技术领域technical field
本发明涉及纤维的制备方法，具体地涉及一种具有二恶英分解功能的聚四氟乙烯纤维的制备方法。The invention relates to a method for preparing fibers, in particular to a method for preparing polytetrafluoroethylene fibers with dioxin decomposition function.
背景技术Background technique
随着世界各国现代工业化进程的快速发展，大气污染已成为一个日益严重的全球性问题，二恶英、呋喃、氮氧化物、硫化物等废气的排放和控制得到世界各国的重视。城市生活垃圾焚烧处理方法目前已成为各国处理废弃物最主要的和最有效的技术之一。垃圾焚烧处理不但能将垃圾变废为宝，汽电共生使能量资源得到再生利用，而且能减少约90％的废物体积。但是，焚烧过程中不可避免地会产生大量的污染物，如颗粒物、酸性气体、重金属以及二恶英。这些污染物对人体健康存在着极大的危害，而尤以二恶英的毒害最大，去除难度也最高。目前，二恶英催化氧化分解去除技术得到迅速发展。催化剂在一定的温度下(180-250℃)可将二恶英分解为二氧化碳、水和微量的盐酸气体等。With the rapid development of modern industrialization in various countries in the world, air pollution has become an increasingly serious global problem. The emission and control of waste gases such as dioxins, furans, nitrogen oxides, and sulfides have attracted the attention of countries all over the world. Municipal solid waste incineration has become one of the most important and effective technologies for waste disposal in various countries. Waste incineration treatment can not only turn waste into treasure, but also regenerate energy resources through gas-electric co-generation, and reduce the volume of waste by about 90%. However, the incineration process will inevitably produce a large amount of pollutants, such as particulate matter, acid gas, heavy metals and dioxins. These pollutants are extremely harmful to human health, and dioxin is the most harmful and the most difficult to remove. At present, the catalytic oxidation decomposition and removal technology of dioxin has been developed rapidly. The catalyst can decompose dioxin into carbon dioxide, water and a trace amount of hydrochloric acid gas at a certain temperature (180-250°C).
催化氧化分解技术中采用的催化剂多以氧化钨、氧化锰等为活性成分，以二氧化钛为载体。催化剂粉体经过特殊的成型技术加工成“蜂窝”形状被使用，存在对废气的分解效率低和催化温度高等缺点。Most of the catalysts used in the catalytic oxidation decomposition technology use tungsten oxide, manganese oxide, etc. as active components and titanium dioxide as the carrier. The catalyst powder is processed into a "honeycomb" shape by special molding technology, which has the disadvantages of low decomposition efficiency of exhaust gas and high catalytic temperature.
若将催化剂加工成粉体使用则可大大提高分解效率，降低分解温度。但使用粉体材料需要特殊载体。其中膨体聚四氟乙烯最为理想，它具有以下优点：耐温性能好；可通过特殊加工方法制备出多微孔的结构，便于废气和催化剂充分接触。美国GORE公司的专利(Marc Plinke，Baltimore，Md.，et al.，US Patent5620669，1997，4，15)则是采用此方法。它是采用催化剂浆料和聚四氟乙烯分散液混和(即湿法混合)，加入阳离子表面活性剂，然后凝结干燥。挤出片材，然后压延，后在270℃下拉伸成含有催化剂粉体的PTFE纤维。而后加工成针刺毡后复合PTFE微孔薄膜。该材料具有截留微尘(效率99.95％)和分解废气(效率98.4％)双重功效。由于我国缺乏湿法混合所必须的设备(如高精度的切削设备)和原材料，因此该方法在我国不适用。If the catalyst is processed into powder and used, the decomposition efficiency can be greatly improved and the decomposition temperature can be reduced. But the use of powder materials requires a special carrier. Among them, expanded polytetrafluoroethylene is the most ideal, and it has the following advantages: good temperature resistance; a microporous structure can be prepared by special processing methods, which is convenient for full contact between exhaust gas and catalyst. The patent (Marc Plinke, Baltimore, Md., et al., US Patent 5620669, 1997, 4, 15) of U.S. GORE Company then adopts this method. It uses catalyst slurry and polytetrafluoroethylene dispersion to mix (that is, wet mixing), adds cationic surfactant, and then condenses and dries. The sheet was extruded, then calendered, and stretched at 270°C to form PTFE fibers containing catalyst powder. Then it is processed into needle felt and compounded with PTFE microporous film. The material has dual effects of trapping fine dust (efficiency 99.95%) and decomposing waste gas (efficiency 98.4%). Due to the lack of equipment (such as high-precision cutting equipment) and raw materials necessary for wet mixing in our country, this method is not applicable in our country.
专利(用于废气分解的膨体聚四氟乙烯纤维的制备方法，申请号200610154943.5)公开了一种用于废气分解的膨体聚四氟乙烯纤维的制备方法，该方法是将废气的分解催化剂粉体混和到纤维原料中，并加工出具有废气分解功能的聚四氟乙烯纤维。该方法由于采用直接挤出纺丝方法，纺丝压力较高，对纺丝设备的要求高。The patent (preparation method of expanded polytetrafluoroethylene fiber for waste gas decomposition, application number 200610154943.5) discloses a preparation method of expanded polytetrafluoroethylene fiber for waste gas decomposition. The powder is mixed into the fiber raw material, and the PTFE fiber with exhaust gas decomposition function is processed. Because the method adopts the direct extrusion spinning method, the spinning pressure is relatively high, and the requirements for spinning equipment are high.
专利(有催化分解二噁英功能的膨体聚四氟乙烯纤维的制备方法，申请号200810060356.9)，涉及一种具有催化分解二恶英功能的膨体聚四氟乙烯纤维的制备方法，该方法是将膨体聚四氟乙烯树脂粉末和二恶英催化剂粉体混和，再混和液体润滑剂，经过挤出、压延、纵向拉伸、烧结定型、开纤等工艺加工而成。The patent (Preparation method of expanded polytetrafluoroethylene fiber with catalytic decomposition of dioxin, application number 200810060356.9) relates to a preparation method of expanded polytetrafluoroethylene fiber with catalytic decomposition of dioxin. It is made by mixing expanded polytetrafluoroethylene resin powder and dioxin catalyst powder, and then mixing liquid lubricant, and then processing it through extrusion, calendering, longitudinal stretching, sintering and setting, and fiber opening.
专利(高温烟气/粉尘一体化处理用覆膜过滤材料的制备方法，专利号ZL200610155052.1)，该方法是将废气分解的膨体聚四氟乙烯纤维、其他耐高温纤维经过开松、混和、给料、梳理、纤网、叠网、预针刺、主针刺、高温汽蒸等工序加工成耐高温支撑材料，再在高温下与聚四氟乙烯微孔薄膜复合而成。Patent (preparation method of film-coated filter material for integrated treatment of high-temperature flue gas/dust, patent number ZL200610155052.1), the method is to open and mix expanded polytetrafluoroethylene fibers decomposed by waste gas and other high-temperature resistant fibers , Feeding, carding, web, stacking, pre-needling, main needling, high-temperature steaming and other processes are processed into high-temperature resistant support materials, and then compounded with PTFE microporous film at high temperature.
专利(高温烟气和粉尘处理用的聚四氟乙烯微孔薄膜制备方法，申请号200710069975.X)，公开了高温烟气/粉尘一体化处理用聚四氟乙烯微孔薄膜制备方法。本发明将聚四氟乙烯树脂粉末和催化剂废气催化剂粉体混和，在混和液体润滑剂，经过挤出、压延、纵向拉伸、横向拉伸和热定型等工艺加工而成。The patent (preparation method of polytetrafluoroethylene microporous film for high temperature flue gas and dust treatment, application number 200710069975.X) discloses the preparation method of polytetrafluoroethylene microporous film for high temperature flue gas/dust integrated treatment. The invention mixes the polytetrafluoroethylene resin powder and the catalyst exhaust gas catalyst powder, and mixes the liquid lubricant, and processes such processes as extrusion, calendering, longitudinal stretching, transverse stretching and heat setting.
专利(一种除尘及二恶英分解双效过滤材料及其制备方法，申请号200810124334.4；一种除尘及二噁英分解一体化过滤材料及其制备方法，申请号200810124335.9)，是将负载二恶英分解催化剂的聚四氟乙烯纤维或聚四氟乙烯薄膜，与耐高温纤维(包括聚四氟乙烯纤维、聚酰亚胺纤维、聚苯硫醚纤维、玻璃纤维、芳纶纤维等)通过针刺的方法加工出具有除尘及二恶英分解多功能的过滤材料。Patents (a double-effect filter material for dust removal and dioxin decomposition and its preparation method, application number 200810124334.4; an integrated filter material for dust removal and dioxin decomposition and its preparation method, application number 200810124335.9), is to load dioxin PTFE fiber or PTFE film with British decomposition catalyst, and high temperature resistant fiber (including PTFE fiber, polyimide fiber, polyphenylene sulfide fiber, glass fiber, aramid fiber, etc.) through the needle The thorn method is used to process filter materials with multiple functions of dust removal and dioxin decomposition.
以上专利涉及到添加催化剂的聚四氟乙烯纤维或薄膜(200610154943.5、200810060356.9、200610155052.1、200810124334.4、200710069975.X、200810124335.9)，但均是采用催化剂和聚四氟乙烯共混加工而成，二者之间缺少可连接的成分，故催化剂和聚四氟乙烯之间结合牢度较差。在将纤维针刺成毡制作成过滤袋应用于垃圾焚烧场合，高温尾气是以一定风速冲击过滤袋，因此容易造成催化剂的流失，使过滤袋较快地失去对二恶英的分解功能。The above patents relate to polytetrafluoroethylene fibers or films with added catalysts (200610154943.5, 200810060356.9, 200610155052.1, 200810124334.4, 200710069975.X, 200810124335.9), but they are all blended with catalysts and polytetrafluoroethylene. Lack of connectable components, so the bonding fastness between the catalyst and PTFE is poor. When fibers are needle-punched into felt and made into filter bags for waste incineration, the high-temperature exhaust gas impacts the filter bag at a certain wind speed, so it is easy to cause the loss of catalyst, and the filter bag quickly loses its ability to decompose dioxins.
为了克服现有技术各种方法所存在的缺陷，本发明提供了一种采用聚四氟乙烯乳液表面改性催化剂方法，然后与聚四氟乙烯树脂粉末共混，在后续的热定型加工中将聚四氟乙烯乳液熔融，起到连接的作用，从而防止过滤袋使用过程中催化剂的流失。同时，该方法工艺简单易行，加工成本低，对设备要求较低。In order to overcome the defects in the various methods of the prior art, the present invention provides a method of surface modification catalyst using polytetrafluoroethylene emulsion, and then blending with polytetrafluoroethylene resin powder, in the follow-up heat setting processing The polytetrafluoroethylene emulsion melts and plays the role of connection, thereby preventing the loss of catalyst during the use of the filter bag. At the same time, the method has the advantages of simple process, low processing cost and low requirements on equipment.
发明内容Contents of the invention
本发明的目的是提供一种具有二恶英分解功能的聚四氟乙烯纤维的制备方法，该方法首先采用聚四氟乙烯乳液表面改性催化剂粉体，然后将改性后的催化剂粉体与聚四氟乙烯树脂粉末共混，加工含有催化剂的聚四氟乙烯薄膜，最后通过裂膜方法加工成具有二恶英分解功能的聚四氟乙烯纤维。具体的，本发明具有二恶英分解功能的聚四氟乙烯纤维的制备方法包括以下步骤：The purpose of this invention is to provide a kind of preparation method of the polytetrafluoroethylene fiber with dioxin decomposition function, this method adopts polytetrafluoroethylene emulsion surface modification catalyst powder at first, then the catalyst powder after the modification is mixed with The polytetrafluoroethylene resin powder is blended, the polytetrafluoroethylene film containing the catalyst is processed, and finally the polytetrafluoroethylene fiber with the function of dioxin decomposition is processed by the film splitting method. Concretely, the preparation method of the polytetrafluoroethylene fiber with dioxin decomposition function of the present invention comprises the following steps:
(1)催化剂粉体的表面改性：将聚四氟乙烯乳液倒入催化剂粉体中，搅拌，在105℃的烘箱内将乳液中的水分烘干；(1) Surface modification of the catalyst powder: pour the polytetrafluoroethylene emulsion into the catalyst powder, stir, and dry the moisture in the emulsion in an oven at 105°C;
(2)混料：将聚四氟乙烯树脂粉末和表面改性后的催化剂粉体混和，再加入液体润滑剂，聚四氟乙烯树脂粉末对液体润滑剂的重量比为1∶0.2-0.28混和均匀，在20～40℃的温度下静置96～144小时，然后在40～80℃的温度下静置10～16小时，使树脂粉末、液体润滑剂、表面改性后的催化剂三者充分混合，形成聚四氟乙烯物料；(2) Mixing: mix polytetrafluoroethylene resin powder with surface-modified catalyst powder, then add liquid lubricant, the weight ratio of polytetrafluoroethylene resin powder to liquid lubricant is 1: 0.2-0.28 and mix Evenly, let stand at a temperature of 20-40°C for 96-144 hours, and then stand at a temperature of 40-80°C for 10-16 hours, so that the resin powder, liquid lubricant, and surface-modified catalyst are fully mixed to form polytetrafluoroethylene material;
(3)压坯与压延：将所述的聚四氟乙烯物料在20～30℃下，在压坯机上压制成圆柱形毛坯，将毛坯通过柱塞挤出机在40～60℃的温度下挤出棒状物，然后经压延机在40～60℃下压延成聚四氟乙烯基带；(3) Compacting and calendering: press the polytetrafluoroethylene material on a compacting machine at 20-30°C to form a cylindrical blank, and pass the blank through a plunger extruder at a temperature of 40-60°C Extrude rods, and then calender them into polytetrafluoroethylene-based tapes at 40-60°C through a calender;
(4)纵向拉伸：将所述聚四氟乙烯基带在180～300℃的烘箱中进行纵向拉伸，获得脱脂基带；(4) Longitudinal stretching: longitudinally stretching the polytetrafluoroethylene base tape in an oven at 180-300°C to obtain a degreased base tape;
(5)烧结定型：将所述脱脂基带在320～420℃烧结定型，烧结时间20～80秒，获得烧结基带；(5) Sintering and shaping: the degreased base tape is sintered and shaped at 320-420° C. for 20-80 seconds to obtain a sintered base tape;
(6)开纤：将所述烧结基带在开纤设备上开纤，加工成具有二恶英分解功能的聚四氟乙烯纤维。(6) Fiber opening: the sintered base tape is opened on a fiber opening device to be processed into polytetrafluoroethylene fibers having a dioxin decomposition function.
在上述步骤(1)中，所述聚四氟乙烯乳液是在分散乳液中聚合制备得到聚四氟乙烯分散乳液，或将四氟乙烯聚合后分散在分散液中，浓缩该分散液至一定的重量百分比浓度，并以非离子型表面活性剂稳定的水分散液。其中聚四氟乙烯的重量百分比浓度大约为50％-70％，聚四氟乙烯粒径为0.05-0.2um，乳液的运动粘度为6-15mm2/s(25℃)，酸碱性pH≥8，密度为1.50-1.55g/cm3(20℃)。所述聚四氟乙烯乳液可以采用市售产品，如中昊晨光化工研究院的SFN-1、SFN-3、SFN-A中的一种或上述产品的混合物。In the above step (1), the polytetrafluoroethylene emulsion is prepared by polymerizing in a dispersion emulsion to obtain a polytetrafluoroethylene dispersion emulsion, or the tetrafluoroethylene is dispersed in the dispersion liquid after polymerization, and the dispersion liquid is concentrated to a certain Concentration by weight, and stabilized aqueous dispersion with non-ionic surfactant. The weight percent concentration of polytetrafluoroethylene is about 50%-70%, the particle size of polytetrafluoroethylene is 0.05-0.2um, the kinematic viscosity of the emulsion is 6-15mm2 /s (25°C), and the acid-base pH≥ 8. The density is 1.50-1.55g/cm3 (20°C). The polytetrafluoroethylene emulsion can be a commercially available product, such as one of SFN-1, SFN-3, and SFN-A of Zhonghao Chenguang Chemical Research Institute or a mixture of the above products.
在上述步骤(1)中，所述的催化剂粉体直径从纳米级到微米级，为20纳米-5微米(德国BASF公司提供)。In the above step (1), the diameter of the catalyst powder is from nanometer to micrometer, ranging from 20 nanometers to 5 micrometers (provided by German BASF company).
在上述步骤(1)中，所述的催化剂与聚四氟乙烯乳液的重量比为1∶0.01-1。In the above step (1), the weight ratio of the catalyst to the polytetrafluoroethylene emulsion is 1:0.01-1.
在上述步骤(2)中，所述的聚四氟乙烯树脂粉末和表面改性后的催化剂粉体的重量比为1∶0.3-0.6。In the above step (2), the weight ratio of the polytetrafluoroethylene resin powder to the surface-modified catalyst powder is 1:0.3-0.6.
在上述步骤(2)中，所述的液体润滑剂为液体石蜡、石油醚或煤油。In the above step (2), the liquid lubricant is liquid paraffin, petroleum ether or kerosene.
在上述步骤(2)中，所述的聚四氟乙烯树脂粉末的结晶度为98～99.9％、分子量为200万～1000万。采用市售产品，如日本大金公司F106、日本旭硝子公司CD123的产品。In the above step (2), the crystallinity of the polytetrafluoroethylene resin powder is 98-99.9%, and the molecular weight is 2 million-10 million. Commercially available products, such as F106 from Daikin Company of Japan and CD123 from Asahi Glass Company of Japan, were used.
通过本发明的上述方法制备的具有二恶英分解功能的聚四氟乙烯纤维，纤维直径40-80微米；在220℃对二恶英的去除率高达97-99％(针刺成非织造布，该纤维含量为520克/平方米)；在1米/秒的风速下，80小时内每1000克聚四氟乙烯纤维中催化剂的损失量为2-8克，显著低于申请专利(200810060356.9)中催化剂损失46克。The polytetrafluoroethylene fiber with dioxin decomposition function prepared by the above method of the present invention has a fiber diameter of 40-80 microns; the removal rate of dioxin is as high as 97-99% at 220 ° C (needled into a nonwoven fabric) , the fiber content is 520 grams per square meter); at a wind speed of 1 meter per second, the loss of catalyst per 1000 grams of polytetrafluoroethylene fibers in 80 hours is 2-8 grams, which is significantly lower than the patent application (200810060356.9 ) catalyst loss of 46 grams.
本发明与已有技术相比，具有的有益效果是：Compared with the prior art, the present invention has the beneficial effects of:
在纤维的制备过程中，需要320～420℃的烧结定型，烧结时间20～80秒，在此条件下，聚四氟乙烯树脂粉末不熔融，而包覆在催化剂粉体表面聚四氟乙烯乳液熔融，因此可起到连接催化剂和聚四氟乙烯纤维的目的，防止在使用过程中纤维内催化剂粉体的流失；另一方面，聚四氟乙烯乳液熔融后发生收缩现象，使催化剂粉体表面大部分裸露出来，由于催化剂是在和二恶英接触的条件下才能发生催化反应，催化剂粉体表面的裸露确保了催化效率。In the process of fiber preparation, sintering at 320-420°C is required, and the sintering time is 20-80 seconds. Under this condition, the polytetrafluoroethylene resin powder does not melt, but the polytetrafluoroethylene emulsion is coated on the surface of the catalyst powder. Melting, so it can serve the purpose of connecting the catalyst and the PTFE fiber, preventing the loss of the catalyst powder in the fiber during use; on the other hand, the PTFE emulsion shrinks after melting, making the surface of the catalyst powder Most of them are exposed, because the catalytic reaction can only occur under the condition of contacting with dioxin, and the exposed surface of the catalyst powder ensures the catalytic efficiency.
具体实施方式Detailed ways
实施例1：Example 1:
1、催化剂粉体的表面改性：将聚四氟乙烯乳液(SFN-1，中昊晨光化工研究院提供)倒入催化剂粉体(5微米直径，德国BASF公司提供)(催化剂与聚四氟乙烯乳液的重量比为1∶0.01)中，搅拌，在105℃的烘箱内将乳液中的水分烘干；1. Surface modification of catalyst powder: Pour polytetrafluoroethylene emulsion (SFN-1, provided by Zhonghao Chenguang Chemical Research Institute) into catalyst powder (5 micron diameter, provided by BASF, Germany) (catalyst and polytetrafluoroethylene The weight ratio of the ethylene emulsion is 1:0.01), stirring, and drying the moisture in the emulsion in an oven at 105°C;
2、混料：将聚四氟乙烯树脂粉末(日本大金公司F106)、表面改性后的催化剂粉体(按重量比1∶0.3均匀混和，再加入液体石蜡(聚四氟乙烯树脂粉末对液体石蜡的重量比为1∶0.2)混和均匀，在20℃的温度下静置144小时，然后在40℃的温度下静置10小时，使树脂粉末与液体润滑剂充分混合，形成聚四氟乙烯物料；2. Mixing: mix polytetrafluoroethylene resin powder (Dakin Corporation F106 in Japan), surface-modified catalyst powder (by weight ratio 1:0.3, and then add liquid paraffin (polytetrafluoroethylene resin powder to The weight ratio of liquid paraffin is 1:0.2) and mix evenly, let stand at a temperature of 20°C for 144 hours, and then stand at a temperature of 40°C for 10 hours to fully mix the resin powder and liquid lubricant to form polytetrafluoroethylene Vinyl material;
3、压坯与压延：将所述的聚四氟乙烯物料在20℃下在压坯机上压制成圆柱形毛坯，将毛坯通过柱塞挤出机在40℃的温度下挤出棒状物，然后经压延机在40℃下压延成聚四氟乙烯基带；3. Compacting and calendering: press the polytetrafluoroethylene material on a compacting machine at 20°C to form a cylindrical blank, and extrude the blank into a rod at a temperature of 40°C through a plunger extruder, and then Calendered at 40°C by a calender to form a polytetrafluoroethylene base tape;
4、纵向拉伸：将所述的聚四氟乙烯基带在180℃烘箱中纵向拉伸，获得脱脂基带；4. Longitudinal stretching: stretch the polytetrafluoroethylene base tape longitudinally in an oven at 180°C to obtain a degreased base tape;
5、烧结定型：将所述脱脂基带在320℃烧结定型，烧结时间80秒，获得烧结基带；5. Sintering and shaping: the degreased base tape was sintered and shaped at 320°C for 80 seconds to obtain a sintered base tape;
6、开纤：将所述烧结基带在开纤设备上开纤，加工成具有二恶英分解功能的聚四氟乙烯纤维。6. Fiber opening: the sintered base belt is opened on a fiber opening equipment, and processed into polytetrafluoroethylene fibers with dioxin decomposition function.
通过本发明的上述方法制备的具有二恶英分解功能的聚四氟乙烯纤维，纤维直径80微米；在220℃对二恶英的去除率高达97％(针刺成非织造布，该纤维含量为520克/平方米)；在1米/秒的风速下，80小时内每1000克聚四氟乙烯纤维中催化剂的损失量为8克，显著低于申请专利(200810060356.9)中催化剂损失46克。The polytetrafluoroethylene fiber with dioxin decomposition function prepared by the above-mentioned method of the present invention has a fiber diameter of 80 microns; the removal rate of dioxin is as high as 97% at 220 ° C (needling into a nonwoven fabric, the fiber content 520 grams per square meter); at a wind speed of 1 m/s, the loss of catalyst per 1000 grams of polytetrafluoroethylene fiber in 80 hours is 8 grams, which is significantly lower than the loss of 46 grams of catalyst in the patent application (200810060356.9) .
实施例2：Example 2:
1、催化剂粉体的表面改性：将聚四氟乙烯乳液(SFN-3，中昊晨光化工研究院提供)倒入催化剂粉体(1微米直径，德国BASF公司提供)(催化剂与聚四氟乙烯乳液的重量比为1∶1)中，搅拌，在105℃的烘箱内将乳液中的水分烘干；1. Surface modification of catalyst powder: Pour polytetrafluoroethylene emulsion (SFN-3, provided by Zhonghao Chenguang Chemical Research Institute) into catalyst powder (1 micron diameter, provided by German BASF company) (catalyst and polytetrafluoroethylene The weight ratio of the ethylene emulsion is 1:1), stirring, and drying the moisture in the emulsion in an oven at 105°C;
2、混料：将聚四氟乙烯树脂粉末(日本大金公司F106)和表面改性后的催化剂粉体按重量比1∶0.6均匀混和，再加入石油醚(聚四氟乙烯树脂粉末对石油醚的重量比为1∶0.25)混和均匀，在30℃的温度下静置121小时，然后在60℃的温度下静置12小时，使树脂粉末与液体润滑剂充分混合，形成聚四氟乙烯物料；2. Mixing: Mix polytetrafluoroethylene resin powder (Dakin Corporation F106 in Japan) and surface-modified catalyst powder uniformly in a weight ratio of 1:0.6, then add petroleum ether (polytetrafluoroethylene resin powder has an effect on petroleum The weight ratio of ether is 1:0.25) and mix evenly, let it stand at a temperature of 30°C for 121 hours, and then stand at a temperature of 60°C for 12 hours, so that the resin powder and liquid lubricant are fully mixed to form polytetrafluoroethylene materials;
3、压坯与压延：将所述的聚四氟乙烯物料在25℃下在压坯机上压制成圆柱形毛坯，将毛坯通过推压机在50℃的温度下挤出棒状物，然后经压延机在50℃下压延成聚四氟乙烯基带；3. Compacting and calendering: press the polytetrafluoroethylene material on a compacting machine at 25°C to form a cylindrical blank, and extrude the blank into a rod at a temperature of 50°C through a pusher, and then calender The machine is calendered at 50°C to form a PTFE base tape;
4、纵向拉伸：将所述的聚四氟乙烯基带在250℃烘箱中纵向拉伸，获得脱脂基带；4. Longitudinal stretching: stretch the polytetrafluoroethylene base tape longitudinally in an oven at 250°C to obtain a degreased base tape;
5、烧结定型：将所述脱脂基带在420℃烧结定型，烧结时间20秒，获得烧结基带；5. Sintering and shaping: the degreased base tape was sintered and shaped at 420°C for 20 seconds to obtain a sintered base tape;
6、开纤：将所述烧结基带在开纤设备上开纤，加工成具有二恶英分解功能的聚四氟乙烯纤维。6. Fiber opening: the sintered base belt is opened on a fiber opening equipment, and processed into polytetrafluoroethylene fibers with dioxin decomposition function.
通过本发明的上述方法制备的具有二恶英分解功能的聚四氟乙烯纤维，纤维直径60微米；在220℃对二恶英的去除率高达99％(针刺成非织造布，该纤维含量为520克/平方米)；在1米/秒的风速下，80小时内每1000克聚四氟乙烯纤维中催化剂的损失量为2克，显著低于申请专利(200810060356.9)中催化剂损失46克。The polytetrafluoroethylene fiber with dioxin decomposition function prepared by the above method of the present invention has a fiber diameter of 60 microns; the removal rate of dioxin is as high as 99% at 220 ° C (needling into nonwoven fabric, the fiber content 520 grams/square meter); at a wind speed of 1 m/s, the loss of catalyst per 1000 grams of polytetrafluoroethylene fiber in 80 hours is 2 grams, which is significantly lower than the loss of 46 grams of catalyst in the patent application (200810060356.9) .
实施例3：Example 3:
1、催化剂粉体的表面改性：将聚四氟乙烯乳液(SFN-A和SFN-1，重量比为1∶1，中昊晨光化工研究院提供)倒入催化剂粉体(20纳米直径，德国BASF公司提供)(催化剂与聚四氟乙烯乳液的重量比为1∶0.5)中，搅拌，在105℃的烘箱内将乳液中的水分烘干；1. Surface modification of catalyst powder: Pour polytetrafluoroethylene emulsion (SFN-A and SFN-1, the weight ratio is 1:1, provided by Zhonghao Chenguang Chemical Research Institute) into catalyst powder (20 nanometer diameter, Germany BASF company provides) (the weight ratio of catalyst and polytetrafluoroethylene emulsion is 1: 0.5), stir, and the moisture in the emulsion is dried in the baking oven of 105 ℃;
2、混料：将聚四氟乙烯树脂粉末(日本旭硝子公司CD123)和表面改性后的催化剂粉体按重量比1∶0.4均匀混和，再加入煤油(聚四氟乙烯树脂粉末对煤油的重量比为1∶0.28)混和均匀，在40℃的温度下静置144小时，然后在80℃的温度下静置16小时，使树脂粉末与液体润滑剂充分混合，形成聚四氟乙烯物料；2. Mixing: mix polytetrafluoroethylene resin powder (CD123 of Japan Asahi Glass Co., Ltd.) and surface-modified catalyst powder in a weight ratio of 1:0.4, and then add kerosene (the weight of polytetrafluoroethylene resin powder to kerosene ratio of 1:0.28) and mix evenly, let stand at a temperature of 40°C for 144 hours, then stand at a temperature of 80°C for 16 hours to fully mix the resin powder and liquid lubricant to form a polytetrafluoroethylene material;
3、压坯与压延：将所述的聚四氟乙烯物料在30℃下在压坯机上压制成圆柱形毛坯，将毛坯通过推压机在60℃的温度下挤出棒状物，然后经压延机在60℃下压延成聚四氟乙烯基带；3. Compacting and calendering: press the polytetrafluoroethylene material on a compacting machine at 30°C to form a cylindrical blank, extrude the blank into a rod at a temperature of 60°C through a pusher, and then calender The machine is calendered at 60°C to form a PTFE base tape;
4、纵向拉伸：将所述的聚四氟乙烯基带在300℃烘箱中纵向拉伸，获得脱脂基带；4. Longitudinal stretching: stretch the polytetrafluoroethylene base tape longitudinally in a 300°C oven to obtain a degreased base tape;
5、烧结定型：将所述脱脂基带在380℃烧结定型，烧结时间50秒，获得烧结基带；5. Sintering and shaping: the degreased base tape was sintered and shaped at 380°C for 50 seconds to obtain a sintered base tape;
6、开纤：将所述烧结基带在开纤设备上开纤，加工成具有催化分解二恶英功能的聚四氟乙烯纤维。6. Fiber opening: the sintered base tape is opened on a fiber opening equipment, and processed into polytetrafluoroethylene fibers with the function of catalytically decomposing dioxins.
通过本发明的上述方法制备的具有二恶英分解功能的聚四氟乙烯纤维，纤维直径40微米；在220℃对二恶英的去除率高达98％(针刺成非织造布，该纤维含量为520克/平方米)；在1米/秒的风速下，80小时内每1000克聚四氟乙烯纤维中催化剂的损失量为4克，显著低于申请专利(200810060356.9)中催化剂损失46克。The polytetrafluoroethylene fiber with dioxin decomposition function prepared by the above-mentioned method of the present invention has a fiber diameter of 40 microns; the removal rate of dioxin is as high as 98% at 220 ° C (needling into nonwoven fabric, the fiber content 520 grams/square meter); at a wind speed of 1 m/s, the loss of catalyst per 1000 grams of polytetrafluoroethylene fiber in 80 hours is 4 grams, which is significantly lower than the loss of 46 grams of catalyst in the patent application (200810060356.9) .
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100977932ACN101580973B (en) | 2009-04-23 | 2009-04-23 | Method for preparing polyfluortetraethylene fiber with dioxin decomposition function |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100977932ACN101580973B (en) | 2009-04-23 | 2009-04-23 | Method for preparing polyfluortetraethylene fiber with dioxin decomposition function |
| Publication Number | Publication Date |
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| CN101580973Atrue CN101580973A (en) | 2009-11-18 |
| CN101580973B CN101580973B (en) | 2011-02-02 |
| Application Number | Title | Priority Date | Filing Date |
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| CN2009100977932AExpired - Fee RelatedCN101580973B (en) | 2009-04-23 | 2009-04-23 | Method for preparing polyfluortetraethylene fiber with dioxin decomposition function |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967708A (en)* | 2010-09-10 | 2011-02-09 | 常州市兴诚高分子材料有限公司 | Production process of high-strength polytetrafluoroethylene wire for stitching |
| CN102051703A (en)* | 2010-11-25 | 2011-05-11 | 辽宁省金氟龙环保新材料有限公司 | Manufacturing method of film split polytetrafluoroethylene fibers |
| CN102071483A (en)* | 2010-11-22 | 2011-05-25 | 宋朋泽 | Preparation method of polytetrafluoroethylene chopped fiber |
| WO2015109572A1 (en)* | 2014-01-26 | 2015-07-30 | 浙江格尔泰斯环保特材科技有限公司 | Method for processing polytetrafluoroethylene filament with circular cross-section using cutting and hot-melt forming process |
| CN106637451A (en)* | 2016-12-27 | 2017-05-10 | 常州市兴诚高分子材料有限公司 | Method for preparing polytetrafluoroethylene microfibers |
| CN106731238A (en)* | 2017-02-28 | 2017-05-31 | 武汉科技大学 | A kind of production method of the polytetrafluoroethylfilter filter material with catalysis |
| CN108212221A (en)* | 2017-12-29 | 2018-06-29 | 成都优纳新材料有限公司 | A kind of visible light catalytic type PTFE/TiO2Biaxial tension tablet membrane preparation method |
| CN110354584A (en)* | 2019-08-27 | 2019-10-22 | 上海市凌桥环保设备厂有限公司 | A kind of preparation method of polytetrafluoroethylene (PTFE) catalysis filtrate |
| CN110424062A (en)* | 2019-07-31 | 2019-11-08 | 江苏华跃纺织新材料科技股份有限公司 | A kind of polytetrafluoroethylene (PTFE) coloured cut staple and preparation method thereof |
| CN113476959A (en)* | 2021-06-28 | 2021-10-08 | 南京玻璃纤维研究设计院有限公司 | High-temperature catalytic filtering material |
| CN118048707A (en)* | 2024-02-19 | 2024-05-17 | 浙江大学台州研究院 | A method for preparing a catalytic fiber and a catalytic filter bag for removing dioxins, NOx and dust from flue gas at low temperature |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5620669A (en)* | 1995-08-15 | 1997-04-15 | W. L. Gore & Associates, Inc. | Catalytic filter material and method of making same |
| CN100447317C (en)* | 2006-11-30 | 2008-12-31 | 浙江理工大学 | Preparation method of expanded polytetrafluoroethylene fiber for waste gas decomposition |
| CN100488610C (en)* | 2007-07-10 | 2009-05-20 | 浙江理工大学 | Method for preparation of polytetrafluorethylene microporous film for the processing of high-temperature fume and dust |
| CN101255615B (en)* | 2008-04-08 | 2010-06-02 | 浙江理工大学 | Preparation method of expanded polytetrafluoroethylene fiber with catalytic decomposition of dioxin |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967708A (en)* | 2010-09-10 | 2011-02-09 | 常州市兴诚高分子材料有限公司 | Production process of high-strength polytetrafluoroethylene wire for stitching |
| CN102071483A (en)* | 2010-11-22 | 2011-05-25 | 宋朋泽 | Preparation method of polytetrafluoroethylene chopped fiber |
| CN102051703A (en)* | 2010-11-25 | 2011-05-11 | 辽宁省金氟龙环保新材料有限公司 | Manufacturing method of film split polytetrafluoroethylene fibers |
| CN102051703B (en)* | 2010-11-25 | 2012-10-17 | 辽宁省金氟龙环保新材料有限公司 | Manufacturing method of polytetrafluoroethylene fiber by membrane splitting method |
| WO2015109572A1 (en)* | 2014-01-26 | 2015-07-30 | 浙江格尔泰斯环保特材科技有限公司 | Method for processing polytetrafluoroethylene filament with circular cross-section using cutting and hot-melt forming process |
| CN106637451A (en)* | 2016-12-27 | 2017-05-10 | 常州市兴诚高分子材料有限公司 | Method for preparing polytetrafluoroethylene microfibers |
| CN106731238A (en)* | 2017-02-28 | 2017-05-31 | 武汉科技大学 | A kind of production method of the polytetrafluoroethylfilter filter material with catalysis |
| CN108212221A (en)* | 2017-12-29 | 2018-06-29 | 成都优纳新材料有限公司 | A kind of visible light catalytic type PTFE/TiO2Biaxial tension tablet membrane preparation method |
| CN110424062A (en)* | 2019-07-31 | 2019-11-08 | 江苏华跃纺织新材料科技股份有限公司 | A kind of polytetrafluoroethylene (PTFE) coloured cut staple and preparation method thereof |
| CN110424062B (en)* | 2019-07-31 | 2022-03-15 | 江苏华跃纺织新材料科技股份有限公司 | Polytetrafluoroethylene colored short fiber and preparation method thereof |
| CN110354584A (en)* | 2019-08-27 | 2019-10-22 | 上海市凌桥环保设备厂有限公司 | A kind of preparation method of polytetrafluoroethylene (PTFE) catalysis filtrate |
| CN113476959A (en)* | 2021-06-28 | 2021-10-08 | 南京玻璃纤维研究设计院有限公司 | High-temperature catalytic filtering material |
| CN118048707A (en)* | 2024-02-19 | 2024-05-17 | 浙江大学台州研究院 | A method for preparing a catalytic fiber and a catalytic filter bag for removing dioxins, NOx and dust from flue gas at low temperature |
| CN118048707B (en)* | 2024-02-19 | 2024-12-03 | 浙江大学台州研究院 | A method for preparing catalytic fiber and catalytic filter bag for removing dioxins, NOx and dust from flue gas at low temperature |
| Publication number | Publication date |
|---|---|
| CN101580973B (en) | 2011-02-02 |
| Publication | Publication Date | Title |
|---|---|---|
| CN101580973A (en) | Method for preparing polyfluortetraethylene fiber with dioxin decomposition function | |
| Huang et al. | Hierarchical electrospun nanofibers treated by solvent vapor annealing as air filtration mat for high-efficiency PM2. 5 capture | |
| CN100488610C (en) | Method for preparation of polytetrafluorethylene microporous film for the processing of high-temperature fume and dust | |
| Su et al. | Hierarchically structured TiO2/PAN nanofibrous membranes for high-efficiency air filtration and toluene degradation | |
| CN101255615B (en) | Preparation method of expanded polytetrafluoroethylene fiber with catalytic decomposition of dioxin | |
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| Zhu et al. | Preparation of polytetrafluoroethylene ultrafine fiber mats with electrospinning process |
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