CN113329813B - 氟化物去除方法 - Google Patents

氟化物去除方法 Download PDF

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Publication number
CN113329813B
CN113329813B CN201980089658.5A CN201980089658A CN113329813B CN 113329813 B CN113329813 B CN 113329813B CN 201980089658 A CN201980089658 A CN 201980089658A CN 113329813 B CN113329813 B CN 113329813B
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composite material
fluoride
water
zro
hybrid
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CN113329813A (zh
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张庆瑞
R·梅曾加
S·博利塞缇
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Eidgenoessische Technische Hochschule Zurich ETHZ
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Eidgenoessische Technische Hochschule Zurich ETHZ
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Abstract

本发明涉及水处理/氟化物去除领域以及用于这种方法的材料/装置。具体而言，本发明提供了包含淀粉样原纤维和ZrO2的杂化材料；以及进一步包含支持材料的复合材料。本发明进一步提供了使用这种杂化或复合材料进行水处理。

Description

氟化物去除方法
本发明涉及水处理/氟化物去除领域以及用于此类方法的材料/装置。
水中的氟化物污染是一个世界性的环境问题，主要源于地球化学过程和工业生产。WHO授权严格控制饮用水的1.5mg/L。有效且选择性地从水中去除氟化物对于饮用水和废水污染修复而言是非常理想的；然而，目前大多数吸附剂表现出差的去除能力和低的活性。开发具有强大能力的新功能材料，特别是对于高(>50mg/l)和低(<10mg/L)浓度的氟化物净化仍然是一个巨大的挑战。
CN101555078描述了一种通过使用纳米活性二氧化锆去除氟化物的方法。该方法包括含氟化物的水的预处理、纳米吸附和再生处理三部分。含氟化物的水通过管道送入至过滤装置；所述过滤装置与含纳米过滤材料的氟化物去除塔的进水口连接；所述氟化物去除塔的出水口符合排放标准；所述氟化物去除塔分别与碱性罐和再生罐连接；解吸液经所述处理后流入沉淀罐。
EP1381440公开了适用于检测分析物的包含金纳米颗粒和淀粉样原纤维的纳米结构。
因此，本发明的一个目的是减少现有技术的这些缺点中的至少一些。特别地，本发明的目的是提供用于处理水和从含水组合物中去除氟化物的方法，以及可用于这种方法的材料和装置。
这些目的通过如权利要求1中限定的材料和如权利要求10中限定的方法来实现。本发明的其他方面在说明书和独立权利要求中公开，优选的实施方案在说明书和从属权利要求中公开。
下面将参照本发明的第一和第二方面更详细地描述本发明。所述第一方面涉及新材料、装置、它们的制造和它们的用途。所述第二方面涉及使用这种材料和装置处理水的方法。应当理解，本发明中提供/公开的各种实施例、参数选择和范围可以随意组合。此外，根据具体实施方案，所选择的定义、实施方案或范围可能不适用。
除非另有说明，以下定义应适用于本发明：
如本文所使用的，在本发明的上下文中所使用的术语不定冠词(“a”,“an”)、定冠词(“the”)和类似的术语应理解为涵盖单数和复数，除非本文另外指出或与上下文明显矛盾。
如本文所使用的，术语“包括”、“含有”和“包含”在本文中以其开放的、非限制性的意义使用。术语“含有”应包括“包含”、“基本上由……组成”和“由……组成”。
参考附图将更好地理解本发明。
图1：本发明的复合材料的结构表征：
a)示出了制造本发明的淀粉样原纤维限制的纳米ZrO2的示意图(左：β-乳球蛋白；中：淀粉样原纤维，右：本发明的复合物)，如实施例1中进一步描述的；
b)淀粉样原纤维的TEM图像，比例尺500nm；
c)淀粉样原纤维限制的纳米ZrO2的TEM图像，比例尺200nm；
d)淀粉样原纤维限制的纳米ZrO2的高分辨率TEM图像，比例尺5nm；
e)淀粉样原纤维的AFM图像，比例尺300nm；
f)淀粉样原纤维限制的纳米ZrO2的AFM图像，比例尺300nm；
g)纳米ZrO2涂层之前和之后的高度对比；y轴：高度[nm]；x轴长度[nm]。
图2：溶液pH对CAF-Zr上的氟化物净化和Zr离子释放的影响，以商用ZrO2为参考(初始F＝10.2mg/L，过滤在室温进行)：
x轴：进料中的溶液pH值；
y轴(左)：氟化物去除率，[％]y轴(右Zr释放[mg/l]。
图3：竞争性离子对CAF-Zr膜(本发明，虚线条)和IRA-900(对比，实线条)上的氟化物去除的选择性评估(a-c)效应；
(a)x轴：硫酸根离子，y轴：氟化物吸附率[％]；
(b)x轴：氯离子，y轴：氟化物吸附率[％]；
(c)x轴：硝酸根离子；y轴：氟化物吸附率[％]；
(d)CAF-Zr膜(本发明，虚线)和IRA-900(用于比较，实线)的离子分布系数Kd比较；y轴：Kd[mL/g]；x轴：硫酸根离子添加量[mg/L]。
图4：快速过滤比较(a-d)：对不同浓度和溶液环境下过滤到系列市购的吸附剂上的氟化物去除进行比较(根据本发明的CAF-Zr膜，表面积：0.0002m2，直径：1.6cm，厚度：2mm；自来水取自瑞士，溶液pH＝7.2-7.6，酸性废水组分：HCO3 -＝50mg/L、Cl-＝250mg/L、SO4 2-＝150mg/L、NO3 -＝120mg/L、Ca2+＝55mg/L、Na+＝280mg/L，pH＝2.5-2.8)：
y轴：氟化物吸附率[％]；
x轴从左到右：CAF-Zr(本发明的材料，虚线)–碳–CAF–纳米ZrO2–IRA-900–Al2O3(每个均用于比较，实线)。
图5：真实应用评估：(a)杂化膜CAF-Zr去除氟化物的处理能力，x轴：处理能力[升水/m2膜]；y轴：过滤后的氟化物含量[mg/L](进料来自被氟化物污染的真正的天然水，F＝2.8mg/L，pH＝7.5-7.8)，(b)吸附-再生性能(再生：1％NaOH+5％NaCl，10mL)。
更一般而言，在第一方面，本发明提供了包含以下的新型材料：(a)淀粉样原纤维；(b)纳米颗粒ZrO2；和(c)任选的支持材料。在不存在组分(c)的情况下，则这些材料被称为杂化材料。在存在组分(c)的情况下，则这些材料被称为复合材料。本发明的这方面将在下面更详细地解释：
令人惊讶地发现，当处理含氟化物的水时，成分(a)和(b)协同地相互作用。在所述淀粉样原纤维和所述纳米颗粒ZrO2密切接触的情况下，这种协同效应特别显著，因此是有利的。两种成分的比率可以在很宽的范围内变化，这取决于具体材料、预期用途和含有复合材料的装置。在比率(a)/(b)为1/0.1至1/300(w/w)，特别优选1/1至1/100(w/w)的范围的情况下，获得了特别好的结果。
这类复合材料展示出优良的去除性能，去除率可以达到99.2％以上，其也适用于低浓度(10ppm以下)和高浓度(50ppm以上)的F污染水，流出物可以降低至约0.1ppm。此外，该复合材料可以用于低浓度和高浓度F污染水的处理，其也适用于中性天然水和酸性废水。所述杂化材料是环境友好的，对饮用水净化非常重要。
杂化材料：根据本发明，成分(a)和(b)密切接触。所述个体的成分在完成的结构中保持独立(separate)和区分(distinct)，但彻底且随机地混合。这一点由制造过程确保。该材料表现出淀粉样原纤维和ZrO2二者的特性，因此被称为杂化材料。
本发明的杂化材料可以被描述为淀粉样原纤维限制的纳米ZrO2。如图1所示，淀粉样原纤维是载体，纳米ZrO2颗粒与淀粉样原纤维结合。通常，杂化材料的尺寸为1微米至5毫米的范围，而ZrO2的尺寸通常为10纳米或更小的范围。
复合材料：上述杂化材料可以与支持材料结合从而获得复合材料。所述支持材料(c)可以是单独的层(例如在过滤膜的情况下)，从而形成具有层状结构的复合材料。或者，所述支持材料(c)可以与杂化材料结合以形成颗粒外观的复杂的复合材料(例如在吸附材料的情况下)。通常这类材料的颗粒大小为1微米到5毫米的范围。这类材料可以用于深层滤器和/或用作吸附介质。因此，本发明还提供了一种包含这类复合材料的过滤装置，所述复合材料通常是深层滤器或吸附柱。
淀粉样原纤维：术语“淀粉样原纤维”是本领域公知的，特别描述了原纤维由普遍以β-片二级结构存在的蛋白质或肽制成。因此，术语淀粉样原纤维不包括天然蛋白质。
有利地，所述淀粉样原纤维具有高纵横比，优选半径≤10nm且长度≥0.5μm，特别优选半径≤5nm且长度≥1μm。
有利地，所述淀粉样原纤维具有高度带电的表面。术语高度带电的表面是本领域公知的，并且具体描述了显示出电泳迁移率在pH4下为2μm·cm/V·s数量级(order)的表面。电泳迁移率可以根据ζ电位测量来确定，即电子场下的胶体的漂移迁移率。
纳米颗粒ZrO2：ZrO2是本身已知的材料。在本发明的上下文中，纳米颗粒尺寸的ZrO2是优选的，例如小于50nm的ZrO2(“亚50nm的ZrO2”)，优选小于10nm(“亚10nm的ZrO2”)。发现亚10nm的ZrO2特别有用，因为它具有超高的活性和去除氟化物的能力，它还可以方便地沉积在活性炭上用于膜制备。此外，不同于纳米颗粒的复杂制备，如下所述的简单的自组装特征也赋予了工业用途的大规模生产前景。
有利地，如本文所述，ZrO2可方便地获得并原位沉积。因此优选不使用市购的的纳米颗粒ZrO2。相反，本淀粉样原纤维包含超细尺寸(例如亚10nm)的复合ZrO2颗粒。不拘囿于理论，认为这是使得高活性纳米ZrO2沉积和形成的非常重要的特征。进一步认为，自组装特征也与淀粉样原纤维限制的纳米ZrO2的有关。所述复合材料因此可以被描述为包含受限的纳米ZrO2的淀粉样原纤维。
支持材料：如上所述，杂化材料不含支持材料，而复合材料包含这样的支持物。对于许多应用，优选复合材料，例如包括层状结构或复杂结构的上述复合材料。支持材料可以选自广泛范围的已知材料。支持材料的选择取决于其预期用途。合适的支持材料例如多孔支持材料，包括沸石、活性氧化铝、活性炭等。优选的支持材料是活性炭。
活性炭：该术语是本领域已知的，并且包括其所有商业等级。合适的活性炭可以由含碳的材料来源(例如可再生来源，包括坚果壳、椰子壳、泥炭、木材、椰壳纤维)生产，也可以由常规来源(包括褐煤、煤和石油沥青)生产。合适的活性炭可以通过化学活化或物理活化来生产。物理活化包括通过气体或蒸汽的活化。
装置：杂化材料和复合材料在包括过滤装置和吸附装置的大量装置中进行商业应用。
在一个有利的实施方案中，本发明涉及一种如本文所述的过滤装置形式的复合材料，所述过滤装置包含成分(a)、(b)和(c)。因此，本发明还提供了一种包含这种复合材料的过滤装置。这类滤器可以是本领域已知的任何类型的滤器，通常是表面滤器，包括压力表面滤器和真空表面滤器。
在这种过滤装置的一个实施方案中，成分(a)、(b)和(c)被密切地混合。这种复合材料位于过滤膜(例如纤维素膜)的顶部。
在这类过滤装置的一个替代的实施方案中，(a)、(b)被布置在上游，而支持材料(c)被布置在下游。
在这种过滤装置的一个替代的实施方案中，所有组分(组分(a)、(b)和(c))与粘合材料(d)(例如纤维素纸浆或聚合物材料)结合以制备过滤材料/过滤膜。这类过滤材料/过滤膜可以包含在过滤装置或吸附装置中。
制造：本发明的复合材料制造简单；使用现成的原材料进行大规模产生是可期的。所述复合材料便宜，因为所有组分(a)、(b)和(c)都是现成的。组分(a)可以从包括乳清蛋白在内的多种蛋白质来源获得，乳清蛋白是奶酪工业的副产品。乳清也可以直接使用。组分(b)可以原位获得；组分(c)是市售品。这被认为是一个很大的优势，因为它允许一次性使用(即不需要回收所述复合材料或所述滤器)。
本发明因此提供了一种制造如本文所述的复合材料的方法，所述方法包括以下步骤：(i)在酸性含水条件下合并包含Zr(IV)前体的溶液和淀粉样原纤维；(ii)调节pH直至出现沉淀，优选至pH3.5-4.0，从而获得第一悬浮液；(iii)合并由此获得的所述第一悬浮液和包含支持材料如活性炭的分散物，从而获得第二悬浮液；以及(iv)过滤所述第二悬浮液，从而获得所述复合材料。
所述制造可以在室温下或在稍微升高的温度下进行。
步骤(i)：淀粉样原纤维的合成是已知技术。特别合适的是蛋白质水解，然后是β-片层驱动的原纤维形成，如例如Jung等(Biomacromolecules.2008,9,2477–2486)所述。合适的起始材料是食品级蛋白质，其结构稳定、可广泛获取且价格低廉。这类起始材料能够制备淀粉样原纤维，例如β-乳球蛋白。合适的蛋白质可以选自β-乳球蛋白、溶菌酶、卵清蛋白和血清白蛋白。自组装过程是容易的且可控的。典型的过程参数包括在酸性条件(例如约pH2)、低离子强度(例如I≤20mM)、高温(例如T约90℃)下长时间(例如6小时)孵育蛋白质溶液(例如2重量％β-乳球蛋白)。合适的Zr(IV)前体是已知的并且包括ZrOCl2，特别是作为水性溶液。通常，首先制备淀粉样原纤维，然后加入水性溶液形式的Zr(IV)前体。
步骤(ii)、(iii)和(iv)完全是常规的。
用途：如上所述，本发明的材料(即杂化材料和复合材料)和本发明的装置(例如过滤装置和吸附装置)可用于处理水和/或去除氟化物。因此，本发明提供了如本文所述的材料和装置用于处理水和/或去除氟化物的用途。本领域技术人员将理解，并在下文进一步概述，术语“进行过滤(filtering)”和“过滤(filtration)”在广义上使用，特别是包括从水或水性组合物中去除溶解的氟化物。
如本文所使用的，术语水包括城市废水、工业废水、饮用水和天然水。
术语“去除氟化物”应包括从任何来源，特别是从任何液体、半固体或固体材料中去除氟化物。观察到的去除效率的范围为95％以上，例如99％以上，特别是99.5％以上。
在第二方面，本发明涉及一种处理水的方法，所述方法包括使所述水与本文所述的本发明的材料接触的步骤。已知方法适用于本发明的材料；从而避免新过程或高投资。这被认为是一个优势，即可以通过用本文所述的本发明的材料简单地替换现有的吸附剂/过滤材料来调整现有的方法/过程。本发明的这方面将在下面更详细地解释：
在一个实施方案中，本发明涉及一种用于处理水的方法，所述方法包括以下步骤：(i)提供如本文所述的复合材料和含氟化物的水；(ii)使所述水与所述复合材料接触，从而获得纯化的水和负载的复合材料；(iii)将所述纯化的水与所述负载的复合材料分离。任选重复步骤(ii)和(iii)以进一步降低氟化物含量。
术语“对水进行处理”特别包括减少氟化物含量。通过本发明的方法，可以通过一个单处理循环去除超过95％的氟化物。如本文所述的方法具有极其广泛的应用范围，包括对所有类型的水进行处理。它适用于连续和不连续过程、小型和大型设施、作为独立单元或作为较大的处理系统的一部分。术语“水”如上定义；因此，“废水”是指氟化物含量高的水，而“纯化的水”是指氟化物含量降低的水。
上述提到的个体步骤在本领域中是完全常规的——但尚未使用如本文所述的本发明的材料进行应用，并且尚未应用于如上所述的水来源。下面将进一步阐述上述步骤的有利的实施方案。
在优选的实施方案中，在所述方法的步骤(i)中，所述复合材料以过滤装置的形式提供；步骤(ii)和(iii)将所述含氟化物的水过滤通过所述滤器来进行。
在优选的实施方案中，在所述方法的步骤(i)中，所述复合材料以颗粒材料的形式提供。在步骤(ii)中，所述含氟化物的水和所述复合材料接触0.1至24小时，任选进行搅拌。任选地，温度被控制在例如5℃至95℃的温度范围。在步骤(iii)中，将获得的材料进行分离。分离可以通过过滤、离心或沉降来进行。可以重复步骤(ii)和(iii)。
在一个实施方案中，所述复合材料可以以滤器的形式提供，所述废水可以连续地提供。步骤(ii)和(iii)可以通过将所述废水过滤通过所述滤器而同时地进行。
本领域技术人员应理解，本文描述的方法提供了优于现有技术的显著优势：首先，所述方法经济、简单、安全稳健且快速。其次，扩大规模简单。最后，所述方法可以通过使用几个循环、通过调整所使用的本发明的材料和其他参数来进行微调。
为了进一步说明本发明，提供以下实施例。提供这些实施例不旨在限制本发明的范围。
1.杂化膜的制备
淀粉样原纤维限制的ZrO2纳米颗粒
根据Sreenath B.和Raffaele M.Nat.Nanotechnol.2016，11，365-371制备淀粉样原纤维。简而言之，将10重量％的β-乳球蛋白(pH＝4.6)在15000rpm下完全离心15分钟以实现固液分离。将上清液调至pH2并使用0.22μm微孔注射器滤膜进行过滤。然后，通过透析膜(spectra/por透析MWCO：6-8kDa)进行进一步的纯化过程，以去除最终pH值为4.5-4.8的存在离子种类。透析结束后，将纯化的溶液重新调至pH2，并冷冻干燥；通过在90℃下将2重量％的蛋白质单体加热5小时来制备淀粉样原纤维。
对于所述淀粉样原纤维限制的纳米ZrO2，首先，将4g ZrOCl2*7H2O溶解在20mL的2重量％的淀粉样原纤维中，振荡3小时。原纤维的氨基会通过强络合亲和力与溶液中的Zr(IV)离子相互作用，然后用1％的NaOH将溶液pH值调至pH＝3.5-4.0，直至形成白色沉淀，从而获得淀粉样原纤维限制的ZrO2纳米颗粒。所述杂化吸附膜用以下程序进一步制备；将2ml的10重量％的活性炭分散物与2ml淀粉样原纤维限制的ZrO2纳米颗粒混合。接下来，使用0.22μm纤维素滤器真空过滤1ml体积的该混合物进行。淀粉样原纤维的强粘附性保证了所得ZrO2纳米颗粒均匀组装到多孔碳上，用于制备杂化膜(表面积：0.0002m2，直径：1.6cm，厚度：2mm)，其可以用于后续的氟化物去除。
2.批量过滤用于F去除
批量过滤测试是通过传统的瓶点法进行的。详细的实验方法描述如下，结果如图2-5所示。
在此，将5mL氟化物污染的溶液(F＝10ppm)通过杂化膜(表面积：0.0002m2，直径：1.6cm和厚度：2mm)进行快速真空过滤，各种溶液pH值(2.0-13.0)用1％NaOH和1％HNO3调节；收集流出物以确定氟化物浓度，并且还使用ICP-Ms研究了相应的Zr释放。结果如图2所示。
氟化物去除也是典型的pH依赖过程，其最佳pH值范围为2.0至9.5。结果表现出稳定的去除效率为约92.3％以上，相比之下，市购的氧化锆颗粒(1μm至2μm)在pH>3.0的氟化物吸附环境中较差。此外，在pH>10时吸附作用显著降低。值得注意的是，流出物中可忽略的Zr释放也证明了用于水净化的出色的稳定性和安全性。
还使用不同浓度的泛在SO4 2-/Cl-/NO3 -离子进行了共存离子影响，并且还使用市购的离子交换树脂IRA-900用于比较，结果见图3。
可观察到，CAF-Zr膜表现为有效的氟化物清除剂，去除效率>约92％(图3a-c)。在高离子背景下轻微的吸附作用影响表明了强大的选择性；相比之下，在相同条件下，IRA-900上的氟化物去除显著下降，特别是当离子添加量在400mg/L以上时，吸附效率下降至几乎为零。CAF-Zr膜还显示出约7000ml/g的优异Kd值(图3d)，这是市购的离子交换树脂的约180倍，证实了氟化物去除的特殊选择性。
此外，还选择了真实的自来水和合成的酸性废水作为进料，以评估应用能力。市购的碳、活性氧化铝(AA)和离子交换树脂被认为是用于比较的模型吸附剂(图4)。自来水取自瑞士，溶液pH＝7.2-7.6，酸性废水组分：HCO3 -＝50mg/L、Cl-＝250mg/L、SO4 2-＝150mg/L、NO3 -＝120mg/L、Ca2+＝55mg/L、Na+＝280mg/L，pH＝2.5-2.8。
杂化CAF-Zr膜显示出显著的氟化物清除性能，对于各种水源，去除效率接近约95％，甚至99.5％，具有痕量级流出物(0.05ppm至0.3ppm)(图a-图b中自来水的进料浓度分别为4.2mg/L和10.8mg/L，而图c-图d中酸性废水的进料浓度分别为22.6mg/L和202mg/L)。
然后，分别在中性和酸性条件下通过以系列进料氟化物含量(F＝10ppm、50ppm、100ppm、200ppm、300ppm、400ppm、500ppm)过滤对最大吸附能力进行了很好的测试。
与碳基质(1.88mg/g和1.93mg/g)相比，通过过滤，自来水和酸性废水中的最大氟化物容量分别为约21.8mg/g和28.9mg/g。
还使用所述杂化膜进行了实际应用能力测试(图5)，进料源取自罗马市的自来水，初始F＝2.8ppm，进行连续过滤以评估应用能力。此外，所使用的膜也使用1％NaOH+5％NaCl混合物进行再生。
结果表明，基于WHO的饮用水标准，所述杂化膜在氟化物应用方面表现出出色的性能，平均处理能力为约1750升水/m2膜。此外，吸附再生测试还验证了可能的重复使用，有效脱除氟化物为约94.8％。
还进行了合成的高浓度(200ppm)和低浓度(5ppm)进料，以评估实际的F去除能力。详细结果在下面列出。
分析和表征
氟离子的浓度由离子选择性电极计(EXTECH，FL700)测定，淀粉样原纤维限制的纳米ZrO2和杂化膜的形态通过高分辨率透射电子显微镜(HR-TEM)(JEOL JEM-2100，日本)进行了很好的研究，加速电压为200kV。TEM样品是通过将其滴在涂有蕾丝碳的200目Cu网格上制备的。在环境条件下使用AFM悬臂(Bruker)以150kHz的振动频率以敲击模式在MultiModeVIII扫描力显微镜(Bruker)上进行AFM。所述显微镜覆盖有隔音罩，以最小化振动噪音。将20μL液滴沉积在新鲜裂解的云母上，孵育2分钟，用1mL的Milli-Q水冲洗并通过加压的空气干燥。使用NanoScope Analysis 1.5软件简单地平化图像，未进行进一步的图像处理。使用NanoScope Analysis 1.5软件获得高度谱。
这对应于99.65％的减少并且显示了本发明的复合材料的极高吸附率。

Claims (19)

1.一种杂化材料，包含淀粉样原纤维(a)和小于50nm的纳米颗粒ZrO2(b)；
其中，在所述杂化材料中，所述淀粉样原纤维和所述纳米颗粒ZrO2
(i) 密切接触，
(ii) 保持独立和区分，并且
(iii) 彻底地并随机的混合。
2.根据权利要求1所述的杂化材料，其特征在于，
• 比率(a)/(b)为1/0.1至1/300的重量比范围；和/或
• 所述淀粉样原纤维(a)选自半径≤10 nm且长度≥0.5 μm的原纤维，和/或
• 所述淀粉样原纤维(a)显示出根据ζ电位测量所确定的电泳迁移率在pH 4下为2 μm·cm/V·s数量级，和/或
• 所述纳米颗粒ZrO2的颗粒尺寸为小于10 nm。
3.根据权利要求1或2所述的杂化材料，其特征在于，所述纳米颗粒ZrO2是原位获得的。
4.一种复合材料，包含根据权利要求1-3中任一项的杂化材料并且还包含支持材料(c)；其特征在于，所述杂化材料位于所述支持材料的表面上。
5.根据权利要求4所述的复合材料，其特征在于，
•比率(a)/(b)为1/0.1至1/300的重量比范围；和/或
• 所述淀粉样原纤维(a)选自半径≤10 nm且长度≥0.5 μm的原纤维，和/或
• 所述淀粉样原纤维(a)显示出根据ζ电位测量所确定的电泳迁移率在pH 4下为2 μm·cm/V·s数量级，和/或
• 所述纳米颗粒ZrO2的颗粒尺寸为小于10 nm；和/或
• 所述支持材料选自多孔支持材料。
6.根据权利要求5所述的复合材料，其特征在于，所述多孔支持材料是活性炭。
7.根据权利要求4-6所述中任一项的复合材料，其特征在于，所述纳米颗粒ZrO2是原位获得的。
8.根据权利要求4-6所述中任一项的复合材料，选自
• 滤膜，包括杂化材料和膜形式的支持物；或
• 颗粒材料，包括杂化材料和颗粒形式的支持物。
9.一种过滤装置，包括根据权利要求4-8中任一项的复合材料，所述复合材料任选进一步与粘合剂材料(d)结合。
10.一种制造根据权利要求4-8中任一项的复合材料的方法，所述方法包括以下步骤：
(i) 在酸性水性条件下合并包含Zr(IV)前体的溶液和淀粉样原纤维；
(ii) 调节pH直至出现沉淀，从而获得第一悬浮液；以及
(iii) 合并由此获得的所述第一悬浮液和包含所述支持材料的分散物，从而获得第二悬浮液；以及
(iv) 过滤所述第二悬浮液，从而获得所述复合材料。
11.根据权利要求10所述的方法，其中，所述pH调节至3.5-4.0。
12.根据权利要求10所述的方法，其中，所述支持材料是活性炭。
13.根据权利要求1-3中任一项所述的杂化材料或根据权利要求4-8中任一项的复合材料或根据权利要求9的过滤装置用于处理水和/或用于去除氟化物的用途。
14.根据权利要求13的用途，其中，所述水选自城市废水、工业废水、饮用水和天然水。
15.根据权利要求13或14的用途，用于去除氟化物。
16.一种处理水方法，所述方法包括以下步骤：
(i) 提供根据权利要求4-8中任一项的复合材料和含氟化物的水；
(ii) 使所述含氟化物的水与所述复合材料接触，从而获得纯化的水和负载的复合材料；
(iii)将所述纯化的水与所述负载的复合材料分离；
由此可以连续地或不连续地在步骤(i)中提供所述含氟化物的水，并且由此任选重复步骤(ii)和(iii)。
17.根据权利要求16的方法，其中
• 在步骤(i)中，所述复合材料以过滤装置的形式提供；以及
• 步骤(ii)和(iii)通过将所述含氟化物的水过滤通过所述过滤装置来进行。
18.根据权利要求16的方法，其中
• 在步骤(i)中，所述复合材料以颗粒材料的形式提供；
• 在步骤(ii)中，使所述含氟化物的水和所述复合材料接触，任选进行搅拌；以及
• 在步骤(iii)中分离所获得的材料。
19.根据权利要求18的方法，其中，在步骤(ii)中，使所述含氟化物的水在5℃-95℃的温度范围和所述复合材料接触，持续0.1小时-24小时。
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