CN111826042B - 一种防钋-210内墙涂料及其制备方法 - Google Patents
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Abstract
本发明提供一种防钋‑210内墙涂料及其制备方法,本发明技术方案通过在内墙涂料中添加凹凸棒石粉、有机膨润土、磁铁矿粉和氧化石墨烯溶液提高内墙涂料对钋‑210的吸附能力,从而在粉煤灰被资源化利用作为混凝土的掺合料被大量应用在建筑工程中的时候,内墙涂料可以吸附钋‑210,将钋‑210封闭在内墙涂料中,防止钋‑210挥发进入人体,提高粉煤灰资源化利用的安全性,市场应用前景广。
Description
技术领域
本发明涉及节能环保技术领域,特别涉及一种防钋-210内墙涂料及其制备方法。
背景技术
钋-210,核素符号Po,主要来源于铀系天然放射性核素,Po-210的毒性是氰化物的2.5亿倍,钋-210的放射能为铀的400倍,发射的α粒子比相同重量的镭高5000倍以上,被称为世界上最毒的物质。不过钋-210发射的α粒子在空气中的射程很短,不能穿透纸或者皮肤,所以在人的体外不会构成外照射危险。但是,钋-210容易形成放射性气溶胶,污染环境和空气,可通过吸入、进食或伤口进入人体,长期辐射会引起肿瘤;吸收剂量越高,癌症发生的概率越高。进入体内后,可以在局部迁移或随血液到达各个器官,主要滞留于骨、肺、肾和肝中。进入血液中的钋-210能对骨髓和造血系统造成严重的放射性损伤。
粉煤灰,是从煤燃烧后的烟气中收捕下来的细灰,粉煤灰是燃煤电厂排出的主要固体废物。随着电力工业的发展,燃煤电厂的粉煤灰排放量逐年增加,成为我国当前排量较大的工业废渣之一。大量的粉煤灰不加处理,就会产生扬尘,污染大气;若排入水系会造成河流淤塞,而其中的有毒化学物质还会对人体和生物造成危害。但粉煤灰可资源化利用,如作为混凝土的掺合料被大量应用在建筑工程中。
煤炭中普遍含有铀、钍、镭和钋-210等放射性物质,粉煤灰是煤粉进入1300~1500℃的高温炉膛后,在悬浮燃烧条件下经受热面吸热后冷却而形成的。高温下,煤粉中处于化合物的放射性核素钋-210被分解和排出。钋-210会产生高度富集,钋-210经过完全蒸发后温度压力下降,会引发一些化学反应和凝结。一部分钋-210单质凝结在悬浮于尾气中的固体颗粒表面,另一部分钋-210单质凝结在自凝结物质,即粉煤灰上面。粉煤灰中的钋-210具有很强的挥发性,传统的建筑及装饰材料不足以密封或吸附放射性钋-210,给处于室内环境中的人体造成严重危害,限制了粉煤灰的资源化利用。
发明内容
本发明的主要目的是提供一种防钋-210内墙涂料,旨在解决粉煤灰在应用到建筑材料时对人体造成辐射污染的问题。
为实现上述目的,本发明提出一种防钋-210内墙涂料,按重量份计包括:凹凸棒石粉80~100份,有机膨润土10~12份,磁铁矿粉0.5~3.0份,氧化石墨烯溶液0.2~2.0份。
可选地,按重量份计还包括:钛白粉160~220份,聚合物乳液130~180份,乙二醇12~15份,分散剂1~4份,消泡剂3~5份,湿润剂1~2份,防腐剂2~4份,增稠剂2~4份,流平剂1~3份,杀菌剂1~2份,PH调节剂1~2份,去离子水320~350份。
可选地,所述磁铁矿粉包括钛磁铁矿粉、钒磁铁矿粉或钒钛磁铁矿粉中的任意一种或多种。
可选地,所述氧化石墨烯溶液是由氧化石墨烯和水按质量比为1:8~1:10配制而成。
可选地,所述氧化石墨烯溶液的浓度为0.03~0.12mg/ml。
可选地,所述有机膨润土为钠基膨润土、钙基膨润土或铝基膨润土中的任意一种。
可选地,所述流平剂为羧甲基纤维素。
可选地,所述消泡剂为乳化硅油、高碳醇脂肪酸酯复合物、聚氧乙烯聚氧丙烯季戊四醇醚、聚氧乙烯聚氧丙醇胺醚、聚氧丙烯甘油醚和聚氧丙烯聚氧乙烯甘油醚和聚二甲基硅氧烷中的一种或多种。
本发明还提出一种防钋-210内墙涂料的制备方法,包括以下步骤:
按比例取80%的去离子水,倒入容器中,然后按比例将浓度0.08mg/ml的氧化石墨烯溶液倒入,超声搅拌30min,然后静置15min;
低速搅拌,按比例分别加入PH调节剂、分散剂、消泡剂、湿润剂、增稠剂、流平剂、防腐剂和杀菌剂,搅拌均匀;
中速搅拌,按比例分别加入钛白粉、凹凸棒石粉、有机膨润土、钛磁铁矿粉(或钒磁铁矿粉、钒钛磁铁矿粉),再加入乙二醇及5%的调整水,搅拌均匀得粗浆料;
高速分散,将所述粗浆料放进砂磨机研磨得到细浆料;
调整所述细浆料的PH=4.7±0.1后,缓慢加到成比例的聚合物乳液中,然后加入剩余量的消泡剂、防腐剂,继续搅拌约30min;
用剩余去离子水调整粘度;
过滤包装。
本发明技术方案通过在内墙涂料中添加凹凸棒石粉、有机膨润土、磁铁矿粉和氧化石墨烯溶液提高内墙涂料对钋-210的吸附能力,从而在粉煤灰被资源化利用作为混凝土的掺合料被大量应用在建筑工程中的时候,内墙涂料可以吸附钋-210,将钋-210封闭在内墙涂料中,防止钋-210挥发进入人体,提高粉煤灰资源化利用的安全性,市场应用前景广。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明的一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
本发明提出一种防钋-210内墙涂料,按重量份计包括:凹凸棒石粉80~100份,有机膨润土10~12份,磁铁矿粉0.5~3.0份,氧化石墨烯溶液0.2~2.0份。
本发明技术方案通过在内墙涂料中添加凹凸棒石粉、有机膨润土、磁铁矿粉和氧化石墨烯溶液提高内墙涂料对钋-210的吸附能力,从而在粉煤灰被资源化利用作为混凝土的掺合料被大量应用在建筑工程中的时候,内墙涂料可以吸附钋-210,将钋-210封闭在内墙涂料中,防止钋-210挥发进入人体,提高粉煤灰资源化利用的安全性,市场应用前景广。
具体的,凹凸棒石具有高孔隙率,大的比表面积,以及表面上的活性位点和阳离子交换的性质,它通过离子交换吸附、离子络合和静电吸附,物质进入孔道稳定存在,形成氢氧化物微沉淀等方式吸附核素。
具体的,膨润土可以为钠基膨润土、钙基膨润土或铝基膨润土。膨润土不仅具有良好的防水和抗渗性能,钠基膨润土具有更大的膨胀性和阳离子交换容量,良好的吸附性、阳离子交换性、分散悬浮性、可塑性和膨胀性等性能,可用作核素吸附剂。
具体的,所述磁铁矿粉包括钛磁铁矿粉、钒磁铁矿粉或钒钛磁铁矿粉中的任意一种或多种。钋-210发射的α射线带正电,如果穿过磁场,会产生偏转。钛磁铁矿、钒磁铁矿或钒钛磁铁矿属于强磁性矿石,可以使从被封闭材料中散发出的钋-210离子排斥或吸引到凹凸棒石粉等吸附材料中。
具体的,氧化石墨烯是石墨烯的氧化物,经氧化后,其含氧官能团增多而使性质较石墨烯更加活泼,可经由各种与含氧官能团的反应而改善本身性质。氧化石墨烯是单一的原子层,可以随时在横向尺寸上扩展到数十微米,表面丰富的活性含氧基团通常为羟基和羧基。其中,羟基和羧基在一定pH值范围内发生去质子化作用,使氧化石墨烯形成带负电荷的酸性表面,致使片层之间存在较强的静电斥力而均匀分散,从而具有极大的比表面积(2600m2/g)和较强的静电吸附力,因而其具有较强的亲水性和吸附性,是一种性能优异的新型碳材料。
具体的,所述氧化石墨烯溶液是由氧化石墨烯和水按质量比为1:8~1:10配制而成。更具体地,所述氧化石墨烯溶液的浓度为0.03~0.12mg/ml,更优选地,所述氧化石墨烯溶液的浓度为0.08mg/ml。
优选地,所述防钋-210内墙涂料按重量份计还包括:钛白粉160~220份,聚合物乳液130~180份,乙二醇12~15份,分散剂1~4份,消泡剂3~5份,湿润剂1~2份,防腐剂2~4份,增稠剂2~4份,流平剂1~3份,杀菌剂1~2份,PH调节剂1~2份,去离子水320~350份。
具体的,钛白粉学名为二氧化钛,是一种染料及颜料,是白色颜料中着色力最强的一种,具有优良的遮盖力和着色牢度,适用于不透明的白色制品。
具体的,乙二醇在内墙涂料中作为添加辅料主要起到防冻、防腐效果,提高内墙涂料的性能。
具体的,分散剂的作用是使用润湿分散剂减少完成分散过程所需要的时间和能量,稳定所分散的颜料分散体,改性颜料粒子表面性质,调整颜料粒子的运动性,具体体现在以下几个方面:缩短分散时间,提高光泽,提高着色力和遮盖力,改善展色性和调色性,防止浮色发花,防止絮凝,防止沉降。
具体的,消泡剂是为了降低表面张力,抑制泡沫产生或消除已产生泡沫的添加剂。我国许可使用的消泡剂有乳化硅油、高碳醇脂肪酸酯复合物、聚氧乙烯聚氧丙烯季戊四醇醚、聚氧乙烯聚氧丙醇胺醚、聚氧丙烯甘油醚和聚氧丙烯聚氧乙烯甘油醚、聚二甲基硅氧烷等。
具体的,润湿剂主要作用是降低水的表面张力或界面张力,使固体表面能被水所润湿。
具体的,所述流平剂为羧甲基纤维素。流平剂是一种常用的涂料助剂,它能促使涂料在干燥成膜过程中形成一个平整、光滑、均匀的涂膜,能有效降低涂饰液表面张力,提高其流平性和均匀性。流平剂可改善涂饰液的渗透性,能减少刷涂时产生斑点和斑痕的可能性,增加覆盖性,使成膜均匀、自然。
具体的,酸碱度主要影响建筑材料的强度,腻子或砂浆过酸或过碱,都不利于它的强度。同时,PH也是影响重金属离子吸附性能的关键因素,吸附体系的PH不仅影响着吸附剂表面吸附点位的状态,也在很大程度上影响着重金属离子的水溶液化学反应。
本发明还提出一种防钋-210内墙涂料的制备方法,包括以下步骤:
按比例取80%的去离子水,倒入容器中,然后按比例将浓度0.08mg/ml的氧化石墨烯溶液倒入,超声搅拌30min,然后静置15min;
低速搅拌,按比例分别加入PH调节剂、分散剂、消泡剂、湿润剂、增稠剂、流平剂、防腐剂和杀菌剂,搅拌均匀;
中速搅拌,按比例分别加入钛白粉、凹凸棒石粉、有机膨润土、钛磁铁矿粉(或钒磁铁矿粉、钒钛磁铁矿粉),再加入乙二醇及5%的调整水,搅拌均匀得粗浆料;
高速分散,将所述粗浆料放进砂磨机研磨得到细浆料;
调整所述细浆料的PH=4.7±0.1后,缓慢加到成比例的聚合物乳液中,然后加入剩余量的消泡剂、防腐剂,继续搅拌约30min;
用剩余去离子水调整粘度;
过滤包装。
下面将结合具体实施例对本发明的实施方案进行详细描述,但是本领域技术人员将会理解,下列实施例仅用于说明本发明,而不应视为限制本发明的范围。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
实施例1
防钋-210内墙涂料原料(重量份):
凹凸棒石粉80份、有机膨润土10份、钛磁铁矿粉0.5份、浓度为0.08mg/ml的氧化石墨烯溶液0.5份、钛白粉160份、丙烯酸聚合物乳液150份、羧甲基纤维素1份、乙二醇12份、分散剂1份、消泡剂3份、湿润剂1份、防腐剂2份、增稠剂2份、流平剂1份、杀菌剂1份、PH调节剂1份、去离子水330份。
该防钋-210内墙涂料的制备方法:
取264份的去离子水,倒入容器中,然后加入浓度为0.08mg/ml的氧化石墨烯溶液0.5份,超声搅拌30min,然后静置15min;
低速搅拌,分别加入PH调节剂1份、分散剂1份、消泡剂2份、湿润剂1份、增稠剂2份、流平剂1份、防腐剂1份和杀菌剂1份,搅拌均匀;
中速搅拌,在容器中分别加入钛白粉160份、凹凸棒石粉80份、有机膨润土10份、钛磁铁矿粉0.5份,再加入乙二醇12份及16.5份的去离子水,搅拌均匀得粗浆料;
高速分散,将所述粗浆料放进砂磨机研磨得到细浆料;
调整所述细浆料的PH至4.7后,缓慢加到150份的丙烯酸聚合物乳液中,然后加入剩余量的1份消泡剂和1份防腐剂,继续搅拌约30min;
最后用剩余去离子水调整粘度;
过滤包装。
实施例2
防钋-210内墙涂料原料(重量份):
凹凸棒石粉90份、有机膨润土11份、钛磁铁矿粉1.5份、浓度为0.08mg/ml的氧化石墨烯溶液1.0份、钛白粉160份、丙烯酸聚合物乳液150份、羧甲基纤维素1份、乙二醇12份、分散剂1份、消泡剂3份、湿润剂1份、防腐剂2份、增稠剂2份、流平剂1份、杀菌剂1份、PH调节剂1份、去离子水330份。
该防钋-210内墙涂料的制备方法:
取264份的去离子水,倒入容器中,然后加入浓度为0.08mg/ml的氧化石墨烯溶液1.0份,超声搅拌30min,然后静置15min;
低速搅拌,分别加入羧甲基纤维素1份、PH调节剂1份、分散剂1份、消泡剂2份、湿润剂1份、增稠剂2份、流平剂1份、防腐剂1份和杀菌剂1份,搅拌均匀;
中速搅拌,在容器中分别加入钛白粉160份、凹凸棒石粉90份、有机膨润土11份、钛磁铁矿粉1.5份,再加入乙二醇12份及16.5份的去离子水,搅拌均匀得粗浆料;
高速分散,将所述粗浆料放进砂磨机研磨得到细浆料;
调整所述细浆料的PH至4.7后,缓慢加到150份的丙烯酸聚合物乳液中,然后加入剩余量的1份消泡剂和1份防腐剂,继续搅拌约30min;
最后用剩余去离子水调整粘度;
过滤包装。
实施例3
防钋-210内墙涂料原料(重量份):
凹凸棒石粉100份、有机膨润土12份、钛磁铁矿粉3.0份、浓度为0.08mg/ml的氧化石墨烯溶液2.0份、钛白粉160份、丙烯酸聚合物乳液150份、羧甲基纤维素1份、乙二醇12份、分散剂1份、消泡剂3份、湿润剂1份、防腐剂2份、增稠剂2份、流平剂1份、杀菌剂1份、PH调节剂1份、去离子水330份。
该防钋-210内墙涂料的制备方法:
取264份的去离子水,倒入容器中,然后加入浓度为0.08mg/ml的氧化石墨烯溶液2.0份,超声搅拌30min,然后静置15min;
低速搅拌,分别加入羧甲基纤维素1份、PH调节剂1份、分散剂1份、消泡剂2份、湿润剂1份、增稠剂2份、流平剂1份、防腐剂1份和杀菌剂1份,搅拌均匀;
中速搅拌,在容器中分别加入钛白粉160份、凹凸棒石粉100份、有机膨润土12份、钛磁铁矿粉3.0份,再加入乙二醇12份及16.5份的去离子水,搅拌均匀得粗浆料;
高速分散,将所述粗浆料放进砂磨机研磨得到细浆料;
调整所述细浆料的PH至4.7后,缓慢加到150份的丙烯酸聚合物乳液中,然后加入剩余量的1份消泡剂和1份防腐剂,继续搅拌约30min;
最后用剩余去离子水调整粘度;
过滤包装。
对比例
本对比例与实施例1~3的内墙涂料的制备方法相同,不同之处在于,本对比例的原料中未添加凹凸棒石粉、有机膨润土、钛磁铁矿粉、氧化石墨烯溶液。
试验例Po-210活度测定实验
采用α表面污染检测仪检测,主要参数:
1、探测器:ZnS涂敷塑料闪烁体探测器
2、探头有效直径:80mm±5mm
3、显示单位:Bq/cm3,换算成Bq/L,则1Bq/L=10-3Bq/cm3,统一按α总浓度的20%计算钋-210活度浓度,钋-210活度浓度=0.2×10-3×ɑ总浓度。
4、实施例年平均钋-210活度浓度=钋-210活度浓度×365×0.8(室内活动时间按365天、80%计算)。
目前,我国没有钋-210排放限值的规定。美国NRC规定,空气中钋-210年平均公众照射限值为3.33×10-5Bq/L;俄罗斯NRB的限值为3.40×10-5Bq/L。煤炭燃烧逸出飞灰的放射性核素Po-210平均浓度约1700Bq/kg,约为0.8Bq/L,为该照射限值的2.3万倍。
本试验例通过测定不同实施例和对比例内墙涂料的室内环境中的年平均钋-210活度浓度,来与NRC规定的年平均公众照射限值对比,判断内墙涂料防钋-210的效果,具体测定结果见表1。
表1.年平均钋-210活度浓度测定结果
从实施例1-3以及对比例的实验结果可看出,本发明技术方案的防Po-210内墙涂料年平均钋-210活度浓度低于NRC年平均公众照射限值,符合公众健康要求,其中,实施例3年平均钋-210活度浓度最低,对钋-210的吸收最好,而传统腻子年平均钋-210活度浓度远高于NRC年平均公众照射限值,不能满足公众健康需求,证明本发明实施例的防钋-210内墙涂料对钋-210的吸收效果很好。
以上所述仅为本发明的可选实施例,并非因此限制本发明的专利范围,凡是在本发明的发明构思下,利用本发明说明书内容所作的等效变换,或直接/间接运用在其他相关的技术领域均包括在本发明的专利保护范围内。
Claims (8)
1.一种防钋-210内墙涂料,其特征在于,由下列重量份计的原料组成:凹凸棒石粉80~100份,有机膨润土10~12份,磁铁矿粉0.5~3.0份,氧化石墨烯溶液0.2~2.0份,钛白粉160~220份,聚合物乳液130~180份,乙二醇12~15份,分散剂1~4份,消泡剂3~5份,湿润剂1~2份,防腐剂2~4份,增稠剂2~4份,流平剂1~3份,杀菌剂1~2份,pH调节剂1~2份,去离子水320~350份。
2.如权利要求1所述的一种防钋-210内墙涂料,其特征在于,所述磁铁矿粉包括钛磁铁矿粉、钒磁铁矿粉或钒钛磁铁矿粉中的任意一种或多种。
3.如权利要求1所述的一种防钋-210内墙涂料,其特征在于,所述氧化石墨烯溶液是由氧化石墨烯和水按质量比为1:8~1:10配制而成。
4.如权利要求3所述的一种防钋-210内墙涂料,其特征在于,所述氧化石墨烯溶液的浓度为0.03~0.12mg/mL。
5.如权利要求1所述的一种防钋-210内墙涂料,其特征在于,所述有机膨润土为钠基膨润土、钙基膨润土或铝基膨润土中的任意一种。
6.如权利要求1所述的一种防钋-210内墙涂料,其特征在于,所述流平剂为羧甲基纤维素。
7.如权利要求1所述的一种防钋-210内墙涂料,其特征在于,所述消泡剂为乳化硅油、高碳醇脂肪酸酯复合物、聚氧乙烯聚氧丙烯季戊四醇醚、聚氧乙烯聚氧丙醇胺醚、聚氧丙烯甘油醚、聚氧丙烯聚氧乙烯甘油醚和聚二甲基硅氧烷中的一种或多种。
8.如权利要求1所述的防钋-210内墙涂料的制备方法,其特征在于,包括以下步骤:
按比例取80%的去离子水,倒入容器中,然后按比例将浓度0.08mg/mL的氧化石墨烯溶液倒入,超声搅拌30min,然后静置15min;
低速搅拌,按比例分别加入pH调节剂、分散剂、消泡剂、湿润剂、增稠剂、流平剂、防腐剂和杀菌剂,搅拌均匀;
中速搅拌,按比例分别加入钛白粉、凹凸棒石粉、有机膨润土、磁铁矿粉,再加入乙二醇及5%的去离子水,搅拌均匀得粗浆料;
高速分散,将所述粗浆料放进砂磨机研磨得到细浆料;
调整所述细浆料的pH=4.7±0.1后,缓慢加到成比例的聚合物乳液中,然后加入剩余量的消泡剂、防腐剂,继续搅拌约30 min;
用剩余去离子水调整粘度;
过滤包装。
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