CN114557364A - 一种二氧化氯缓释空气清新剂 - Google Patents
一种二氧化氯缓释空气清新剂 Download PDFInfo
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Abstract
本发明公开一种二氧化氯缓释空气清新剂,所述清新剂由微孔陶瓷材料、多孔吸附材料、二氧化氯发生组分和粘合剂组成,所述微孔陶瓷材料为两个半球形的壳体,所述多孔吸附材料吸附有所述二氧化氯发生组分,所述吸附有二氧化氯发生组分的多孔吸附材料包覆在所述微孔陶瓷材料中,微孔陶瓷材料之间通过粘合剂粘合成型。本发明空气清新剂通过自呼吸材料的调控随着环境变化进行调整,大大提高了二氧化氯发生剂的利用率,提升了个人空间内使用二氧化氯空气清新剂的用户的使用体验。
Description
技术领域
本发明属于日用空气清新剂领域,尤其涉及一种二氧化氯缓释空气清新剂。
背景技术
二氧化氯由于具有极强的氧化、漂白性能,能够分解空气中的氨类、含硫化合物、不饱和烃类,以及部分VOC,并对空气中弥漫的微量异味能进行有效去除。同时,对细菌、真菌、藻类的蛋白质也有强大破坏效果,能快速杀灭空气中和附着在一般物体表面的微生物,从而进一步消灭霉味、腐败味等空气中难以根除的气味,是一种十分适用于进行空气清新剂的物质。
二氧化氯在浓度较高的时候具有明显的刺激性臭味,会对人造成不适,有研究表明,二氧化氯进行空气消杀并不需要使人察觉得出异样的高浓度,0.01ppm~0.1ppm就能对大多数致病菌,霉菌有良好的杀灭效果。人体对二氧化氯的感知下限为0.3ppm,国家标准《工作场所有害因素职业接触限值》(GBZ 2-2007),规定二氧化氯在工作场所中允许的浓度为0.3mg/m3,折合0.236ppm。因此,让空气中的二氧化氯浓度保持在0.2ppm以下,即可进行十分有效的空气消毒,将二氧化氯气体控制在这个范围内,使得空气中平均二氧化氯浓度为0.01~0.2ppm之间,即有较为良好的空气清新效果。
为此二氧化氯缓释类消毒剂、空气清新剂类产品已经通过很多方式得到运用。如凝胶类,颗粒类以及液体类等,其通常通过含有空穴的大分子对二氧化氯的缓冲溶液进行包裹增稠,使得新生成的二氧化氯无法在发生之后迅速往凝胶/颗粒或者其他难以渗透的物质外侧迁移,实现二氧化氯的缓释。
但是这类缓释方法大体上依赖溶液和水凝胶进行活化,二氧化氯在水溶液中,极易发生自我氧化还原的歧化反应,分解成无法再度生成二氧化氯的物质,此类副反应在pH值维持在弱酸性至弱碱性的时候倾向于发生,且温度的升高,反应速度极易加快,会造成大量反应物损失或缓释失控,二氧化氯短时间内大量放出。二氧化氯及其前反应物容易受到光照的影响,在强光照射催化下,二氧化氯会很快分解,生成有毒的氯气,失去利用二氧化氯进行安全空气消杀的作用。
发明内容
为了解决上述技术问题,本发明提供一种二氧化氯缓释空气清新剂,该清新剂使用独特烧制的自呼吸微孔陶瓷材料作为多孔材料的外壳材料,多孔吸附材料吸附有二氧化氯发生组分,进行缓释空气清新剂内部的温湿度调控。实现亚氯酸钠反应的启停智能控制,可用于室内除味,防霉,杀菌,对容易残留异味和病菌的物体表面消毒,将各种胺类、含硫化合物,甲醛等有害物质进行有效分解。为实现本发明目的所使用的技术方案为:
一种二氧化氯缓释空气清新剂,所述清新剂由微孔陶瓷材料、多孔吸附材料、二氧化氯发生组分和粘合剂组成,所述微孔陶瓷材料为两个半球形的壳体,所述多孔吸附材料吸附有所述二氧化氯发生组分,所述吸附有二氧化氯发生组分的多孔吸附材料包覆在所述微孔陶瓷材料中,微孔陶瓷材料之间通过粘合剂粘合成型;
所述微孔陶瓷材料由高岭土、硅藻土、铁电气石、脂肪酸钠、碳酸钾、晶红石二氧化钛、纳米碳黑制成。
组装产品时,将吸附二氧化氯发生组分的多孔吸附材料,填充进半球形的微孔陶瓷材料壳体中,并用粘合剂封死球壳,操作空间的温度<30℃,湿度<50%。
完成组装后,用塑料袋或者铝塑袋中真空包装热合封口储存,真空抽气应该小于-0.1Mpa,抽真空后的热合封口应牢固。
本发明的优选技术方案中,所述微孔陶瓷材料的直径为5~8mm,厚度为1.5~2.5mm。
本发明的优选技术方案中,所述二氧化氯发生组分由亚氯酸钠、多元弱酸或弱酸盐、弱碱盐和增稠分散剂组成,所述多元弱酸或弱酸盐为邻苯二甲酸氢钾、EDTA、酒石酸氢钾、磷酸二氢钾或硫酸铝的一种;所述弱碱盐为磷酸氢二钠、EDTA二钠、柠檬酸钠或醋酸钠的一种;所述增稠分散剂为聚乙二醇6000、羧甲基纤维素钠或明胶的一种。
本发明的优选技术方案中,所述组分的质量分数为:亚氯酸钠55%~70%、多元弱酸或弱酸盐10%~15%、弱碱盐10%~15%和增稠分散剂5%~15%;pH值控制在6.5~7.0之间。
本发明的优选技术方案中,所述多孔吸附材料为沸石、3A分子筛、5A级分子筛、硅藻土、钙基膨润土的一种,所述多孔吸附材料孔径为3~10nm。
本发明的优选技术方案中,所述粘合剂为环氧树脂、天门冬氨酸聚脲的一种或两种。
本发明的优选技术方案中,所述微孔陶瓷材料的制备方法包括如下步骤:
(1)称取高岭土30~50份、硅藻土20~30份、铁电气石5~15份、脂肪酸钠5~10份、碳酸钾5~10份、晶红石二氧化钛5~10份、纳米碳黑1~5份,备用;
(2)将步骤(1)物料进行球磨粉碎30~60min,所制得粒径为500~800目,将粉末分为两份;
(3)将步骤(2)的一份物料通过喷雾造粒,在磨具上形成半球形的壳体,再在600~900℃的温度下隔绝空气,在氮气作为保护气下烧制30~60min;
(4)将步骤(2)的另一份物料用淋釉法和盖釉法在球壳表面成形后,在1100~1150℃下,烧釉时间为30~45min,通入空气烧釉成形;釉质表面通过微孔烧蚀,形成200~300nm的微孔;
(5)将步骤(3)和步骤(4)获得壳体冷却至室温,打磨后即得。
通过煅烧得来的釉层微孔陶瓷经过进一步短时间的热处理将其中预留用于升华的纳米金属微粒升华开出细孔后制成。
本发明的优选技术方案中,所述多孔吸附材料吸附二氧化氯发生组分的步骤为:将二氧化氯发生组分按质量比1:20的量与去离子水混合后,在氮气保护的环境中搅拌溶解完全,并在氮气保护的环境下,按溶液:多孔吸附材料质量比2:1的比例混合搅拌,搅拌时间15~30min后,再进行减压风干,风干的温度为45℃,时间为2~5h,压力为0.085~0.090mPa。
本发明的优选技术方案中,所述清新剂为球形或药锭形。
本发明的优选技术方案中,所述清新剂使用PE袋或铝塑包装袋真空包装。
由于微孔陶瓷自呼吸材料对湿度存在动态调控作用,微孔陶瓷材料是一种拥有一定的水汽吸附能力,能使得密闭空间内,通过微孔陶瓷本身的吸水能力,使得密闭的内部空间的湿度和温度,在外部环境变化不甚剧烈时,保持一个相对较为稳定的状态,在此情况下,材料内部的二氧化氯发生组分可以一个较为平稳的速率释放,得益于电气石类矿物所具有的易吸水且吸水后由于晶型改变,通透性发生变化的效果,实现稳定二氧化氯缓释。
本申请清新剂对空气的调控方式如下:
由于微孔陶瓷自呼吸作用,通过对材料内部进行动态的湿度控制,从而实现材料内部相对外界环境保持恒湿以及温度的稳定性,促使材料内吸附包裹的二氧化氯生成体系可以在湿度(50%~80%)条件下,在外界的温度、湿度适宜且只有些许变化的情况下,以稳定的影响的状态进行活化释放二氧化氯,起到空气清新剂的作用。
当外部湿度大于微孔陶瓷所能缓冲的阈值(>80%)后,陶瓷将停止调控湿度成为水气的宽松通道,激发内部二氧化氯发生组分快速反应。针对此时空气中高湿高温情况引发的霉菌滋生,发挥空间消杀消毒的效果。
二氧化氯可以自由从微孔陶瓷的孔道进出,由于陶瓷身为硅钙类无机物的高化学稳定性,通常不会影响二氧化氯的稳定性。
当外部湿度极低(<50%)的情况下,材料则可以成为干燥内部空气的屏障,使得水汽只有极少可以进入内部激活反应,使材料在干燥低温,异味往往较少的环境中暂停释放。此时空气清新剂反应速度被大幅度减慢,如有必要,也可以通过向材料泼洒水来激活。自呼吸材料能阻挡空气中的水分,大幅度延缓二氧化氯的释放,进入休眠,大大延长了产品的生效时间。
综上所述,由于本发明采用了上述技术方案,本发明具有以下技术效果:
本发明清新剂采用微孔陶瓷制成,微孔陶瓷具有自呼吸作用,采用微孔陶瓷外壳包裹的多孔材料吸附的二氧化氯发生组分能够根据温湿度智能调节的材料内环境调控,使得二氧化氯的发生组分能通过自呼吸材料的调控随着环境变化进行调整,大大提高了二氧化氯发生剂的利用率:针对不同季节和环境情况的变化,如容易滋生霉菌的暖寒交替时节,材料能提高二氧化氯释放量,在较为干爽的秋冬材料能降低甚至停止二氧化氯释放的智能调控效果,大大提升了在个人空间内使用二氧化氯空气清新剂的用户的使用体验。
综上所述,本发明的二氧化氯缓释固态空气清新剂,具有自呼吸式作用,能够智能识别个人空间的温湿度变化及环境质量变化,自动根据空间内环境调节二氧化氯的释放量。
附图说明
图1是实施例1空气清新剂结构示意图;
图2是实施例1制备的清新剂在72h内释放曲线和湿度曲线图;
图3是实施例2空气清新剂结构示意图;
图4是实施例2制备的清新剂在72h内释放曲线和湿度曲线图。
具体实施方式
为使本发明的目的、技术方案及优点更加清楚明白,以下参照附图并举出优选实施例,对本发明进一步详细说明。然而,需要说明的是,说明书中列出的许多细节仅仅是为了使读者对本发明的一个或多个方面有一个透彻的理解,即便没有这些特定的细节也可以实现本发明的这些方面。
实施例1
按高岭土37份,硅藻土23份,铁电气石10份,脂肪酸钠8份,碳酸钾7份,晶红石二氧化钛10份,纳米炭黑5份,进行球磨粉碎30~60min,所得粒径为500~800目,将所得陶瓷粉末分为两部分,一份喷淋制作胚为直径8mm的半球,厚度为1.5mm,先在650℃±10℃的温度下,经过30min烧制成形。烧制过程中,使用向炉中持续通入常压氮气进行保护。
另一部分通过喷雾造釉,使得陶瓷球表面形成0.1~0.2mm的釉。通入空气至常压,在1130℃±10℃的温度下,烧釉30min成形。此时纳米碳粉反应,留下微孔。釉质表面想通过微孔烧蚀,形成200~300nm的微孔。
将微孔陶瓷材料冷却至室温,制得微孔陶瓷外壳厚度为1.5~2.5mm,直径8mm,备用。
配置二氧化氯发生溶液,用磷酸二氢钾1.5份,磷酸一氢钾1份,亚氯酸钠6.5份,聚乙二醇6000 1份,以及200份水,溶解在三口烧瓶中,溶液所占烧瓶体积为1/3到1/4,持续向烧瓶内通入常压氮气,待反应物完全溶解后,向溶液中加入直径为5.0~5.5mm的沸石100份进行搅拌30min,然后将烧瓶至于旋转蒸发器中,在减压蒸发的过程中将溶液中的水全部蒸干。
所得吸附二氧化氯发生组分的多孔吸附材料,装配在微孔陶瓷材料中,然后用环氧密封胶粘合,即得。产品效果如图1所示。
将制备的清新剂置于避光且体积为10L的容器中,外界空气以1L/h速度流动,与外界进行循环气体交换,并用精度为0.01ppm的电化学检测器测量容器中的二氧化氯气体浓度,每30min检测一次。所检测材料在72h内释放曲线和湿度曲线如图2所示。结果表明,二氧化氯的释放能够根据环境湿度进行调控。
实施例2
按高岭土40份,硅藻土20份,铁电气石10份,脂肪酸钠8份,碳酸钾7份,晶红石二氧化钛10份,纳米炭黑5份,球磨过筛。所得陶瓷粉末分为两部分,喷淋制作胚为直径8mm的半球,厚度为1.5mm,先在650℃±10℃的温度下,经过30min烧制成形。
烧制过程中,使用向炉中持续通入常压氮气进行保护。
另一部分通过喷雾造釉,使得陶瓷球表面形成0.1~0.2mm的釉。
通入空气至常压,在1140℃±10℃的温度下,烧釉30min成形。
所得微孔陶瓷材料备用。
配置二氧化氯发生溶液,用磷酸二氢钾1.5份,磷酸一氢钾1份,亚氯酸钠6.5份,聚乙二醇6000 1份,以及200份水,溶解在三口烧瓶中,溶液所占烧瓶体积为1/3到1/4,持续向烧瓶内通入常压氮气,待反应物完全溶解后,向溶液中加入直径为0.5~1.0mm的沸石100份进行搅拌30min,然后将烧瓶至于旋转蒸发器中,在减压蒸发的过程中将溶液中的水全部蒸干。
所得吸附了二氧化氯发生组分的多孔吸附材料,装配在微孔陶瓷材料中,然后用环氧树脂密封胶粘合,其效果如图3所示。
将制备的清新剂置于避光且体积为10L的容器中,外界空气以1L/h速度流动,与外界进行循环气体交换,并用精度为0.01ppm的电化学检测器测量容器中的二氧化氯气体浓度,每30min检测一次。所检测材料在72h内释放曲线和湿度曲线如图4所示。结果表明,二氧化氯的释放量随着湿度的增加而增大,并且释放量在0.2ppm以下。
实施例3
按高岭土30份,硅藻土25份,铁电气石5份,脂肪酸钠10份,碳酸钾5份,晶红石二氧化钛8份,纳米炭黑3份,进行球磨粉碎60min,所得粒径为500~800目,将所得陶瓷粉末分为两部分,一份喷淋制作胚为直径8mm的半球,厚度为1.5mm,先在750℃±10℃的温度下,经过30min烧制成形。烧制过程中,使用向炉中持续通入常压氮气进行保护。
另一部分通过喷雾造釉,使得陶瓷球表面形成0.1~0.2mm的釉。通入空气至常压,在1110℃±10℃的温度下,烧釉30min成形。此时纳米碳粉反应,留下微孔。釉质表面想通过微孔烧蚀,形成200~300nm的微孔。
将微孔陶瓷材料冷却至室温,制得微孔陶瓷外壳厚度为1.5~2.5mm,直径8mm,备用。
配置二氧化氯发生溶液,酒石酸氢钾1.5份,柠檬酸钠1份,亚氯酸钠6.5份,羧甲基纤维素钠1份,以及200份水,溶解在三口烧瓶中,溶液所占烧瓶体积为1/3到1/4,持续向烧瓶内通入常压氮气,待反应物完全溶解后,向溶液中加入直径为5.0~5.5mm的3A分子筛100份进行搅拌30min,然后将烧瓶至于旋转蒸发器中,在减压蒸发的过程中将溶液中的水全部蒸干。所得吸附二氧化氯发生组分的多孔吸附材料,装配在微孔陶瓷材料中,然后用环氧树脂和天门冬氨酸聚脲密封胶粘合,陶瓷微孔材料通过压缩程序与粘合剂压缩成形后,待成型剂固化后,作成8~10mm的球形,即得。
实施例4
按高岭土50份,硅藻土30份,铁电气石15份,脂肪酸钠10份,碳酸钾10份,晶红石二氧化钛10份,纳米炭黑5份,进行球磨粉碎60min,所得粒径为500~800目,将所得陶瓷粉末分为两部分,一份喷淋制作胚为直径8mm的半球,厚度为1.5mm,先在850℃±10℃的温度下,经过30min烧制成形。烧制过程中,使用向炉中持续通入常压氮气进行保护。
另一部分通过喷雾造釉,使得陶瓷球表面形成0.1~0.2mm的釉。通入空气至常压,在1110℃±10℃的温度下,烧釉30min成形。此时纳米碳粉反应,留下微孔。釉质表面想通过微孔烧蚀,形成200~300nm的微孔。
将微孔陶瓷材料冷却至室温,制得微孔陶瓷外壳厚度为1.5~2.5mm,直径8mm,备用。
配置二氧化氯发生溶液,邻苯二甲酸氢钾1.5份,EDTA二钠1份,亚氯酸钠6.5份,明胶1份,以及200份水,溶解在三口烧瓶中,溶液所占烧瓶体积为1/3到1/4,持续向烧瓶内通入常压氮气,待反应物完全溶解后,向溶液中加入直径为5.0~5.5mm的钙基膨润土100份进行搅拌30min,然后将烧瓶至于旋转蒸发器中,在减压蒸发的过程中将溶液中的水全部蒸干。所得吸附二氧化氯发生组分的多孔吸附材料,装配在微孔陶瓷材料中,然后用天门冬氨酸聚脲密封胶粘合,陶瓷微孔材料通过压缩程序与粘合剂压缩成形后,待成型剂固化后,作成8~10mm的药锭形,即得。
应用实例
应用例1
分别取实施例1-4的空气清新剂3g,并分别置于空间为1m3、细菌含量为250-290cfu/m3、湿度为60%的密闭测试容器进行杀菌测试,容器内温度控制在26-28℃,杀菌时间为2小时,以白色葡萄球菌为测试对象,测试结果如表1所示。
序号 | 起始细菌含量cfu/m<sup>3</sup> | 终止细菌含量cfu/m<sup>3</sup> | 杀菌率% |
实施例1 | 259 | 17 | 93.4 |
实施例2 | 280 | 21 | 92.5 |
实施例3 | 265 | 18 | 93.2 |
实施例4 | 275 | 12 | 95.6 |
表1结果表明,本发明使用率具有良好的杀菌效果,杀菌率在92%以上,具有良好的空气净化效果。
应用例2
分别取实施例1-4的空气清新剂3g,并分别置于空间为1m3、湿度为45%的透明玻璃容器进行二氧化氯释放量测试,将容器光照强度设置为5000~8000Lux,容器内温度控制在33~35℃,采用精度为0.001ppm的电化学检测器测量二氧化氯气体浓度,每30min检测一次,采集3次,测试结果如
表2所示。
序号 | 30min浓度(ppm) | 60min浓度(ppm) | 90min浓度(ppm) |
实施例1 | 0.0012 | 0.0024 | 0.0038 |
实施例2 | 0.0011 | 0.0022 | 0.0042 |
实施例3 | 0.0013 | 0.0020 | 0.0032 |
实施例4 | 0.0016 | 0.0023 | 0.0035 |
表2结果表明,在强光、低湿度环境下,实施例1-4的二氧化氯释放量极低,基本不释放二氧化氯。
综上所述,本发明空气清新剂接触在空气湿度(50%~80%)条件,空气清新剂即刻开始生效,可以有效依靠缓释二氧化氯分解空气中的有害物质,并杀灭治病微生物和霉菌,减少异味,并可以通过湿度和温度智能调整释放量以满足不同季节和场景的空气净化需求。因此自呼吸材料二氧化氯缓释固态空气清新剂的具有良好的运用前景。
本发明很大程度了改善了现有二氧化氯缓释剂产品释放极易因为光照、温度、湿度、气流等因素影响释放量无法稳定的问题。极其适用于个人空间,车内,衣柜和厕卫等环境的除臭,除味以及空气清新的效果,也可用于冬春换季冷热交替季节的防霉,灭菌作业。其使用便捷,有效期长,释放量稳定适量,对金属、织物、无腐蚀性,对人体,宠物无有害影响,具有良好的商业应用前景。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以作出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (9)
1.一种二氧化氯缓释空气清新剂,其特征在于,所述清新剂由微孔陶瓷材料、多孔吸附材料、二氧化氯发生组分和粘合剂组成,所述微孔陶瓷材料为两个半球形的壳体,所述多孔吸附材料吸附有所述二氧化氯发生组分,所述吸附有二氧化氯发生组分的多孔吸附材料包覆在所述微孔陶瓷材料中,微孔陶瓷材料之间通过粘合剂粘合成型;
所述微孔陶瓷材料由高岭土、硅藻土、铁电气石、脂肪酸钠、碳酸钾、晶红石二氧化钛、纳米碳黑制成。
2.根据权利要求1所述二氧化氯缓释空气清新剂,其特征在于,所述微孔陶瓷材料的直径为5~8mm,厚度为1.5~2.5mm。
3.根据权利要求1所述二氧化氯缓释空气清新剂,其特征在于,所述二氧化氯发生组分由亚氯酸钠、多元弱酸或弱酸盐、弱碱盐和增稠分散剂组成,所述多元弱酸或弱酸盐为邻苯二甲酸氢钾、EDTA、酒石酸氢钾、磷酸二氢钾或硫酸铝的一种;所述弱碱盐为磷酸氢二钠、EDTA二钠、柠檬酸钠或醋酸钠的一种;所述增稠分散剂为聚乙二醇6000、羧甲基纤维素钠或明胶的一种。
4.根据权利要求3所述二氧化氯缓释空气清新剂,其特征在于,所述组分的质量分数为:亚氯酸钠55%~70%、多元弱酸或弱酸盐10%~15%、弱碱盐10%~15%和增稠分散剂5%~15%。
5.根据权利要求1所述二氧化氯缓释空气清新剂,其特征在于,所述多孔吸附材料为沸石、3A分子筛、5A级分子筛、硅藻土、钙基膨润土的一种,所述多孔吸附材料孔径为3~10nm。
6.根据权利要求1所述二氧化氯缓释空气清新剂,其特征在于,所述粘合剂为环氧树脂、天门冬氨酸聚脲的一种或两种。
7.根据权利要求1所述二氧化氯缓释空气清新剂,其特征在于,所述微孔陶瓷材料的制备方法包括如下步骤:
(1)称取高岭土30~50份、硅藻土20~30份、铁电气石5~15份、脂肪酸钠5~10份、碳酸钾5~10份、晶红石二氧化钛5~10份、纳米碳黑1~5份,备用;
(2)将步骤(1)物料进行球磨粉碎30~60min,所制得粒径为500~800目,将粉末分为两份;
(3)将步骤(2)的一份物料通过喷雾造粒,在磨具上形成半球形的壳体,再在600~900℃的温度下隔绝空气,在氮气作为保护气下烧制30~60min;
(4)将步骤(2)的另一份物料用淋釉法和盖釉法在球壳表面成形后,在1100~1150℃下,烧釉时间为30~45min,通入空气烧釉成形;
(5)将步骤(3)和步骤(4)获得壳体冷却至室温,打磨后即得。
8.根据权利要求1所述二氧化氯缓释空气清新剂,其特征在于,所述多孔吸附材料吸附二氧化氯发生组分的步骤为:将二氧化氯发生组分按质量比1:20的量与去离子水混合后,在氮气保护的环境中搅拌溶解完全,并在氮气保护的环境下,按溶液:多孔吸附材料质量比2:1的比例混合搅拌,搅拌时间15~30min后,再进行减压风干,风干的温度为45℃,时间为2~5h,压力为0.085~0.090mPa。
9.根据权利要求1所述二氧化氯缓释空气清新剂,其特征在于,所述清新剂为球形或药锭形。
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