CN115178226B - 一种钛掺杂介孔二氧化硅及其制备方法与应用 - Google Patents
一种钛掺杂介孔二氧化硅及其制备方法与应用 Download PDFInfo
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Abstract
本发明涉及一种钛掺杂介孔二氧化硅及其制备方法与应用,所述钛掺杂介孔二氧化硅由介孔二氧化硅负载二氧化钛得到,其比表面积为300~1000m2/g,孔体积为0.4~1.5cm3/g,平均孔径为2~20nm。本发明提供的钛掺杂介孔二氧化硅具有适当的孔径和表面反应活性,对水中草甘膦吸附效果好,吸附量大且吸附速度快,其制备方法步骤简单可控,反应条件温和,制备过程绿色环保,有望实现工业化生产。
Description
技术领域
本发明属于水、废水、污水或污泥的处理技术领域,具体涉及一种钛掺杂介孔二氧化硅及其制备方法与应用。
背景技术
草甘膦是全球市场上产量和需求量最大的一种灭生性除草剂。与其他除草剂相比,草甘膦具有简单、有效、经济的优点,因此在农业和城市环境中被广泛使用,导致草甘膦除草剂的使用量急剧增加。过量的草甘膦容易进入自然水体中,对水环境和人体健康造成极大危害。因此,水中草甘膦的处理问题已经成为水处理领域的重点。
草甘膦废水的处理方法主要有:化学氧化法、生物法、化学沉淀法、膜分离法、吸附法等。其中吸附法因操作方便、成本低、处理效率高、对污染物适应能力强而得到了广泛的研究。其原理是通过吸附剂表面与草甘膦分子中的官能团产生物理或化学相互作用从而吸附草甘膦。目前用于吸附草甘膦的材料主要有活性炭、树脂等。
介孔二氧化硅材料具有比表面积大、表面易修饰、对环境无污染等优点,是一种具有潜力的吸附剂材料。但二氧化硅介孔材料化学活性不高,由于其化学惰性对草甘膦吸附能力差,应用于草甘膦的吸附效果仍然不够理想。
发明内容
本发明所要解决的技术问题是针对现有技术中存在的上述不足,提供一种钛掺杂介孔二氧化硅及其制备方法与应用,该钛掺杂介孔二氧化硅具有适当的孔径和比表面积,对草甘膦吸附量大。
为解决上述技术问题,本发明提供的技术方案是:
提供一种钛掺杂介孔二氧化硅,其由介孔二氧化硅负载二氧化钛得到,其比表面积为300~1000m2/g,孔体积为0.4~1.5cm3/g,平均孔径为2~20nm。
按上述方案,所述钛掺杂介孔二氧化硅中钛元素质量百分含量为1~50%。
本发明还包括上述钛掺杂介孔二氧化硅的制备方法,具体步骤如下:
1)将P123加入盐酸溶液中,加热搅拌溶解得到P123溶液,再加入正硅酸乙酯(TEOS),保持加热,并搅拌20~60h后进行晶化处理,结束后待温度降至室温,滤出固体,洗涤,干燥,最后焙烧除去P123,得到介孔二氧化硅;
2)将步骤1)所得介孔二氧化硅超声分散于异丙醇中,然后在搅拌条件下逐滴滴加钛酸四丁酯(TBOT),再加入水,15~35℃下搅拌反应1~6h,反应结束后将反应得到的混合物离心,将离心所得沉淀物洗涤、干燥,最后煅烧得到钛掺杂介孔二氧化硅(SBA-15-T1)。
按上述方案,步骤1)所述盐酸溶液浓度为0.1~2mol/L,所述P123溶液质量浓度为10~50g/L。
按上述方案,步骤1)加热搅拌温度为25~50℃。
按上述方案,步骤1)所述P123与正硅酸乙酯的质量比为1:1~3。
按上述方案,步骤1)晶化处理温度为60~140℃,晶化处理时间为20~60h。
按上述方案,步骤1)焙烧工艺条件为:室温下以1~5℃/m1n的升温速率升温至500~600℃,保温3~8h。
按上述方案,步骤2)所述介孔二氧化硅与异丙醇的质量体积比为1g/5~50mL。
按上述方案,步骤2)所述介孔二氧化硅与钛酸四丁酯的质量比为1:0.1~10。
按上述方案,步骤2)所述钛酸四丁酯与水的质量比为1:5~20。
按上述方案,步骤2)锻烧工艺条件为:室温下以1~5℃/m1n的升温速率升温至200~500℃,保温2~6h。
本发明还包括上述钛掺杂介孔二氧化硅作为吸附剂在去除水中草甘膦方面的应用,具体使用方法为:将所述钛掺杂介孔二氧化硅加入含草甘膦的水体中,钛掺杂介孔二氧化硅的加入量为0.2~2g/L,调节体系pH值为1~13,搅拌处理5~1000m1n。
本发明采用P123为模板剂,正硅酸乙酯为硅源先合成介孔二氧化硅,然后以钛酸四丁酯为钛源通过水解法使二氧化钛负载到介孔二氧化硅中。通过钛源与介孔二氧化硅表面的硅羟基结合而将二氧化钛键接上去。二氧化钛对磷酸盐具有较强的吸附能力,而草甘膦含有一个膦酸基团,与磷酸盐有类似性质,因此二氧化钛对草甘膦也有一定的吸附效果。二氧化钛在钛掺杂介孔二氧化硅材料吸附草甘膦过程作为活性中心,提高了其对草甘膦的吸附能力。
本发明的有益效果在于:1、本发明提供的钛掺杂介孔二氧化硅具有适当的孔径和表面反应活性,对水中草甘膦吸附效果好,吸附量大且吸附速度快。2、本发明的制备方法步骤简单可控,反应条件温和,制备过程绿色环保,有望实现工业化生产。
附图说明
图1为本发明实施例1所制备的钛掺杂介孔二氧化硅的氮气吸脱附等温线及孔径分布图;
图2为实施例1所制备的钛掺杂介孔二氧化硅在25℃时对不同pH值的草甘膦溶液的平衡吸附性能;
图3为实施例1所制备的钛掺杂介孔二氧化硅在25℃时对不同初始浓度的草甘膦溶液的平衡吸附性能;
图4为实施例1所制备的钛掺杂介孔二氧化硅在25℃时吸附时间对平衡吸附量的影响;
图5为实施例1所制备的钛掺杂介孔二氧化硅TEM图;
图6为对比例1所制备的SBA-15的氮气吸脱附等温线及孔径分布图。
具体实施方式
为使本领域技术人员更好地理解本发明的技术方案,下面结合附图对本发明作进一步详细描述。
实施例1
一种钛掺杂介孔二氧化硅,其制备方法如下:
1)取10g P123溶于350mL浓度为2mol/L的盐酸溶液中,在35℃下搅拌至澄清,使P123完全溶解,然后匀速滴加21g正硅酸乙酯,在35℃下搅拌48h后,转入水热反应釜中于100℃晶化反应48h,将所得物质过滤,洗涤,然后在110℃下干燥12h,最后放入马弗炉中,以1℃/m1n的升温速率升温至550℃锻烧6h除去模板剂,得到介孔二氧化硅;
2)取1.5g介孔二氧化硅作为载体,超声使其分散于40.5mL异丙醇中,然后在搅拌条件下逐滴滴加2.73mL钛酸四丁酯,再加入27.3mL水,室温搅拌反应2h,将反应得到的混合物离心,离心所得沉淀物用乙醇洗涤2次,再次离心,将所得固体在60℃下干燥12h,最后放入马弗炉中,以2℃/m1n的升温速率升温至350℃煅烧4h,得到钛掺杂介孔二氧化硅(SBA-15-T1)。
采用等离子体发射光谱仪(ICP)测得本实施例钛掺杂介孔二氧化硅中钛元素质量百分含量为17.29%。
图1为本实施例所制备的钛掺杂介孔二氧化硅的氮气吸脱附等温线及孔径分布图,由图可知,本实施例制备的钛掺杂介孔二氧化硅的比表面积为607.7m2/g,孔体积为0.842cm3/g,平均孔径为4.87nm,具有良好的介孔材料的特性。
取多份浓度为100mg/L的草甘膦溶液,每份50mL,分别调节pH值为2~11,每份草甘膦溶液中加入0.05g本实施例所制备的钛掺杂介孔二氧化硅作为吸附剂,在温度为25℃下,吸附720m1n,测试钛掺杂介孔二氧化硅对草甘膦的吸附效果(每个样品重复两次,取平均值),图2为本实施例所制备的钛掺杂介孔二氧化硅在25℃时对不同pH值的草甘膦溶液的平衡吸附曲线图,结果发现,当溶液pH值在2.0时,吸附剂对草甘膦的吸附量最大,能达到86.8mg/g。在pH值为2-11范围内,随着溶液pH值的升高,吸附量迅速下降。
取多份不同浓度的草甘膦溶液(浓度25~300mg/L),每份50mL,调pH值为2,每份草甘膦溶液中加入0.05g本实施例所制备的吸附剂钛掺杂介孔二氧化硅,在温度为25℃下吸附720m1n,测试钛掺杂介孔二氧化硅对不同浓度草甘膦溶液的吸附效果。图3为本实施例所制备的钛掺杂介孔二氧化硅在25℃时对不同初始浓度的草甘膦溶液的平衡吸附曲线图。可见,草甘膦溶液初始浓度C0低于150mg/L时,吸附量随C0的增加而迅速增加。这是由于随着浓度增加,溶液与吸附剂表面的草甘膦浓度梯度增大,导致其传质推动力增大,平衡吸附量逐渐增大。当草甘膦初始浓度大于150mg/L时,随着浓度增加平衡吸附量变化不大,这是因为在草甘膦初始浓度大于150mg/L时,吸附活性位点逐渐被草甘膦占满,吸附逐渐达到饱和状态。在C0=300mg/L时吸附量最高,达到121.3mg/g。
取多份浓度为100mg/L的草甘膦溶液,每份50mL,调节pH值为2,每份草甘膦溶液中加入0.05g本实施例所制备的吸附剂钛掺杂介孔二氧化硅,在温度为25℃下,吸附时间分别为30、60、120、240、480、600、720m1n,测试钛掺杂介孔二氧化硅吸附草甘膦时间对平衡吸附量的影响。图4为本实施例所制备的钛掺杂介孔二氧化硅在25℃时吸附时间对平衡吸附量的影响,可见SBA-15-T1对草甘膦表现出较快的吸附速率,草甘膦在30m1n内迅速吸附,吸附量能达到平衡吸附量的70%左右,吸附120m1n能达到平衡吸附量的83%左右,120m1n后吸附量随着时间的增加趋势变缓,在240m1n后逐渐达到平衡吸附。
图5为本实施例所制备的钛掺杂介孔二氧化硅的透射电镜图,从图中可以看出SBA-15-T1具有与SBA-15类似结构的二维六方相的介孔结构。钛负载在SBA-15上材料仍保持有序中孔结构。
对比例1
SBA-15,具体制备步骤如下:
取350mL浓度为2mol/L的盐酸溶液,加入10g的P123,于35℃下搅拌至澄清,使P123完全溶解,然后,匀速滴加21g正硅酸乙酯,继续加热搅拌48h后,转入水热反应釜中于100℃晶化反应48h,将所得固体物质过滤,洗涤,然后将滤饼在110℃下干燥12h,最后放入马弗炉中,以1℃/m1n的升温速率升温至550℃焙烧6h除去模板剂,得到SBA-15。
图6为本对比例制备的SBA-15的氮气吸脱附等温线及孔径分布图,由图可知,SBA-15材料的氮气吸脱附曲线为IV型等温线,氮气吸脱附曲线显示H1型滞后环,说明SBA-15具有介孔结构。SBA-15的比表面积为848.4m2/g,孔体积为1.35cm3/g,平均孔径为6.56nm,具有良好的介孔材料的特性。
取2份浓度为100mg/L的草甘膦溶液,每份50mL,调节pH值为2,向每份草甘膦溶液中加入0.05g本对比例制备的SBA-15,在温度为25℃下吸附720m1n,测试SBA-15对草甘膦的吸附效果,取平均值,测得SBA-15对草甘膦的吸附量为1.1mg/g。相同条件下实施例1制备的SBA-15-T1对草甘膦的吸附量达到86.8mg/g。说明实施例1钛掺杂改性SBA-15大幅度改善了SBA-15对草甘膦的吸附性能。
Claims (10)
1.一种用作去除水中草甘膦的吸附剂钛掺杂介孔二氧化硅,其特征在于,其由介孔二氧化硅负载二氧化钛得到,其比表面积为300~1000m2/g,孔体积为0.4~1.5cm3/g,平均孔径为2~20nm;
其制备方法具体步骤如下:
1)将P123加入盐酸溶液中,加热搅拌溶解得到P123溶液,再加入正硅酸乙酯,保持加热,并搅拌20~60h后进行晶化处理,结束后待温度降至室温,滤出固体,洗涤,干燥,最后焙烧除去P123,得到介孔二氧化硅;
2)将步骤1)所得介孔二氧化硅超声分散于异丙醇中,然后在搅拌条件下逐滴滴加钛酸四丁酯,再加入水,15~35℃下搅拌反应1~6h,反应结束后将反应得到的混合物离心,将离心所得沉淀物洗涤、干燥,最后煅烧得到钛掺杂介孔二氧化硅。
2.根据权利要求1所述的钛掺杂介孔二氧化硅,其特征在于,所述钛掺杂介孔二氧化硅中钛元素质量百分含量为1~50%。
3.一种权利要求1或2所述的钛掺杂介孔二氧化硅的制备方法,其特征在于,具体步骤如下:
1)将P123加入盐酸溶液中,加热搅拌溶解得到P123溶液,再加入正硅酸乙酯,保持加热,并搅拌20~60h后进行晶化处理,结束后待温度降至室温,滤出固体,洗涤,干燥,最后焙烧除去P123,得到介孔二氧化硅;
2)将步骤1)所得介孔二氧化硅超声分散于异丙醇中,然后在搅拌条件下逐滴滴加钛酸四丁酯,再加入水,15~35℃下搅拌反应1~6h,反应结束后将反应得到的混合物离心,将离心所得沉淀物洗涤、干燥,最后煅烧得到钛掺杂介孔二氧化硅。
4.根据权利要求3所述的钛掺杂介孔二氧化硅的制备方法,其特征在于,步骤1)所述盐酸溶液浓度为0.1~2mol/L,所述P123溶液质量浓度为10~50g/L;步骤1)加热搅拌温度为25~50℃。
5.根据权利要求3所述的钛掺杂介孔二氧化硅的制备方法,其特征在于,步骤1)所述P123与正硅酸乙酯的质量比为1:1~3。
6.根据权利要求3所述的钛掺杂介孔二氧化硅的制备方法,其特征在于,步骤1)晶化处理温度为60~140℃,晶化处理时间为20~60h。
7.根据权利要求3所述的钛掺杂介孔二氧化硅的制备方法,其特征在于,步骤1)焙烧工艺条件为:室温下以1~5℃/min的升温速率升温至500~600℃,保温3~8h。
8.根据权利要求3所述的钛掺杂介孔二氧化硅的制备方法,其特征在于,步骤2)所述介孔二氧化硅与异丙醇的质量体积比为1g/5~50mL;步骤2)所述介孔二氧化硅与钛酸四丁酯的质量比为1:0.1~10;步骤2)所述钛酸四丁酯与水的质量比为1:5~20。
9.根据权利要求3所述的钛掺杂介孔二氧化硅的制备方法,其特征在于,步骤2)锻烧工艺条件为:室温下以1~5℃/min的升温速率升温至200~500℃,保温2~6h。
10.一种权利要求1或2所述的钛掺杂介孔二氧化硅作为吸附剂在去除水中草甘膦方面的应用,其特征在于,具体使用方法为:将所述钛掺杂介孔二氧化硅加入含草甘膦的水体中,钛掺杂介孔二氧化硅的加入量为0.2~2g/L,调节体系pH值为1~13,搅拌处理5~1000min。
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