CN110408282B - 一种防止超低排放机组低温换热设备堵塞的涂料及制备方法 - Google Patents
一种防止超低排放机组低温换热设备堵塞的涂料及制备方法 Download PDFInfo
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Abstract
本发明公开了一种防止超低排放机组低温换热设备堵塞的涂料及制备方法。该涂料主要由一种新型的树脂四氟乙烯‑乙烯基三烷氧基硅烷共聚物、增强填料纳米二氧化硅、导热填料硅烷改性氮化硼、乳化剂和水组成。涂料制备方法包括共聚物乳液制备、改性氮化硼制备及涂料复配等三个工艺。本发明公开的涂料兼具聚四氟乙烯涂料的不粘性和有机硅涂料的成膜性,以致涂层耐高温、抗酸蚀、硬度高、与基体结合强度高、抗冲刷。同时,本发明公开的涂料制备方法由常见工业生产工艺组成,工艺简单、易于实现规模化生产。总之,本发明公开的涂料及其制备方法在超低排放机组低温换热设备堵塞防治方面具有广阔的应用前景。
Description
技术领域
本发明属于涂料技术领域,具体涉及一种防止超低排放机组低温换热设备堵塞的涂料及制备方法。
背景技术
超低排放改造是近年来燃煤发电行业大力推进的一项大气污染物整治工程。目前,国内大型燃煤电站已基本完成超低排放改造,大气主要污染物排放总量显著降低,但改造给机组也带了影响。其中,低温换热设备(空预器与烟冷器)堵塞是超低排放机组普遍存在的问题,对锅炉效率和机组安全运行构成了严重危险。究其原因,主要是超低排放改造过程中,为获得较高脱硝效率,SCR催化剂用量增加、喷氨量增大,导致烟气中逃逸氨与三氧化硫浓度均增加。氨、三氧化硫与水反应生成的硫酸氢铵(Ammonium bisulfate,ABS)也增加,而液态ABS具有粘性,极易沉积在空预器传热元件上并吸附飞灰,造成空预器堵塞。同时,许多超低排放机组还采用了基于低温省煤器的余热利用技术,ABS也可在烟冷器管壁上凝结并沾灰导致烟冷器堵塞。由此可见,因ABS引起的换热设备堵塞已成为超低排放机组一个亟待解决的共性问题。
自清洁涂层是解决飞灰堵塞的重要技术途径。目前,文献(CN 107401950A,CN106010122A,CN 105199497A,CN104987032A,CN106752132A,CN102390936B)报道了许多可用于换热面防堵塞的涂层,但由于超低排放机组运行工况恶劣,需要涂层具有抗冲刷(烟速10m/s,粉尘含量30g/m3左右)、耐高温(长期运行温度200~150℃)、耐硫酸腐蚀、导热、粘接性强,涂覆简单等特点,上述涂层均不适用于超低排放机组。因此,开发新型的自清洁涂层显得非常必要与重要。
发明内容
本发明的目的在于克服上述涂层均不适用于超低排放机组的缺点,提供了一种防止超低排放机组低温换热设备堵塞的涂料及制备方法。
本发明采用如下技术方案来实现的:
一种防止超低排放机组低温换热设备堵塞的涂料,由如下重量份数的组分组成:
四氟乙烯-乙烯基三烷氧基硅烷共聚物乳液:90~110份;
纳米二氧化硅:3~5份;
改性氮化硼:5~10份。
本发明进一步的改进在于,所述四氟乙烯-乙烯基三烷氧基硅烷共聚物乳液是指四氟乙烯-乙烯基三甲氧基硅烷共聚物乳液和四氟乙烯-乙烯基三乙氧基硅烷共聚物乳液中的任一种。
本发明进一步的改进在于,所述改性氮化硼是指用γ-氨丙基三乙氧基硅烷和γ-缩水甘油醚氧丙基三甲氧基硅烷中的任一种物质改性的氮化硼颗粒。
一种可防止超低排放机组低温换热设备堵塞的涂料的制备方法,包括如下步骤:
(1)四氟乙烯-乙烯基三烷氧基硅烷共聚物乳液的制备;
(2)改性氮化硼制备;
(3)涂料的配制。
本发明进一步的改进在于,步骤(1)中,四氟乙烯-乙烯基三烷氧基硅烷共聚物乳液的制备工艺为:将30~40份重量的水、0.02份重量的过硫酸铵、0.2~0.5份重量全氟辛酸铵加入反应釜搅拌均匀后,关闭反应釜,用高纯氮气置换釜内氧气;然后在搅拌状态下,向反应釜中缓慢滴加四氟乙烯和乙烯基三烷氧基硅烷的混合单体,并将反应釜内温度升至70~80℃,压力控制在1~2MPa,共聚反应开始,调控混合单体的滴加速率以维持反应压力;混合单体中,四氟乙烯与乙烯基三烷氧基硅烷的重量比为5:1,所述混合单体投料量与引发剂过硫酸铵的重量比为(4400~5300):1。
本发明进一步的改进在于,步骤(2)中,改性氮化硼的制备工艺为:将10份重量的硅烷改性剂溶于100份重量的无水乙醇中,然后再加入100份重量的氮化硼粉末,在60℃搅拌状态下反应2小时后,过滤,所得固体产物于80℃真空干燥24小时,即得到改性氮化硼;所述硅烷改性剂为γ-氨丙基三乙氧基硅烷和γ-缩水甘油醚氧丙基三甲氧基硅烷中的任一种。
本发明进一步的改进在于,步骤(3)中,涂料的配制工艺为:将90~110份重量的四氟乙烯-乙烯基三烷氧基硅烷共聚物乳液与3~5份重量的纳米二氧化硅及5~10份重量的改性氮化硼在室温下搅拌混合均匀,得到可防止超低排放机组低温换热设备堵塞的涂料。
与现有技术相比,本发明具有如下有益的技术效果:
(1)聚四氟乙烯涂料是常见的自清洁涂料,可用于换热面的防堵塞,但由于其成膜性差,涂料固化后存在大量微孔,酸液可以通过微孔渗入涂层/基体界面,腐蚀基体(换热面)。此外,这也会加速涂层从基体表面的剥离。因此,常规的聚四氟乙烯涂料耐酸腐蚀性较差,且易脱落。而有机硅涂料成膜性好,耐高温,附着力强。本发明以一种四氟乙烯-有机硅烷共聚物为主要组分,并复配与该共聚物相容性好的增强填料(纳米二氧化硅)和导热填料(改性氮化硼),形成一种全新的涂料,将兼具有机硅涂料优异的成膜性、聚四氟乙烯涂料的不粘性及其共有的耐高温性,克服了传统不粘涂层的缺点,在换热器防堵塞方面具有广阔的应用前景。
(2)本发明公开的涂料是一种水性涂料,绿色环保。同时成型工艺简单:可用常规液体涂料喷涂工艺进行施工;涂料固化主要基于硅氧烷之间的溶胶-凝胶反应,可实现低温甚至常温固化。
(3)本发明公开的涂料制备方法,所涉及的工艺及设备在工业上常见,技术成熟可靠,适合规模化生产,有助于涂料的工程应用。
具体实施方式
以下结合实施例对本发明做出进一步的说明。
本发明提供的一种防止超低排放机组低温换热设备堵塞的涂料,由如下重量份数的组分组成:
四氟乙烯-乙烯基三烷氧基硅烷共聚物乳液:90-110份;所述四氟乙烯-乙烯基三烷氧基硅烷共聚物乳液是指四氟乙烯-乙烯基三甲氧基硅烷(TFE-A171)共聚物乳液和四氟乙烯-乙烯基三乙氧基硅烷(TFE-A151)共聚物乳液中的任一种。
纳米二氧化硅(增强填料):3~5份。
改性氮化硼(导热填料):5~10份;所述改性氮化硼是指用γ-氨丙基三乙氧基硅烷(KH550)和γ-缩水甘油醚氧丙基三甲氧基硅烷(KH560)中的任一种物质改性的氮化硼颗粒。
实施例
本发明提供的一种可防止超低排放机组低温换热设备堵塞的涂料的制备方法,将30~40份重量的水、0.02份重量的过硫酸铵、0.2~0.5份重量的全氟辛酸铵加入反应釜搅拌均匀后,关闭反应釜,用高纯氮气置换釜内氧气。然后在搅拌状态下,向反应釜中慢慢滴加(四氟乙烯+乙烯基三烷氧基硅烷)混合单体,并将反应釜内温度升至70~80℃,压力控制在1~2MPa,共聚反应开始,调控混合单体的滴加速率以维持反应压力。混合单体中,四氟乙烯与乙烯基三烷氧基硅烷的重量比为5:1,通过控制混合单体与引发剂过硫酸铵用量比((4400~5300):1)来获得不同的共聚物乳液。
将10份重量的硅烷改性剂溶于100份重量的无水乙醇中,然后再加入100份重量的氮化硼粉末,在60℃搅拌状态下反应2小时后,过滤,所得固体产物于80℃真空干燥24小时,即得到改性氮化硼。
将90~110份重量的四氟乙烯-乙烯基三烷氧基硅烷共聚物乳液与3~5份重量纳米二氧化硅及5~10份改性氮化硼在室温下搅拌混合均匀,得到一种可防止超低排放机组低温换热设备堵塞的涂料。
采用高压喷涂工艺将上述涂料涂覆在打磨后的不锈钢表面,在150~160℃固化2小时,再于300~320℃固化30分钟,完成涂层固化。
用划格法测定涂层着附力,用接触角评价涂层不粘性,用铅笔硬度评价涂层硬度,用硫酸浸泡法评价涂层抗腐蚀性,用漆膜冲击器评价涂层抗冲刷性,用热失重法评价涂层耐温性。
表1 实施例中相关工艺参数
*括号中的比例表示TFE与A171或A151的投料质量比实施例中,所得涂层性能如表2所示。
Claims (4)
1.一种防止超低排放机组低温换热设备堵塞的涂料,其特征在于,由如下重量份数的组分组成:
四氟乙烯-乙烯基三烷氧基硅烷共聚物乳液:90~110份;
纳米二氧化硅:3~5份;
改性氮化硼:5~10份。
2.根据权利要求1所述一种防止超低排放机组低温换热设备堵塞的涂料,其特征在于,所述四氟乙烯-乙烯基三烷氧基硅烷共聚物乳液是指四氟乙烯-乙烯基三甲氧基硅烷共聚物乳液和四氟乙烯-乙烯基三乙氧基硅烷共聚物乳液中的任一种。
3.根据权利要求1所述一种防止超低排放机组低温换热设备堵塞的涂料,其特征在于,所述改性氮化硼是指用γ-氨丙基三乙氧基硅烷和γ-缩水甘油醚氧丙基三甲氧基硅烷中的任一种物质改性的氮化硼颗粒。
4.一种可防止超低排放机组低温换热设备堵塞的涂料的制备方法,其特征在于,包括如下步骤:
(1)四氟乙烯-乙烯基三烷氧基硅烷共聚物乳液的制备;
四氟乙烯-乙烯基三烷氧基硅烷共聚物乳液的制备工艺为:将30~40份重量的水、0.02份重量的过硫酸铵、0.2~0.5份重量全氟辛酸铵加入反应釜搅拌均匀后,关闭反应釜,用高纯氮气置换釜内氧气;然后在搅拌状态下,向反应釜中缓慢滴加四氟乙烯和乙烯基三烷氧基硅烷的混合单体,并将反应釜内温度升至70~80℃,压力控制在1~2MPa,共聚反应开始,调控混合单体的滴加速率以维持反应压力;混合单体中,四氟乙烯与乙烯基三烷氧基硅烷的重量比为5:1,所述混合单体投料量与引发剂过硫酸铵的重量比为(4400~5300):1;
(2)改性氮化硼制备;
改性氮化硼的制备工艺为:将10份重量的硅烷改性剂溶于100份重量的无水乙醇中,然后再加入100份重量的氮化硼粉末,在60℃搅拌状态下反应2小时后,过滤,所得固体产物于80℃真空干燥24小时,即得到改性氮化硼;所述硅烷改性剂为γ-氨丙基三乙氧基硅烷和γ-缩水甘油醚氧丙基三甲氧基硅烷中的任一种;
(3)涂料的配制;
配制工艺为:将90~110份重量的四氟乙烯-乙烯基三烷氧基硅烷共聚物乳液与3~5份重量的纳米二氧化硅及5~10份重量的改性氮化硼在室温下搅拌混合均匀,得到可防止超低排放机组低温换热设备堵塞的涂料。
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