CN108854961B - 一种具备室内除甲醛和杀菌防霉功能的负载活性炭 - Google Patents
一种具备室内除甲醛和杀菌防霉功能的负载活性炭 Download PDFInfo
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Abstract
本发明提供了一种具备室内除甲醛和杀菌防霉功能的负载活性炭,该负载活性炭包括活性炭载体、水溶性无机碱、杀菌剂和水分,任选的,所述负载活性炭中还包括有占负载活性炭质量0‑1%的杀霉菌物质。本发明提供的负载活性炭中负载有水溶性无机碱、杀菌剂和水分,可以通过化学反应捕获空气中的低浓度甲醛,对于室内甲醛的去除有良好效果,提高室内空气质量。
Description
技术领域
本发明涉及一种活性炭,特别涉及一种具备室内除甲醛和杀菌防霉功能的负载活性炭。
背景技术
众所周知,甲醛是一种室内常见的致癌物质,众多公开的论文资料报道了甲醛对人的危害以及国内室内甲醛污染的现状,室内甲醛对人体健康产生巨大的潜在危害。
甲醛的处理方式众多,例如,生物法,在论文《几种室内植物对苯和甲醛复合污染响应的研究》中,研究了金边虎尾兰、芦荟、金心吊兰、黄金葛、铁线蕨和鸟巢蕨等植物对苯和甲醛污染的响应。生物法除甲醛能被大多数人接受,有一定效果还能美化环境;缺点是见效慢,处理浓度低,针对性强,对其他污染物的处理能力差。
又例如催化法,专利CN107694564A、CN101274281A、 CN102658115A、CN201711184289.7等都属于此类。通过将钛、铂和钯等金属或其氧化物负载于载体上,在光照或者常温条件下催化氧化甲醛。该方法使用寿命长,但甲醛可能催化氧化不完全形成新的污染物,并且对甲苯等化学结构稳定的污染物基本没有氧化作用。
专利CN101642698A中,在活性炭表面附着-NH、-NH2和 -NH3中的一种或多种,-NH、-NH2和-NH3的前体物是碳酸铵、碳酸氢铵、硫酸铵、硝酸铵、氯化铵、乙二胺、己二胺、苯胺、尿素中的一种。这种类型的负载活性炭能吸附甲醛,但处理速率较低;负载的物质本身就有异味或者不稳定,很容易在使用过程中分解产生氨气等异味;并且活性炭在室内使用过程中容易滋生细菌和霉菌。
由于上述原因,本发明人对现有技术进行改进,研究出了一种具备室内除甲醛和杀菌防霉功能的负载活性炭。
发明内容
为了解决上述问题,本发明人进行了锐意研究,结果发现,将胍类物质和碱性物质负载在活性炭上,可以起到杀菌和除甲醛的效果;通过进一步负载杀 霉菌物质,使得活性炭具有室内除甲醛和杀菌防霉作用,从而完成了本发明。
本发明的目的在于提供以下方面:
第一方面,本发明提供了一种负载活性炭,其包括活性炭载体、水溶性无机碱、杀菌剂和水分,任选的,所述负载活性炭中还包括有占负载活性炭质量0-1%的杀霉菌物质。
第二方面,提供了该负载活性炭的制备方法,包括,将水溶性无机碱和杀菌剂溶于水中,加入活性炭载体,浸渍后,烘干;任选的,在烘干后,将产物浸渍于含有杀霉菌物质的甲醇溶液中,取出,烘干,得到负载活性炭。
第三方面,提供了负载活性炭在室内除甲醛和/或杀菌防霉中的用途。
根据本发明提供的负载活性炭,具有以下有益效果:
(1)本发明提供的负载活性炭中负载有水溶性无机碱、杀菌剂和水分,可以通过化学反应捕获空气中的低浓度甲醛,对于室内甲醛的去除有良好效果;
(2)本发明提供的负载活性炭还可以通过吸附作用,去除空气中包括甲醛、甲苯等有机气体污染物,提高室内空气质量;
(3)本发明提供的负载活性炭中,负载物结构稳定,不易分解,具有非常好的安全性,不仅可以去除空气中的细菌,还具有杀菌防霉的效果。
附图说明
图1示出实验例2中甲醛去除速率图;
图2示出实验例3中活性炭寿命测试结果图;
图3示出实验例3中活性炭寿命测试系统示意图。
附图标记说明
1-空气泵
2-干燥塔
3-流量调节器
4-冰水浴
5-吸附柱前取样点
6-固定床吸附塔
7-吸附柱后取样点
8-甲醛鼓泡发生器
具体实施方式
下面通过对本发明进行详细说明,本发明的特点和优点将随着这些说明而变得更为清楚、明确。
在这里专用的词“示例性”意为“用作例子、实施例或说明性”。这里作为“示例性”所说明的任何实施例不必解释为优于或好于其它实施例。尽管在附图中示出了实施例的各种方面,但是除非特别指出,不必按比例绘制附图。
在本发明的描述中,需要说明的是,术语“上”、“下”、“内”、“外”、“前”、“后”、“左”和“右”等指示的方位或位置关系为基于本发明工作状态下的方位或位置关系,仅是为了便于描述本发明和简化描述,而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作,因此不能理解为对本发明的限制。此外,术语“第一”、“第二”、“第三”和“第四”仅用于描述目的,而不能理解为指示或暗示相对重要性。
以下详述本发明。
本发明提供了一种具备室内除甲醛和杀菌防霉功能的负载活性炭,所述负载活性炭包括活性炭载体和杀菌剂。
其中,所述活性炭载体起负载、支承和分散负载物的作用,所述负载物包括杀菌剂,还可以包括其他成分,例如水分、杀灭霉菌的物质。该活性炭载体可以选用现有技术中任一种活性炭,例如由煤质、椰壳、果壳或木质材料制成的活性炭。
本发明中提供的负载活性炭主要用于吸附空气中的气体污染物,活性炭载体的吸附性能可以显著影响制得的负载活性炭的吸附性能。较好的,所述活性炭载体的四氯化碳吸附值在60%以上;优选所述活性炭载体的四氯化碳吸附值为70-100%,最好为85-100%。所述活性炭载体的四氯化碳吸附值越高,对气体污染物的去除效果越好。
本发明中使用具有广谱杀菌作用的杀菌剂,可以杀灭室内空气中的多种病菌;优选使用胍类物质作为杀菌剂。胍类杀菌剂起效浓度低,安全有效,可以用于人类生活用品中;其具有水溶性,便于活性炭负载和使用。
优选所述杀菌剂选自十二烷基胍盐酸盐、聚六亚甲基单胍盐酸盐、聚六亚甲基单胍磷酸盐和聚六亚甲基双胍盐酸盐中的一种或者多种,例如聚六亚甲基双胍盐酸盐。
所述杀菌剂无色、无嗅、无毒、无腐蚀性;不燃、不爆、使用安全;并且杀菌谱广、有效浓度低、作用速度快、抑菌时间长;其性质稳定、易溶于水,可在常温下使用,便于制备和长期存储、使用。
本发明提供的负载活性炭,特别的,还可以通过活性炭吸附和杀菌剂捕获的方式除去空气中的甲醛。
本发明中活性炭载体上负载的杀菌剂,特别是胍类杀菌剂中的-NH-、-NH2基团可以与甲醛发生化学反应,从而捕获空气中的甲醛。在家庭使用条件下,甲醛通过该化学反应被捕获后,基本不会有释放的可能。
另外,由于活性炭载体的吸附性能,使得甲醛气体浓集在活性炭周围,甲醛气体的浓度相对较高;这也促进了胍类杀菌剂捕获甲醛的反应几率,提高了反应速度,即去除甲醛的速度。
所述杀菌剂占负载活性炭质量的1-15%,优选为5-15%;较好的,所述杀菌剂占负载活性炭质量的8-13%,可以杀灭室内空气中的多种病菌,和提高其捕获甲醛的能力与速度。
进一步的,研究发现,胍类杀菌剂捕获甲醛的速度在碱性条件下时较中性条件下有明显的增加。
因此,优选的,在本发明提供的负载活性炭中还负载有可以提供碱性环境的碱性物质,以提高杀菌剂捕获甲醛的反应速度。
所述碱性物质包括有机碱和无机碱,优选为无机碱,更优选为水溶性无机碱。较好的,所述水溶性无机碱为氢氧化钠或氢氧化钾。该无机碱易得,安全性高,无挥发性,碱性强,用量极少即可满足碱性要求。同时,利用该水溶性无机碱制备负载活性炭的制备工艺也相对容易,处理步骤少,有效缩短了工艺流程。
水溶性无机碱占负载活性炭质量的1-10%,优选为1-6%,最好为3-6%时,可以促进杀菌剂捕获甲醛反应的顺利进行。
将水溶性无机碱负载在活性炭载体后,当活性炭载体上负载有水分时,在水分存在的条件下,该无机碱可以产生游离碱离子,从而为活性炭上负载的杀菌剂提供碱性环境。
较好的,在活性炭上负载有水分,活性炭载体上负载的水分可以为杀菌剂捕获甲醛提供良好的微反应环境。
研究发现,活性炭过于干燥和含水量过大都会影响负载活性炭去除甲醛的速度和效果。当活性炭过于干燥时,水溶性无机碱无法有效提供碱性环境,更无法提高杀菌剂捕获甲醛的速度。当活性炭负载水分的含量过高时,活性炭的吸附性能降低,不利于浓集甲醛气体和促进杀菌剂捕获甲醛;长期使用时,尤其当室内空气潮闷时,活性炭会吸收空气中的水分,很容易滋生霉菌,不仅影响吸附性能和使用寿命,还会增加健康隐患。
所述水分占负载活性炭质量的1-10%,优选为3-9%,最优选为4-8%,例如6%。此时,负载活性炭的吸附性能最优。
任选的,所述负载活性炭中还可以负载有杀霉菌物质,以杀灭空气中的霉菌。
在一种优选的实施方式中,所述负载活性炭中负载有广谱杀霉菌物质,优选该杀霉菌物质选自3-碘-2-丙炔基-N-丁基氨基甲酸酯、二硫氰基甲烷和水杨菌胺的一种或几种。
在一种优选的实施方式中,所述负载活性炭中负载有3-碘 -2-丙炔基-N-丁基氨基甲酸酯,其为广谱杀菌,可以有效杀灭霉菌、酵母菌、藻类和细菌,对真菌有特效;另外,该物质稳定性强,不具有挥发性,在室温条件可以长期使用,有效提高了活性炭的使用寿命。
所述杀霉菌物质的负载量为占负载活性炭质量0-1%,较好的,为0.1-0.6%,最优选为0.3-0.6%,例如0.5%,可以很好地防止负载活性炭霉变和杀灭空气中的霉菌物质。
通过负载不同的物质,本发明提供的负载活性炭不仅可以去除空气中的细菌,还可以通过化学反应捕获空气中的低浓度甲醛;另外,活性炭载体本身还具有强烈的吸附作用,可以吸附空气中包括甲醛、甲苯等有机气体污染物。
本发明提供的负载活性炭中,负载物结构稳定,不易分解,具有非常好的安全性;该负载活性炭中负载物不仅可以杀菌防霉,净化空气质量;还可以延长负载活性炭的使用寿命。
本发明还提供了一种上述负载活性炭的制备方法,该方法包括以下步骤:
(1)将活性炭载体负载水溶性无机碱和杀菌剂,得到负载杀菌剂的活性炭。
优选将水溶性无机碱和杀菌剂溶于水中,加入活性炭载体,浸渍后,烘干,得到负载杀菌剂的活性炭。
其中,水溶性无机碱与水的质量比为1-10%,优选为2-8%,最优选为3-7%;杀菌剂与水的质量比为5-20%,优选为5-16%,最优选为8-13%;所述质量比的水溶性无机碱和杀菌剂可以使活性炭载体负载足量的负载物。
当活性炭上杀菌剂的负载量较低时,会影响杀菌剂对空气中细菌的杀灭效果,还会影响杀菌剂捕获空气中甲醛的性能和速度;当活性炭上负载的水溶性无机碱的含量较低时,起不到提高杀菌剂捕获甲醛的促进作用。
将活性炭载体加入溶解有水溶性无机碱和杀菌剂的溶液中,优选活性炭载体与该溶液的质量比为0.4-0.8:1,例如0.5:1,可以快速制得大量负载有水溶性无机碱和杀菌剂的负载活性炭。
在本发明提供的制备方法中,在设定浓度的水溶性无机碱和杀菌剂溶液中,优选将活性炭载体浸渍在溶液中0.5-3h,使活性炭载体与溶液中的物质充分接触和被吸附,可以使得制得的负载有杀菌剂的活性炭负载足量的杀菌剂和水溶性无机碱;同时,生产工艺的时间相对较短,基本可以全部吸附溶液中的负载物,减少物料的浪费,降低生产成本。
吸附完成后,过滤溶液取出活性炭,干燥。优选干燥温度在100℃以上,更优选在100-150℃下干燥。当干燥温度过高时会破坏活性炭上负载的杀菌剂,影响其稳定性;当干燥温度过低时,会使得干燥时间延长,影响生产效率。
进一步的,干燥时间为1-6h;更优选为3-6h,可以使得活性炭干燥至水分为1-10%,更优选3-9%。干燥后的产品即为负载有杀菌剂的活性炭。
(2)将负载杀菌剂的活性炭继续负载杀霉菌物质,得到负载活性炭。
根据需要,还可以在活性炭上负载杀霉菌物质。
当制备负载有杀霉菌物质的负载活性炭时,将上述步骤制得的活性炭浸渍于含有杀霉菌物质的溶液中,取出,烘干,得到负载活性炭。
为了便于制备,优选将所述杀霉菌物质溶解于甲醇溶液中,以便活性炭均匀充分吸附。
较好的,杀霉菌物质与甲醇溶液的质量比为0.1-1:200,优选为0.2-0.8:200,更优选为0.3-0.5:200。
优选的,将活性炭浸渍于含有杀霉菌物质的甲醇溶液中时,活性炭与甲醇溶液的质量比为0.2-0.6:1,优选为0.4-0.6,例如 0.5:1,可以充分吸附甲醇溶液中的杀霉菌物质。
优选浸渍时间为0.5-2h,例如为1h或1.5h。此时,可以满足杀霉菌物质的负载量,和,有效缩短生产工艺的时间。
吸附完毕后,过滤取出活性炭,烘干,优选烘干温度为 50~80℃,更优选为65~75℃,此时,可以在不影响负载物的稳定性的前提下,缩短干燥时间。
优选烘干1~5小时,更优选为1~4h,例如3h,可以明显缩短生产工艺的生产时间,提高生产效率。
较好的,在干燥时回收活性炭中的甲醇;活性炭干燥后,即得到负载活性炭。
本发明提供的负载活性炭制备方法步骤少,处理简单,容易操作,重复性高;制得的负载活性炭兼具除甲醛、抗菌和抗霉菌作用,可以提高室内空气质量,并具有较长的使用寿命。
由此,本发明还提供了该负载活性炭在室内除甲醛和/或杀菌防霉中的用途,特别是利用杀菌剂进行化学反应捕获甲醛的用途。
实施例
实施例1
配置氢氧化钠和聚六亚甲基双胍盐酸盐的混合溶液200g,其中氢氧化钠的质量比为5%,聚六亚甲基双胍盐酸盐的质量比为10.5%。
称取四氯化碳吸附率100%的原碳100克,将原碳浸渍于混合溶液中1小时,浸渍完成后取出,在130℃下烘干3小时,得到 120.5克产品。
通过检测,产品中负载氢氧化钠4.1%,负载聚六亚甲基双胍盐酸盐10.1%,含水率6.3%。
实施例2
配置氢氧化钠和聚六亚甲基双胍盐酸盐的混合溶液200g,其中氢氧化钠的质量比为7%,聚六亚甲基双胍盐酸盐的质量比为12%。
称取四氯化碳吸附率70%的原碳150克,将原碳浸渍于混合溶液中2小时,浸渍完成后取出,在150℃下烘干3小时,得到173 克产品。
通过检测,产品中负载氢氧化钠5.9%,负载聚六亚甲基双胍盐酸盐12.9%,含水率4.7%。
实施例3
配置氢氧化钠和聚六亚甲基双胍盐酸盐的混合溶液200g,其中氢氧化钠的质量比为3%,聚六亚甲基双胍盐酸盐的质量比为8%。
称取四氯化碳吸附率为85%的原碳100克,将原碳浸渍于混合溶液中2小时,浸渍完成后取出,在100℃下烘干6小时,得到 114克产品。
通过检测,产品中负载氢氧化钠2.9%,负载聚六亚甲基双胍盐酸盐8.0%,含水率7.9%。
实施例4
配制含0.5克碘丙炔正丁胺甲酸酯的甲醇溶液200g,称取实施例1中制得的产品100g,置于甲醇溶液中2h,取出,70℃下干燥3h,得到100.4克产品。
通过检测,产品中负载氢氧化钠4.0%,负载聚六亚甲基双胍盐酸盐9.9%,负载碘丙炔正丁胺甲酸酯0.5%,含水率6.2%。
实施例5
配制含0.3克碘丙炔正丁胺甲酸酯的甲醇溶液200g,称取实施例1中制得的产品80g,置于甲醇溶液中,0.5h,取出,65℃下干燥4h,得到80.2克产品。
通过检测,产品中负载氢氧化钠4.0%,负载聚六亚甲基双胍盐酸盐9.9%,负载碘丙炔正丁胺甲酸酯0.25%,含水率6.2%。
实施例6
配制含0.8克碘丙炔正丁胺甲酸酯的甲醇溶液200g,称取实施例1中制得的产品120g,置于甲醇溶液中1h,取出,75℃下干燥2h,得到120.8克产品。
通过检测,产品中负载氢氧化钠4.0%,负载聚六亚甲基双胍盐酸盐10.1%,负载碘丙炔正丁胺甲酸酯0.65%,含水率6.3%。
对比例
对比例1
制备方法与实施例1相同,区别仅在于,在250℃下烘干3 小时,制得的产品中,负载氢氧化钠4.2%,负载聚六亚甲基双胍盐酸盐9.2%,含水率2.1%。
对比例2
制备方法与实施例1相同,区别仅在于,在80℃下烘干3小时,制得的产品中,负载氢氧化钠3.8%,负载聚六亚甲基双胍盐酸盐9.4%,含水率15.2%。
对比例3
制备方法与实施例1相同,区别仅在于,聚六亚甲基双胍盐酸盐的质量比为1%,制得的产品中,负载氢氧化钠4.1%,负载聚六亚甲基双胍盐酸盐1.2%,含水率6.6%。
对比例4
制备方法与实施例1相同,区别仅在于,氢氧化钠的质量比为0.5%,制得的产品中,负载氢氧化钠0.5%,负载聚六亚甲基双胍盐酸盐10.1%,含水率6.2%。
实验例
实验例1
将实施例1-6和对比例1-4制备的产品,按照《GB21551.2-2010家用和类似用途电器的抗菌、除菌、净化功能抗菌材料的特殊要求》进行检测,其中,抗细菌的评价为:抗菌率90%以上为有抗菌作用;
霉菌等级评价为:
0级:完全不长霉菌或细菌;
1级:肉眼可见生长,但生长覆盖面积小于10%;
2级:生长覆盖面积小于30%,不小于10%;
3级:生长覆盖面积小于60%,不小于30%;
4级:生长覆盖面积大于60%。
其中,检测结果如下表:
由上表可知,负载杀霉菌物质后,负载活性炭的防霉杀菌作用显著提升。
实验例2
甲醛去除速率测定
温度为25℃,湿度为60%,在3立方米测试仓内甲醛的初始浓度为1mg/L,测试样品100克,80m3/h的循环风量,测量甲醛浓度的清除速率。测试样品为实施例1、对比例1和4制得的产品。
结果如图1所示,实验表明,在同样测试条件下,实施例1 的产品去除甲醛的速率远高于对比例1和4制得的产品,甲醛去除率达到90%的时间只用了同类产品的一半时间。
可见,产品中含水率和氢氧化钠负载量的不同会对吸附甲醛的速率产生影响。
实验例3
活性炭寿命测试
在固定床反应器中进行实验,待测样品装填于固定床吸附塔中。固定床反应器检测系统如图3所示,空气泵1与干燥塔2 的下端连接,干燥塔2的上端与流量调节器3的入口连接,流量调节器3的出口与甲醛鼓泡发生器8连接,向甲醛鼓泡发生器8 中通入干燥的空气。流量调节器3可以调节通入甲醛鼓泡发生器 8的气体的流量和速度。甲醛鼓泡发生器8的外周设置有冰水浴4 控制甲醛鼓泡发生器8的温度。甲醛鼓泡发生器8的出口与固定床吸附塔6的入口连接,向固定床吸附塔6中通入甲醛气体;在固定床吸附塔6与甲醛鼓泡发生器8之间设有吸附柱前取样点5,在固定床吸附塔6的出口处设置有吸附柱后取样点7。
在甲醛鼓泡发生器8中,利用空气鼓泡甲醛发生器产生甲醛,通过流量调节器3将流经样品的甲醛气体流速稳定在 80ml·min-1,对应质量空速为200000ml·g-1·h-1,进入固定床吸附塔6之前的甲醛浓度为5mg/m3。利用恒温装置对固定床吸附塔6内的样品进行保温,采集25℃下通过样品前后的甲醛气体进行测试,将样品固定在25℃下进行长时间连续反应,计算不同时间间隔下甲醛消除率的变化情况,连续测试24小时。
测试样品为实施例1制得的产品,市售一、市售二和市售催化型产品。其中,市售一,Y100-90ANT柱状煤质活性炭(直径2.0mm);市售二,CZ9210型柱状煤质活性炭(直径2.0mm);市售催化型为负载锰系催化剂的SHY-Mn直径2.0mm煤质除醛活性炭。
结果如图2所示,从图中可以看到,24小时内,实例1的产品性能基本无下降,而市售催化型产品起始效率较低,随着试验的进行,其效率有一定提高,性能24小时内基本保持平稳,但始终低于实施例1;市售一和二的负载型产品,起始清除速率较快,但是随着试验的进行,其清除效率在约8个小时后迅速下降,其寿命比实施例1的产品和市售催化型产品都低很多。
可见,实施例1产品的寿命相较其他市售产品而言,具有非常明显的寿命优势;并且,实施例1产品的消除效率要高于市售催化型产品。
以上结合具体实施方式和范例性实例对本发明进行了详细说明,不过这些说明并不能理解为对本发明的限制。本领域技术人员理解,在不偏离本发明精神和范围的情况下,可以对本发明技术方案及其实施方式进行多种等价替换、修饰或改进,这些均落入本发明的范围内。本发明的保护范围以所附权利要求为准。
Claims (5)
1.一种用于室内除甲醛的负载活性炭的制备方法,其特征在于,所述负载活性炭包括:活性炭载体、水溶性无机碱、杀菌剂和水分,所述水溶性无机碱为氢氧化钠或氢氧化钾,所述杀菌剂为胍类物质,选自十二烷基胍盐酸盐、聚六亚甲基单胍盐酸盐、聚六亚甲基单胍磷酸盐、聚六亚甲基双胍盐酸盐中的一种或者多种,所述水溶性无机碱占负载活性炭质量的1-10%,所述水分占负载活性炭质量的1-10%;
所述方法包括:
将水溶性无机碱和杀菌剂溶于水中,加入活性炭载体,浸渍,烘干,得到负载活性炭。
2.根据权利要求1所述的方法,其特征在于,所述杀菌剂占负载活性炭质量的1-15%。
3.根据权利要求2所述的方法,其特征在于,所述杀菌剂占负载活性炭质量的5-15%。
4.根据权利要求1所述的方法,其特征在于,所述水溶性无机碱占负载活性炭质量的2-6%;
所述水分占负载活性炭质量的3-9%。
5.根据权利要求1所述的方法,其特征在于,所述活性炭载体的四氯化碳吸附值为70-100%。
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