaporation surface of 60 and 80°C, respectively). The complex operation of the three-stage system is modeled in Simulink/MATLAB. The modeling of the process based on the experimental and published data shows a higher efficiency of film distillation with a porous condensing surface in comparison with membrane distillation with a porous condensing surface (4.2 kg of lithium versus 1.4 kg over two months of stationary operation of the system).

本文研究了多孔冷凝表面膜蒸馏(FD-PCS)工艺在含锂溶液浓缩中的应用。溶液的浓缩是三级锂萃取循环的一部分,包括用碳酸钠沉淀Ca2+/Mg2+阳离子(在PHREEQC中计算)软化盐水,然后是一个由膜蒸馏装置和结晶器(NaCl沉积)和膜萃取(Li+萃取)组成的综合系统。研究了膜蒸馏模块的生产流程(在蒸发表面加热温度分别为60°C和80°C时为4.15-7.49 kg m−2 h−1)。在Simulink/MATLAB中对三级系统的复杂操作进行了建模。基于实验和公开数据的过程建模表明,与多孔冷凝表面的膜蒸馏相比,多孔冷凝表面的膜蒸馏效率更高(系统固定运行两个月后,锂的重量为4.2 kg,锂的重量为1.4 kg)。
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引用次数: 4
Influence of Spinning Modes on the Structure and Properties of Polyethersulfone Hollow-Fiber Ultrafiltration Membrane 纺丝方式对聚醚砜中空纤维超滤膜结构和性能的影响
IF 1.6 Q4 CHEMISTRY, PHYSICAL Pub Date : 2022-08-14 DOI: 10.1134/S2517751622040023
A. V. Bildyukevich, T. A. Hliavitskaya, T. N. Nevar

The effect of the main parameters of the spinning process of polyethersulfone (PES) hollow fiber (HF) membranes using the free-fall spinning technique has been studied. The influence of the flow rate of the polymer dope solution, the internal coagulant (bore fluid), the air gap distance, and the bore fluid temperature on the geometric dimensions, structure, and transport properties of the membranes has been analyzed. It has been shown that the variation of these spinning parameters makes it possible to control the transport properties of the obtained membranes in a wide range: the pure water flux (PWF) within 120–950 L/m2 h and the rejection coefficient with respect to PVP K-30 in the range of 20–93%. It has been established that the PWF of PES hollow fiber membranes increases linearly with an increase in the fiber extrusion ratio (ER) regardless of the spinning parameter that is varied. As shown by SEM and AFM, an increase in ER leads to an increase in the proportion of interconnected pores on the selective surface of PES HF membranes and the transformation of the pore shape from round to slitlike. A comparative analysis of the structure and properties of hollow fiber and flat sheet membranes obtained from the same composition of the dope solution has shown that the flat sheet membranes are characterized by an anisotropic spongy structure and the hollow fiber membranes have the support layer filled with finger-shaped vacuoles (macrovoids). It is concluded that the formation of macrovoids, as well as an order of magnitude higher water flux of the PES hollow fiber membranes, is due to a violation of the integrity (microfractures) of the selective layer being formed as a result of fiber drawing in the air gap.

研究了自由落体纺丝技术纺丝聚醚砜(PES)中空纤维(HF)膜过程中主要参数的影响。分析了聚合物溶液的流速、内混凝剂(孔内液)、气隙距离和孔内液温度对膜的几何尺寸、结构和输运性能的影响。结果表明,通过改变这些纺丝参数,可以在较宽的范围内控制膜的输运性能:纯水通量(PWF)在120 ~ 950 L/m2 h之间,PVP K-30的截留系数在20 ~ 93%之间。结果表明,无论纺丝参数如何变化,PES中空纤维膜的PWF均随纤维挤压比的增加而线性增加。SEM和AFM结果表明,ER的增加导致PES HF膜选择性表面互连孔的比例增加,孔的形状由圆形转变为狭缝状。对比分析了由相同成分的浆液制备的中空纤维与平板膜的结构和性能,发现平板膜具有各向异性海绵状结构,而中空纤维膜的支撑层充满了指状液泡(大孔)。综上所述,大孔洞的形成,以及PES中空纤维膜水通量的一个数量级的提高,是由于纤维在气隙中拉伸而形成的选择性层的完整性(微裂缝)的破坏。
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引用次数: 0
Formation of Multilayer Membranes from One Polymer Using IR Treatment 用红外处理一种聚合物形成多层膜
IF 1.6 Q4 CHEMISTRY, PHYSICAL Pub Date : 2022-08-14 DOI: 10.1134/S2517751622040114
A. A. Yushkin, A. V. Balynin, M. N. Efimov, D. G. Muratov, G. P. Karpacheva, A. V. Volkov

In this paper, a new method of layer-by-layer formation of monopolymer membranes based on polyacrylonitrile (PAN) is proposed. The proposed approach allows independent adjustment of the structure and characteristics of individual layers of the membrane to achieve high performance characteristics. IR radiation has been used to modify PAN, the effect of which has allowed to convert the polymer into an insoluble form for the application of subsequent layers. An important feature of IR modification is that the pore size and permeability of the membranes remain unchanged. This makes it possible to form the individual membrane layers under different conditions. The obtained membranes have a well-defined spongy layer on the surface and finger-like pores in the other part of the membrane volume. The presence of the spongy layer on the surface reduces the probability of formation of undesirable defects, which reduce the membrane retention. As a result, defect-free membranes that combine a low molecular weight of MWCO cut-off equal to 1800 g/mol and a fairly good for such a dense membrane permeability of 38.7 L/m2 h atm have been obtained. The pore size of the obtained membranes is 3.7 nm.

本文提出了一种以聚丙烯腈(PAN)为基材,逐层制备单聚膜的新方法。所提出的方法允许独立调整膜的各个层的结构和特性,以实现高性能特性。红外辐射已被用于改性PAN,其效果已允许将聚合物转化为不溶形式,用于后续层的应用。红外改性的一个重要特点是膜的孔径和通透性保持不变。这使得在不同条件下形成单独的膜层成为可能。所制得的膜表面有明确的海绵状层,膜体积的另一部分有指状孔。表面海绵状层的存在减少了形成不良缺陷的可能性,从而减少了膜潴留。结果,获得了MWCO截止分子量为1800 g/mol的低分子量无缺陷膜,并获得了相当好的致密膜渗透率38.7 L/m2 h / atm。所得膜的孔径为3.7 nm。
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引用次数: 1
Thermopervaporation with a Porous Condenser for Triethylene Glycol Dehydration 用多孔冷凝器进行三甘醇脱水的热过蒸发
IF 1.6 Q4 CHEMISTRY, PHYSICAL Pub Date : 2022-08-14 DOI: 10.1134/S2517751622040047
G. S. Golubev, A. V. Balynin, I. L. Borisov, A. V. Volkov

For the task of triethylene glycol (TEG) dehydration by thermopervaporation with a porous condenser (TPV-PC), the transport and separation characteristics of known commercial composite membranes with hydrophobic and hydrophilic properties are experimentally studied with respect to both the individual components (water, triethylene glycol) and TEG–water binary mixtures with various compositions. It is found that the most effective membrane for the TPV-PC dehydration of TEG is a PolyAn hydrophobic membrane (PolyAn GmbH, Germany) which demonstrates the maximum values of the permeate flux and pervaporation separation index. During the thermopervaporation separation of a TEG–water mixture (the water content in TEG of 30 wt %), a PolyAn membrane demonstrates the values of the water/TEG separation factor of 74 000 and permeate flux of 0.95 kg m−2 h−1. A long-term experiment on drying of 5 kg of a TEG–water solution is for the first time carried out using a PolyAn membrane. It turns out to be possible to reduce the water content from 30 down to 5 wt % over 113 hours of the thermopervaporation experiment on the dehydration of TEG.

对于用多孔冷凝器(TPV-PC)热蒸发脱水三甘醇(TEG)的任务,实验研究了已知的具有疏水性和亲水性的商用复合膜在单个组分(水,三甘醇)和不同组分的TEG -水二元混合物中的运输和分离特性。结果表明,对于TEG的TPV-PC脱水最有效的膜是PolyAn疏水膜(PolyAn GmbH, Germany),其渗透通量和渗透蒸发分离指数均达到最大值。在TEG -水混合物(TEG中含水量为30 wt %)的热蒸发分离过程中,PolyAn膜的水/TEG分离系数为74000,渗透通量为0.95 kg m−2 h−1。首次使用聚安膜进行了5kg teg水溶液的长期干燥实验。结果表明,通过113小时的热蒸发脱水实验,可以将TEG的含水量从30%降低到5%。
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引用次数: 0
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Membranes and Membrane Technologies
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