CN109126714B - 一种TiO2/SiO2-香蕉皮生物炭复合吸附材料及其制备方法 - Google Patents
一种TiO2/SiO2-香蕉皮生物炭复合吸附材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种TiO2/SiO2–香蕉皮生物炭复合吸附材料制备方法及其制成的吸附材料,其包括:将香蕉皮清洗,烘干,粉碎,过筛,得粉末状材料,与磷酸溶液混合振荡,过滤,烘干,制得磷酸改性香蕉皮粉末。采用溶胶凝胶法将TiO2和SiO2负载在改性的香蕉皮生物炭表面,制得TiO2/SiO2–香蕉皮生物炭复合吸附材料。本发明利用农业生产废弃物香蕉皮制备生物炭,原料丰富,变废为宝,且制备方法工艺简单,成本低,制得的复合吸附材料对除草剂二氯喹啉酸吸附效果显著,复合材料中具有光降解有机污染物的TiO2,在解决吸附能力的同时,可利用该复合吸附材料对二氯喹啉酸的吸附与光催化降解协同作用,更高效、快速、无污染地彻底吸附去除的同时降解该类有机污染物。
Description
技术领域
本发明涉及复合吸附材料,具体涉及一种TiO2/SiO2–香蕉皮生物炭复合吸附剂及其制备方法。
背景技术
随着我国城市化的加速发展,农村劳动力大量向城市转移,致使农村劳动力严重不足,加上近几年农村地区土地规模化种植经营加速,人工除草逐渐减少,化学除草日益被农民接受,因而我国除草剂需求量日益加大,除草剂作为重要的农业生产投入物资,能促进农业发展、减轻工作量,因而被广泛应用于农业和林业生产中。但除草剂的大量使用也带来一系列的环境问题,尤其是一些残留期较长的除草剂,给下茬作物生长带来不良影响,研究发现,发生药害的长残效除草剂性质稳定,在环境中很难降解,具有持久性、生物累积性和高毒性,对下茬作物产生药害的主要原因是其在土壤中的残留。目前,利用物理吸附法、化学解毒法及微生物降解法在一定程度上可缓解长残效除草剂对后茬作物药害的影响。物理吸附法主要是通过往污染土壤中添加吸附剂将污染物吸附纯化,减小其对作物的活性。物理吸附法虽能将土壤中污染物吸附在吸附剂载体上,但从根本上没有改变污染物的毒性,一旦对这些吸附材料处置不当,容易造成环境的二次污染,因此,亟需研发一种吸附去除同时能够降解有机污染物的吸附材料。
发明内容
本发明要解决的技术问题是,克服现有技术的不足,提供一种吸附容量高,吸附速度快的吸附材料,在解决吸附能力的同时加入光降解有机污染物的TiO2,使其能够更高效、无污染地吸附去除的同时降解有机污染物,并相应提供一种工艺简单,成本低廉的TiO2/SiO2–香蕉皮生物炭复合吸附剂的制备方法。
为解决上述技术问题,本发明提供了一种TiO2/SiO2–香蕉皮生物炭复合吸附材料的制备方法,其包括以下步骤:
1)将香蕉去肉后所得的香蕉皮用蒸馏水洗净,烘干,粉碎,过筛,制得香蕉皮粉末;
2)将步骤1)制得的香蕉皮粉末置于第一容器中,向该容器中加入100mL体积分数30%的磷酸,进行密封振荡,振荡频率为150r/min,温度为25℃,振荡时间为12h,再过滤,所得滤渣在100℃-105℃的烘箱中烘干,制得磷酸改性香蕉皮粉末;
3)在第二容器中依次加入150mL的无水乙醇、20mL钛酸四丁酯、2.5mL冰乙酸制备成TiO2溶胶,再将制备的TiO2溶胶慢慢滴入装有磷酸改性香蕉皮粉末的第一容器中并进行密封振荡,振荡频率为150r/min,温度为25℃,振荡时间为2h,然后向第一容器中加入用磷酸配制成的pH=2的蒸馏水2.5mL,继续进行密封振荡,振荡频率为150r/min,温度为25℃,振荡时间为4h,振荡完成后进行过滤,滤渣在100℃的烘箱中烘10h取出,并放在室温下老化48h,得固化物;
4)将步骤3)中制备所得到的固化物用坩埚盛放后置于马弗炉中500℃炭化2h,让马弗炉冷却至室温,得生物炭,按3g生物炭加入100mL浓度为1moL/L盐酸的标准在生物炭中加入盐酸后进行密封振荡,振荡频率为150r/min,温度为25℃,振荡时间为12h,抽滤,用蒸馏水洗至中性,而后滤渣在100℃的烘箱中烘干,时间为2h,室温冷却;
5)按0.5g二氧化硅加入40mL无水乙醇的标准在二氧化硅中加入无水乙醇,搅拌5min,得二氧化硅混合液,按二氧化硅与生物炭的质量比例为0.5:1的比例在步骤4制备所得的生物炭中均速滴入二氧化硅混合液,然后超声5min,之后进行密封振荡,振荡频率为150r/min,温度为25℃,振荡时间为12h,振荡完后进行过滤,滤渣在100℃的烘箱中烘干,即制得TiO2/SiO2–香蕉皮生物炭复合吸附材料。
上述方案中,所述香蕉皮用蒸馏水洗净,转移至烘箱中,在100℃条件下烘干,并用粉碎机粉碎,过100目筛。
为解决上述技术问题,本发明还提供了一种上述方法制备的TiO2/SiO2–香蕉皮生物炭复合吸附材料。
为解决上述技术问题,本发明还提供了一种上述方法制备的TiO2/SiO2–香蕉皮生物炭复合吸附材料在吸附去除溶液中有机污染物二氯喹啉酸中的应用,溶液中二氯喹啉酸的浓度为0-60mg/L可被吸附去除,去除率高达96%以上。
生物炭具有丰富的微孔和表面官能团结构及巨大的比表面积,导致其对有机污染物具有超强的吸附能力,土壤中添加生物炭,一方面将增强土壤对有机污染物的吸附、减小其生物有效性。然而,另一方面,生物炭可为土壤中的微生物提供氮、碳等其它微量元素,促进了土壤中微生物繁殖,从而加快土壤中有机污染物的生物降解。好的活性炭需要选择适合制备活性炭的原材料,原材料的好坏直接决定了制备的活性炭性能是否好,而好的原材料需要其本身结构多孔。
香蕉皮中主要含果胶、低聚糖、纤维素、半纤维素、木质素,另外,还含有总糖以及一些矿物质,角质。纤维素是香蕉皮中含量最高的成分,其含量达到了35%,而半纤维素和木质素的含量达到了15%,大量的纤维素、木质素和半纤维素存在,其特点在于内部结构疏松多孔,香蕉皮细胞中有许多气孔器和起支持作用的维管束,它们都是多孔结构,因此香蕉皮是制作活性生物炭的理想材料。
光催化是在一定波长光照条件下,半导体材料发生载流子的分离,然后光生电子和空穴再与离子或分子结合生成具有氧化性或还原性的活性自由基,这种自由基能将有机物大分子降解为CO2、H2O和其它无机小分子物质,在反应过程中这种半导体材料也是光催化剂,本身不会发生变化。理想的光催化技术是以半导体材料为光催化剂,利用自然界太阳光源的激发,使催化剂表面产生有效的活性物种,并且在多重转化和界面作用下达到降解环境中有害有机物质的目的。因光解最终矿化形成CO2、H2O和其它无机小分子物质,无附加二次污染的形成,是一种绿色环保的技术。我们知道实现光催化技术的关键环节在于良好光催化剂的设计与合成,性能优良的光催化剂可以在太阳光下激发,通过一系列的物理化学作用,产生强氧化性的自由基,进而实现有机污染物质的降解及矿化。半导体金属氧化物在降解有机污染物领域具有较大的发展潜力。常用的光催化剂有SnO2、ZnO、ZnS及TiO2等,其中TiO2具有较高的光催化活性、物理化学性质稳定、廉价易得、反应后不产生二次污染而受到广大科学研究者的青睐。但是TiO2粒子具有较大禁带宽度(锐钛矿3.2eV,金红石3.0eV),在光催化作用时,只能利用波长较短、能量较高的紫外光,高温处理后容易团聚,以及产生的光生电子-空穴复合率高,严重影响着对太阳能的利用率。因此扩大TiO2对可见光的响应范围,抑制粒子之间的团聚,提高光生电子-空穴对的分离效率,在提高光催化性能过程中起着重要的作用。
本发明通过掺杂改性、复合、负载等方法制备具有较高光催化活性和稳定性的复合光催化剂,利用SiO2对TiO2进行掺杂改性,提高其比表面积,形成锐钛矿型结构,提高其光催化性能,且制成的复合催化剂TiO2-SiO2既具有大的比表面积和大的体积,又有较好的热稳定性,将复合催化剂TiO2-SiO2和香蕉皮生物炭复合,使两者的优点相结合,可以提高活性炭的吸附选择性和再生效果,进而提高其光催化效率。
与现有技术相比,本发明具有以下优点:
1.本发明使用的生物炭原料为香蕉皮,其来源广泛、成本低廉,可使香蕉皮废弃物变废为宝,实现香蕉皮的资源化利用。
2.本发明制备工艺简单,制备过程环境友好,生产过程不会产生二次污染,制备不需要特殊设备和严酷反应条件,易于工业化生产。
3.本发明制备的TiO2/SiO2–香蕉皮生物炭复合材料吸附溶液中的二氯喹啉酸,去除率达96%以上,吸附效果好,同时还能光降解二氯喹啉酸,使其能够利用吸附与光催化降解协同作用,更高效、无污染地吸附去除的同时降解有机污染物。
附图说明
图1为本发明制备的TiO2/SiO2–香蕉皮生物炭复合吸附材料在放大倍数为2000下的扫描电镜图。
图2为本发明制备的TiO2/SiO2–香蕉皮生物炭复合吸附材料在放大倍数为11000下的扫描电镜图。
图3为本发明制备的TiO2/SiO2–香蕉皮生物炭复合吸附材料的XRD衍射电镜图。
图4为本发明制备的TiO2/SiO2–香蕉皮生物炭复合吸附材料的红外光谱图。
图5为本发明实施例中制得的TiO2/SiO2–香蕉皮生物炭复合吸附材料对不同初始浓度值下水溶液中二氯喹啉酸的吸附影响变化图。
具体实施方式
以下结合说明书附图和具体优选的实施例对本发明作进一步描述,但并不因此而限制本发明的保护范围。
实施例1
一种TiO2/SiO2–香蕉皮生物炭复合吸附材料的制备方法,包括以下步骤:
(1)将1.5kg香蕉去肉后所得的香蕉皮用蒸馏水洗净,转移至烘箱中,在100℃条件下烘干,用万能粉碎机进行粉碎,过100目筛子,制得香蕉皮粉末。
(2)将步骤(1)制得的香蕉皮粉末置于具塞三角瓶中,向具塞三角瓶中加入100mL体积分数30%的磷酸,进行加塞密封振荡,振荡频率为150r/min,温度为25℃,振荡时间为12h,过滤,所得滤渣在100℃-105℃的烘箱中烘干,制得磷酸改性香蕉皮粉末。
(3)将步骤(2)制得的磷酸改性香蕉皮粉末全部转移至具塞三角瓶中,另取一烧杯,向烧杯中先加入150mL的无水乙醇,然后加入20mL钛酸四丁酯,最后往烧杯中加入2.5mL冰乙酸,制备成TiO2溶胶,将烧杯中的TiO2溶胶混合液慢慢滴入装有磷酸改性香蕉皮粉末的具塞三角瓶中,加塞进行密封振荡,振荡频率为150r/min,温度为25℃,振荡时间为2h。然后向具塞三角瓶中加入用磷酸配制成pH=2的蒸馏水2.5mL,然后继续进行密封振荡,振荡频率为150r/min,温度为25℃,振荡时间为4h,振荡完后进行过滤,滤渣在100℃的烘箱中烘10h取出,然后放在室温下老化2d。
(4)将上述步骤(3)中制备所得到的固化物用坩埚盛放,然后置于马弗炉中500℃炭化2h,马炉冷却至室温,取3g炭化的生物炭置于锥形瓶中,向其加入100mL 1moL/L盐酸,进行密封振荡,振荡频率为150r/min,温度为25℃,振荡时间为12h,抽滤,用蒸馏水洗至中性,而后滤渣在100℃的烘箱中烘干,时间为2h,室温冷却。
(5)称量0.5g二氧化硅,置于烧杯中,再往其中加入40mL无水乙醇,搅拌5min,取上述步骤4制备所得的生物炭1g于锥形瓶中(二氧化硅与生物炭的质量比例为0.5:1),将烧杯中的配制好的二化硅混合液均速滴入装有上述步骤(4)制备所得的生物炭的锥形瓶中,然后超声5min,之后进行密封振荡,振荡频率为150r/min,温度为25℃,振荡时间为12h,振荡完后进行过滤,滤渣在100℃的烘箱中烘干,即制得TiO2/SiO2–香蕉皮生物炭复合吸附材料。如图1和图2所示该复合吸附剂表面结构不规则,为不定型块状,表面存在一些不均一小颗粒,总体呈层叠、多坑、多孔结构,该结构有利于对污染物的吸附和截留,该复合吸附剂的元素利用Thermo scientific公司移动座式X荧光元素分析仪对香蕉皮生物炭和TiO2/SiO2–香蕉皮生物炭复合材料组成元素进行了检测,结果如表1所示。
表1TiO2/SiO2–香蕉皮生物炭复合材料负载改性前后主要元素变化
通过对TiO2/SiO2–香蕉皮生物炭复合材料进行负载改性前后的元素变化,发现负载改性后Si元素由改性前的0.532%提高到11.756%,Ti元素由改性前0.011%,提高到9.131%,利用X-射线衍射分析仪(XRD)和傅里叶变换红外光谱仪(FT—IR)检结果如图3和图4所示,也发现明显的Si、Ti的尖锐峰,说明TiO2/SiO2被成功地负载到在香蕉皮生物炭内。经测定,该TiO2/SiO2–香蕉皮生物炭复合材料的有机碳含量2690.730,总孔容为24.899cm3/g,比表面积为108.389m2/g,平均孔径为0.162nm2。
为考察本发明的TiO2/SiO2–香蕉皮生物炭复合材料的吸附效果,进行了以下实验:
将上述方法中制备所得的TiO2/SiO2–香蕉皮生物炭复合材料以10.00g·L-1的投加量置于离心管中,分别加入20.00mL初始浓度为0、5、10、20、30、40、50、60mg·L-1的二氯喹啉酸溶液,于恒温振荡器(150r·min-1,25℃)中振荡24h后离心,取上清液经0.45μm滤膜过滤后供HPLC分析,空白实验结果表明,吸附过程中二氯喹啉的降解及离心管对其的吸附可以忽略不计,每个实验平行3次。吸附量和去除率分别按公式(1)、(2)计算:
吸附量q=(C0-Ce)×V m (1)
去除率=(C0-Ce)C0×100% (2)
式中:q为吸附剂对二氯喹啉酸的吸附容量,mg·g-1;C0、Ce分别为初始时刻、平衡时溶液中二氯喹啉酸的浓度,mg·L-1;V为二氯喹啉酸溶液体积,mL;m为吸附剂质量,g。
经测定,在一定浓度范围内(5-60mg·L-1),本发明吸附复合材料对二氯喹啉酸的吸附量随二氯喹啉酸的初始浓度的升高而增大,当初始浓度为5-30mg·L-1时,去除率达100%,初始浓度为40-60mg·L-1时,去除率达96%以上(见图5),显著大于已有的报道,说明本发明的吸附复合材料对二氯喹啉酸的处理有非常大的潜力。
以上所述仅是本发明的优选实施方式,并非对本发明任何形式上的限制。任何熟悉本领域的技术人员,在不脱离本发明的精神实质和技术方案的情况下,都可利用上述揭示的方法和技术内容对本发明技术方案做出许多可能的变动和修饰,皆应属本发明的涵盖范围。
Claims (4)
1.一种用于降解二氯喹啉酸的TiO2/SiO2–香蕉皮生物炭复合吸附材料的制备方法,其特征在于包括以下步骤:
1)将香蕉去肉后所得的香蕉皮用蒸馏水洗净,烘干,粉碎,过筛,制得香蕉皮粉末;
2)将步骤1)制得的香蕉皮粉末置于第一容器中,向该容器中加入100mL体积分数30%的磷酸,进行密封振荡,振荡频率为150r/min,温度为25℃,振荡时间为12h,再过滤,所得滤渣在100℃-105℃的烘箱中烘干,制得磷酸改性香蕉皮粉末;
3)在第二容器中依次加入150mL的无水乙醇、20mL钛酸四丁酯、2.5mL冰乙酸制备成TiO2溶胶,再将制备的TiO2溶胶慢慢滴入装有磷酸改性香蕉皮粉末的第一容器中并进行密封振荡,振荡频率为150r/min,温度为25℃,振荡时间为2h,然后向第一容器中加入用磷酸配制成的pH=2的蒸馏水2.5mL,继续进行密封振荡,振荡频率为150r/min,温度为25℃,振荡时间为4h,振荡完成后进行过滤,滤渣在100℃的烘箱中烘10h取出,并放在室温下老化48h,得固化物;
4)将步骤3)中制备所得到的固化物用坩埚盛放后置于马弗炉中500℃炭化2h,让马弗炉冷却至室温,得生物炭,按3g生物炭加入100mL浓度为1moL/L盐酸的标准在生物炭中加入盐酸后进行密封振荡,振荡频率为150r/min,温度为25℃,振荡时间为12h,抽滤,用蒸馏水洗至中性,而后滤渣在100℃的烘箱中烘干,时间为2h,室温冷却;
5)按0.5g二氧化硅加入40mL无水乙醇的标准在二氧化硅中加入无水乙醇,搅拌5min,得二氧化硅混合液,按二氧化硅与生物炭的质量比例为0.5:1的比例在步骤4制备所得的生物炭中均速滴入二氧化硅混合液,然后超声5min,之后进行密封振荡,振荡频率为150r/min,温度为25℃,振荡时间为12h,振荡完后进行过滤,滤渣在100℃的烘箱中烘干,即制得TiO2/SiO2–香蕉皮生物炭复合吸附材料。
2.根据权利要求1所述的一种用于降解二氯喹啉酸的TiO2/SiO2–香蕉皮生物炭复合吸附材料的制备方法,其特征在于,所述香蕉皮用蒸馏水洗净,转移至烘箱中,在100℃条件下烘干,并用粉碎机粉碎,过100目筛。
3.一种权利要求1-2中任一项方法制备的TiO2/SiO2–香蕉皮生物炭复合吸附材料。
4.一种权利要求1-2中任一项方法制备的TiO2/SiO2–香蕉皮生物炭复合吸附材料在吸附去除二氯喹啉酸中的应用。
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CN101585532A (zh) * | 2009-06-08 | 2009-11-25 | 浙江工业大学 | 一种利用生物质残渣制备高比表面微孔碳材料的方法 |
CN101856620A (zh) * | 2010-05-20 | 2010-10-13 | 浙江大学 | 一种改性固体酸催化剂的制备方法及其制备的催化剂 |
CN105688875A (zh) * | 2016-01-11 | 2016-06-22 | 湖南大学 | 一种生物炭负载TiO2复合材料及其制备方法与用途 |
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101585532A (zh) * | 2009-06-08 | 2009-11-25 | 浙江工业大学 | 一种利用生物质残渣制备高比表面微孔碳材料的方法 |
CN101856620A (zh) * | 2010-05-20 | 2010-10-13 | 浙江大学 | 一种改性固体酸催化剂的制备方法及其制备的催化剂 |
CN105688875A (zh) * | 2016-01-11 | 2016-06-22 | 湖南大学 | 一种生物炭负载TiO2复合材料及其制备方法与用途 |
Non-Patent Citations (2)
Title |
---|
Direct and indirect photolysis of two quinolinecarboxylic herbicides in aqueous systems;Maria Vittoria Pinna等;《Chemosphere》;20111130;摘要 * |
硅胶负载氯掺杂二氧化钛光催化剂的水热制备与光催化活性评价;邓培昌等;《物理化学学报》;20100430;第920页第3段 * |
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