CN111233459A - 一种环保陶瓷及其制备方法 - Google Patents

一种环保陶瓷及其制备方法 Download PDF

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CN111233459A
CN111233459A CN202010163793.4A CN202010163793A CN111233459A CN 111233459 A CN111233459 A CN 111233459A CN 202010163793 A CN202010163793 A CN 202010163793A CN 111233459 A CN111233459 A CN 111233459A
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ceramic
composite phosphate
rare earth
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Abstract

本发明公开了一种环保陶瓷及其制备方法，所述环保陶瓷由复合磷酸盐材料、改性粘土、钾长石、钠长石、麦饭石和尖晶石制作而成；制备所述复合磷酸盐材料的原料包括如下重量份的组分：贝壳粉80‑100份、40％‑45％磷酸35‑50份、银盐溶液5‑15份和稀土元素无机化合物10‑20份。本发明以贝壳粉为原料，通过化学改性掺杂银离子和稀土元素，制备成磷酸钙基纳米陶瓷材料，与改性粘土、钾长石、钠长石、麦饭石和尖晶石共同制备成的陶瓷既能满足市场所需白度、粘性和硬度的要求，又能改善现有陶瓷的强度和耐磨度不足的问题，且具有抗菌和净化空气的功能。

Description

一种环保陶瓷及其制备方法
技术领域
本发明涉及陶瓷领域，具体涉及一种环保陶瓷及其制备方法。
背景技术
目前用于建筑陶瓷的坯体的主要原料为耐火粘土、长石和石英，辅以化工添加剂改善陶瓷的白度、硬度和孔隙率等性能，由于添加了化工添加剂，陶瓷可能会释放出危害人体的物质。而随着建筑陶瓷的广泛应用，亟需一种能够净化空气的具有多种功能效果的陶瓷。
常用的抗菌陶瓷以钛系抗菌陶瓷和银系抗菌陶瓷应用最广，然而两者的应用也有缺点，银离子分量如果不足，杀菌效果不理想，且高温烧制时银离子会有损失，抗菌效果差强人意。而钛系抗菌陶瓷多为光触媒催化陶瓷，应用于陶瓷时的抗菌效果不佳。因此，能够有效承载抗菌活性成分且能稳定灭菌以及净化空气的瓷砖越来越受青睐。
发明内容
本发明的一个目的是提供一种环保陶瓷，该环保陶瓷为掺杂有银离子的磷酸钙基陶瓷纳米粉制作而成，利用无机物载体的层状结构缓释银离子激活空气或水中的氧，并添加稀土元素与缓释的银离子协同作用，产生活性氧及羟基自由基去除空气中的挥发性气体、烟气、甲醛和细菌等物质，达到净化空气的目的。
为了达到上述目的，本发明采用了如下的技术方案：
一种环保陶瓷，所述环保陶瓷由掺杂有抗菌材料的复合磷酸盐材料与改性粘土、钾长石、钠长石、麦饭石和尖晶石制备而成，制备所述环保陶瓷的组分为：复合磷酸盐材料30-50份、改性粘土30-50份、钾长石3-8份、钠长石5-10份、麦饭石5-15份、尖晶石2-5份；制备所述复合磷酸盐材料的原料包括如下重量份的组分：贝壳粉80-100份、40％-45％磷酸35-50份、银盐溶液5-15份、稀土元素无机化合物10-20份和水20-50份。
贝壳粉是用牡蛎、河蚌、哈利、螺蛳等去肉后的外壳经粉碎加工而成的粉状物，贝壳粉作为天然的生物材料，多被作为固体垃圾丢弃，一直未得到有效的利用。
需要说明的是，贝壳粉中碳酸钙的重量含量至少为95％。使用的磷酸溶液重量浓度为40％-45％。本发明采用贝壳粉为原料，一方面，贝壳粉富含钙元素，陶瓷产品中钙含量增加可以增加其孔隙率，吸附有害气体的效率增加，另一方面，钙在建筑陶瓷中可以有效降低陶瓷的干燥收缩率，防止产品开裂。
麦饭石的化学成分以硅酸盐为主，同时又含有高岭石和埃洛石等黏土矿物，呈多孔性，表面积大且有十分强烈的静电吸引力，能够有效吸附毒素。将麦饭石原料初破碎，煅烧、球磨得到的麦饭石的粒度为200目，200目麦饭石粉体的粒径主要分布在60μm以下。
尖晶石中主要含有氧化镁和氧化铝，具有高强度、高硬度等优点。
发明人通过大量实验发现，通过合理搭配磷酸钙基复合材料、钾钠长石、麦饭石和尖晶石，能够在现有陶瓷的基础上增强陶瓷的硬度和强度，烧制得到的瓷砖既能大量吸附银离子，又能长时间稳定释放银离子，且瓷砖的强度和硬度也能达到建筑陶瓷的要求，可以满足各种建筑的应用需求。
在本发明的一些实施方案中，所述银盐溶液为0.5-2mol/L的硝酸银溶液。
在本发明的一些实施方案中，所述稀土元素无机化合物为镧、铈、镨、钕或钇的化合物中的一种或多种的混合物。
在本发明的一些实施方案中，所述稀土元素无机化合物为镧、铈、镨、钕或钇的硝酸盐。
本发明还提供了上述的环保陶瓷的制备方法，包括步骤：
(1)原材料预处理：分别将钾长石和钠长石在1000-1100℃煅烧5-6小时，冷却至室温，研磨，过200目筛；分别将麦饭石、尖晶石在800-900℃下煅烧8-9小时，冷却至室温，研磨，过200目筛；对粘土进行改性处理；制备复合磷酸盐材料；
(2)坯料制备：取复合磷酸盐材料、改性粘土、钾长石、钠长石、麦饭石和尖晶石作为坯料原料，投入球磨机，加入适量水，研磨18-36小时，除杂，压泥、练泥；
(3)将步骤(2)制备的坯料压制成型，干燥，在850-1000℃下素烧6-10小时，冷却至室温；
(4)对素烧产品施釉，送入窑炉中在1000-1100℃下烧成，得到所述环保陶瓷。
在本发明的一些实施方案中，所述复合磷酸盐材料的制备方法包括以下步骤：
S1、将贝壳粉在800-1000℃下煅烧3-4小时；
S2、将S1煅烧得到的粉末与磷酸、水混合均匀，降至室温后投入球磨机中，然后向球磨机中投入稀土元素无机化合物，球磨0.5-2小时；
S3、向球磨机中加入银盐溶液，球磨0.5-2小时，干燥，然后送入超细球磨机中球磨0.5-1小时，过200目筛。
在本发明的一些实施方案中，所述复合磷酸盐材料中稀土元素的重量百分含量是银元素的重量百分含量的1.5-2.5倍。
在本发明的一些实施方案中，所述改性粘土的制备方法为：按照质量比为5-10:2-6称取铝矾土、高岭土，混合均匀后，加入强酸溶液酸化，加热至50-80℃，保温0.5-2小时，过滤，洗涤至中性，干燥，并在450-550℃下煅烧1-2小时，过120目筛；称取适量的壳聚糖于醋酸溶液中，配制浓度为10％-20％的壳聚糖胶体溶液，然后加入所述壳聚糖胶体溶液百分含量3％-6％硝酸银、活2％-5％性炭、1％-3％纳米二氧化钛和1％-2％有机硅烷，搅拌0.5-1小时，然后与前述步骤处理的粘土按照1-3:1的重量比混合，干燥，粉碎，过300目筛，即得所述改性粘土。
贝壳粉为一种天然的生物材料，但至今扔被作为固体垃圾丢弃，未被有效利用，而实际上贝壳粉具有良好的韧性以及优异的机械性能，贝壳粉经过改良后具有净化抗菌的功能，可以有效去除SO2、NOx等污染物。此外，贝壳粉加工后的废料可以直接掩埋用于改善土壤，如调节土壤的pH值，不会对环境造成污染。
本发明环保陶瓷的主要原料为贝壳粉，先将贝壳粉高温煅烧处理成氧化钙混合物，然后加入磷酸和水，经再次高温煅烧得到磷酸钙混合物，加入含银离子的盐溶液以及稀土元素，稀土元素与银、锌、铜等过渡金属协同增效，产生大量的羟基自由基，从而使陶瓷具有优良的抗菌性能和空气净化性能。
贝壳粉制成的磷酸钙混合物为离子交换性能良好的层状晶体结构，其作为金属离子的载体，缓释的银离子可以激活空气或水中的氧，产生活性氧及羟基自由基。活性氧的化学活性高，很容易和空气中的各种挥发性气体、烟气或细菌反应。例如，当缓释的银离子与甲醛接触时，银离子使富氧化合物产生氢氧自由基的同时，产生的氢氧负离子可使甲醛转变为甲酸，甲酸又受高价态银离子的作用放出质子氢，使其自身成自由基与氢氧自由基结合成过氧甲酸，过氧甲酸分解为二氧化碳和水。与此同时，当缓释的银离子与细菌接触时，其与细胞以及细胞壁中的蛋白结合，干扰其DNA复制，并促进活性氧的合成。由于DNA合成受到干扰，细菌的遗传物质被破坏，最终通过阻止细菌遗传物质的复制来阻止细菌的复制。而当细菌死亡后，银离子又由细菌尸体中游离出来再与其它细菌接触，从而使其杀菌具有持久性。
本发明选择稀土元素，是因为稀土元素电子层结构具有较多空轨道(4f，6p，5d)，这些轨道的能级差很小，在外界的光、热或极性化合物的极化作用下，易于杂化形成稳定的络合键。研究表明，稀土元素可与细胞壁、细胞膜、酶、蛋白质、DNA、RNA作用。而且，稀土离子有强烈的渗透到生物体内的独特特性。有研究者认为稀土铈离子对细菌的抑制作用与细菌的特殊结构有关。例如，铈离子可直接破坏细菌的鞘和壁的结构，引起细菌鞘和壁通透性发生变化。铈离子易进入细菌核心，进入细菌核心后，由于铈离子与钙离子半径相近，且与O、N、S的配位能力大于钙离子，是钙离子的优异的拮抗剂，会取代细菌中钙离子的结合位点，在细菌核心中形成更为稳定的配合物，进而引起细菌死亡。
本发明具有如下优点：
(1)本发明环保陶瓷以贝壳粉制作而成的磷酸钙基陶瓷粉料搭配改性粘土、钾长石、钠长石、麦饭石、尖晶石等原料，得到的陶瓷既能达到市场所需的白度、粘性和硬度，改善了现有陶瓷的强度和耐磨度，又具有良好的孔隙率，稳定负载稀土元素和银离子，抗菌效果优异，抗菌率可达99％，并能长时间稳定发挥抗菌作用；本发明的环保陶瓷还有良好的空气净化作用，能够有效去除空气中的甲醛、苯、氨和TVOC等物质；
(2)本发明环保陶瓷的主要原料为贝壳粉，减少了丢弃贝壳对环境造成的危害，而且本发明的制备方法操作简单易实施、成品率高，成本低，利于推广。
具体实施方式
下面将对本发明技术方案的实施例进行详细的描述。以下实施例仅用于更加清楚地说明本发明的技术方案，因此只作为示例，而不能以此来限制本发明的保护范围。需要注意的是，除非另有说明，本申请使用的技术术语或者科学术语应当为本发明所属领域技术人员所理解的通常意义。
下面的实施例中的实验方法，如无特殊说明，均为常规方法。下述实施例中所用的试验材料，如无特殊说明，均为自常规生化试剂商店购买得到。以下实施例中的定量试验，均设置三次重复实验，数据为三次重复实验的平均值或平均值±标准差。
本发明提供了一种环保陶瓷及其制备方法。制备所述环保陶瓷的组分为：复合磷酸盐材料30-50份、改性粘土30-50份、钾长石3-8份、钠长石5-10份、麦饭石5-15份、尖晶石2-5份。
本发明以贝壳粉为原料，通过化学改性掺杂银离子和稀土元素，制备成磷酸钙基纳米陶瓷材料，与改性粘土、钾长石、钠长石、麦饭石和尖晶石共同制备成的陶瓷既能满足市场所需白度、粘性和硬度，又能改善现有陶瓷的强度和耐磨度不足的问题，且具有优异抗菌效果和空气净化效果，能够有效去除空气中的甲醛、苯、氨和TVOC。
具体地，银离子的引入通过添加硝酸银熔盐。稀土元素为镧、铈、镨、钕或钇，通过添加其硝酸盐引入。
具体地，磷酸钙基纳米陶瓷材料的制备方法包括以下步骤：
S1、将贝壳粉在800-1000℃下煅烧3-4小时；
S2、将S1煅烧得到的粉末与磷酸、水混合均匀，降至室温后投入球磨机中，然后向球磨机中投入稀土元素无机化合物，球磨0.5-2小时；
S3、向球磨机中加入银盐溶液，球磨0.5-2小时，干燥，然后送入超细球磨机中球磨0.5-1小时，过200目筛。
具体地，所述复合磷酸盐材料中稀土元素的重量百分含量是银元素的重量百分含量的1.5-2.5倍。
具体地，改性粘土的制备方法为：按照质量比为5-10:2-6称取铝矾土、高岭土，混合均匀后，加入强酸溶液酸化，加热至50-80℃，保温0.5-2小时，过滤，洗涤至中性，干燥，并在450-550℃下煅烧1-2小时，过120目筛；称取适量的壳聚糖于醋酸溶液中，配制浓度为10％-20％的壳聚糖胶体溶液，然后加入所述壳聚糖胶体溶液百分含量3％-6％硝酸银、2％-5％活性炭、1％-3％纳米二氧化钛和1％-2％有机硅烷，搅拌0.5-1小时，然后与前述步骤处理的粘土按照1-3:1的重量比混合，干燥，粉碎，过300目筛，即得改性粘土。
实施例1
本实施例提供了一种环保陶瓷，制备方法包括以下步骤：
(1)原料预处理：
分别将钾长石和钠长石在1100℃煅烧5小时，冷却至室温，研磨，过200目筛；将麦饭石和尖晶石在900℃下煅烧8小时，冷却至室温，研磨，过200目筛；
对粘土进行改性处理：将铝矾土和高岭土按照质量为7:3混合均匀，加入适量的2M盐酸酸化，加热至60℃，保温1.5小时，过滤，洗涤至中性，干燥，并在500℃下煅烧1.5小时，过120目筛；取壳聚糖于醋酸溶液中，配制浓度为15％的壳聚糖胶体溶液，然后加入壳聚糖胶体溶液百分含量5％硝酸银、4％活性炭、2％纳米二氧化钛和2％有机硅烷，搅拌1小时，然后与前述步骤处理的粘土按照2:1的重量比混合，干燥，粉碎，过300目筛，即得改性粘土；
制备复合磷酸盐材料：取贝壳粉100重量份、42％(w/w)的磷酸水溶液50重量份、0.5mol/L的硝酸银溶液10重量份和0.2mol/L的硝酸铈溶液10重量份。
将贝壳粉在900℃下煅烧4小时，研磨成粉，向50℃浓度为42％的磷酸水溶液中缓慢加入得到的粉末，边加边搅拌；反应结束后，将制得的泥浆降至室温，送入球磨机中，然后向球磨机中加入硝酸铈溶液，球磨1小时；向球磨机中加入硝酸银溶液，球磨1小时，干燥，然后送入超细球磨机中球磨1小时，过200目筛，得到掺杂有银离子的含稀土的复合磷酸盐材料粉体。
(2)坯料制备：取复合磷酸盐材料50重量份、改性粘土40重量份、钾长石5重量份、钠长石8重量份、麦饭石10重量份和尖晶石3重量份作为坯料原料，投入球磨机，加入适量水，研磨20小时，除杂，压泥、练泥；
(3)将步骤(2)制备的坯料压制成型，干燥，在900℃下素烧8小时，冷却至室温；
(4)对素烧得到产品施釉，送入窑炉中在1050℃下烧成，得到环保陶瓷。
具体地，坯料制备时采用磁铁除杂，然后除水压泥，练泥至泥料中水的重量含量为20％-25％。
实施例2
本实施例提供了一种环保陶瓷，其与实施例1的区别在于，制备环保陶瓷的步骤略有差异。
步骤(2)：取复合磷酸盐材料40重量份、改性粘土30重量份、钾长石8重量份、钠长石10重量份、麦饭石15重量份和尖晶石5重量份作为坯料原料，投入球磨机，加入适量水，研磨20小时，除杂，压泥、练泥；
步骤(3)：将步骤(2)制备的坯料压制成型，干燥，在850℃下素烧10小时，冷却至室温；
步骤(4)：对素烧得到产品施釉，送入窑炉中在1100℃下烧成，得到环保陶瓷。
实施例3
本实施例提供了一种环保陶瓷，其与实施例1的区别在于，制备复合磷酸盐材料时稀土元素略有差异：取贝壳粉100重量份、42％(w/w)的磷酸水溶液50重量份、0.5mol/L的硝酸银溶液10重量份、0.2mol/L的硝酸镧溶液10重量份。
实施例4
本实施例提供了一种环保陶瓷，其与实施例1的区别在于，制备复合磷酸盐材料时稀土元素略有差异：取贝壳粉100重量份、42％(w/w)的磷酸水溶液50重量份、0.5mol/L的硝酸银溶液10重量份、0.2mol/L的硝酸铈溶液10重量份和0.2mol/L的硝酸镧溶液10重量份。
步骤(2)：取复合磷酸盐材料50重量份、改性粘土30重量份、钾长石4重量份、钠长石8重量份、麦饭石5重量份和尖晶石2.2重量份作为坯料原料，投入球磨机，加入适量水，研磨20小时，除杂，压泥、练泥；
步骤(3)：将步骤(2)制备的坯料压制成型，干燥，在1000℃下素烧6小时，冷却至室温；
步骤(4)：对素烧得到产品施釉，送入窑炉中在1000℃下烧成，得到环保陶瓷。
对比例
制备方法包括以下步骤：
(1)原料预处理：
分别将钾长石和钠长石在1100℃煅烧5小时，冷却至室温，研磨，过200目筛；将麦饭石和尖晶石在900℃下煅烧8小时，冷却至室温，研磨，过200目筛；
制备复合磷酸盐材料：取贝壳粉100重量份、42％(w/w)的磷酸水溶液50重量份、0.5mol/L的硝酸银溶液10重量份和0.5mol/L的硝酸铈溶液10重量份。
将贝壳粉在900℃下煅烧4小时，研磨成粉，向50℃浓度为42％的磷酸水溶液中缓慢加入得到的粉末，边加边搅拌；反应结束后，将制得的泥浆降至室温，送入球磨机中，然后向球磨机中加入硝酸铈溶液，球磨1小时；向球磨机中加入硝酸银溶液，球磨1小时，干燥，然后送入超细球磨机中球磨1小时，过200目筛，得到掺杂有银离子的含稀土的复合磷酸盐材料粉体。
(2)坯料制备：取复合磷酸盐材料50重量份、高岭土30重量份、钾长石5重量份、钠长石8重量份、麦饭石10重量份和尖晶石3重量份作为坯料原料，投入球磨机，加入适量水，研磨20小时，除杂，压泥、练泥；
(3)将步骤(2)制备的坯料压制成型，干燥，在900℃下素烧8小时，冷却至室温；
(4)对素烧得到产品施釉，送入窑炉中在1050℃下烧成，得到对比例陶瓷。
性能效果
1、抗菌效果
将实施例1-4和对比例的陶瓷的抗菌性能按照重量份B/T 21510-2008进行检测。陶瓷的抗菌率通过计算两个时间节点的细菌数量得到，分别为接触时间试样上测得的细菌的平均值(cfu/片)和24小时培养后测得的细菌数的平均值(cfu/片)。抗菌性能测试中实验菌种的金黄色葡萄球菌(ATCC 6538)和大肠杆菌(ATCC 25922)由广东省微生物所菌种保藏中心提供。
抗菌率如下表所示。
表1陶瓷抗菌性能
实施例1 实施例2 实施例3 实施例4 对比例
大肠杆菌 97.56％ 97.60％ 97.45％ 97.32％ 70.56％
金黄色葡萄球菌 98.69％ 98.72％ 98.65％ 99.04％ 78.43％
2、结构性能
对实施例1-4和对比例的陶瓷进行性能检测，并取实施例1-4制备得到的环保陶瓷的10cm×10cm×0.5cm试样进行1000℃/20min氧化，得到的结果如表2所示。
表2陶瓷结构性能
密度(重量份/cm<sup>3</sup>) 耐磨度 抗弯曲强度(MPa) 气孔率(％)
实施例1 48.84 ≥5 48.06 44.49
实施例2 48.42 ≥5 48.14 44.64
实施例3 48.93 ≥5 48.25 44.86
实施例4 49.09 ≥5 48.28 44.97
对比例 42.41 3 45.36 41.12
3、空气净化效果
对实施例1-4和对比例的陶瓷进行甲醛、苯、氨和TVOC去除实验。实验方法参照QB/T 2761-2006室内空气净化产品净化效果测定方法测定。
表3陶瓷空气净化效果
Figure BDA0002406702500000101
Figure BDA0002406702500000111
从以上检测结果可以看出，本发明环保陶瓷的杀菌率高，对大肠杆菌抗菌率在97％以上，对金黄色葡萄球菌抗菌率在98％以上，甚至能达到99％，抗菌效果优异。陶瓷缓释的银离子与稀土元素协同增效，能够有效去除空气中的甲醛和TVOC(总挥发性有机化合物)，去除率在80％以上，且对苯和氨也能有效去除。
此外，环保陶瓷的抗弯曲强度均能达到48MPa以上，耐磨度都能到达5以上，能够达到市场建筑陶瓷所需的强度、硬度和粘性。
而且，经过试验发现，该陶瓷的白度也能满足市场建筑陶瓷的要求，陶瓷无变黄等现象。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围，其均应涵盖在本发明的权利要求和说明书的范围当中。

Claims (8)

1.一种环保陶瓷，其特征在于，所述环保陶瓷由掺杂有抗菌材料的复合磷酸盐材料与改性粘土、钾长石、钠长石、麦饭石和尖晶石制备而成，制备所述环保陶瓷的组分为：复合磷酸盐材料30-50份、改性粘土30-50份、钾长石3-8份、钠长石5-10份、麦饭石5-15份、尖晶石2-5份；制备所述复合磷酸盐材料的原料包括如下重量份的组分：贝壳粉80-100份、40％-45％磷酸35-50份、银盐溶液5-15份和稀土元素无机化合物10-20份。
2.根据权利要求1所述的环保陶瓷，其特征在于，所述银盐溶液为0.5-2mol/L的硝酸银溶液。
3.根据权利要求1所述的环保陶瓷，其特征在于，所述稀土元素无机化合物为镧、铈、镨、钕或钇的化合物中的一种或多种的混合物。
4.根据权利要求3所述的环保陶瓷，其特征在于，所述稀土元素无机化合物为镧、铈、镨、钕或钇的硝酸盐。
5.权利要求1-4任意一项所述的环保陶瓷的制备方法，其特征在于，包括步骤：
(1)原材料预处理：分别将钾长石和钠长石在1000-1100℃煅烧5-6小时，冷却至室温，研磨，过200目筛；分别将麦饭石、尖晶石在800-900℃下煅烧8-9小时，冷却至室温，研磨，过200目筛；对粘土进行改性处理；制备复合磷酸盐材料；
(2)坯料制备：取复合磷酸盐材料、改性粘土、钾长石、钠长石、麦饭石和尖晶石作为坯料原料，投入球磨机，加入适量水，研磨18-36小时，除杂，压泥、练泥；
(3)将步骤(2)制备的坯料压制成型，干燥，在850-1000℃下素烧6-10小时，冷却至室温；
(4)对素烧产品施釉，送入窑炉中在1000-1100℃下烧成，得到所述环保陶瓷。
6.根据权利要求5所述的制备方法，其特征在于，所述复合磷酸盐材料的制备方法包括以下步骤：
S1、将贝壳粉在800-1000℃下煅烧3-4小时；
S2、将S1煅烧得到的粉末与磷酸、水混合均匀，降至室温后投入球磨机中，然后向球磨机中投入稀土元素无机化合物，球磨0.5-2小时；
S3、向球磨机中加入银盐溶液，球磨0.5-2小时，干燥，然后送入超细球磨机中球磨0.5-1小时，过200目筛。
7.根据权利要求5所述的制备方法，其特征在于，所述复合磷酸盐材料中稀土元素的重量百分含量是银元素的重量百分含量的1.5-2.5倍。
8.根据权利要求5所述的制备方法，其特征在于，所述改性粘土的制备方法为：按照质量比为5-10:2-6称取铝矾土、高岭土，混合均匀后，加入强酸溶液酸化，加热至50-80℃，保温0.5-2小时，过滤，洗涤至中性，干燥，并在450-550℃下煅烧1-2小时，过120目筛；称取适量的壳聚糖于醋酸溶液中，配制浓度为10％-20％的壳聚糖胶体溶液，然后加入所述壳聚糖胶体溶液百分含量3％-6％硝酸银、2％-5％活性炭、1％-3％纳米二氧化钛和1％-2％有机硅烷，搅拌0.5-1小时，然后与前述步骤处理的粘土按照1-3:1的重量比混合，干燥，粉碎，过300目筛，即得所述改性粘土。
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