CN114950358A - 一种锰钛氧化物-生物质炭复合材料及其制备方法和应用 - Google Patents
一种锰钛氧化物-生物质炭复合材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种锰钛氧化物‑生物质炭复合材料,由生物质炭、二氧化锰颗粒和二氧化钛颗粒构成,所述二氧化锰颗粒均匀分布在生物质炭上,所述二氧化钛颗粒均匀分布在生物炭和二氧化锰颗粒上。本发明还公开了上述锰钛氧化物‑生物质炭复合材料的制备方法和其作为吸附剂用于吸附去除水体中染料罗丹明B的应用。本发明的锰钛氧化物‑生物质炭复合材料具有低成本、吸附快、稳定性好的优点,是一种优良的吸附材料,具有较好的应用前景。
Description
技术领域
本发明涉及吸附材料技术领域,尤其涉及一种锰钛氧化物-生物质炭复合材料及其制备方法和应用。
背景技术
伴随着人口增长、全球变暖、工业化生产的快速发展从而直接造成水资源污染严重,造成人类饮水问题。有机染料具有完整色谱、颜色亮丽、牢固性能好广泛应用于纺织、印染、化妆品等大型工业生产中,如果染料废水未经处理就排放到水中,造成植物的光合作用降低影响其生长,同时会造成水体生物和农作物吸收从而对人体致癌。其中,罗丹明B(Rhodamine B),又称若丹明B、玫瑰红B、玫瑰精B、碱性玫瑰精,分子式为C28H31ClN2O3,是一种具有鲜桃红色的人工合成的染料。易溶于水、乙醇,微溶于丙酮、氯仿、盐酸和氢氧化钠溶液。呈红色至紫罗兰色粉末,水溶液为蓝红色,稀释后有强烈荧光,醇溶液有红色荧光。常用作实验室中细胞荧光染色剂、广泛应用于有色玻璃、特色烟花爆竹等行业。它也和苏丹红一样会直接危害人体健康,具有潜在的致癌、致突变性和心脏毒性。
吸附法操作简便、绿色环保、价格低廉、去除效果好等特点,目前为去除废水中染料的有效方法之一。但是,多数的活性炭对废水中染料的吸附性能一般且价格高。因此,制备吸附性优良且价格便宜的吸附剂对含染料废水的处理有着重要意义。
发明内容
基于背景技术存在的技术问题,本发明提出了一种锰钛氧化物-生物质炭复合材料及其制备方法和应用。
本发明提出的一种锰钛氧化物-生物质炭复合材料,由生物质炭、二氧化锰颗粒和二氧化钛颗粒构成,所述二氧化锰颗粒均匀分布在生物质炭上,所述二氧化钛颗粒均匀分布在生物炭和二氧化锰颗粒上;
所述二氧化锰颗粒为多孔球形或半球形结构,粒径为3-8μm;所述二氧化钛颗粒的粒径为1-2μm。
优选地,所述复合材料中,炭、二氧化锰与二氧化钛的摩尔比为1:(1-3):(1-2)。
优选地,所述生物质炭是以香蕉皮为原料经过高温炭化制得;优选地,所述高温炭化的温度为300-400℃,时间为2-4h。
优选地,将香蕉皮清洗、干燥后,酸化活化,然后在300-400℃下高温炭化2-4h,研磨成粉末后中和酸化,然后过滤,洗涤至中性,干燥,即得。
优选地,所述酸化活化的具体方法为:加入盐酸溶液浸泡处理,所述盐酸的浓度为4-8mol/L,浸泡处理时间为10-20h;所述中和酸化的具体方法为:加入氢氧化钠溶液搅拌反应,所述氢氧化钠溶液的浓度为4-8mol/L,搅拌反应时间为2-4h。
一种所述的锰钛氧化物-生物质炭复合材料的制备方法,包括下述步骤:
S1、称取生物质炭、二氧化钛和二氧化锰,加入盐酸溶液将二氧化钛和二氧化锰溶解完全,然后加入氢氧化钠溶液搅拌反应将pH调至中性,得到反应液;
S2、将所述反应液进行水热反应,即得。
优选地,S1中,所述盐酸溶液的浓度为1-5mol/L。
优选地,S1中,加入浓度为1-5mol/L氢氧化钠溶液搅拌反应2-4h将pH调至中性。
优选地,S2中,水热反应的条件为:温度为120-180℃,时间为24-72h。
所述的锰钛氧化物-生物质炭复合材料作为吸附剂在吸附去除水体中染料罗丹明B的应用。
本发明的有益效果如下:
本发明以MnO2为锰源,生物质炭和TiO2进行复合改性,通过水热合成法制备锰钛氧化物-生物质炭复合材料,该三元复合材料对染料罗丹明B具有优异的吸附性能,可以作为吸附去除水体中的染料罗丹明B的吸附剂,吸附性优良且价格便宜,有助于染料废水吸附剂应用的产业化。
附图说明
图1为本发明实施例中制备的生物质炭和锰钛氧化物-生物质炭复合材料的SEM图。
图2为本发明实施例中制备的锰钛氧化物-生物质炭复合材料的BET吸附与解吸附曲线。
图3为本发明实施例中制备的锰钛氧化物-生物质炭复合材料的XRD图。
图4为本发明实施例中制备的生物质炭和锰钛氧化物-生物质炭复合材料对水体中染料罗丹明B的吸附曲线。
图5为本发明实施例中制备的生物质炭和锰钛氧化物-生物质炭复合材料对水体中染料罗丹明B的拟一级动力学方程拟合曲线。
图6为本发明实施例中制备的生物质炭和锰钛氧化物-生物质炭复合材料对水体中染料罗丹明B的拟二级动力学方程拟合曲线。
图7为本发明锰钛氧化物-生物质炭复合材料吸附罗丹明B的机理图。
具体实施方式
下面,通过具体实施例对本发明的技术方案进行详细说明。
实施例1
制备生物质炭:
取一定量的香蕉皮用去离子水洗净、切块,在烘箱中于105℃下干燥8h,用100mL浓度为6mol/L的盐酸溶液浸泡12h,然后取出放入坩埚中,在马弗炉中于360℃下煅烧3h,自然冷却至室温,研磨均匀后将得到的粉末置于100mL浓度为6mol/L的氢氧化钠溶液中搅拌反应3h,抽滤、洗涤至中性,最后在烘箱中于105℃下干燥12h,得到生物质炭。
制备锰钛氧化物-生物质炭复合材料:
称取一定量上述制得的生物质炭和一定量的TiO2、MnO2,用25mL浓度为3mol/L的盐酸溶液浸泡6h完全溶解,然后加入30mL浓度为3mol/L的氢氧化钠溶液,搅拌反应3h,再置于反应釜中,在烘箱中于160℃下水热反应48h,冷却至室温后抽滤、洗涤至中性,于105℃下干燥6h,得到锰钛氧化物-生物质炭复合材料;按照上述制备方法得到的锰钛氧化物-生物质炭复合材料,由生物质炭、二氧化锰颗粒和二氧化钛颗粒构成,二氧化锰颗粒均匀分布在生物质炭上,二氧化钛颗粒均匀分布在生物炭和二氧化锰颗粒上;其中二氧化锰颗粒为多孔球形或半球形结构,粒径为3-8μm;所述二氧化钛颗粒的粒径为1-2μm。
按照上述制备方法分别制得锰钛氧化物-生物质炭复合材料中,炭、二氧化锰与二氧化钛的摩尔比为1:1:1的样品记为1:1:1(Mn-Ti-C),炭、二氧化锰与二氧化钛的摩尔比为1:2:1的样品记为1:2:1(Mn-Ti-C),炭、二氧化锰与二氧化钛的摩尔比为1:3:1的样品记为1:3:1(Mn-Ti-C)。制得的活性炭样品记为C。
图1为本发明实施例中制备的生物质炭和锰钛氧化物-生物质炭复合材料的SEM图。其中,图1a为生物质炭,图1b为1:3:1(Mn-Ti-C),图1c为1:2:1(Mn-Ti-C),图1d为1:1:1(Mn-Ti-C)。由图1可知,由SEM图1a、b、c、d可以看到因复合比例的锰氧化物逐渐变成“球形或半球形”结构,一些区域出现带球核壳结构的形貌,均匀的分布在生物质炭上,具有多孔结构,有相对较大的比表面积。并且表面有着白色的颗粒物质,非常均匀的分布在锰氧化物表面,说明了TiO2成功的负载在锰氧化物的表面,有利于对污染物吸附。为锰氧化物提供了活性点位,当锰氧化物添加量过大会导致复合材料的活性降低从而降低吸附效率。
图2为本发明实施例中制备的锰钛氧化物-生物质炭复合材料的BET吸附与解吸附曲线。通过BET检测发现锰钛氧化物-生物质炭复合材料样品1:1:1(Mn-Ti-C)的比表面积为27.627m2/g,孔隙直径为2.403nm,孔体积为0.110cm3/g。通过BET数据易知本发明制备的锰钛氧化物-生物质炭复合材料的比表面积的孔径较大,能够有效的提供吸附点位,有利于罗丹明B的去除。由图2吸附曲线可以看出曲线出现磁带现象,并且孔径的分布非常均匀。主要是介孔组成。
图3为本发明实施例中制备的锰钛氧化物-生物质炭复合材料的XRD图。由图3可知,生物质炭在(111)晶面有个很明显的衍射峰,TiO2在(211)、(301)晶面上有着明显的衍射峰,说明复合材料有TiO2晶体组分。MnO2在(220)晶面上有着明显的衍射峰,且强度较高,结晶度较好,有利于物质活性的体现。TiO2-MnO2的结合物在(521)晶面处有着明显的衍射峰,说明复合材料表面有着锰钛氧化物的结合物。Ti-C在(311)晶面处有着明显的衍射峰,Mn-C在(200)晶面处有着明显的衍射峰,综上所述三者有效复合并且有着明显的衍射峰,结晶度较好,有利于物质催化吸附活性的体现。
分别以本发明制备的锰钛氧化物-生物质炭复合材料样品1:1:1(Mn-Ti-C)、1:2:1(Mn-Ti-C)、1:3:1(Mn-Ti-C),以及生物质炭为吸附剂,对罗丹明B进行吸附试验,具体如下:量取100mL浓度为100mg/L的罗丹明B溶液于250mL的锥形瓶中,加入0.5g吸附剂,在超声波中超声15min后取出,在25℃避免光照的通风橱中进行吸附6h,再进行取样、离心,表征在554nm处离心分离后罗丹明B上清液的浓度,重复实验3次。计算吸附率,结果如图4所示。
图4为本发明实施例中制备的生物质炭和锰钛氧化物-生物质炭复合材料对水体中染料罗丹明B的吸附曲线。如图4所示,当吸附1h后,不同配比生物质炭复合材料和生物炭分别基本达到吸附平衡,锰钛氧化物-生物质炭复合材料样品1:1:1(Mn-Ti-C)的吸附去除率最高,达到平衡时间也最短。因此,在去除染料废水时,若用量比例均匀时,可以有效地缩短平衡时间,从而提高复合材料对罗丹明B的去除率。伴随着吸附时间的变化,当吸附时间为1h时,生物质炭的吸附去除率为90.46%,锰钛氧化物-生物质炭复合材料样品1:1:1(Mn-Ti-C)的去除率为98.27%、样品1:2:1(Mn-Ti-C)的去除率为91.48%、样品1:3:1(Mn-Ti-C)的去除率为96.74%。时间越长,吸附去除率也在缓慢增大直至达到吸附平衡。所以,总体上对罗丹明B的吸附去除率是增大的。可以看出,本发明制备的复合材料吸附罗丹明B的吸附效果明显高于单独的生物质炭。
拟一级动力学方程对上式积分,并代入t=0,qt=0;t=t,qt=qt可得:ln(qe-qt)=-k1t+lnqe;式中的qe代表的是吸附剂对罗丹明B的平衡吸附量(mg·g-1);qt代表的是t时刻吸附剂对罗丹明B的吸附量(mg·g-1);k1(min-1)为拟一级动力学的吸附速率常数。
图5为本发明实施例中制备的生物质炭和锰钛氧化物-生物质炭复合材料对水体中染料罗丹明B的拟一级动力学方程拟合曲线,图6为本发明实施例中制备的生物质炭和锰钛氧化物-生物质炭复合材料对水体中染料罗丹明B的拟二级动力学方程拟合曲线。从图5和图6中线性相关系数可知拟二级动力学对平衡数据拟合的最好(R2=0.9945),这说明罗丹明B在吸附剂上的吸附过程主要由化学吸附控制。拟二级动力学模型包含液膜扩散、表面吸附过程和颗粒内部扩散过程等,能较为真实地反映罗丹明B在吸附剂上的吸附机理。
锰钛氧化物-生物质炭复合材料吸附罗丹明B的机理图如图7所示。一方面,锰钛氧化物-生物质炭复合材料中的生物质炭表面的含有较多的羟基和羧基通过静电作用和氢键作用吸附罗丹明B。又因为罗丹明B本身是一种环状芳香型的分子,从而会发生耦合反应形成π-π共轭健相互作用和其他相互作用从而促进对罗丹明B的吸附但是对罗丹明B的吸附具有次要作用。另一方面,吸附的罗丹明B分子被二氧化锰、二氧化钛分解氧化成二氧化碳和其他分子。所以,锰钛氧化物-生物质炭复合材料对罗丹明B的吸附过程既具有氧化分解又具有静电吸附。除此之外,整个吸附过程中还伴随着分子间的范德华力的过程。因此,通过利用废弃的生物质与金属氧化物制备廉价高效复合吸附剂,是有效去除废水中环境污染物的重要途径之一。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种锰钛氧化物-生物质炭复合材料,其特征在于,由生物质炭、二氧化锰颗粒和二氧化钛颗粒构成,所述二氧化锰颗粒均匀分布在生物质炭上,所述二氧化钛颗粒均匀分布在生物炭和二氧化锰颗粒上;
所述二氧化锰颗粒为多孔球形或半球形结构,粒径为3-8μm;所述二氧化钛颗粒的粒径为1-2μm。
2.根据权利要求1所述的锰钛氧化物-生物质炭复合材料,其特征在于,所述复合材料中,炭、二氧化锰与二氧化钛的摩尔比为1:(1-3):(1-2)。
3.根据权利要求1所述的锰钛氧化物-生物质炭复合材料,其特征在于,所述生物质炭是以香蕉皮为原料经过高温炭化制得;优选地,所述高温炭化的温度为300-400℃,时间为2-4h。
4.根据权利要求1所述的锰钛氧化物-生物质炭复合材料,其特征在于,所述生物质炭的制备方法为:将香蕉皮清洗、干燥后,酸化活化,然后在300-400℃下高温炭化2-4h,研磨成粉末后中和酸化,然后过滤,洗涤至中性,干燥,即得。
5.根据权利要求4所述的锰钛氧化物-生物质炭复合材料,其特征在于,所述酸化活化的具体方法为:加入盐酸溶液浸泡处理,所述盐酸的浓度为4-8mol/L,浸泡处理时间为10-20h;所述中和酸化的具体方法为:加入氢氧化钠溶液搅拌反应,所述氢氧化钠溶液的浓度为4-8mol/L,搅拌反应时间为2-4h。
6.一种如权利要求1-5任一项所述的锰钛氧化物-生物质炭复合材料的制备方法,其特征在于,包括下述步骤:
S1、称取生物质炭、二氧化钛和二氧化锰,加入盐酸溶液将二氧化钛和二氧化锰溶解完全,然后加入氢氧化钠溶液搅拌反应将pH调至中性,得到反应液;
S2、将所述反应液进行水热反应,即得。
7.根据权利要求6所述的锰钛氧化物-生物质炭复合材料的制备方法,其特征在于,S1中,所述盐酸溶液的浓度为1-5mol/L。
8.根据权利要求6所述的锰钛氧化物-生物质炭复合材料的制备方法,其特征在于,S1中,加入浓度为1-5mol/L氢氧化钠溶液搅拌反应2-4h将pH调至中性。
9.根据权利要求6所述的锰钛氧化物-生物质炭复合材料的制备方法,其特征在于,S2中,水热反应的条件为:温度为120-180℃,时间为24-72h。
10.权利要求1-5任一项所述的锰钛氧化物-生物质炭复合材料作为吸附剂在吸附去除水体中染料罗丹明B的应用。
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