CN111944162A - 一种超支化聚酯改性负载银离子硅藻土的制备方法 - Google Patents
一种超支化聚酯改性负载银离子硅藻土的制备方法 Download PDFInfo
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Abstract
本发明提供一种超支化聚酯改性负载银离子硅藻土的制备方法，利用氨基硅烷修饰负载银离子硅藻土，最后利用酰胺化反应接枝超支化聚酯，得到超支化聚酯改性负载银离子硅藻土材料。该材料对印染废水中重金属离子、有机污染物具有较强的吸附能力，同时具备光催化降解有机污染物的性能，可以实现富集并降解污染水体中罗丹明B，具有潜在的实际应用价值。
Description
技术领域
本发明属于污水处理技术领域，具体涉及一种超支化聚酯改性负负载银离子硅藻土的制备方法。
背景技术
染料有机污染物是一种常见的水体环境污染物，可以通过生物链富集在人体，从而影响人体的身体健康，严重会导致癌变。因此针对印染废水中染料有机污染物的治理迫在眉睫。目前处理此类污染物的方法最常用的是吸附法，但吸附能力、降解能力相对较弱。因此，研发一种高效、针对性强、可降解污染物的处理技术成为当前的关注热点。
硅藻土是一种由硅藻遗骸所形成的多孔材料，具有比表面积大、抗腐蚀性好和绿色无毒等优点。作为一种原料易得、价格低廉的吸附与催化载体材料，硅藻土在水处理方面表现出广泛的应用前景。天然硅藻土中含有不同比例的金属氧化物杂质，会降低硅藻土的孔隙率和影响其吸附及催化活性。因此，表面修饰和复合改性增强硅藻土吸附及催化性能是目前硅藻土材料应用于水处理方向的研究重点。目前已有许多专利涉及硅藻土复合材料吸附污染物的研究。例如，专利号为CN107486160A的专利公开了一种纳米纤维素/硅藻土复合吸附材料的制备方法。专利号为107376849A的专利公开了一种乙二胺四乙酸改性的硅藻土吸附剂及其制备方法和处理废水中重金属离子的应用。
从现有技术分析，现有的硅藻土材料大多制备复杂，容易造成二次污染，而且针对有机污染物降解功能的硅藻土材料鲜有报道。因此，开展以天然矿物质硅藻土为绿色原料、高效吸附、针对染料分子为目标污染物、具有光催化降解功能的复合硅藻土材料的研究极为重要。
发明内容
为解决目前印染废水中染料有机污染物污染严重的问题，本发明提供一种具有高效吸附、催化降解功能的超支化聚酯改性负负载银离子硅藻土的制备方法，可以实现富集印染水体中有机污染物、光催化降解有机污染物的目的，具有潜在的应用价值。
本发明是通过以下技术方案实现的：
一种超支化聚酯改性负负载银离子硅藻土的制备方法，包括以下步骤：
(1)负载银离子硅藻土(Ag@DE)的制备
硅藻土先在抗坏血酸溶液中完全润湿，烘干到恒重，然后在硝酸银溶液中完全润湿，静止24～32h后，烘干，即得硅藻土负载银离子材料(Ag@DE),银离子的负载使得硅藻土材料具有光催化降解有机染料的性能，所述的抗坏血酸溶液的浓度为0.20～0.25mol/L，所述的硝酸银溶液的浓度为0.02～0.025mol/L，作为优选，烘干温度为100～110℃。
(2)氨基硅烷改性负载银离子硅藻土(A-Ag@DE)的制备
将步骤(1)所制备的载银硅藻土材料Ag@DE先在NaOH溶液中活化，将活化后的硅藻土粉体在乙醇溶液超声分散30～60min，制得分散性良好的硅藻土悬浮液，将氨基硅烷滴加至悬浮液中，采用乙酸调节pH为5.5～6，40～50℃下水浴搅拌24～28h，洗涤，烘干制得氨基硅烷改性负载银离子硅藻土，记为A-Ag@DE。所述的负载银离子硅藻土材料Ag@DE、NaOH的质量比为2.0～3.0：1，作为优选，NaOH溶液的摩尔浓度为0.5～0.6mol/L，所述的活化后的硅藻土粉体、氨基硅烷的质量比为1.4～1.6：1。所述的氨基硅烷偶联剂为3-氨丙基-三甲氧基硅烷、3-氨丙基-三乙氧基硅烷、N-β-氨乙基-γ-氨丙基-甲基二甲氧基硅烷中的一种或是多种，作为优选，乙酸的质量分数为35～38％。作为优选，烘干的温度为80～90℃。
(3)超支化聚酯改性负载银离子硅藻土(CA-Ag@DE)的制备
将步骤(2)制备的氨基硅烷改性负载银离子硅藻土粉末分散于丙酮溶液中，逐步加入超支化聚酯CHBP、对甲苯磺酸反应40-60min后取出，过滤、洗涤、干燥，得到超支化聚酯改性负载银离子硅藻土(CA-Ag@DE)材料。
其具体的制备路线为：
所述的氨基硅烷改性负载银离子硅藻土粉末、超支化聚酯CHBP、对甲苯磺酸、丙酮的质量体积比为10g：4～4.5g：1～1.5g：25～30mL。
作为优选超支化聚酯CHBP的质量分数为5-6％，所述的洗涤先用甲醇洗涤2-3次，再用去离子水洗至中性，作为优选，干燥的条件为90-100℃下真空干燥12-15h。
本发明取得有益效果：
1、本发明提供了一种具有光催化降解功能的超支化聚酯改性负载银离子硅藻土
可有效针对印染废水中的有机染料，进行高效吸附；材料采用天然无机矿物质硅藻土为基底，负载银离子进行超支化改性，具有操作简便、吸附效率高、催化降解有机污染物，可广泛应用于含有机污染物的污水体系的特异性吸附，具有良好的发展前景。
2、本发明提供了一种具有光催化降解功能的超支化聚酯改性负载银离子硅藻土
具有原材料廉价易得、应用范围广、生产成本低、环保等优点。
附图说明
图1为实施例2制备的负载银离子硅藻土(Ag@DE)的SEM图；
图2为实施例1所制备的超支化聚酯改性负载银离子硅藻土(CA-Ag@DE)的吸附曲线图；
图3实施例3所制备的超支化聚酯改性负载银离子硅藻土(CA-Ag@DE)的光催化降解罗丹明B的曲线图。
具体实施方式
以下结合具体实施方式和附图对本发明的技术方案作进一步详细描述：
实施例1：
超支化聚酯改性负载银离子硅藻土(CA-Ag@DE)的制备，包括以下步骤：
(1)负载银离子硅藻土(Ag@DE)的制备
取15g烘干的硅藻土，加入0.20mol/L抗坏血酸溶液，直至硅藻土完全润湿，于105℃烘干到恒重，然后将产物粉碎加入0.02％硝酸银溶液，直至硅藻土完全润湿，静至24h后，于105℃烘干，即得负载银离子硅藻土(Ag@DE)。
(2)氨基硅烷改性负载银离子硅藻土(A-Ag@DE)的制备
准确称取10g负载银离子硅藻土粉体，放入盛有250mL浓度为0.5mol/L的NaOH溶液中，常温搅拌1h，抽滤，洗涤，烘干备用。
准确称取1.5g活化后的硅藻土粉体，放入盛有30mL乙醇溶液的烧杯中，将烧杯置于磁力搅拌器上室温下搅拌10min，放入超声清洗器中超声分散30min，制得分散性良好的硅藻土悬浮液；量取0.8mL的3-氨基丙基三乙氧基硅烷加入硅藻土悬浮液中，采用质量分数为36％的乙酸调节pH至6，40℃水浴搅拌24h，抽滤，洗涤，烘干制得氨基硅烷改性负载银离子硅藻土。
(3)超支化聚酯改性负载银离子硅藻土(CA-Ag@DE)的制备
以丙酮为溶剂，加入1g氨基硅烷改性负载银离子硅藻土(A-Ag@DE)，超声搅拌30min后得到分散均匀的溶液，接着开始磁力搅拌，逐步加入8mL 5％的CHBP及0.1g对甲苯磺酸，40min后取出过滤，先用甲醇洗涤2～3次，再用去离子水洗至中性；90℃干燥12h，得到超支化聚酯改性负载银离子硅藻土(CA-Ag@DE)材料。
实施例2：
负载银离子硅藻土(Ag@DE)的制备，为以下步骤：
取5g烘干的硅藻土，加入0.25mol/L抗坏血酸溶液，直至硅藻土完全润湿，于105℃烘干到恒重，然后将产物粉碎并且加入0.025％硝酸银溶液，直至硅藻土完全润湿，静至30h后，于105℃烘干，即得负载银离子硅藻土(Ag@DE)；
实施例3：
超支化聚酯改性负载银离子硅藻土(CA-Ag@DE)的制备，包括以下步骤：
(1)负载银离子硅藻土(Ag@DE)的制备
取10g烘干的硅藻土，加入0.20mol/L抗坏血酸溶液，直至硅藻土完全润湿，于105℃烘干到恒重，然后将产物捣碎并且加入0.02％硝酸银溶液，直至硅藻土完全润湿，静至24h后，于105℃烘干，即得负载银离子硅藻土(Ag@DE)。
(2)氨基硅烷改性负载银离子硅藻土(A-Ag@DE)的制备
准确称取10g的负载银离子硅藻土粉体，放入盛有250mL浓度为0.5mol/L的NaOH溶液中，常温搅拌1h，抽滤，洗涤，烘干备用。
准确称取3g活化后的硅藻土粉体，放入盛有60mL乙醇溶液的烧杯中，将烧杯置于磁力搅拌器上室温下搅拌10min，放入超声清洗器中超声分散30min，制得分散性良好的硅藻土悬浮液，量取1.6mL的3-氨丙基-三甲氧基硅烷加入硅藻土悬浮液中，采用质量分数为38％的乙酸调节pH为5.5，40℃水浴搅拌24h，抽滤，洗涤，烘干制得氨基硅烷改性负载银离子硅藻土(A-Ag@DE)。
(3)超支化聚酯改性负载银离子硅藻土(CA-Ag@DE)的制备
以丙酮为溶剂，加入3g氨基硅烷改性负载银离子硅藻土(A-Ag@DE)，超声搅拌30min后得到分散均匀的溶液，接着开始磁力搅拌，逐步加入24mL 5％的CHBP及0.3g对甲苯磺酸，40min后取出过滤，先用甲醇洗涤2～3次，再用去离子水洗至中性；90℃干燥12h。得到超支化聚酯改性负载银离子硅藻土(CA-Ag@DE)材料。
试验例1—负载银离子硅藻土(Ag@DE)的结构表征
试验样品：实施例2所制备的负载银离子硅藻土(Ag@DE)。
1、扫描电镜图片分析：对实施例2所制备的负载银离子硅藻土(Ag@DE)进行了扫面电镜分析，电镜照片如附图1所示。从图中可以看出硅藻土拥有大的空腔和大量的壳穴(图1A)可以用来负载纳米银微粒，纳米银微粒粒径大约为30nm左右，硅藻土空穴较大，可以较好的负载纳米银微粒。从图1B可以看出纳米银负载于硅藻土上，活性中心分布均匀，可进行有效的吸附降解。
试验例2—超支化聚酯改性负载银离子硅藻土(CA-Ag@DE)的吸附性能测试
试验样品：实施例1所制备的超支化聚酯改性负载银离子硅藻土(CA-Ag@DE)。
分别取实施例1中所制备的1g超支化聚酯改性负载银离子硅藻土(CA-Ag@DE)吸附铅离子和染料罗丹明B。选取初始浓度为10、20、30、50、80、100、120、150、180、200mg/L，测定吸附含量，如附图2所示。可以看出随着污染物初始浓度的提高，超支化聚酯改性负载银离子硅藻土的吸附含量越高。当初始浓度为120mg/L,吸附材料对铅离子和罗丹明B的吸附含量分别达176.12、103.60mg/g。证明超支化聚酯改性负载银离子硅藻土(CA-Ag@DE)的吸附性能良好。
试验例3—超支化聚酯改性负载银离子硅藻土(CA-Ag@DE)的光降解性能测试。
试验样品：实施例3所制备得超支化聚酯改性负载银离子硅藻土(CA-Ag@DE)。
在可见光照射的情况下，取实施例3中所制备的1mg CA-Ag@DE吸附罗丹明B，选取时间间隔0.25、1.5、2.5、3.5、4.5、5.5、7h测定溶液中污染物罗丹明B的含量变化，做出降解率随着时间变化的曲线，如附图3所示。可以看出随着，时间的推移，曝露在可见光下的时间越长，溶液中罗丹明B的浓度越低，降解率越高，证明超支化聚酯改性负载银离子硅藻土(CA-Ag@DE)光降解性能良好。
Claims (8)
1.一种超支化聚酯改性负载银离子硅藻土的制备方法，其特征在于，所述的制备方法为以下步骤：
(1)负载银离子硅藻土的制备
硅藻土先在抗坏血酸溶液中完全润湿，烘干到恒重，然后在硝酸银溶液中完全润湿，静止24～32h后，烘干，即得硅藻土负载银离子材料；
(2)氨基硅烷改性负载银离子硅藻土的制备
将步骤(1)所制备的负载银离子硅藻土材料先在NaOH溶液中活化，之后将活化后的硅藻土粉体在乙醇溶液超声分散30～60min，制得分散性良好的硅藻土悬浮液，将氨基硅烷滴加至悬浮液中，采用乙酸调节pH为5.5～6，40～50℃下水浴搅拌24～28h，洗涤，烘干制得氨基硅烷改性负载银离子硅藻土；
(3)超支化聚酯改性负载银离子硅藻土的制备
将步骤(2)制备的氨基硅烷改性负载银离子硅藻土粉末分散于丙酮中，逐步加入超支化聚酯CHBP、对甲苯磺酸反应40～60min后取出，过滤、洗涤、干燥，得到超支化聚酯改性负载银离子硅藻土材料。
2.根据权利要求1所述的一种超支化聚酯改性负载银离子硅藻土的制备方法，其特征在于，步骤(1)中抗坏血酸溶液的浓度为0.20～0.25mol/L。
3.根据权利要求1所述的一种超支化聚酯改性负载银离子硅藻土的制备方法，其特征在于，步骤(1)中硝酸银溶液的浓度为0.02～0.025mol/L。
4.根据权利要求1所述的一种超支化聚酯改性负载银离子硅藻土的制备方法，其特征在于，步骤(2)中负载银离子硅藻土材料与NaOH的质量比为2.0～3.0：1，其中NaOH溶液的摩尔浓度为0.5～0.6mol/L。
5.根据权利要求1所述的一种埃洛石基分子印迹纳米材料的制备方法，其特征在于，步骤(2)中活化后的硅藻土粉体与氨基硅烷的质量比为1.4～1.6：1。
6.根据权利要求1所述的一种超支化聚酯改性负载银离子硅藻土的制备方法，其特征在于，步骤(2)中氨基硅烷选自3-氨丙基-三甲氧基硅烷、3-氨丙基-三乙氧基硅烷、N-β-氨乙基-γ-氨丙基-甲基二甲氧基硅烷中的一种或是多种。
7.根据权利要求1所述的一种超支化聚酯改性负载银离子硅藻土的制备方法，其特征在于，步骤(3)中氨基硅烷改性负载银离子硅藻土粉末、超支化聚酯CHBP、对甲苯磺酸、丙酮的质量体积比为10g：(4～4.5g)：(1～1.5g)：25～30mL。
8.根据权利要求1所述的一种超支化聚酯改性负载银离子硅藻土的制备方法，其特征在于，步骤(3)中洗涤先用甲醇洗涤2～3次，再用去离子水洗至中性。
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