技术领域Technical field
本发明属于膜分离技术领域，具体涉及一种碳氢基无氟磺酸羧酸复合型阳离子交换膜及其在双极膜电渗析或其它电解设备中的应用。The invention belongs to the field of membrane separation technology, and specifically relates to a hydrocarbon-based fluorine-free sulfonic acid carboxylic acid composite cation exchange membrane and its application in bipolar membrane electrodialysis or other electrolysis equipment.
背景技术Background technique
离子交换膜技术是当代高新技术之一。离子交换膜是一种含离子基团、对溶液里的离子具有选择透过能力的高分子膜。1950年W.Juda首先合成了离子交换膜，1956年首次成功地用于电渗析脱盐工艺上，经过几十年的研究和发展，现在离子交换膜已广泛用于氯碱工业、湿法冶金、医药工业、海水淡化制盐、工业废水处理等方面。Ion exchange membrane technology is one of the contemporary high technologies. Ion exchange membrane is a polymer membrane that contains ionic groups and has the ability to selectively permeate ions in the solution. W. Juda first synthesized ion exchange membranes in 1950 and successfully used them in electrodialysis desalination processes for the first time in 1956. After decades of research and development, ion exchange membranes have now been widely used in the chlor-alkali industry, hydrometallurgy, and medicine. Industry, seawater desalination and salt production, industrial wastewater treatment, etc.
阳离子交换膜（简称阳离子膜或阳膜）是对阳离子有选择作用的膜。阳膜的一大用途是用于盐溶液电解获取碱产品（NaOH、KOH、LiOH等），阳膜电解法得到的碱产品浓度大、纯度高、能耗也低。为了提高电流效率，氯碱工业上电解氯化钠盐水制取NaOH所用的阳膜通常为全氟磺酸羧酸阳离子复合膜，它具有双层结构，由较厚的磺酸层和较薄的羧酸层组成，使用时较薄的羧酸层朝向阴极，较厚的磺酸层朝向阳极，由于羧酸层的存在，能够有效阻挡OH-返迁移，确保了高的电流效率（＞95%），又因磺酸层电阻低，能够在高电流密度下运行，因此，由于兼有磺酸膜和羧酸膜的优点，使全氟磺酸羧酸复合膜具有低电压和高电流效率的特点。Cation exchange membrane (referred to as cation membrane or cation membrane) is a membrane that has a selective effect on cations. A major use of the anode membrane is to use the electrolysis of salt solutions to obtain alkali products (NaOH, KOH, LiOH, etc.). The alkali products obtained by the anode membrane electrolysis method have high concentration, high purity, and low energy consumption. In order to improve the current efficiency, the cation membrane used in the chlor-alkali industry to electrolyze sodium chloride brine to produce NaOH is usually a perfluorosulfonic acid carboxylic acid cation composite membrane. It has a double-layer structure, consisting of a thicker sulfonic acid layer and a thinner carboxylic acid layer. Acid layer composition, when used, the thinner carboxylic acid layer faces the cathode, and the thicker sulfonic acid layer faces the anode. Due to the existence of the carboxylic acid layer, it can effectively block OH- back migration and ensure high current efficiency (>95%) , and because the sulfonic acid layer has low resistance, it can operate at high current density. Therefore, due to the advantages of both the sulfonic acid membrane and the carboxylic acid membrane, the perfluorosulfonic acid carboxylic acid composite membrane has the characteristics of low voltage and high current efficiency. .
由于全氟磺酸羧酸复合型阳离子膜具有上述优点，在氯碱工业的应用中取得巨大成功，目前全世界的烧碱（NaOH）几乎都采用这种膜电解生产。但是，在双极膜电渗析分解盐制取酸碱的设备中，这种膜却很少应用，主要原因有：全氟磺酸羧酸复合阳膜虽然具有高效率等优点，但价格昂贵，比一般碳氢聚合物材料的阳离子膜价格高5～10倍；同时，这种膜要求的工作温度很高（85～90℃），低于80℃时性能将产生不可逆下降（电流效率降低、膜电压升高），配对的双极膜和阴膜都无法在这样高温下正常工作。由于这些问题，尚未见双极膜电渗析设备或类似工作条件的电解设备采用全氟磺酸羧酸复合膜的报道。Due to the above-mentioned advantages, the perfluorosulfonate carboxylic acid composite cationic membrane has achieved great success in the application of the chlor-alkali industry. Currently, almost all caustic soda (NaOH) in the world is produced by electrolysis of this membrane. However, in equipment for bipolar membrane electrodialysis to decompose salts to produce acids and bases, this membrane is rarely used. The main reasons are: although the perfluorosulfonic acid carboxylic acid composite cationic membrane has the advantages of high efficiency, it is expensive. The price is 5 to 10 times higher than that of cationic membranes made of general hydrocarbon polymer materials; at the same time, this membrane requires a very high working temperature (85 to 90°C). When the temperature is lower than 80°C, the performance will be irreversibly reduced (current efficiency is reduced, The membrane voltage increases), and the paired bipolar membrane and cathode membrane cannot work properly at such high temperatures. Due to these problems, there have been no reports of bipolar membrane electrodialysis equipment or electrolysis equipment with similar working conditions using perfluorosulfonic acid carboxylic acid composite membranes.
目前，双极膜电渗析生产酸碱使用的阳膜，几乎全部采用碳氢聚合物材料的磺酸型阳离子膜，这种膜含水率高、电阻低，化学稳定性优良，成本也较低，但膜内固定离子浓度低，对OH-排斥能力小，致使OH-返迁移的数量大，电流效率＜80%，产碱浓度也低（一般≤2mol/L），使设备的生产能力和经济性难以提高。而排斥OH-返迁移力量强的羧酸型阳膜(电流效率＞95%），由于电阻大使膜电压高，而且只能工作在PH＞3的溶液中，也不适合在双极膜电渗析设备或类似工作条件的电解设备中使用。At present, the cationic membranes used in bipolar membrane electrodialysis to produce acids and bases are almost all sulfonic acid-type cationic membranes made of hydrocarbon polymer materials. This membrane has high moisture content, low resistance, excellent chemical stability, and low cost. However, the fixed ion concentration in the membrane is low and the OH- repelling ability is small, resulting in a large number of OH- remigration, the current efficiency is <80%, and the alkali production concentration is also low (generally ≤2mol/L), which reduces the production capacity and economy of the equipment. Sexuality is difficult to improve. The carboxylic acid-type cationic membrane (current efficiency >95%) with strong OH- repellent back-migration force, because the resistance increases the membrane voltage, can only work in solutions with pH >3, and is not suitable for bipolar membrane electrodialysis. equipment or electrolysis equipment with similar working conditions.
发明内容Contents of the invention
为了解决上述问题，本发明借鉴全氟磺酸羧酸复合膜的基本工作原理，采用碳氢聚合物高分子材料制备了一种碳氢基无氟磺酸羧酸复合型阳离子交换膜，其具有高电流效率，且成本低，适合在双极膜电渗析设备或类似工作条件的电解设备中使用。In order to solve the above problems, the present invention draws on the basic working principle of perfluorosulfonic acid carboxylic acid composite membrane and uses hydrocarbon polymer polymer materials to prepare a hydrocarbon-free fluorinated sulfonic acid carboxylic acid composite cation exchange membrane, which has It has high current efficiency and low cost, and is suitable for use in bipolar membrane electrodialysis equipment or electrolysis equipment with similar working conditions.
为实现上述目的，本发明采用如下技术方案：In order to achieve the above objects, the present invention adopts the following technical solutions:
一种碳氢基无氟磺酸羧酸复合型阳离子交换膜，其是以碳氢聚合物为原料制备的具有双层结构的阳离子膜，其中较厚的一层为磺酸层，较薄的一层为羧酸层。A hydrocarbon-based fluorine-free sulfonic acid carboxylic acid composite cation exchange membrane, which is a cationic membrane with a double-layer structure prepared from hydrocarbon polymers. The thicker layer is a sulfonic acid layer, and the thinner layer is a sulfonic acid layer. One layer is the carboxylic acid layer.
进一步地，所述磺酸层的厚度为0.05-0.50mm。Further, the thickness of the sulfonic acid layer is 0.05-0.50mm.
进一步地，所述羧酸层的厚度为0.01-0.10mm。Further, the thickness of the carboxylic acid layer is 0.01-0.10mm.
进一步地，所述复合型阳离子交换膜的制备方法包括刮涂、流延、粘合、含浸聚合以及其它能够形成双层复合结构的工艺中的任意一种。Further, the preparation method of the composite cation exchange membrane includes any one of scraping, casting, bonding, impregnation polymerization and other processes capable of forming a double-layer composite structure.
进一步地，根据成膜材料的强度和使用要求，在所述磺酸层中可加入或不加入增加膜强度的加强网。Furthermore, according to the strength and use requirements of the film-forming material, a reinforcing net to increase the strength of the film may or may not be added to the sulfonic acid layer.
本发明所得碳氢基无氟磺酸羧酸复合型阳离子交换膜可用于双极膜电渗析或其它电解槽中。The hydrocarbon-based fluorine-free sulfonic acid carboxylic acid composite cation exchange membrane obtained by the invention can be used in bipolar membrane electrodialysis or other electrolytic cells.
进一步地，如图1，其应用方法是将所述碳氢基无氟磺酸羧酸复合型阳离子交换膜的羧酸层一侧朝向阴极，磺酸层一侧朝向阳极。羧酸层一侧接触NaOH、KOH、LiOH等强碱溶液，磺酸层一侧接触pH 1~14的盐溶液或盐与酸、碱的混合溶液，且这些溶液中均不能含有或者生成氧化剂(总氧化剂含量＜0.1ppm），以实现双极膜电渗析分解盐制碱或盐碱的电解分离；其工作温度为20~60℃。Further, as shown in Figure 1, the application method is to place the carboxylic acid layer side of the hydrocarbon-based fluorine-free sulfonic acid carboxylic acid composite cation exchange membrane facing the cathode, and the sulfonic acid layer side facing the anode. One side of the carboxylic acid layer is in contact with strong alkaline solutions such as NaOH, KOH, LiOH, etc., and one side of the sulfonic acid layer is in contact with a salt solution of pH 1~14 or a mixed solution of salt, acid, and alkali, and these solutions cannot contain or generate oxidants ( The total oxidant content is <0.1ppm) to achieve bipolar membrane electrodialysis to decompose salt to produce alkali or electrolytic separation of salt and alkali; its working temperature is 20~60℃.
与现有碳氢基磺酸型或羧酸型阳膜相比，本发明无氟磺酸羧酸复合型阳离子交换膜具有如下优点：Compared with the existing hydrocarbon sulfonic acid type or carboxylic acid type cation membrane, the fluorine-free sulfonic acid carboxylic acid composite cation exchange membrane of the present invention has the following advantages:
1. 复合膜结合了磺酸膜和羧酸膜的优点，具有低电压和高电流效率的特点。1. The composite membrane combines the advantages of sulfonic acid membrane and carboxylic acid membrane, and has the characteristics of low voltage and high current efficiency.
2. 电流效率高(可达86～95%），产品NaOH（或KOH、LiOH等）溶液的浓度高。2. The current efficiency is high (up to 86~95%), and the concentration of the product NaOH (or KOH, LiOH, etc.) solution is high.
3. 能够在20～60℃范围内正常工作，与双极膜和阴离子膜的工作温度匹配。3. Able to operate normally within the range of 20 to 60°C, matching the working temperatures of bipolar membranes and anionic membranes.
4. 可以在pH 1~14的盐水中正常工作。4. Can work normally in salt water with pH 1~14.
5. 由于不使用昂贵的全氟或部分氟化材料，生产成本低（相当于全氟膜价格的10～15%）。5. Since expensive perfluorinated or partially fluorinated materials are not used, the production cost is low (equivalent to 10-15% of the price of perfluorinated membrane).
6. 本发明制备的无氟磺酸羧酸复合型阳离子交换膜还具有结构牢固、使用寿命长的优点，能有效解决现有双极膜电渗析设备或类似工作条件的电解设备中磺酸型阳膜存在的问题。6. The fluorine-free sulfonic acid carboxylic acid composite cation exchange membrane prepared by the present invention also has the advantages of solid structure and long service life, and can effectively solve the problem of sulfonic acid type in existing bipolar membrane electrodialysis equipment or electrolysis equipment with similar working conditions. Problems with the positive film.
在实际生产应用中，采用普通磺酸型阳膜的双极膜电渗析设备更换无氟磺酸羧酸复合膜以后，在其它运行条件不变的情况下，碱（NaOH、KOH、LiOH等）的产能提高15~25%，产品碱浓度可从2mol/L提高到3mol/L以上，运行成本降低20~25%左右，经济效益十分显著。In actual production applications, after replacing the fluorine-free sulfonic acid carboxylic acid composite membrane with a bipolar membrane electrodialysis equipment using an ordinary sulfonic acid type cation membrane, when other operating conditions remain unchanged, alkali (NaOH, KOH, LiOH, etc.) The production capacity is increased by 15~25%, the product alkali concentration can be increased from 2mol/L to more than 3mol/L, the operating cost is reduced by about 20~25%, and the economic benefits are very significant.
附图说明Description of the drawings
图1为本发明碳氢基无氟磺酸羧酸复合型阳离子交换膜横断面和两侧工作溶液的示意图。Figure 1 is a schematic diagram of the cross section of the hydrocarbon-based fluorine-free sulfonic acid carboxylic acid composite cation exchange membrane of the present invention and the working solutions on both sides.
图2为本发明碳氢基无氟磺酸羧酸复合型阳离子交换膜在双极膜电渗析中分解盐制取酸碱的原理示意图，其中，BP-双极膜，A-阴膜，C复合膜（红色表示羧酸层）。Figure 2 is a schematic diagram of the principle of the hydrocarbon-based fluorine-free sulfonic acid carboxylic acid composite cation exchange membrane of the present invention for decomposing salts to produce acids and bases in bipolar membrane electrodialysis, wherein BP-bipolar membrane, A-anion membrane, C Composite membrane (red indicates carboxylic acid layer).
图3为本发明碳氢基无氟磺酸羧酸复合型阳离子交换膜在电解槽中分离盐碱的原理示意图，其中，C复合膜（红色表示羧酸层）。Figure 3 is a schematic diagram of the principle of the hydrocarbon-based fluorine-free sulfonic acid carboxylic acid composite cation exchange membrane of the present invention for separating salt and alkali in an electrolytic cell, in which the C composite membrane (red indicates the carboxylic acid layer).
具体实施方式Detailed ways
一种碳氢基无氟磺酸羧酸复合型阳离子交换膜，其是以碳氢聚合物为原料制备的具有双层结构的阳离子膜，其中较厚的一层为磺酸层，较薄的一层为羧酸层。A hydrocarbon-based fluorine-free sulfonic acid carboxylic acid composite cation exchange membrane, which is a cationic membrane with a double-layer structure prepared from hydrocarbon polymers. The thicker layer is a sulfonic acid layer, and the thinner layer is a sulfonic acid layer. One layer is the carboxylic acid layer.
其中，所述磺酸层的厚度为0.05-0.50mm。所述羧酸层的厚度为0.01-0.10mm。Wherein, the thickness of the sulfonic acid layer is 0.05-0.50mm. The thickness of the carboxylic acid layer is 0.01-0.10mm.
所述复合型阳离子交换膜的制备方法可采用刮涂法，即在碳氢基磺酸膜的一面刮涂一层含羧酸成分的碳氢基膜液，然后加热烘干，使生成的羧酸层牢固地附着在磺酸型阳膜上形成所述复合膜。所述含羧酸成分的碳氢基膜液中含有：各种羧酸及羧酸盐、交联剂、粘合剂及溶液等，所述溶剂可为二甲基甲酰胺（DMF）、二甲基乙酰胺（DMAc）、N-甲基吡咯烷酮(NMP)、甲醇、乙醇、二氯乙烷、去离子水等。The preparation method of the composite cation exchange membrane can adopt the scraping method, that is, scraping a layer of hydrocarbon-based membrane liquid containing carboxylic acid components on one side of the hydrocarbon-based sulfonic acid membrane, and then heating and drying to make the generated carboxylic acid membrane liquid. The acid layer is firmly attached to the sulfonic acid type cation film to form the composite film. The hydrocarbon-based membrane liquid containing carboxylic acid components contains: various carboxylic acids and carboxylates, cross-linking agents, adhesives and solutions, etc. The solvent can be dimethylformamide (DMF), dimethyl formamide (DMF), etc. Methylacetamide (DMAc), N-methylpyrrolidone (NMP), methanol, ethanol, dichloroethane, deionized water, etc.
可选地，所述复合型阳离子交换膜的制备方法可采用流延法，即采用流延法制取较厚的碳氢基磺酸型阳膜，烘干定型后再在其上流延一层较薄的碳氢基羧酸层，形成所述复合膜。Optionally, the preparation method of the composite cation exchange membrane can be a casting method, that is, a thicker hydrocarbon sulfonic acid type cation membrane is prepared by the casting method, and then a thicker layer of hydrocarbon sulfonic acid type cation membrane is cast on it after drying and shaping. A thin layer of hydrocarbon carboxylic acid forms the composite film.
可选地，所述复合型阳离子交换膜的制备方法可采用粘合法，即先流延制取厚度很薄但具有一定强度的碳氢基羧酸型阳膜，然后用能通过阳离子的粘合剂将其粘贴在碳氢基磺酸型阳膜上形成所述复合膜。或用流延法分别制取较厚的碳氢基磺酸型阳膜和较薄的碳氢基羧酸型阳膜，然后用能通过阳离子的粘合剂将两张膜紧密粘合，烘干后形成所述复合膜。Optionally, the composite cation exchange membrane can be prepared by a bonding method, that is, a hydrocarbon carboxylic acid-type cation film with a very thin thickness but a certain strength is first produced by casting, and then a bonding agent capable of passing cations is used. The mixture is pasted on the hydrocarbon sulfonic acid type cation film to form the composite film. Or use the casting method to separately prepare a thicker hydrocarbon sulfonic acid type cation film and a thinner hydrocarbon carboxylic acid type cation film, and then use an adhesive that can pass cations to tightly bond the two films and bake them. After drying, the composite film is formed.
可选地，所述复合型阳离子交换膜的制备方法还可采用含浸聚合的方法，即在碳氢基磺酸型阳膜的一侧，含浸吸收有羧酸成分的碳氢基聚合物溶液（成分有丙烯酸、苯乙烯、二乙烯苯等），通过调整含浸温度和时间控制磺酸型阳膜吸收聚合物溶液形成的羧酸层厚度，然后在热压机中热压一段时间，让羧酸聚合液固化，形成所述复合膜。Optionally, the preparation method of the composite cation exchange membrane can also adopt an impregnation polymerization method, that is, impregnating one side of the hydrocarbon sulfonic acid type cation membrane with a hydrocarbon polymer solution that absorbs carboxylic acid components ( (Ingredients include acrylic acid, styrene, divinylbenzene, etc.). By adjusting the impregnation temperature and time, the thickness of the carboxylic acid layer formed by the sulfonic acid-type cation film absorbing the polymer solution is controlled, and then hot-pressed in a hot press for a period of time to allow the carboxylic acid to The polymerization liquid solidifies to form the composite film.
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。In order to make the content of the present invention easier to understand, the technical solutions of the present invention will be further described below in conjunction with specific embodiments, but the present invention is not limited thereto.
实施例1：Example 1:
1）羧酸聚合液的制备：在搅拌条件下向烧瓶中依次加入二甲基乙酰胺200g、甲基丙烯酸60g、苯乙烯30g、二乙烯基苯10g、偶氮二异丁腈0.5g、过氯乙烯粉3~7g，使各组分溶解并混合均匀后，将烧瓶密闭并置于35℃恒温箱中预聚合24小时，之后将所得羧酸聚合液置于3~5℃的冷藏箱中保存，以防止其进一步聚合；1) Preparation of carboxylic acid polymerization solution: Add 200g of dimethylacetamide, 60g of methacrylic acid, 30g of styrene, 10g of divinylbenzene, 0.5g of azobisisobutyronitrile, and 3~7g of vinyl chloride powder. After each component is dissolved and mixed evenly, the flask is sealed and placed in a 35°C thermostat for pre-polymerization for 24 hours. Afterwards, the resulting carboxylic acid polymerization solution is placed in a 3~5°C refrigerator. Preserved to prevent further aggregation;
2）在干燥的致密型异相磺酸阳膜（浙江金华金秋公司生产的C21型膜，厚度为0.40～0.45mm）上刮涂一层羧酸聚合液，然后在60℃的烘箱中烘干4小时，生成厚度为0.03～0.10mm的羧酸层，再浸水24小时，得到无氟磺酸羧酸复合型阳离子交换膜。2) Apply a layer of carboxylic acid polymerization liquid on the dry dense heterogeneous sulfonic acid cation membrane (C21 membrane produced by Zhejiang Jinhua Jinqiu Company, thickness is 0.40~0.45mm), and then dry it in an oven at 60°C After 4 hours, a carboxylic acid layer with a thickness of 0.03 to 0.10 mm was formed, and then soaked in water for 24 hours to obtain a fluorine-free sulfonic acid carboxylic acid composite cation exchange membrane.
将所得复合膜安装在电解硫酸钠盐水制取NaOH的测试电解槽中，使其羧酸层的一面朝向碱室并与10% NaOH接触，磺酸层一面朝向盐室并与pH 7的10%硫酸钠盐水接触，在电流密度600A/m2、温度40℃下，膜的两侧电压降为0.35V，电解生成NaOH的电流效率为86%。相比之下，未增加羧酸层结构的C21型阳膜在同等条件下膜的两侧电压降为0.30V，电解生成NaOH的电流效率只有67%。The obtained composite membrane was installed in a test electrolytic cell for electrolyzing sodium sulfate brine to produce NaOH, with the side of the carboxylic acid layer facing the alkali chamber and in contact with 10% NaOH, and the side of the sulfonic acid layer facing the salt chamber and in contact with 10% of pH 7 In contact with sodium sulfate salt water, at a current density of 600A/m2 and a temperature of 40°C, the voltage drop on both sides of the membrane is 0.35V, and the current efficiency of electrolysis to generate NaOH is 86%. In contrast, under the same conditions, the voltage drop on both sides of the membrane of a C21-type cation membrane without adding a carboxylic acid layer structure is 0.30V, and the current efficiency of electrolysis to generate NaOH is only 67%.
实施例2：Example 2:
将步骤2）中所使用的异相磺酸阳膜替换为均相磺酸阳膜（浙江绍兴佰辰公司生产，厚度0.16mm），其他操作同实施例1，所得复合膜在与实施例1相同的检测条件下运行，其膜的两侧电压降为0.25V，电解生成NaOH的电流效率为91%。相比之下，未增加羧酸层的均相磺酸阳膜在同等条件下膜的两侧电压降为0.18V，电解生成NaOH的电流效率为75%。Replace the heterogeneous sulfonic acid cation membrane used in step 2) with a homogeneous sulfonic acid cation membrane (produced by Zhejiang Shaoxing Baichen Company, thickness 0.16mm). Other operations are the same as in Example 1. The obtained composite membrane is the same as in Example 1. Operating under the same detection conditions, the voltage drop on both sides of the membrane is 0.25V, and the current efficiency of electrolysis to generate NaOH is 91%. In contrast, for a homogeneous sulfonic acid cation membrane without adding a carboxylic acid layer, the voltage drop on both sides of the membrane is 0.18V under the same conditions, and the current efficiency of electrolysis to generate NaOH is 75%.
经测试，利用各种碳氢材料与工艺制取的均相磺酸阳膜（离子交换基团通式为R-SO3-）按上述操作增加羧酸层，均可得到电流效率提高的相同结果。After testing, homogeneous sulfonic acid cationic membranes (the general formula of the ion exchange group is R-SO3- ) prepared by using various hydrocarbon materials and processes can obtain the same improvement in current efficiency by adding a carboxylic acid layer according to the above operations. result.
实施例3：Example 3:
1）羧酸聚合液的制备：同实施例1；1) Preparation of carboxylic acid polymerization liquid: same as Example 1;
2）磺酸型阳膜溶液的制备：取80g二甲基乙酰胺或二甲基甲酰胺加入烧瓶中，置于40℃水浴锅中，在搅拌条件下加入20g磺化聚苯醚，搅拌至完全溶解后停止搅拌，得到浓度为20%的磺化聚苯醚溶液，密闭备用；2) Preparation of sulfonic acid type cation film solution: Add 80g of dimethylacetamide or dimethylformamide into a flask, place it in a 40°C water bath, add 20g of sulfonated polyphenylene ether under stirring conditions, and stir until After complete dissolution, stop stirring to obtain a sulfonated polyphenylene ether solution with a concentration of 20%, which should be sealed for later use;
3）在平整的玻璃板上流延一层步骤2）制备的磺化聚苯醚溶液，在60℃的烘箱中加热烘干4小时，生成厚度为0.10～0.20mm的磺化聚苯醚阳膜层，然后其表面上再流延一层羧酸聚合液，在60℃的烘箱中加热烘干2小时，形成厚度为0.02～0.10mm的羧酸层，再浸水24小时，得到无氟磺酸羧酸复合型阳离子交换膜。3) Cast a layer of the sulfonated polyphenylene ether solution prepared in step 2) on a flat glass plate, and heat and dry it in an oven at 60°C for 4 hours to form a sulfonated polyphenylene ether positive film with a thickness of 0.10~0.20mm. layer, and then cast a layer of carboxylic acid polymerization liquid on the surface, heat and dry it in an oven at 60°C for 2 hours to form a carboxylic acid layer with a thickness of 0.02~0.10mm, and then soak it in water for 24 hours to obtain fluorine-free sulfonic acid Carboxylic acid composite cation exchange membrane.
所得复合膜在与实施例1相同的检测条件下运行，其膜的两侧电压降为0.26V，电解生成NaOH的电流效率为93%。相比之下，对未加羧酸层的磺化聚苯醚阳膜在同等条件下检测膜的两侧电压降为0.19V，电解生成NaOH的电流效率为76%。The obtained composite membrane was operated under the same detection conditions as in Example 1. The voltage drop on both sides of the membrane was 0.26V, and the current efficiency of electrolyzing NaOH was 93%. In contrast, for a sulfonated polyphenylene ether cation membrane without a carboxylic acid layer, the voltage drop on both sides of the membrane was detected to be 0.19V under the same conditions, and the current efficiency of electrolysis to generate NaOH was 76%.
实施例4：Example 4:
将实施例3中步骤2）替换为磺化聚醚醚酮溶液的制备，即将24g磺化聚醚醚酮在40℃、搅拌条件下溶解于80g二甲基乙酰胺、二甲基甲酰胺或N-甲基吡咯烷酮中，得到浓度为24%的磺化聚醚醚酮溶液，其他操作同实施例3，所得复合膜在与实施例1相同的检测条件下，膜的两侧电压降为0.22V，电解生成NaOH的电流效率为95%。相比之下，未加羧酸层的磺化聚醚醚酮阳膜在同等条件下检测膜的两侧电压降为0.15V，电解生成NaOH的电流效率为75%。Step 2) in Example 3 is replaced with the preparation of sulfonated polyetheretherketone solution, that is, 24g of sulfonated polyetheretherketone is dissolved in 80g of dimethylacetamide, dimethylformamide or under stirring conditions at 40°C. In N-methylpyrrolidone, a sulfonated polyetheretherketone solution with a concentration of 24% was obtained. Other operations were the same as in Example 3. Under the same detection conditions as in Example 1, the voltage drop on both sides of the composite membrane was 0.22 V, the current efficiency of electrolysis to generate NaOH is 95%. In contrast, for a sulfonated polyetheretherketone cationic membrane without a carboxylic acid layer, the voltage drop on both sides of the membrane was detected to be 0.15V under the same conditions, and the current efficiency of electrolysis to generate NaOH was 75%.
实施例5：Example 5:
1）磺化聚醚醚酮阳膜的制备：按实施例4制备磺化聚醚醚酮溶液，将其真空脱泡后在玻璃板上用流延法制取磺化聚醚醚酮膜，其厚度为0.10～0.18mm。1) Preparation of sulfonated polyether ether ketone cationic membrane: Prepare the sulfonated polyether ether ketone solution according to Example 4, degas it in vacuum and then use the casting method on a glass plate to prepare a sulfonated polyether ether ketone membrane. Thickness is 0.10~0.18mm.
2）羧酸阳膜的制备：在烧瓶中加入二甲基甲酰胺100g、丙烯酸70g、苯乙烯20g、二乙烯基苯10g、偶氮二异丁腈0.5g、聚氯乙烯粉3~7g，使各组分溶解并混合均匀后，将烧瓶密闭并置于40℃恒温箱中预聚合10小时，真空脱泡后在玻璃板上用流延法制取羧酸阳膜，其厚度为0.02～0.10mm。2) Preparation of carboxylic acid cation film: add 100g of dimethylformamide, 70g of acrylic acid, 20g of styrene, 10g of divinylbenzene, 0.5g of azobisisobutyronitrile, and 3~7g of polyvinyl chloride powder in a flask. After each component is dissolved and mixed evenly, the flask is sealed and placed in a 40°C incubator for pre-polymerization for 10 hours. After vacuum degassing, a carboxylic acid cationic film is produced by casting on a glass plate with a thickness of 0.02 to 0.10 mm.
3）用浓度18%的磺化聚醚醚酮为胶粘剂，在双橡胶辊粘合机上将上述两种膜滚动粘合，再进入烘箱60℃下烘干2小时，得到无氟磺酸羧酸复合型阳离子交换膜。3) Use sulfonated polyetheretherketone with a concentration of 18% as adhesive, roll and bond the above two films on a double rubber roller bonding machine, and then dry them in an oven at 60°C for 2 hours to obtain fluorine-free sulfonic acid carboxylic acid. Composite cation exchange membrane.
将所得复合膜在与实施例1相同的检测条件下运行，其膜的两侧电压降为0.27V，电解生成NaOH的电流效率为93.5%。相比之下，未增加羧酸层的单一磺化聚醚醚酮阳膜在同等条件下膜的两侧电压降为0.15V，电解生成NaOH的电流效率为75%。The obtained composite membrane was operated under the same detection conditions as in Example 1. The voltage drop on both sides of the membrane was 0.27V, and the current efficiency of NaOH generated by electrolysis was 93.5%. In contrast, for a single sulfonated polyetheretherketone cation membrane without adding a carboxylic acid layer, the voltage drop on both sides of the membrane is 0.15V under the same conditions, and the current efficiency of electrolysis to generate NaOH is 75%.
实施例6：Example 6:
将实施例5步骤1）中所用磺化聚醚醚酮溶液替换成实施例3步骤2）所制备的磺化聚苯醚溶液，制成磺化聚苯醚阳膜，其他操作同实施例5，所得复合膜在与实施例1相同的检测条件下运行，其膜的两侧电压降为0.29V，电解生成NaOH的电流效率为94%。相比之下，未增加羧酸层的单一磺化聚苯醚阳膜在同等条件下膜的两侧电压降为0.19V，电解生成NaOH的电流效率为77.5%。Replace the sulfonated polyether ether ketone solution used in step 1) of Example 5 with the sulfonated polyphenylene ether solution prepared in step 2) of Example 3 to prepare a sulfonated polyphenylene ether positive film. Other operations are the same as in Example 5. , the obtained composite membrane was operated under the same detection conditions as Example 1, the voltage drop on both sides of the membrane was 0.29V, and the current efficiency of electrolysis to generate NaOH was 94%. In contrast, for a single sulfonated polyphenylene ether cation membrane without adding a carboxylic acid layer, the voltage drop on both sides of the membrane is 0.19V under the same conditions, and the current efficiency of electrolysis to generate NaOH is 77.5%.
实施例7：Example 7:
将实施例5步骤1）中所用磺化聚醚醚酮溶液替换成磺化聚砜与磺化聚醚醚酮混合膜液（将9.6g磺化聚砜和14.4g磺化聚醚醚酮共同在40℃、搅拌条件下溶解于80g二甲基乙酰胺、二甲基甲酰胺或N-甲基吡咯烷酮中制得），其他操作同实施例5，所得复合膜在与实施例1相同的检测条件下运行，膜的两侧电压降为0.31V，电解生成NaOH的电流效率为93%。这种复合膜的特点是耐热性较好，可以在50～60℃温度下长期工作。The sulfonated polyetheretherketone solution used in step 1) of Example 5 was replaced with a mixed membrane solution of sulfonated polysulfone and sulfonated polyetheretherketone (9.6g of sulfonated polysulfone and 14.4g of sulfonated polyetheretherketone were mixed together Prepared by dissolving in 80g dimethylacetamide, dimethylformamide or N-methylpyrrolidone under stirring conditions at 40°C), other operations are the same as in Example 5, and the obtained composite membrane is tested in the same way as in Example 1 When operating under the conditions, the voltage drop on both sides of the membrane is 0.31V, and the current efficiency of electrolysis to generate NaOH is 93%. This composite membrane is characterized by good heat resistance and can work at temperatures of 50 to 60°C for a long time.
实施例8：Example 8:
将普通均相磺酸阳膜的单侧与羧酸聚合液（成分：丙烯酸70%，苯乙烯20%，二乙烯基苯10%，偶氮二异丁腈1%，余量为水）接触，在40℃下含浸吸收10～60分钟（调整温度和吸收时间可以改变羧酸层的厚度），然后将磺酸阳膜平铺在热压机中，用0.1mm厚度的聚四氟乙烯膜隔离迭放，在80℃下热压固化4小时，得到无氟磺酸羧酸复合型阳离子交换膜。将所得复合膜在与实施例1相同的检测条件下运行，其膜的两侧电压降为0.22V，电解生成NaOH的电流效率为85%。相比之下，未经含浸形成羧酸膜的普通均相磺酸阳膜在同等条件下膜的两侧电压降为0.18V，电解生成NaOH的电流效率为76%。Contact one side of the ordinary homogeneous sulfonic acid cation film with the carboxylic acid polymerization liquid (composition: 70% acrylic acid, 20% styrene, 10% divinylbenzene, 1% azobisisobutyronitrile, the balance is water) , impregnate and absorb at 40°C for 10 to 60 minutes (the thickness of the carboxylic acid layer can be changed by adjusting the temperature and absorption time), then lay the sulfonic acid cationic film flat in a hot press, and use a 0.1mm thick polytetrafluoroethylene film The membranes were isolated and stacked, and hot-pressed and cured at 80°C for 4 hours to obtain a fluorine-free sulfonic acid carboxylic acid composite cation exchange membrane. The obtained composite membrane was operated under the same detection conditions as in Example 1. The voltage drop on both sides of the membrane was 0.22V, and the current efficiency of NaOH generated by electrolysis was 85%. In comparison, for an ordinary homogeneous sulfonic acid cation membrane that has not been impregnated to form a carboxylic acid membrane, the voltage drop on both sides of the membrane is 0.18V under the same conditions, and the current efficiency of electrolysis to generate NaOH is 76%.
本发明形成磺酸羧酸复合型阳离子交换膜使用的碳氢聚合物高分子材料和离子交换基团形式可以有多种，不局限于本发明中所列举的品种。The hydrocarbon polymer polymer materials and ion exchange group forms used to form the sulfonic acid-carboxylic acid composite cation exchange membrane in the present invention can be in various forms and are not limited to the varieties listed in the present invention.
构成所述复合型阳离子交换膜的磺酸膜和羧酸膜不一定包含纯粹的磺酸基团或羧酸基团，为了提高膜的性能，有时需要掺入部分其它离子形式的交换基团，这些也都在本发明的保护范围内。The sulfonic acid membrane and carboxylic acid membrane that constitute the composite cation exchange membrane do not necessarily contain pure sulfonic acid groups or carboxylic acid groups. In order to improve the performance of the membrane, it is sometimes necessary to incorporate some exchange groups in other ionic forms. These are also within the protection scope of the present invention.
对于本技术领域的技术人员来说，在不脱离本发明原理的前提下，可以对本发明进行若干化学成分和工艺的调整变动或改进，这些也都在本发明权利要求的保护范围内。For those skilled in the art, without departing from the principle of the invention, the invention can be adjusted, changed or improved in several chemical components and processes, which are also within the protection scope of the claims of the invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311347163.2ACN117123073A (en) | 2023-10-18 | 2023-10-18 | Hydrocarbon-based fluorine-free sulfonic acid carboxylic acid composite cation exchange membrane and application thereof |
| PCT/CN2024/113531WO2025082024A1 (en) | 2023-10-18 | 2024-08-21 | Hydrocarbon-based fluorine-free sulfonic acid-carboxylic acid composite cation exchange membrane and use thereof |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311347163.2ACN117123073A (en) | 2023-10-18 | 2023-10-18 | Hydrocarbon-based fluorine-free sulfonic acid carboxylic acid composite cation exchange membrane and application thereof |
| Publication Number | Publication Date |
|---|---|
| CN117123073Atrue CN117123073A (en) | 2023-11-28 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311347163.2APendingCN117123073A (en) | 2023-10-18 | 2023-10-18 | Hydrocarbon-based fluorine-free sulfonic acid carboxylic acid composite cation exchange membrane and application thereof |
| Country | Link |
|---|---|
| CN (1) | CN117123073A (en) |
| WO (1) | WO2025082024A1 (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2025082024A1 (en)* | 2023-10-18 | 2025-04-24 | 南平市浩翔科技有限公司 | Hydrocarbon-based fluorine-free sulfonic acid-carboxylic acid composite cation exchange membrane and use thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4670146A (en)* | 1981-06-24 | 1987-06-02 | Asahi Kasei Kogyo Kabushiki Kaisha | Composite hydrophilic membrane and method for manufacture thereof |
| CN1324880A (en)* | 2001-07-05 | 2001-12-05 | 上海交通大学 | Polyether ketone with pendant sulfonate radical and pendant carboxylate radical and its prepn. |
| CN102325926A (en)* | 2009-02-23 | 2012-01-18 | 旭硝子株式会社 | Cation exchange membrane, method for producing same, and electrolyzer using same |
| KR20200029929A (en)* | 2018-09-11 | 2020-03-19 | 한국전력공사 | Double layer ion exchange membrane of chlor-alkali process with improved chemical stability and fabrication method of the same |
| CN112313269A (en)* | 2018-06-21 | 2021-02-02 | 株式会社益诺医疗科技 | Cation exchange membrane comprising polymer carrier and method for producing same |
| WO2025082024A1 (en)* | 2023-10-18 | 2025-04-24 | 南平市浩翔科技有限公司 | Hydrocarbon-based fluorine-free sulfonic acid-carboxylic acid composite cation exchange membrane and use thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4670146A (en)* | 1981-06-24 | 1987-06-02 | Asahi Kasei Kogyo Kabushiki Kaisha | Composite hydrophilic membrane and method for manufacture thereof |
| CN1324880A (en)* | 2001-07-05 | 2001-12-05 | 上海交通大学 | Polyether ketone with pendant sulfonate radical and pendant carboxylate radical and its prepn. |
| CN102325926A (en)* | 2009-02-23 | 2012-01-18 | 旭硝子株式会社 | Cation exchange membrane, method for producing same, and electrolyzer using same |
| CN112313269A (en)* | 2018-06-21 | 2021-02-02 | 株式会社益诺医疗科技 | Cation exchange membrane comprising polymer carrier and method for producing same |
| KR20200029929A (en)* | 2018-09-11 | 2020-03-19 | 한국전력공사 | Double layer ion exchange membrane of chlor-alkali process with improved chemical stability and fabrication method of the same |
| WO2025082024A1 (en)* | 2023-10-18 | 2025-04-24 | 南平市浩翔科技有限公司 | Hydrocarbon-based fluorine-free sulfonic acid-carboxylic acid composite cation exchange membrane and use thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2025082024A1 (en)* | 2023-10-18 | 2025-04-24 | 南平市浩翔科技有限公司 | Hydrocarbon-based fluorine-free sulfonic acid-carboxylic acid composite cation exchange membrane and use thereof |
| Publication number | Publication date |
|---|---|
| WO2025082024A1 (en) | 2025-04-24 |
| Publication | Publication Date | Title |
|---|---|---|
| US4101395A (en) | Cathode-structure for electrolysis | |
| US4683040A (en) | Process for electrolysis of sodium chloride | |
| US4090931A (en) | Anode-structure for electrolysis | |
| US9023554B2 (en) | Perfluorinated ion exchange resin, preparation method and use thereof | |
| JPS63297406A (en) | Sulfonic fluoro polymer with low equivalent weight | |
| CN118324973A (en) | Composite resin dispersion liquid and preparation method and application thereof | |
| WO2025082024A1 (en) | Hydrocarbon-based fluorine-free sulfonic acid-carboxylic acid composite cation exchange membrane and use thereof | |
| CA1265472A (en) | Cation exchange fluoropolymer membrane | |
| JPS5911674B2 (en) | Electrolysis method and electrolyzer | |
| JPS6216964B2 (en) | ||
| US5716504A (en) | Cation exchange membrane for electrolysis and process for producing potassium hydroxide of high purity | |
| CN110699706B (en) | Fluoride ion exchange membrane for alkali chloride electrolysis | |
| EP0192261B1 (en) | Multilayer cation exchange membrane | |
| US4486277A (en) | Electrolytic cation exchange membrane | |
| CN111188060B (en) | Diaphragm of reinforced low-resistance chlor-alkali electrolytic cell and preparation method thereof | |
| US4686120A (en) | Multilayer cation exchange membrane | |
| CN116100916B (en) | A method for preparing a cation exchange membrane for industrial sodium sulfate electrolysis | |
| JPH02279732A (en) | Toughened cation exchange membrane and its preparation | |
| CN114506139B (en) | A main chain fluorocarbon alkali-resistant bipolar membrane and its preparation method | |
| JP2504135B2 (en) | Cation exchange membrane for electrolysis | |
| CN113814007B (en) | Preparation and application of crosslinked imidazole functionalized polyvinyl chloride anion exchange membrane | |
| CN112126355B (en) | Preparation method of coating solution for ion exchange membrane | |
| CN111499916B (en) | Preparation method of monolithic polyaryletherketone bipolar membrane with phthalocyanine group-containing side group | |
| JPS6264834A (en) | ion exchange membrane | |
| Vasudevan | Membranes and Diaphragms for Electrochemical Processes (Part-I) |
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |