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WO2017176163A1 - Membrane échangeuse d'anions modifiée et procédé de sa fabrication - Google Patents

Membrane échangeuse d'anions modifiée et procédé de sa fabrication Download PDF

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Publication number
WO2017176163A1
WO2017176163A1 PCT/RU2017/000184 RU2017000184W WO2017176163A1 WO 2017176163 A1 WO2017176163 A1 WO 2017176163A1 RU 2017000184 W RU2017000184 W RU 2017000184W WO 2017176163 A1 WO2017176163 A1 WO 2017176163A1
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Prior art keywords
exchange membrane
solution
anion exchange
fluoropolymer
manufacturing
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Ceased
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PCT/RU2017/000184
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English (en)
Russian (ru)
Inventor
Дмитрий Сергеевич ЛОПАТИН
Олег Алексеевич БАРАНОВ
Елизавета Сергеевна КОРЖОВА
Наталия Дмитриевна ПИСЬМЕНСКАЯ
Виктор Васильевич НИКОНЕНКО
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms

Definitions

  • the invention relates to membrane technology, in particular, to anion-exchange membranes and methods for manufacturing ion-exchange membranes with improved mass transfer characteristics, and can be used in electrodialysis apparatus for processing various solutions, obtaining high-purity water, and adjusting the pH of the treated solution.
  • a two-layer strongly basic ion-exchange membrane consisting of a heterogeneous membrane — a substrate and a homogeneous perfluorocarbon modifier layer, 5–10 ⁇ m thick, cast from a 5% (mass.) solution of polyvinylidene fluoride (PVDF) in dimethylformamide (DMF).
  • PVDF polyvinylidene fluoride
  • the disadvantage of this membrane is the lack of pores in the range of 1 to 500 microns and low transport capacity, as well as the high consumption of expensive reagents.
  • the disadvantage of this method is the low stability of the obtained membranes at high electric field densities and high pH values of the processed solutions.
  • the method was applied only to Nafion cation-exchange membranes on fuel cells, and only conductive Nafion-based polymers with metal additives were used.
  • a positive effect is achieved by treating the anion-exchange membranes with acid to the full protonation of weakly basic amino groups with its subsequent immersion with a five or more percent organic solution of a copolymer of acrylonitrile with dimethyldiallylammonium chloride in an organic solvent until quaternary amino groups form in the modified membrane [Patent RF W 2,410,147 IPC (8) B01 D71 / 06-71 / 82].
  • the technical task of the invention is to increase the degree of hydrophobicity and improve mass transfer characteristics, increase electroconvection and limit changes in the potential jump and current limit of the modified composite anion exchange membrane.
  • the technical problem is also a method of modifying homogeneous anion-exchange membranes to weaken their ability to generate H +, OH-ions and improve mass transfer characteristics in ultra-limiting current modes.
  • a composite anion-exchange membrane consisting of a homogeneous anion-exchange substrate membrane, coated with a thin layer of a hydrophobic fluoropolymer with a variable thickness from 0 to 500 micrometers and a percent surface filling.
  • the main difference from the prototype is the ability to control the proportion of the conductive surface, and the structure of the resulting non-conductive material on this surface from a fluoropolymer instead of a continuous one obtained from aerosols of fluoropolymers, and the membrane structure does not change.
  • the structure can be formed in the form of fibers and tons of thin circles.
  • the coating may consist of an array of flat circles with a diameter of 50-500 micrometers and a thickness of up to 100 microns and a distance between the centers of circles from 100 to 700 microns.
  • the technical problem is solved by the method of manufacturing the membrane, while inert hydrophobic is used as a modifier a fluoropolymer dissolved in an organic solvent containing a mixture of ketones and esters at a concentration of fluoropolymer from 0.3 to 5%, which is sprayed in an electric field with a strength of 2 to 8 kilovolts per centimeter and deposited on the surface of the anion exchange membrane over a period of 3 to 120 seconds, (Fig. 1).
  • the diameter of the circles is determined by the distance of the spraying needle from the surface being modified: from 4 to 7 cm.
  • the fraction of the surface occupied by the fluoropolymer depends on the exposure time (3 to 120 seconds) of the sample and the viscosity of the modifying solution.
  • fluoropolymers can act
  • Fluoroplast-42 (-CF 2 -CF 2 -CH 2 -CF2-) n
  • a homogeneous AMX membrane can serve as a substrate membrane.
  • FIG. 1 is a block diagram of a device for spraying fluoropolymer solutions in an electric field onto the surface of anion exchange membranes.
  • the device of FIG. 1 contains a container containing a solution of fluoropolymer 1, a metal electrode-needle 2, a high voltage source 3, an anion exchange membrane 4, an electrode-substrate 5, a precision syringe pump 6, which doses a solution of fluoropolymer 1, a worm gear screw 7.
  • Electrospray of a liquid from a container containing a solution of fluoropolymer 1 onto an anion exchange membrane 4 from a capillary needle electrode 2 in air under the action of pressure applied from a precision syringe pump 6 by moving the screw of the worm gear 7, moving the atomizer occurs along three axes. Spraying occurs under the influence of an electric field of high tension (from 2.3 to 8 kilovolts per centimeter). The difference is that a solution of a non-conductive inert polymer is sprayed.
  • the substrate electrode 5, on which the anion exchange membrane 4 is fixed, is made of conductive material and is connected to an external high voltage source 3 with zero voltage.
  • the needle electrode 2 is connected to a high voltage source 3 with a constant potential of 8-25 kilovolts and an alternating voltage of 3 kilovolts and a frequency of 70 kHz, which adds ionization to the sprayed solution.
  • the distance between the electrode-needle 2 and the electrode-substrate 5 varies from 4 to 7 centimeters.
  • the device of FIG. 2 contains the same components 1-7, as well as an additional laser 8, a photosensor 9, a computer 10 that controls a stepper motor connected to a screw of a worm gear 7, a metal ring electrode 11, a primary drop 12 of a solution of fluoropolymer 1, a microdrop 13 of electrospray fluorine polymer solution.
  • the device of FIG. 2 also monitors the spraying conditions of fluoropolymer 1, under which the electrospray effect occurs, for this the applied pressure is additionally adjusted with a syringe pump 6 through the screw of the worm gear 7 of the stepper motor from the computer 10, which receives the signal from the photosensors 9, which measure the light flux from the laser 8 passing through a drop 12 of a solution of fluoropolymer 1 at the end of a metal electrode-needle 2.
  • the diameter of the laser beam is chosen so as to capture micro-drops 13 elektrosprey and the primary drop 12 electr da needle.
  • micro-drops 13 of the fluorine-polymer solution are accelerated and crushed by a metal ring electrode 1 1 with a connected voltage 2-5 kilovolts higher than on the needle electrode, that is, about 10-30 kilovolts.
  • the fraction of the surface occupied by the fluoropolymer depends on the exposure time (from 35 to 120 seconds) of the sample and the viscosity of the modifying solution.
  • a mesh with a mesh size of 1 to 4 mm made of fine wire with a diameter of 0.1 mm is placed in front of the membrane at a distance of 5-20 mm, and a voltage identical to the charge of micro-droplets is connected to them.
  • Example 1 To confirm the achievement of the result, the surface of the homogeneous anion exchange membrane ⁇ (Astom, Tokuyama Corp., Japan) was modified with a solution of a hydrophobic fluoropolymer of the F-42 brand in an electric field with a given voltage of 4 kV / cm (Fig. 3) and solvent concentration.
  • FIG. Figure 3 shows the potential jump values for the control membrane and modified membranes.
  • the fluoropolymer was dissolved in ethyl acetate (concentration of fluoropolymer in ethyl acetate 0.6-1.8%) or in ketone acetone (concentration of fluoropolymer in acetone 0.6-1.2%).
  • Table 1 presents the comparative characteristics of the original, proposed modified and anion-exchange membranes, taken as a prototype.
  • Prototype -3.5 In FIG. 4 shows the pH imbalance of the original, modified membranes and it is seen that the pH imbalance of the anion exchange membrane, taken as a prototype, is greater than that of the proposed modified membranes. This suggests that treatment of the membranes leads to a less pronounced decrease in pH than treatment with a copolymer of acrylonitrile with dimethyldiallylammonium chloride
  • FIG. Figure 5 shows the limiting current found experimentally by the initial and modified samples, and it can be seen that the experimental limiting current of the modified samples is higher than that of the initial membrane.
  • This modification reduces the fraction of the conductive surface on a homogeneous membrane while increasing electroconvection, and hence the value of the limiting current on it. This condition applies to all homogeneous membranes.
  • the greatest hydrophobicity is demonstrated by the surface of the modified sample N-> 3 of the AMX membrane, on the surface of which the modifier is applied in the form of drops.
  • the most hydrophilic is the surface of the original AMX membrane.
  • the hydrophobicity of the surface is determined by the chemical nature of its constituent components and the texture (nano- and microrelief) of the surface.
  • hydrophobic / hydrophilic balance of the surface of the studied ion-exchange membranes is determined not only by the chemical nature of the polymer matrix material or inert binder, whose hydrophobicity is usually high, but also by polar fixed amino groups that attract water molecules.
  • the morphology of ion-exchange materials of these membranes can be represented as a system of hydrophilic conducting channels enclosed in a hydrophobic phase of the polymer. The higher the content of fixed groups (exchange capacity) in the membrane and its moisture capacity, the more hydrophilic the surface of this membrane can be.
  • the modified membranes have a larger wetting angle, regardless of which of the solvents (in acetone or in ethyl acetate) Ftoroplast-42 was dissolved.
  • the amount of applied modifier affects the wetting angle. This is clearly seen in the examples of samples N ° 4 and 1, since a small amount of Ftoroplast-42 was deposited on the surface of these samples.
  • FIG. Figure 6 shows the current-voltage characteristics (I – V characteristics) of the studied samples on the surface of which are micro-droplets and the initial AMX membrane
  • the ohmic resistance of the membrane system ⁇ 0 ⁇ is found from the CP by extrapolation to zero time in the coordinates ⁇ ⁇ ( - t ° ' 5.
  • Using the reduced potential jump ⁇ 5 ⁇ - ⁇ 0 ⁇ allows us to exclude from consideration the initial ohmic resistance, which depends on the distance between the measuring electrodes, membrane thicknesses and other parameters, which are often not critical for membrane behavior, but are hardly taken into account when moving from one membrane system to another.
  • ⁇ ⁇ includes ohmic jumps over potential in all layers of the system: a membrane, two diffusion layers, two solution layers between the measuring electrodes and the external boundaries of the diffusion layers.
  • the current density is normalized to the limiting current density in order to be able to compare the behavior of membrane systems in various electrolyte solutions at approximately the same degree of polarization.
  • the limiting current density is calculated by the Pierce formula.
  • the thickness of the diffusion layer for these calculations was determined using the convective-diffusion model.
  • FIG. Figure 9 shows the experimentally found transition time in the initial sections of the CP.
  • m is determined by the following expression:
  • the parameter m corresponds, within the framework of the model, to the moment when the electrolyte concentration at the membrane surface becomes zero, and the potential drop tends to infinity. It is assumed that the concentration of counterions in the depth of the solution in the systems under study does not differ from the concentration of electrolyte with 0 at the entrance to the electrochemical cell. It follows from equation (1) that, in super-limiting current modes, the value of the product i - T does not depend on the current density if the mass transfer in the electrochemical system is controlled by electrodiffusion, which is not complicated by the conjugate effects of concentration polarization.
  • the value of m can be defined as the time it takes for the electrolyte concentration at the membrane / solution interface to decrease to values c s «from 0 at which the conjugate effects begin to appear. Since the effect of these effects is expressed in the retardation of the growth of ⁇ , the transition time can be approximately determined by the inflection point of the initial CP site.
  • Transition time in membrane systems of modified AMX membrane samples is reached later than in the original membrane.
  • FIG. Figure 9 shows examples of modified membranes, the transition time of which increases most significantly.
  • the potential jump on a membrane with a heterogeneous surface should increase faster with time and reach higher stationary values than on a homogeneous membrane, if the contribution of other transport mechanisms, such as electroconvection, is insignificant.
  • the decrease in the near-surface concentration of counterions in the conducting sections is partially compensated by the tangential diffusion of the electrolyte from the solution adjacent to the non-conducting sections.
  • FIG. Figure 12 (a, b) shows the dependence of the stationary values of the potential jump (12a) and the pH difference at the outlet and inlet of the desalination channel (126) on the wetting angle of the sample surface at currents close to the limiting value.
  • the drop in the potential jump as compared with the initial membrane is already marked in prelimit current modes (Fig. 12a).
  • the desalted solution does not acidify, therefore, there is no generation of H + , OH " ions near the surface of the anion-exchange membrane (Fig. 126).
  • FIG. 13 (a, b) show the dependence of the contact angle on the potential jump 13a and on pH 136 in limiting current conditions.
  • the potential jump decreases (Fig. 13 a), the generation of H +, OH ions is suppressed (Fig. 136) compared with the initial membrane.
  • Electroconvection vortices deliver a more concentrated solution to the membrane surface.
  • the resistance of the near-membrane solution decreases, and the recorded potential jump decreases. This effect is all the more noticeable the more hydrophobic the surface of the modified membranes becomes.
  • FIG. 15-20 show photographs of membrane samples obtained at different distances, times, and solution concentrations.
  • Fig. 15 (a, b) shows micro-droplets on the surface of the AMX membrane for two different samples.
  • FIG. 16 (a, b) shows micro-droplets on the surface of the AMX membrane after prolonged spraying in at a distance of 16a - 7 cm in 5 minutes, 166 - at a distance of 4 cm in 3 minutes
  • FIG. 17 shows a microscopic photograph of an AMX membrane onto which a fluoropolymer dissolved in ethyl acetate (0.5 g of fluoropolymer per 30 ml of ethyl acetate) was applied at a distance of 4 cm for 5 min
  • FIG. 18 is a microscopic photograph of an AMX membrane onto which a fluoropolymer dissolved in ethyl acetate (0.5 g per 30 ml) was applied at a distance of 4 cm for 20 sec.
  • FIG. 19 shows a microscopic photograph of an AMX membrane onto which a fluoropolymer dissolved in ethyl acetate (0.5 g per 30 ml) was applied at a distance. 4 cm for .2 min using a mask
  • FIG. 20 shows a microscopic photograph of an AMX membrane onto which a fluoropolymer dissolved in ethyl acetate (0.5 g per 30 ml) was applied at a distance of 4 cm for 3 minutes.
  • FIG. 21-22 show samples obtained using a grid at a distance of 1 cm from the membrane with a cell pitch of 2 mm, which helped to make the droplet size more uniform.
  • FIG. 21 shows micro-droplets of a solution of the same size fluoropolymer in ethyl acetate when applied through a grid
  • FIG. 22 shows micro-droplets of a fluoropolymer on the surface of the AMX membrane deposited from a solution of 0.1 grams of fluoropolymer per 30 ml of ethyl acetate through a grid for 7 minutes.
  • Solvents can also be acetone, ⁇ -methyl-pyrrolidone, as well as most ketones (acetylacetone, etc.) and esters.
  • acetone ⁇ -methyl-pyrrolidone
  • ketones acetylacetone, etc.
  • sputtering occurs in the form of micro-fibers and micro-droplets in various ratios, so that at a concentration close to 1%, the ratio of droplets to fibers is more than 90%, and at a concentration close to 5% and more, and at a solution temperature of more than 35 degrees Celsius, the ratio of droplets to fibers is less than 50%.
  • FIG. 23 shows a photograph of a tinted membrane with a mixed coating of micro-droplets and micro-fibers from a solution in ethyl acetate.
  • Photographs were taken on an electron microscope of the surface of the obtained microfibers with the same field strength of 12 kilovolts and the distance from the needle to the substrate 5 cm, but at different concentrations of F-42l fluoropolymer dissolved in acetone (Fig. 24), 4.2% (a ) and (b), the concentration of the fluoropolymer is 3.1% (c) and (d) and the concentration of the fluoropolymer is 1% (e) and 0.5% (f).
  • the surface is obtained in the form of a film.
  • a continuous surface is not obtained, only individual drops.
  • FIG. 25 shows chronopotentiograms of modified samples, on the surface of which there are micro-fibers, and the original AMX membrane.
  • FIG. Figure 26 shows the current-voltage characteristics of the modified samples, on the surface of which structures are made of micro-fibers, and the original AMX membrane
  • FIG. 27 shows a photo of one of the modifications of the installation for the modification of membranes with a dosage from communicating vessels, regulated by a crane.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Health & Medical Sciences (AREA)
  • Urology & Nephrology (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne des équipements à membrane et notamment des membranes échangeuses d'anions modifiées et des procédés de préparation de membranes échangeuses d'anions avec des caractéristiques améliorées en termes d'échange de masses. Le résultat technique consiste à augmenter le degré d'hydrophobie et améliorer les caractéristiques en terme d'échange de masses, augmenter la convection électrique de la membrane échangeuse d'anions modifiée et un procédé de sa fabrication; il est réalisé en ce que la membrane échangeuse d'anions composite modifiée est constituée d'une membrane de substrat échangeuse d'anions homogène recouverte d'une fine couche de fluoropolymère hydrophobe possédant une épaisseur variable de 0 à 500 micromètres. Le résultat technique est obtenu en ce que l'on pulvérise dans un champ électrique à la surface d'une membrane échangeuse d'anions une solution 0,3-5 % d'un fluoropolymère hydrophobe dissout dans un solvant organique, avec une tension de champ électrique prédéterminée et une concentration de solvant pendant 3-120 sec.
PCT/RU2017/000184 2016-04-07 2017-03-29 Membrane échangeuse d'anions modifiée et procédé de sa fabrication Ceased WO2017176163A1 (fr)

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RU2016113324A RU2676621C2 (ru) 2016-04-07 2016-04-07 Модифицированная анионообменная мембрана и способ ее изготовления
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112055652A (zh) * 2017-11-21 2020-12-08 花王株式会社 电纺丝装置及其系统和方法
RU2801035C1 (ru) * 2022-11-23 2023-08-01 Федеральное государственное бюджетное образовательное учреждение высшего образования "Кубанский государственный университет» (ФГБОУ ВО "КубГУ") Способ модификации анионообменной мембраны
CN117654650A (zh) * 2023-12-21 2024-03-08 上海纳米技术及应用国家工程研究中心有限公司 一种改性离子交换膜的制备方法及其产品

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110813386B (zh) * 2019-09-11 2022-04-19 浙江工业大学 一种改性阳离子交换膜的制备方法
RU207737U1 (ru) * 2020-08-18 2021-11-12 Федеральное государственное бюджетное образовательное учреждение высшего образования "Кубанский государственный университет" (ФГБОУ ВО "КубГУ") Анионообменная мембрана

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004026575A1 (fr) * 2002-09-20 2004-04-01 Bha Technologies, Inc. Traitement d'article poreux
RU2410147C2 (ru) * 2008-10-22 2011-01-27 Общество с ограниченной ответственностью "Инновационное предприятие "Мембранная технология" Способ модификации анионообменных мембран
WO2013109337A1 (fr) * 2012-01-16 2013-07-25 W.L. Gore & Associates, Inc. Articles incluant des membranes en polytétrafluoroéthylène expansé présentant des fibrilles ondulées et ercouvertes d'une couche discontinue en fluoropolymère
RU140771U1 (ru) * 2013-11-26 2014-05-20 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Кубанский государственный университет" (ФГБОУ ВПО "КубГУ") Нитратселективная анионообменная мембрана

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2041892C1 (ru) * 1991-06-26 1995-08-20 Акционерное общество открытого типа "Научно-исследовательский институт пластических масс им.Г.С.Петрова с Опытным московским заводом пластмасс" Способ получения слабоосновной анионообменной мембраны
RU2158625C1 (ru) * 1999-03-23 2000-11-10 ТОО фирма "Родник" Способ получения фторполимерных мембран для фильтрации жидкостей
JP4939124B2 (ja) * 2005-11-10 2012-05-23 住友電工ファインポリマー株式会社 フッ素樹脂多孔質膜
EP2067814A4 (fr) * 2006-08-09 2012-09-12 Sumitomo Elec Fine Polymer Inc Membrane de résine fluorée, composite de résine fluorée, composite poreux de résine fluorée, procédés pour la production de ceux-ci et élément de type membrane pour la séparation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004026575A1 (fr) * 2002-09-20 2004-04-01 Bha Technologies, Inc. Traitement d'article poreux
RU2410147C2 (ru) * 2008-10-22 2011-01-27 Общество с ограниченной ответственностью "Инновационное предприятие "Мембранная технология" Способ модификации анионообменных мембран
WO2013109337A1 (fr) * 2012-01-16 2013-07-25 W.L. Gore & Associates, Inc. Articles incluant des membranes en polytétrafluoroéthylène expansé présentant des fibrilles ondulées et ercouvertes d'une couche discontinue en fluoropolymère
RU140771U1 (ru) * 2013-11-26 2014-05-20 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Кубанский государственный университет" (ФГБОУ ВПО "КубГУ") Нитратселективная анионообменная мембрана

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112055652A (zh) * 2017-11-21 2020-12-08 花王株式会社 电纺丝装置及其系统和方法
CN112055652B (zh) * 2017-11-21 2023-11-28 花王株式会社 电纺丝装置及其系统和方法
RU2801035C1 (ru) * 2022-11-23 2023-08-01 Федеральное государственное бюджетное образовательное учреждение высшего образования "Кубанский государственный университет» (ФГБОУ ВО "КубГУ") Способ модификации анионообменной мембраны
RU2801038C1 (ru) * 2022-11-23 2023-08-01 Федеральное государственное бюджетное образовательное учреждение высшего образования "Кубанский государственный университет" (ФГБОУ ВО "КубГУ") Способ модификации анионообменной мембраны
CN117654650A (zh) * 2023-12-21 2024-03-08 上海纳米技术及应用国家工程研究中心有限公司 一种改性离子交换膜的制备方法及其产品

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