CN1190369C - 生产水处理用陶瓷球的方法 - Google Patents
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Abstract
本发明涉及生产能提高水和溶液中杀菌活性的水处理用陶瓷球的方法,尤其涉及生产能杀灭生活或繁殖在水溶液中的微生物或细菌,且具有良好净水功能以及水处理功能陶瓷球的方法。
Description
技术领域
本发明涉及生产能提高水和溶液中杀菌活性的水处理用陶瓷球的方法,尤其是生产能杀灭生活或繁殖在水溶液中的微生物或细菌,且具有良好净水功能以及水处理功能的陶瓷球的方法。
各种陶瓷一般都包括多个内部孔道。由所说多孔陶瓷制成的商品的机械性质和热性质取决于多孔陶瓷内的孔的大小、形状、孔隙率以及孔连续性。
特别地,多孔陶瓷常被用于某种目的的轻质建筑材料,因为陶瓷内部具有人工形成的多孔结构,这样的材料重量轻、密度低。因此,为了生产各种过滤器、烧结工具、除臭剂、保温材料、隔音材料、填料、浸渍材料、花盆石等等,陶瓷的需求大量增加。
背景技术
近来,由于多孔陶瓷在净水、过滤器以及类似利用其本身吸附和除臭性质领域中的应用价值提高,对于这种多孔陶瓷的开发和研究与日俱增。因此,近来有大量关于多孔陶瓷的技术发表。
但是,至今尚没有自身具有杀菌作用的陶瓷。因此,目前需要水处理杀菌的材料必须先用陶瓷净化然后进行单独的杀菌过程。
本发明的目的是提供解决上述问题的生产水处理用陶瓷球的方法,该方法除了利用陶瓷的净化活性,也使陶瓷球自身具有杀菌活性,从而可以有效杀灭水溶液中生活或繁殖的微生物或细菌,最大提高水处理的作用。
发明内容
本发明的目的可通过提供一种生产水处理用陶瓷球的方法实现,该方法包括将硼砂(Na2B4O7·10H2O)和硫酸铜(CuSO4·5H2O)按1∶1的当量比例完全溶解于水中,然后加热干燥该溶液得到一种产品(后面将称作“产品A”);向含有1∶1当量比例的硝酸和银颗粒的单独的容器中加入二氧化硅颗粒,同时加热干燥该混合物得到一种产品(后面将称作“产品B”);将超过3重量%的产品A加入到含有100重量%陶瓷球和200重量%去离子水的单独的容器中并混合,同时进行加热;当容器中所说混合物的总重量减少至少一半时向其中加入超过8重量%的产品B,并加热干燥该混合物;然后将混合物在400℃至500℃下充分脱水。
根据本发明,首先将硼砂(Na2B4O7·10H2O)和硫酸铜(CuSO4·5H2O)按1∶1的当量比例完全溶解于水中,然后加热干燥得到产品A。
此时,硼砂和硫酸铜中的结晶水增加了水溶性,在某种温度以及所需水量的条件下逐渐成为水溶液。同时铜化合物使银化合物更容易附着到球体上,因为铜化合物对其他材料的表面具有强的粘合性。硼砂涂覆到它们的表面,因而赋予可涂覆性。
根据本发明,将二氧化硅颗粒加入到含有1∶1当量比例的硝酸和银颗粒的单独容器中,同时加热得到一种混合物。通过蒸发干燥该混合物得到产品B。
当加热所说硝酸和银颗粒的混合物时,会生成硝酸银,如下列反应方程式1所示。同时,产生的硝酸银变成氧化银(Ag2O),如下列反应方程式2所示。
[反应方程式1]
[反应方程式2]
在碱性状态下,所说氧化银再变成离子类型的氧化银,如下列反应式3所示。
[反应方程式3]
上述反应方程式3生成的氧化银离子(II)导致构成微生物或细菌的蛋白质的氨基酸发生变化,如反应方程式4所示,破坏细菌的细胞膜,从而提供杀菌活性。
[反应方程式4]
特别地,为了使上述反应方程式2生成的氧化银可以有效地附着到陶瓷球上,在硝酸和银颗粒反应期间加入二氧化硅颗粒,以得到高效的杀菌活性。
此处添加的颗粒二氧化硅起到介质的作用,它可以有效地将银化合物附着到陶瓷球上。加入的二氧化硅的量相对于银颗粒(二氧化硅/银颗粒)其重量比不必超过2∶1(w/w)。如果该比例低于2∶0.5(w/w),会出现的问题是不能提供有效的杀菌效果,其原因是因为附着到陶瓷球上的银颗粒的量少。因此,优选的是按照相对于银颗粒以2∶0.5至2∶1(w/w)的比例加入所说二氧化硅颗粒。
根据本发明,为了生产赋予银有效杀菌效果的陶瓷球,将超过3重量%的产品A加入到含有100重量%陶瓷球和200重量%去离子水的单独的容器中并混合,同时进行加热;当总重量至少减少一半时向其中加入超过8重量%的产品B并混合。将所得混合物干燥并在400℃至500℃下充分脱水。
对于所说的陶瓷球,可以使用分离方法生产的大颗粒沙子以及由其他各种方法生产的陶瓷球。陶瓷球不一定非是球状类型,只要它们是无机材料,可以使用任何形状的陶瓷球。
通过将硼砂(Na2B4O7·10H2O)和硫酸铜(CuSO4·5H2O)按1∶1的当量比例完全溶解于水中并加热干燥混合物而得到的产品A被加入到置于去离子水中的所说陶瓷球中同时进行加热。以陶瓷球为100重量%基准记,当产品A的量低于3重量%时,会出现一个问题,即附着到陶瓷球上的银颗粒数量以及帮助银化合物附着到陶瓷表面的铜化合物的量太少,使生成的陶瓷球的表面不光滑,陶瓷球不能显示出杀菌活性。因此,以陶瓷球为100重量%基准记,优选的是加入不低于3重量%,更优选3-7重量%的产品A。当产品A的量超过7重量%时,大量的铜化合物不能附着到陶瓷球上。
当加热上述所得的混合物直至通过水的蒸发使物料的总重量减少一半以上时,加入通过将当量比例为1∶1的硝酸和银颗粒加入到二氧化硅颗粒中并蒸发干燥而得到的产品B。当产品B的量低于8重量%时,会出现一个问题,即附着到陶瓷球上的银颗粒数量太少,使生成的陶瓷球的表面不光滑,从而使其不能显示杀菌活性。因此,以陶瓷球为100重量%基准记,优选的是加入不低于8重量%,更优选8-15重量%的产品B。当产品B的量超过15重量%时,经粘附后余下的银化合物仍会粘到陶瓷球上,这样会增加不必要的成本。
根据本发明,通过将产品A和B加入到去离子水中,干燥并在400℃至500℃下充分脱水,可以制得具有杀菌活性的陶瓷球。
所说脱水温度指除去硼砂和硫酸铜中键合的结晶水需要的温度。当在所说温度下除去粘到陶瓷球上的硼砂和硫酸铜中的结晶水时,硼砂和硫酸铜便以不溶性状态存在于陶瓷球中。
杀菌活性的原理如上面的反应方程式1-4所示,因为硝酸银具有稳定状态,它可以粘到铜化合物上,只有极少量的硝酸银溶解到水溶液中。
下面通过实施例和对比例更详细地描述本发明,但是这些实施例仅是描述性的,因此,它并不限制本发明的范围。
具体实施方式
实施例1至5
将硼砂和硫酸铜(CuSO4·5H2O)按1∶1的当量比例完全溶解于水中,然后加热干燥得到产品A。硝酸和银颗粒按1∶1的当量比例加入到单独的容器中。按照二氧化硅/银颗粒比为2∶1(w/w)的比例向上述容器中加入二氧化硅颗粒,并蒸发干燥得到产品B。
在加热的同时,按下表1的比例将所说的产品A加入到含有200克陶瓷球和400克去离子水的容器中并混合。当总重量减少至一半时,按下表1的比例加入所说产品B,干燥并在500℃下充分脱水得到具有杀菌活性的陶瓷球。通过肉眼观察生成的陶瓷球的表面状态,结果如下表1所示:
表1
产品A的重量(克) | 产品B的重量(克) | 表面状态 | |
实施例1 | 2 | 22 | × |
实施例2 | 6 | 22 | ◎ |
实施例3 | 10 | 22 | ◎ |
实施例4 | 10 | 10 | × |
实施例5 | 10 | 16 | ◎ |
◎:平滑且有光泽
○:有光泽但不平滑
×:没有光泽也不平滑
从表1可以看出,在实施例1-3中,如果都使用22克产品B,当在本发明的范围内使用产品A时所得陶瓷球的表面平滑且有光泽,如实施例2和3。同时,在实施例1中当产品A的量小于本发明的低限时,所得陶瓷球的表面没有光泽也不平滑。实施例1得到的陶瓷球的质量不好。
之所以出现上述结果的原因是因为只有粘到陶瓷球上的银化合物多于某个值时,陶瓷球的表面才会平滑且有光泽;而如果粘到陶瓷球上的银化合物少时,陶瓷球的表面则没有光泽也不平滑。
同样,也可以看出,如果实施例4和5分别使用10克和16克产品B时,在实施例4中,当使用的产品B的量低于本发明要求的范围时,陶瓷球的表面没有光泽也不平滑;而在实施例5中当使用的产品B的量在本发明的范围内时,陶瓷球的表面平滑且有光泽。
之所以出现上述结果的原因是因为只有一定量的银化合物粘到陶瓷球上时,陶瓷球的表面才会平滑且有光泽;而如果粘到陶瓷球上的银化合物小于某个值,从而使粘附的银化合物的量变少时,陶瓷球的表面则没有光泽也不平滑。
基于上述结果,使用实施例3制备的具有平滑表面的陶瓷球进行了杀菌活性试验。
<试验>
向一个容器中加入160克前面制备的陶瓷球,并加入500毫升纯净水,然后在120℃下利用高压蒸汽杀菌15分钟。向容器中再加入0.5毫升(107CFU/ml)利用琼脂培养基平板在37℃培养了5天的菌株漂浮物(buoyant)(Legionella Pneumophila:GIFU 9134),然后摇动。在加入菌株漂浮物后,连续摇动容器3分钟。搅拌容器中的物质,搅拌间隔分别为在5分钟内时每隔20秒搅拌一次,在30分钟内时每隔30秒搅拌一次,12小时内每隔30分钟搅拌一次。
在每个间隔期取出一个所说的反应液体作为样本,利用杀过菌的纯净水稀释液体。使用琼脂培养基平板计算每1毫升反应液中活细菌(CFU)的数目。
表2
活细菌的数目 | ||||||||
开始时间 | 3分钟 | 5分钟 | 30分钟 | 1小时 | 3小时 | 6小时 | 12小时 | |
试验 | 2.3×105 | 1.2×105 | 2.4×104 | 3.2×103 | 2.8×103 | 2.6×103 | 2.3×102 | 9 |
从表2可以很明显地看出,使用本发明制备的陶瓷球进行杀菌试验证实了细菌随时间的延长很快地减少,在12小时后活性细菌的数目少于10。
如上所述,本发明提供了生产在水溶液中显示良好杀菌活性的用于水处理的陶瓷球的方法,该方法通过将一种具有杀菌活性的化合物涂覆到陶瓷球上,从而使陶瓷球具有杀菌性。
Claims (4)
1.一种生产水处理用陶瓷球的方法,包括将硼砂(Na2B4O7·10H2O)和硫酸铜(CuSO4·5H2O)按1∶1的当量比例完全溶解于水中,然后加热干燥该溶液得到产品A;向含有1∶1当量比例的硝酸和银颗粒的单独的容器中加入二氧化硅颗粒,同时加热干燥该混合物得到产品B;以陶瓷球为100重量%基准计,将超过3重量%的产品A加入到含有100重量%陶瓷球和200重量%去离子水的单独的容器中并混合,同时进行加热,当容器中所说混合物的总重量减少至少一半时向其中加入超过8重量%的产品B,并加热干燥该混合物;然后将混合物在400℃至500℃下充分脱水。
2.根据权利要求1的生产水处理用陶瓷球的方法,其中二氧化硅颗粒与银化合物的重量比为2∶0.5至2∶1(w/w)。
3.根据权利要求1或2的生产水处理用陶瓷球的方法,其中产品A的量以陶瓷球为100重量%基准计为3-7重量%。
4.根据权利要求3的生产水处理用陶瓷球的方法,其中产品B的量以陶瓷球为100重量%基准计为8-15重量%。
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CN100463864C (zh) * | 2006-05-22 | 2009-02-25 | 沈阳建筑大学 | 一种二氧化硅冷触媒净水剂的制作方法 |
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US7094374B2 (en) | 2006-08-22 |
EP1309516A1 (en) | 2003-05-14 |
WO2002004366A1 (en) | 2002-01-17 |
AU2001269571A1 (en) | 2002-01-21 |
US20030137068A1 (en) | 2003-07-24 |
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