CN110465180A - 一种高性能空气净化蜂窝模块材料的制备 - Google Patents
一种高性能空气净化蜂窝模块材料的制备 Download PDFInfo
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Abstract
本发明属于材料和空气净化技术领域,公开了一种高性能空气净化蜂窝模块材料及其制备方法。一种高性能空气净化蜂窝模块的制备,具体是将煤质粉末状活性炭和粘结剂、添加剂、造孔剂以及水混合均匀,经炼泥、陈化后通过蜂窝模具挤出成型,再经过干燥、炭化和活化等过程得到蜂窝状结构材料。本发明制备得到的蜂窝模块材料具有制备工艺简单,孔数、厚度可调,微观孔结构可控的特点,并且蜂窝模块材料风阻小,强度高,吸水性能好,具有优异的气体吸附性能,能够快速高效去除空气中多种气态污染物,可广泛用于环境保护,居家使用,食品工程,化学工程等领域的空气净化领域。
Description
技术领域
本发明涉及一种高性能空气净化蜂窝模块材料及其制备方法,属于材料和空气净化技术领域。
背景技术
空气污染是世界性话题,联合国环境署的报告《迈向零污染地球》指出空气污染、淡水污染、土壤污染、废弃物污染、化学污染、海洋污染等已成为当今世界的第一大杀手,其中空气污染是目前全球最大的环境健康因素。空气质量与人们的工作生活息息相关,空气污染防治越来越受到整个社会的关注和重视。现代人超过80 %的时间都是在室内度过的,因此室内空气质量的好坏将直接影响人们的身体健康。世界卫生组织公布的《2018年世界卫生报告》指出,截至2016年世界上有接近91 %的人呼吸不到清洁的空气,2016年世界范围内有380万人死于室内空气污染引起的非传染性疾病(包括心脏病、中风和癌症)。因此,空气污染尤其是室内空气污染的防治工作显得尤为重要。
活性炭由于具有比表面积大、孔结构丰富、化学稳定性好、耐酸碱腐蚀及可再生等特点而被广泛用于空气净化领域。然而,粉末活性炭堆密度低,运输和回收困难,且易造成粉尘污染;颗粒和柱状活性炭则表现出利用率较低,风阻高,压降大等缺点。蜂窝状活性炭由于流体力学性能好、风阻低、机械强度高、耐热、耐水性好、易再生等特点逐渐成为空气净化和材料技术领域从业者的研究热点。
挤出成型法是目前国内外制备蜂窝结构材料最常用的一种方法,CN101972630A公开了一种蜂窝型净化活性炭的制造方法,炭前驱体为化学活性炭、煤质颗粒活性炭和椰壳炭的混合物,流动性助剂为甘油或亚油酸或硫化油,胶粘剂为酚醛树脂或羧甲基纤维素或聚乙烯醇。不同炭前驱体具有不同的物理化学性质,使用混合炭前驱体容易导致材料性能不稳定,也很难保证与其他组分的相容性,而且硫化物助剂在碳化时容易产生含硫化合物,影响空气质量。CN107126923A公开的一种耐水性蜂窝活性炭制备方法中,以聚丙烯腈的二甲基亚砜溶液为粘接剂,聚丙烯腈碳化时会产生氮氧化物,而且二甲基亚砜高温下分解产生大量恶臭型气体,影响环境质量。CN109305682A公开了一种蜂窝形活性炭材料的制备方法,其中以十二烷基苯磺酸钠为乳化剂,需要先得到乳化剂水溶液,增加了生成工艺流程,也提高了成本。CN106946251A公开了一种高性能蜂窝活性炭的制备方法,其中使用氯化锌、磷酸、碳酸钾、氢氧化钠和氢氧化钾作为化学活化剂,由于采用化学用品,不仅会腐蚀设备,污染环境,而且活性炭中残留有化学药品会影响蜂窝材料的安全性,此外化学活化剂用量大,成本高。
综上所述,目前蜂窝活性炭材料的制备还存在着较多问题,例如工艺流程多,使用大量化学活化剂或有机溶剂,成本高且容易污染环境等,此外,蜂窝材料的强度、风阻、吸附性能、空气净化性能都有待改善,因此,一种高性能空气净化蜂窝模块材料的研制具有较大的科研和应用意义。
发明内容
本发明为一种高性能空气净化蜂窝模块材料及其制备技术,属于材料和空气净化技术领域。其特征在于将煤质粉末状活性炭和粘结剂、添加剂、造孔剂以及水混合均匀,经炼泥、陈化后通过蜂窝模具挤出成型,再经过干燥、炭化和活化等过程得到蜂窝状结构材料。该蜂窝材料风阻低,最小可达0.1 Pa,强度高,抗压强度可达15 Mpa,饱和吸水率大于80%,且该材料能够快速高效净化空气中多种气态污染物,如甲醛、氨气、臭氧、甲苯、二甲苯、苯、TVOC等。
本发明提出的高性能空气净化蜂窝模块材料及其制备技术,其制备工艺主要内容为:
1)取炭前驱体、粘结剂、添加剂、造孔剂并加入水,在炼泥机中混炼后陈化得到塑性泥料;
2)用带有蜂窝模具的挤出成型设备将塑性泥料挤出成为蜂窝状;
3)将湿的蜂窝模块材料置于阳光下暴晒或通风处阴干,或者置于蒸汽干燥设备上烘干,使含水量低于5%;
4)将干燥的蜂窝模块放入窑炉中,在惰性气氛下高温焙烧一段时间后,通入水蒸气继续焙烧一段时间得到高性能空气净化蜂窝模块材料。
所述炭前驱体为粉末状煤质活性炭,目数为250-450目,碘值为500~2000 mg/g,比表面积为700~3000 m2/g,灰分< 2 wt%。粉末状煤质活性炭用量为100-600份,优选为150-400份。
所述粘结剂为氧化铝、氧化硅、堇青石、黏土、高岭土、水滑石、海泡石、硅藻土、煤焦油、淀粉、木质素中的一种或几种。粘结剂用量为50~400份,优选为100~200份。
所述添加剂为豆油、棕榈油、花生油、菜籽油中的一种或多种,添加剂用量为0~100份,优选为20~30份。
所述造孔剂为磷钼酸、磷钼酸钠、氧化钼、钼酸铵的一种或多种。造孔剂用量为1~50份,优选为5~15份。
所述陈化时间为5~72小时,优选为10~18小时。
所述蜂窝模具形状为圆柱形、椭圆柱形、长方形和正方形的一种;所述蜂窝模具孔通道为正方形、长方形、菱形、三角形、六边形、圆形的一种。
所述惰性气氛为氮气、氩气中的一种或两种;所述焙烧温度为700~1200 ℃,优选为800~1100 ℃;所述焙烧时间为1~48小时,优选为3~24小时。
所述通入水蒸气持续时间为1~10小时,优选为3~6小时。
本发明提出的一种高性能空气净化蜂窝模块材料及其制备工艺,优势如下:
1)使用单一炭前驱体,避免了不同碳源之间的相互影响,有利于对蜂窝模块材料的质量控制;
2)通过组分配方的调整,可以实现对蜂窝模块材料孔结构的有效调节;
3)制备工艺中不需要使用化学活化剂和其他有机溶剂,避免了对环境的破坏,同时也节约了成本;
4)蜂窝模块材料表现出低风阻,高强度,高吸水性能,高比表面积的特点,能够快速高效处理多种气态污染物。
附图说明
图1是实施例1中高性能空气净化蜂窝模块材料的光学照片。
图2是实施例1中高性能空气净化蜂窝模块材料的氮气吸脱附等温曲线。
图3是实施例1中高性能空气净化蜂窝模块材料的孔径分布图。
图4是实施例2中高性能空气净化蜂窝模块材料的孔径分布图。
图5是实施例3中高性能空气净化蜂窝模块材料的孔径分布图。
表1是实施例1中高性能空气净化蜂窝模块材料对多种气态污染物的净化性能。
具体实施方案
以下通过实例进一步描述本发明。
实施例1
200份粉末状煤质活性炭,碘值为1300 mg/g,比表面积为1500 m2/g,灰分<2 wt%,150份粘接剂(100份黏土和50份淀粉),20份棕榈油,8份氧化钼,50份水在真空炼泥机充分混合均匀后陈化16小时后通过壁厚为1 mm,孔形状为正方形,孔密度为180孔每平方英寸的长方体蜂窝模具挤出成为蜂窝结构,随后蒸汽干燥至含水量低于5%再置于窑炉中,氮气气氛下800 ℃焙烧15小时后通入水蒸气,850 ℃继续焙烧10 小时得到高性能空气净化蜂窝模块材料。饱和吸水率为70 %,抗压强度为9.3 Mpa,1.0 m/s迎面风速下,风阻为2.5 Pa,比表面积为689 m2/g。30 m3实验舱中,温度为25 ℃,相对湿度为50%的条件下,66块该蜂窝模块组成的框架材料对浓度为0.9 mg/m3甲醛的1小时净化率大于99%。
实施例2
150份粉末状煤质活性炭,碘值为1000 mg/g,比表面积为1126 m2/g,灰分<2 wt%,120份粘接剂(70份硅藻土和50份海泡石),20份豆油,8份钼酸铵,50份水在真空炼泥机充分混合均匀后陈化12小时后通过壁厚为1 mm,孔形状为圆形,孔密度为120孔每平方英寸的圆柱型蜂窝模具挤出成为蜂窝结构,随后蒸汽干燥至含水量低于5%再置于窑炉中,氮气气氛下850 ℃焙烧12小时后通入水蒸气,850℃继续焙烧10 小时得到高性能空气净化蜂窝模块材料。饱和吸水率为60 %,抗压强度为8.2 Mpa,1.0 m/s迎面风速下,风阻为2.0 Pa,比表面积为644 m2/g。30 m3实验舱中,温度为25 ℃,相对湿度为50%的条件下,66块该蜂窝模块组成的框架材料对浓度为1.0 mg/m3甲醛的1小时净化率为93%。
实施例3
250份粉末状煤质活性炭,碘值为1500 mg/g,比表面积为1762 m2/g,灰分<2 wt%,200份粘接剂(100份堇青石和100份高岭土),40份花生油,10份磷钼酸,70份水在真空炼泥机充分混合均匀后陈化20小时后通过壁厚为1 mm,孔形状为正方形,孔密度为150孔每平方英寸的正方体蜂窝模具挤出成为蜂窝结构,随后阴凉通风处干燥至含水量低于5%再置于窑炉中,氮气气氛下1100 ℃焙烧6小时后通入水蒸气,1000 ℃继续焙烧3小时得到高性能空气净化蜂窝模块材料。饱和吸水率为51 %,抗压强度为13.2 Mpa,1.0 m/s迎面风速下,风阻为6.2 Pa,比表面积为730 m2/g。30 m3实验舱中,温度为25 ℃,相对湿度为50%的条件下,66块该蜂窝模块组成的框架材料对浓度为0.8 mg/m3甲醛的1小时净化率为96%。
实施例4
350份粉末状煤质活性炭,碘值为1500 mg/g,比表面积为1762 m2/g,灰分<2 wt%,300份粘接剂(200份煤焦油和100份木质素),35份菜籽油,20份磷钼酸铵,90份水在真空炼泥机充分混合均匀后陈化24小时后通过壁厚为1 mm,孔形状为圆形,孔密度为90孔每平方英寸的圆柱体蜂窝模具挤出成为蜂窝结构,随后阳光下暴晒至含水量低于5%再置于窑炉中,氮气气氛下1200 ℃焙烧3小时后通入水蒸气,900 ℃继续焙烧6小时得到高性能空气净化蜂窝模块材料。饱和吸水率为64 %,抗压强度为11.8 Mpa,1.0 m/s迎面风速下,风阻为3.2Pa,比表面积为804 m2/g。30 m3实验舱中,温度为25 ℃,相对湿度为50%的条件下,66块该蜂窝模块组成的框架材料对浓度为1.0 mg/m3甲醛的1小时净化率为87%。
所描述的实施例只是本发明专利的一部分,基于本发明专利的实施例,在蜂窝模块材料和空气净化领域的技术人员在没有创造性劳动前提下所获得的所有其他实施例,都属于本发明专利保护的范围。
表1 实施例1中高性能空气净化蜂窝模块材料对气态污染物的净化性能
检测项目 | 净化率(%) |
甲醛 | >99 |
TVOC | 98 |
苯 | 97 |
甲苯 | >99 |
二甲苯 | >99 |
氨气 | 98 |
臭氧 | >99 |
二氧化硫 | 98 |
二氧化氮 | >99 |
硫化氢 | >99 |
检测条件:30 m3国标舱(GB/T 18801-2015);污染物浓度:GB/T 18883-2002限值的8~12倍;检测时间:60分钟。
Claims (9)
1.一种高性能空气净化蜂窝模块材料及其制备方法,其特征在于,所述高性能空气净化蜂窝模块材料及其制备方法包括以下步骤:
步骤一:称取100~600份炭前驱体,50~400份粘结剂、0~100份添加剂、1~50份造孔剂并加入20-200份水,在炼泥机中混炼后陈化得到塑性泥料;
步骤二:用带有蜂窝模具的挤出成型设备将步骤一中的泥料挤出成为蜂窝状材料;
步骤三:将步骤二得到的湿的蜂窝模块材料置于阳光下暴晒或通风处阴干,或者置于蒸汽干燥设备上烘干,使含水量低于5%;
步骤四:将步骤三得到的干燥的蜂窝模块放入窑炉中,在惰性气氛下高温焙烧一段时间后,通入水蒸气继续焙烧一段时间得到高性能空气净化蜂窝模块材料。
2.如权利要求1所述的一种高性能空气净化蜂窝模块材料及其制备方法,其特征在于,所述炭前驱体为粉末状煤质活性炭,目数为250~450目,碘值为500~2000 mg/g,比表面积为700~3000 m2/g,灰分< 2 wt%,炭前驱体用量为100~600份,优选为150~400份。
3.如权利要求1所述的一种高性能空气净化蜂窝模块材料及其制备方法,其特征在于,所述粘结剂为氧化铝、氧化硅、堇青石、黏土、高岭土、水滑石、海泡石、硅藻土、煤焦油、淀粉、木质素中的一种或几种,粘结剂用量为50~400份,优选为100~200份。
4.如权利要求1所述的一种高性能空气净化蜂窝模块材料及其制备方法,其特征在于,所述添加剂为豆油、棕榈油、花生油、菜籽油中的一种或多种,添加剂用量为0~100份,优选为20~30份。
5.如权利要求1所述的一种高性能空气净化蜂窝模块材料及其制备方法,其特征在于,所述造孔剂为磷钼酸、磷钼酸钠、氧化钼、钼酸铵的一种或多种,造孔剂用量为1~50份,优选为5~15份。
6.如权利要求1所述的一种高性能空气净化蜂窝模块材料及其制备方法,其特征在于,所述陈化时间为5~72小时,优选为10~18小时。
7.如权利要求1所述的一种高性能空气净化蜂窝模块材料及其制备方法,其特征在于,所述蜂窝模具形状为圆柱形、椭圆柱形、长方体和正方体的一种;所述蜂窝模具孔通道为正方形、长方形、菱形、三角形、六边形、圆形的一种。
8.如权利要求1所述的一种高性能空气净化蜂窝模块材料及其制备方法,其特征在于,所述惰性气氛为氮气、氩气中的一种或两种;所述焙烧温度为700~1200 ℃,优选为800~1100 ℃;所述焙烧时间为1~48小时,优选为3~24小时。
9.如权利要求1所述的一种高性能空气净化蜂窝模块材料及其制备方法,其特征在于,所述通入水蒸气持续时间为1~10小时,优选为3~6小时 。
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