CN104470857B - 杀生物过滤器介质 - Google Patents
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Abstract
本发明涉及过滤器介质,特别是净化水的过滤器介质,属于水净化产品的领域。公开了引入其中的过滤器介质、银化合物和氢氧化铜。氢氧化铜和银化合物当存在于所述过滤器介质中时提供了在水中的病毒和细菌的明显更高的对数降低,从而使水更纯。
Description
技术领域
本发明涉及用于净化水的过滤器介质。
背景和相关技术
缺乏获得清洁的饮用水的途经导致用于净化的各种方法和技术的发展。
水通常含有三种类型的杂质。第一种是悬浮或微粒物质;继而是溶解的化学品;接着是微生物。细菌、病毒和孢囊是最常见的微生物。虽然通过沉淀过滤器,如碳块能够去除孢囊,但是对于细菌和病毒更有力的方法是必要的。此方法包括使用化学品和辐射。
氯和碘是最常用的化学品,其通常以次氯酸盐和离子交换树脂的形式使用。然而,对于此类化学品,特别是卤素的使用制定了严格的规定。某些国家通过规定已经制定了可以在净化的水中存在的游离氯或碘的上限。因此,使用此类化学品的水净化器还具有清除过滤器来清除过量的杀生物剂。
卤素的已知替代物包括元素银、铜和锌,以及所述金属的某些化合物。此类化合物包括氧化物和其它的盐,如卤化物。这样的金属和它们的化合物通常浸渍或吸附在多孔介质或载体上。常用的介质包括或者以单体形式,或者以粘合块(bound block)的形式使用的活性炭、粘土和活性氧化铝。JP59066321 A2 (NITTA BELT KK, 1984)公开了灭菌金属,如铜或银或它们的盐附着在其上的多孔载体,如分子筛、硅胶、氧化铝或聚氨酯泡沫。
JP3287508 A2 (NIPPON DENSHI ZAIRYO KK, 1998)公开了用碱溶液和含有二氧化硅的溶液处理多孔活性氧化铝以形成含有能够离子交换的金属的铝硅酸盐的涂膜,并且在铝硅酸盐的膜中通过离子交换携带了具有杀菌作用的金属离子。由于该金属离子具有杀菌作用,因此使用选自Ag、Cu、Zn、Hg、Sn、Pb、Bi、Cd和Cr的金属离子。
JP1258792 A2 (NITSUKO KK, 1989)公开了通过使具有抗菌作用的金属,如银或铜或化合物,如氧化银或氧化铜,或它们的化合物附着到氧化铝溶胶中铝氧化物的表面上来制备抗菌的氧化铝溶胶的方法。在抗菌剂中抗菌金属或化合物的优选含量为10 wt%至7.5 wt%。
WO2006050477 A1 (K2 Concepts)公开了抗微生物的组合物和包含该组合物的装置。还公开了在氧化铝载体材料上具有氧化银和铜氧化物的混合物的流体处理介质。铜氧化物包括氧化亚铜和氧化铜。氧化银和铜氧化物的典型量是大约0.1 wt%至大约2.0wt%。该抗微生物组合物防止或减缓流体中的细菌生长、积垢的形成、从流体去除细菌、从储水容器的表面去除生物膜、控制在储水容器的表面和容器内的水中细菌生长的复发,和防止积垢的形成。
US2008283466 A1 (STREAMLINE CAPITAL INC)也公开了在氧化铝载体材料上具有氧化银和铜氧化物的混合物的过滤器介质。该材料用于控制微生物污染。
WO03076341A2 (APYRON TECHNOLOGIES INC)也公开了在氧化铝载体材料上具有氧化银和铜氧化物的混合物的过滤器介质。该材料用于控制微生物污染。
对数杀灭(log-kill)(或对数去除(log removal))是表明任何净化介质的有效性的标准方法,特别是在水净化的环境中。在安全性和有效性的考量上限制在过滤器介质中银或铜金属的计量。过量的银通常渗入纯化的水中,过量的铜氧化物在过滤器介质的表面上以黑色膜的形式显现其自身。消费者通常不喜欢这样的过滤器介质。
发明内容
我们已经观察到以具有浸渍在其中的银的化合物和氢氧化铜的单一或单位的(single or unitary)过滤器介质(选自氧化铝或钛酸盐)的形式,在银的化合物和氢氧化铜之间具有令人惊讶的协同活性。在氧化铝作为优选的过滤器介质的情况下尤其能够观察到该效应。
协同活性导致对存在于水中的病毒和特别是细菌的较高的对数杀灭,这导致在数量上出人意料的减少,从而使水更纯净。迄今为止,尽管很经常地使用铜氧化物,但考虑到较差的稳定性,发现难以利用氢氧化铜的抗微生物活性。
根据第一个方面,公开了选自氧化铝或钛酸盐的过滤器介质,其具有引入其中的银的化合物和氢氧化铜。
根据第二个方面,公开了用于制备第一个方面的过滤器介质的方法,其包括以下步骤:
(i) 使过滤器介质与铜的水溶性盐的溶液混合;
(ii) 通过加入碱使步骤(i)的混合物的pH至少提高到10;
(iii) 通过用水洗涤步骤(ii)的混合物,从其中去除过量的碱;
(iv) 干燥洗涤后的混合物;
(v) 使干燥后的混合物与硝酸银的水溶液混合;
(vi) 将卤化物盐加入到步骤(v)所获得的混合物中;和
(vii) 过滤和干燥步骤(vi)的混合物。
根据第三个方面,公开了一种水净化装置,其具有第一个方面的过滤器介质。
根据第四个方面,公开了第一个方面的过滤器介质在水净化装置中用于净化水的用途。
本发明现在将进行详细解释。
详细说明
根据第一个方面,公开了一种过滤器介质,其具有引入其中的银的化合物和氢氧化铜。
该介质可以呈微粒、粉末或颗粒形式。该过滤器介质选自氧化铝或钛酸盐。
所观察到的是,或者难以在介质,如活性炭、氧化锌、砂、膨润土和硅藻土上以氢氧化铜的形式浸渍铜,或者一旦通过合适的方法沉积或浸渍,氢氧化铜立即变成铜氧化物,大概是因为其不稳定。当氢氧化铜转化为铜氧化物时,有效性大幅地降低。铜含量的增加也不被认为能够补偿铜氧化物的较低的有效性。不希望被理论所束缚,可以确信的是没有一个熟知的传统过滤器介质显示出氧化铝对氢氧化铜的特殊作用。因此,特别优选的是各个过滤器介质是氧化铝。进一步优选氧化铝是酸洗涤的活性氧化铝。
尽管是次优选的,纤维也可以用作过滤器介质。此纤维是能够原纤化的有机聚合物纤维。因为其异常精细的尺寸和潜在的低成本,原纤化纤维通常是有利的。
这种原纤化纤维包括聚合物,如丙烯酸、丙烯腈;液晶聚合物、离子交换树脂、工程树脂、纤维素、人造丝、苎麻、羊毛、丝、玻璃、金属、陶瓷、其它纤维材料,或它们与之前所公开的介质的组合。这样的过滤器介质还可以呈由纤维,或纤维和微粒介质的组合物制造的平板(flat sheet)介质的形式,其最终可以卷起、分层和/或打褶来增强过滤应用性。在1%铜的较低浸渍含量下,纸张、聚酯和尼龙布没有显示出与铜盐的任何有利的相互作用,使得对于介质而言难以用于浸渍。
优选的是,过滤器介质的表面积为100-400 m2/g,优选为200-400 m2/g和最优选为300-400 m2/g。对于氧化铝,特别优选的是表面积为300-340 m2/g。
优选的是,过滤器介质的孔体积为0.4-0.7 cc/g,优选为0.4-0.6 cc/g和最优选为0.4-0.5 cc/g。对于氧化铝,特别优选的是孔体积为0.4-0.5 cc/g。
优选的是,所述过滤器介质的粒径为75-1000 μm,更优选为75-350 μm,和最优选为75-250 μm。
基于所公开的氧化铝的益处,特别优选的是过滤器介质为氧化铝。
银优选地以卤化银的形式浸渍在过滤器介质上。由于其溶解度的原因,特别优选的卤化物是溴化银。优选的是在过滤器介质中银的百分比为0.2-2 wt%,更优选为0.2-1wt%和最优选为0.4-0.8 wt%。
相似地,优选的是氢氧化铜以对应于0.5-4 wt%铜的百分比的量存在,更优选为1-2 wt%和最优选为1-1.6 wt%。
已知处理的过滤器介质和本文所公开的过滤器介质之间的差异在于使用氢氧化铜来替代铜氧化物。当为了获得可能更强力的过滤器介质而试图增加在介质上的铜氧化物的量时,发现该材料变黑。这表明尽管更多的铜将提供更有效和强力的介质,但是在能够浸渍的铜的质量上有明显的限制。然而,在所公开的过滤器介质的情况下,已经观察到能够有效地浸渍更大量的元素铜,同时避免铜氧化物通常面临的缺点和限制。
通常,在加热到100℃以上或当介质的pH增加到14和超过14时,即使是氢氧化铜也会逐渐变成铜氧化物,但特别地当活性氧化铝用作过滤器介质时,没有观察到此现象。甚至在高达900℃下发现该介质是稳定的。通过选择过滤器介质的合适的等级,尤其是具有更大表面积的等级,可以浸渍超过1.6 wt%的铜。这样的介质可以允许以对应于或等于最高达3wt%铜或甚至最高达4 wt%铜的量浸渍氢氧化铜。
介质可以以游离(free)形式或以粘合块形式使用。熟知的是呈粉末、微粒或纤维形式的热塑性或热固性材料的加入来辅助结合过滤器介质的活性颗粒。这种粘结剂材料可以包括以下类型的任意一种,如聚烯烃、聚卤乙烯、聚乙烯酯、聚乙烯醚、聚乙烯醇、聚乙烯硫酸酯、聚乙烯磷酸酯、聚乙烯胺、聚酰胺、聚酰亚胺、聚噁二唑(polyoxidiazoles)、聚三唑、聚碳二亚胺、聚砜、聚碳酸酯、聚醚、聚亚芳基氧化物、聚酯、聚芳酯(polyoxidiazoles)、苯酚-甲醛树脂、三聚氰胺-甲醛树脂、甲醛-脲、醋酸乙酯-醋酸乙烯酯共聚物、它们的共聚物和嵌段互聚物,以及它们的组合。以上材料的变体和其它有用的聚合物包括基团,如羟基、卤素、低级烷基、低级烷氧基、单环芳基等的取代。其它潜在可应用的材料包括聚合物,如聚苯乙烯和丙烯腈-苯乙烯共聚物、苯乙烯-丁二烯共聚物和其它非晶体或无定形聚合物和结构。
粘结剂材料的详细列表包括封端聚缩醛,如聚(氧基亚甲基)或聚甲醛、聚(三氯乙醛)、聚(正戊醛)、聚(乙醛)和聚(丙醛);丙烯酸类聚合物,如聚丙烯酰胺、聚(丙烯酸)、聚(甲基丙烯酸)、聚(丙烯酸乙酯)和聚(甲基丙烯酸甲酯);氟烃聚合物,如聚(四氟乙烯)、全氟化乙烯-丙烯共聚物、乙烯-四氟乙烯共聚物、聚(氯三氟乙烯)、乙烯-氯三氟乙烯共聚物、聚(偏二氟乙烯)和聚(氟乙烯);聚酰胺,如聚(6-氨基己酸)或聚(ε-己内酰胺)、聚(六亚甲基己二酰胺)、聚(六亚甲基癸二酰胺)和聚(11-氨基十一酸);聚芳酰胺,如聚(亚氨基-1,3-亚苯基亚氨基间苯二酰)或聚(间-亚苯基间苯二甲酰胺);聚对二甲苯,如聚-2-二甲苯,和聚(氯-1-二甲苯);聚芳基醚,如聚(氧基-2,6-二甲基-1,4-亚苯基)或聚(对苯醚);聚芳基砜,如聚(氧基-1,4-亚苯基磺酰基-1,4-亚苯基氧基-1,4-亚苯基异丙叉基-1,4-亚苯基),和聚(磺酰基-1,4-亚苯基-氧基-1,4-亚苯基磺酰基-4',4-亚联苯基);聚碳酸酯,如聚-(双酚A)或聚(羰二氧基-1,4-亚苯基异丙叉基-1,4-亚苯基);聚酯,如聚(对苯二甲酸乙二酯)、聚(对苯二甲酸丁二酯)和聚(对苯二甲酸亚环己基-1,4-二亚甲酯)或聚(氧基亚甲基-1,4-环亚己基亚甲基氧基对苯二甲酰);聚芳基硫化物,如聚(对苯硫醚)或聚(硫基-1,4-亚苯基);聚酰亚胺,如聚(均苯四酰亚胺-1,4-亚苯基);聚烯烃,如聚乙烯、聚丙烯、聚(1-丁烯)、聚(2-丁烯)、聚(1-戊烯)、聚(2-戊烯)、聚(3-甲基-1-戊烯)和聚(4-甲基-1-戊烯);乙烯基聚合物,如聚(醋酸乙烯酯)、聚(偏二氯乙烯)和聚(氯乙烯);二烯聚合物,如1,2-聚-1,3-丁二烯、1,4-聚-1,3-丁二烯、聚异戊二烯和聚氯戊二烯;聚苯乙烯;以及前述的共聚物,如丙烯腈-丁二烯-苯乙烯(ABS)共聚物。
基于聚烯烃的材料是有利的。可以使用聚烯烃粉末,如Equistar Chemical的MICROTHENE®、Houston, Tex.的LP,等等。这些粉末包括具有窄的尺寸分布,适用于广泛的特殊应用的超细、球形颗粒。聚烯烃粉末将聚烯烃树脂的独特性质与微细的粒径相结合。
通常将聚烯烃粉末加入到特定的热塑性和热固性树脂中来改善表观、尺寸稳定性、可挤出性或收缩特性。通常,通过加入1 wt%-6 wt%的聚烯烃粉末,可以改善树脂填料分布、模流和耐湿性,同时成功地保持强度性质。
当使用时,粘结剂在粘合过滤器(bound filter)中的含量是10 wt%-40 wt%,更优选大约15 wt%-25 wt%。对于粘结剂材料所期望的是具有显著地低于过滤器介质的软化点的软化点,从而能够加热核心过滤器介质/粘结剂组合物来活化粘结剂材料,同时该微孔材料不会熔融和因此损失多孔性。
根据另一个方面,公开了具有第一个方面的过滤器介质的水净化装置。水净化装置的优选特征的详细说明可以在例如,WO2005095284 A1 (Unilever)中找到。
在另一个方面中,公开了第一个方面的过滤器介质在水净化装置中用于净化水的用途。
该过滤器介质选自氧化铝或钛酸盐。
因为之前已经描述过的理由,氧化铝是最优选的介质。
在本发明的另一个方面中,公开了单位过滤器介质的制备方法。
根据再一个方面,公开了制备第一个方面的过滤器介质的方法,该方法具有以下步骤:
(i) 使过滤器介质与铜的水溶性盐的溶液混合;
(ii) 通过加入碱使步骤(i)的混合物的pH至少提高到10;
(iii) 通过用水洗涤步骤(ii)的混合物,从其中去除过量的碱;
(iv) 干燥洗涤后的混合物;
(v) 使干燥后的混合物与硝酸银的水溶液混合;
(vi) 将卤盐加入到步骤(v)所获得的混合物中;和
(vii) 过滤和干燥步骤(vi)的混合物。
在非限制性实施例的辅助下,现在将更详细地描述本发明。
实施例
实施例1-优选的过滤器介质的制备方法
具有320 m2/g的表面积和0.45 cc/g的孔体积的市售酸洗涤活性氧化铝通过筛分来分离出75-250 μm的颗粒,其将进一步使用。用蒸馏水将这些颗粒洗涤几次,并且在120℃干燥。
在阶段1,通过将盐溶解在40 ml超纯水中制备6.09 g三水合硝酸铜[Cu(NO3)2.3H2O]的水溶液。将该溶液与100 g氧化铝混合直到氧化铝获得均匀的蓝色色调。使该混合物放置4小时。其后,将4 N NaOH加入到该混合物中直到介质的pH为10。使所得到的浆体放置大约2-3小时,其后用水洗涤它以去除过量的碱,过滤,然后在150℃下干燥8小时。由此得到以氢氧化铜的形式浸渍了1.6%铜的过滤器介质。
在下一个阶段,在相同的介质上以溴化银的形式浸渍银。
在35 ml水中制备1.575 g硝酸银的溶液,将该溶液与100 g的已经浸渍了氢氧化铜的氧化铝混合。使该混合物在黑暗环境中放置4小时。其后,将15 ml的含有1.325 g溶解的溴化钾(卤盐)的水加入到该混合物中,并混合好。然后用水洗涤该混合物,过滤,并且在110℃下干燥以得到在氧化铝上共计具有1%银和在氧化铝上共计具有1.6%铜的浸渍的过滤器介质。适当地改变硝酸银和铜盐的含量,能够制备具有不同含量的银和铜的过滤器介质。
使用135 g的实施例-1的过滤器介质制造高15 cm和直径3.4 cm的填充柱。制备掺入(spiked)细菌和病毒的替代物的不纯测试水样,并使该测试水经过填充柱。为了对照分析,还测试了更多一些的相同尺寸的柱。
结果(对数减少)显示在表1中。还显示了其中以相同含量浸渍两种金属中仅一种的结果。
表-1
过滤器介质 | 细菌的对数减少 | 病毒的对数减少 |
在氧化铝上的仅有的1.6%铜 | 1.6 | 5.3 |
在氧化铝上的仅有的1%银 | 1.5 | 5.3 |
实施例-1 | 7.5 | 5.3 |
表-1中的数据表明了显著优异的对数减少值,尤其是对于细菌。数字7-对数减少表示减少了107的数量级。
此数据表明具有引入其中的银的化合物和氢氧化铜的单位过滤器介质的协同活性。
实施例-2:氧化铜和氢氧化铜之间的对照
制备具有相同形状和包含等量过滤器介质的两个过滤器。这些过滤器用于进行以下实验:其中,使掺入细菌(等价于7 log)和病毒(等价于5 log)的水在相同条件下经过这两个过滤器。结果显示在表2中。该表还包含了关于过滤器的组成的信息。
表-2
过滤器介质 | 细菌对数减少 | 病毒对数减少 |
在氧化铝上的1.6% Cu(作为CuOH2) | 1.8 | 5.0 |
在氧化铝上的5% Cu(作为CuO) | 1.3 | 2.7 |
在氧化铝上的1.6% Cu(作为CuOH2)和0.4% Ag(作为AgBr) | 7.0 | 5.0 |
在氧化铝上的5% Cu(作为CuO)和1.25% Ag(作为AgBr) | 7.0 | 5.0 |
表2中的数据表明由氧化铝制造的包含氢氧化铜和银化合物的过滤器针对细菌及病毒是有效的。另一方面,由氧化铝制造和仅包含铜氧化物的过滤器针对细菌的有效性较低。该数据进一步表明氢氧化铜和银化合物的组合在产生技术效果的实际金属含量方面如何优于氧化铜和银化合物的组合。
Claims (8)
1.一种选自氧化铝或钛酸盐的过滤器介质,其包含引入其中的银的化合物和氢氧化铜。
2.如权利要求1所述的过滤器介质,其中银的百分比为0.2-2wt%。
3.如权利要求1或2所述的过滤器介质,其中铜的百分比为0.5-4wt%。
4.如权利要求1或2所述的过滤器介质,其中所述过滤器介质的表面积为100-400m2/g。
5.如权利要求1或2所述的过滤器介质,其中所述过滤器介质的孔体积为0.4-0.7cc/g。
6.用于制备如权利要求1所述的过滤器介质的方法,所述方法包括以下步骤:
(i)使过滤器介质与铜的水溶性盐的溶液混合;
(ii)通过加入碱使步骤(i)的混合物的pH至少提高到10;
(iii)通过用水洗涤步骤(ii)的混合物,从其中去除过量的碱;
(iv)干燥所述洗涤后的混合物;
(v)使干燥后的混合物与硝酸银的水溶液混合;
(vi)将卤化物盐加入到步骤(v)所获得的混合物中;和
(vii)过滤和干燥步骤(vi)的混合物。
7.一种水净化装置,其包含根据权利要求1-5中任意一项的过滤器介质。
8.根据权利要求1-5中任意一项的过滤器介质在水净化装置中用于净化水的用途。
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