CN111250089A - 一种膨润土芬顿磁性催化剂及其制备方法 - Google Patents
一种膨润土芬顿磁性催化剂及其制备方法 Download PDFInfo
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 38
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- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 12
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 12
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种膨润土芬顿磁性催化剂及其制备方法,属于无机功能材料技术领域,以改性膨润土为负载基体,负载磁性四氧化三铁纳米颗粒,所述四氧化三铁纳米颗粒负载于所述改性膨润土的层间和孔隙;本发明以改性膨润土为主体,负载磁性四氧化三铁纳米颗粒,同时对其制备工艺参数进行了研究,制备出的膨润土芬顿磁性催化剂具有疏松的孔径结构,内外表层均被撑大,提高了对甲基橙的去除效果,有利于对甲基橙的吸附。
Description
技术领域
本发明涉及无机功能材料技术领域,特别是涉及一种膨润土芬顿磁性催化剂及其制备方法。
背景技术
近年来,我国的纺织印染工业迅猛发展,产生了大量亟需处理的染料废水。一般化学染料往往具有耐酸、耐碱、难降解等特性,影响水生动植物的基因遗传,严重威胁其生存,还有可能威胁人类的生命。
膨润土(Bentonite)作为我国储量丰富的粘土矿物资源之一,价格低廉,具有极大的开发利用及研究价值。膨润土主要由含水层状硅铝酸盐构成,基本性能由蒙脱石的特殊结构决定。蒙脱石的结构决定了膨润土的脱色性、稳定性、离子交换性、吸附性、悬浮性等,膨润土的内比表面积为600-800m2/g,吸水后的膨润土体积能增大10-30倍,对染料具有一定的吸附性能;但是未经改性的天然膨润土(Raw Bentonite,RB)对染料的吸附性能较差,且其在水中较强的分散性也使吸附后的膨润土难以实现有效的固液分离,因此必须对膨润土进行有机改性或负载Fe3O4等磁性物质,以提高其吸附性能和固液分离能力。
磁性载体是指将分散性能良好的强磁性物质覆盖或引入到非磁性或着弱磁性材料的表面或内部,进而形成具有一定磁饱和强度的复合材料,其在外加磁场的作用下可以快速固液分离从而回收再利用。纳米Fe3O4颗粒是较为常见的磁性材料之一,其合成工艺简单,拥有良好的磁分离性能,而且纳米Fe3O4颗粒本身具备一定的吸附能力。但是,纳米Fe3O4颗粒易团聚,易氧化,性能不稳定,而膨润土在水体中具有良好的分散性,因此,将膨润土和纳米Fe3O4颗粒相结合,制备磁性膨润土(Magnetic bentonite,MB),不仅能够解决纳米Fe3O4颗粒易团聚,易氧化,性能不稳定的问题,还能提高膨润土的固液分离能力,同时能在一定程度上提高其对染料的吸附能力:王迎亚等用沉淀法制备出纳米Fe3O4颗粒,然后将其附着在碱性钙基膨润土上,再用柠檬酸进行改性,制备出磁性柠檬酸膨润土的复合物,其磁分离效果好,且对Cr(VI)具有良好的吸附效果;任爽等在膨润土悬浮液中加入Fe2(SO4)3和FeSO4,再加入阴(阳)离子复配修饰剂,制备出阴(阳)离子复配修饰两性磁性膨润土,复合物的比表面积和孔容空径明显增大,对苯酚的吸附效果也明显上升,吸附容量达到了491.61mg/g。
现有技术公开了一种新型的四氧化三铁-改性膨润土(Fe3O4-BT)催化剂,其甲基橙的60min脱色率在96.72%左右。但其四氧化三铁的纳米粒子主要存在于改性膨润土的表面和最外层的孔隙中,大部分位于膨润土的表面。这样的结构虽然一定程度上提高了膨润土的分离能力,但表面的纳米四氧化三铁颗粒很容易被氧化而失去部分磁性,因此,单纯的表层结构的纳米四氧化三铁负载修饰的膨润土不仅对染料的吸附效果提升不多,而且由于其磁性易被氧化,所以固液分离效果也不好。
发明内容
本发明的目的是提供一种膨润土芬顿磁性催化剂及其制备方法,以解决上述现有技术存在的问题。
为实现上述目的,本发明提供了如下方案:
本发明提供一种膨润土芬顿磁性催化剂,以改性膨润土为负载基体,负载磁性四氧化三铁纳米颗粒,所述四氧化三铁纳米颗粒负载于所述改性膨润土的层间和孔隙。
进一步地,所述膨润土芬顿磁性催化剂的层间距为1.35-1.58nm,孔径为6.25-6.85nm,孔容为0.48-0.52cm3/g,在300-700℃可保持较好的热稳定性;饱和磁化强度值在25.34-34.28emu/g,在外加磁场作用下2-4s可实现固液分离,在强酸、强碱中微溶。
本发明还提供一种上述的膨润土芬顿磁性催化剂的制备方法,采用水热反应用以合成四氧化三铁/改性膨润土。
进一步地,所述方法包括以下步骤:
将六水合三氯化铁、乙酸钠以及聚乙二醇200的混合物在乙二醇里均匀搅拌,形成均匀溶液;
改性膨润土和环氧氯丙烷被添加入均匀溶液里,不断搅拌;
混合物加热反应,之后将其冷却至室内温度,形成黑色溶液;
经过滤后,用蒸馏水/乙醇冲洗沉淀物,干燥,最后获得膨润土芬顿磁性催化剂。
再进一步地,所述方法包括以下步骤:
(1)将2.16克的六水合三氯化铁、5.76克的乙酸钠以及1.6克的聚乙二醇200的混合物在60毫升的乙二醇里被均匀搅拌18分钟,形成均匀溶液;
(2)将0.5克的改性膨润土和1毫升的环氧氯丙烷添加入均匀溶液里;在43℃下,搅拌1.5小时;
(3)将混合物转移至一个100毫升的高压釜加热至200℃反应9小时,之后将其冷却至室内温度,形成黑色溶液;
(4)经过滤后,用蒸馏水/乙醇(V:V,1:1)冲洗沉淀物,在真空73℃下使其干燥,最后获得膨润土芬顿磁性催化剂。
本发明公开了以下技术效果:
本发明以改性膨润土为主体,负载磁性四氧化三铁纳米颗粒,同时对其制备工艺参数进行了研究,制备出的膨润土芬顿磁性催化剂具有疏松的孔径结构,内外表层均被撑大,提高了对甲基橙的去除效果,原因在于:改性膨润土表面具有大量的OH-,而磁性四氧化三铁纳米颗粒表面含有NH3 +、NH2 +及H+等离子,这些离子通过静电吸引作用与改性膨润土结合,并负载于改性膨润土层间或孔隙内;特殊选择的制备参数使得磁性四氧化三铁纳米颗粒插入改性膨润土的层边缘,改善了改性膨润土的表面孔隙结构,因而可以在一定程度上使改性膨润土的孔径增大,形成介孔材料,提高吸附能力,有利于对甲基橙的吸附。
本发明所制备的膨润土芬顿磁性催化剂的层间距为1.58nm,孔径为6.85nm,孔容为0.52cm3/g,在700℃仍可保持较好的热稳定性;饱和磁化强度值为34.28emu/g,在外加磁场作用下2s可实现固液分离,在强酸、强碱中微溶;四氧化三铁纳米颗粒进入了膨润土层间或孔隙,没有负载于膨润土表面,这种结构有利于为芬顿反应提供稳定的铁源,提高膨润土的吸附性,同时提高其磁响应性,提高固液分离效果。
Fe3O4纳米粒子作为一种超顺磁性氧化物,具有可控的形状和尺寸,并且由于晶格内八面体位置的Fe2+和Fe3+之间发生电子传递,产生独特的电和磁特性,使用Fe3O4纳米粒子具有巨大的应用前景,广泛应用于铁磁流体、生物医学、磁共振成像(MRI)、磁分离等各个领域。但同时Fe3O4纳米粒子极易聚集,极大地阻碍了其应用,而本发明将Fe3O4纳米粒子负载于膨润土层间和孔隙,则避免了该问题,同时大幅提高了膨润土的吸附性能和固液分离效果。
具体实施方式
现详细说明本发明的多种示例性实施方式,该详细说明不应认为是对本发明的限制,而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。
应理解本发明中所述的术语仅仅是为描述特别的实施方式,并非用于限制本发明。另外,对于本发明中的数值范围,应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。
除非另有说明,否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料,但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入,用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时,以本说明书的内容为准。
在不背离本发明的范围或精神的情况下,可对本发明说明书的具体实施方式做多种改进和变化,这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见得的。本申请说明书和实施例仅是示例性的。
本发明所有原料均为商购。所述改性膨润土是购买自中国辽宁省黑山万城膨润土有限公司。在使用前,改性膨润土样品被研磨并通过一个120目筛。其阳离子交换能力(CEC)为每100克改性膨润土108.4毫摩尔。六水合三氯化铁、乙酸钠、乙二醇(EG)、聚乙二醇200(PEG200)和环氧氯丙烷(ECH)是从天津市科密欧化学试剂有限公司(天津,中国)所获得的分析纯试剂。本发明所使用的化学药剂均为分析纯剂级,并未作进一步的纯化。
实施例1
一种膨润土芬顿磁性催化剂的制备方法,包括以下步骤:
(1)2.16克的六水合三氯化铁、5.76克的乙酸钠以及1.6克的聚乙二醇200的混合物在60毫升的乙二醇里被均匀搅拌18分钟;
(2)0.5克的改性膨润土和1毫升的环氧氯丙烷被添加入均匀溶液里;在43℃下,新的混合物被不断搅拌长达1.5小时;
(3)混合物被转移至一个100毫升的高压釜加热至200℃反应9小时,之后将其冷却至室内温度,形成黑色溶液;
(4)经过滤后,用蒸馏水/乙醇(V:V,1:1)冲洗沉淀物,在真空73℃下使其干燥,最后获得膨润土芬顿磁性催化剂。
经检测,所述膨润土芬顿磁性催化剂的层间距为1.58nm,孔径为6.85nm,孔容为0.52cm3/g,在700℃仍可保持较好的热稳定性;饱和磁化强度值为34.28emu/g,在外加磁场作用下2s可实现固液分离,在强酸、强碱中微溶;四氧化三铁纳米颗粒进入了膨润土层间或孔隙,没有负载于膨润土表面,这种结构有利于为芬顿反应提供稳定的铁源,提高膨润土的吸附性,同时提高其磁响应性,提高固液分离效果。
催化性能实验
在连续的磁力机械搅拌下,在250毫升的玻璃烧瓶反应器(75毫升实际反应量)中进行了批次非均相芬顿实验,以去除代表废水污染物的甲基橙。通常情况下,将适量的催化剂使其悬浮于水中(0.5克/升)再将其放入玻璃反应器中。该系统被加热至适当的温度之后将甲基橙(100毫克/升)和过氧化氢(5.66克/升)添加至反应器里。在固定的时间间隔采取溶液样品(1.0毫升),并在固体颗粒脱除后,加入0.5毫升的甲醇用以冷浸。采用紫外-可见分光光度法来分析了上清液中随时间变化的有机污染物浓度。实验结果显示,15min甲基橙溶液脱色率为99.85%。
对比例1
2.16克的六水合三氯化铁,5.76克的乙酸钠以及1.6克的聚乙二醇200的混合物在60毫升的乙二醇里被均匀搅拌30分钟。紧接着,0.5克的改性膨润土和1毫升的环氧氯丙烷被添加入均匀溶液里。在摄氏55度下,新的混合物被不断搅拌长达2小时。接下来,混合物被转移至一个100毫升的高压釜加热至摄氏200度长达12个小时,之后将其冷却至室内温度,于是乎一个黑色溶液将会形成。经过滤后,用一比一的蒸馏水/乙醇(1:1)冲洗沉淀物,在真空摄氏80度下使其干燥,最后获得四氧化三铁/改性膨润土纳米复合物。
检测显示,上述四氧化三铁/改性膨润土纳米复合物的四氧化三铁纳米颗粒大部分负载于膨润土表面。
以实施例1相同的催化性能实验对其进行测试,结果显示,其20min达到平衡,甲基橙溶液脱色率仅为96.72%。
对比例2
一种膨润土芬顿磁性催化剂的制备方法,包括以下步骤:
(1)2.16克的六水合三氯化铁、5.76克的乙酸钠以及1.6克的聚乙二醇200的混合物在60毫升的乙二醇里被均匀搅拌30分钟;
(2)0.5克的改性膨润土和1毫升的环氧氯丙烷被添加入均匀溶液里;在43℃下,新的混合物被不断搅拌长达1.5小时;
(3)混合物被转移至一个100毫升的高压釜加热至200℃反应9小时,之后将其冷却至室内温度,形成黑色溶液;
(4)经过滤后,用蒸馏水/乙醇(V:V,1:1)冲洗沉淀物,在真空73℃下使其干燥,最后获得四氧化三铁/改性膨润土纳米复合物。
检测显示,上述四氧化三铁/改性膨润土纳米复合物的四氧化三铁纳米颗粒大部分负载于膨润土表面。
以实施例1相同的催化性能实验对其进行测试,结果显示,其20min达到平衡,甲基橙溶液脱色率仅为97.65%。
对比例3
一种膨润土芬顿磁性催化剂的制备方法,包括以下步骤:
(1)2.16克的六水合三氯化铁、5.76克的乙酸钠以及1.6克的聚乙二醇200的混合物在60毫升的乙二醇里被均匀搅拌18分钟;
(2)0.5克的改性膨润土和1毫升的环氧氯丙烷被添加入均匀溶液里;在55℃下,新的混合物被不断搅拌长达1.5小时;
(3)混合物被转移至一个100毫升的高压釜加热至200℃反应9小时,之后将其冷却至室内温度,形成黑色溶液;
(4)经过滤后,用蒸馏水/乙醇(V:V,1:1)冲洗沉淀物,在真空73℃下使其干燥,最后获得四氧化三铁/改性膨润土纳米复合物。
以实施例1相同的催化性能实验对其进行测试,结果显示,其20min达到平衡,甲基橙溶液脱色率仅为97.95%。
对比例4
一种膨润土芬顿磁性催化剂的制备方法,包括以下步骤:
(1)2.16克的六水合三氯化铁、5.76克的乙酸钠以及1.6克的聚乙二醇200的混合物在60毫升的乙二醇里被均匀搅拌18分钟;
(2)0.5克的改性膨润土和1毫升的环氧氯丙烷被添加入均匀溶液里;在43℃下,新的混合物被不断搅拌长达2小时;
(3)混合物被转移至一个100毫升的高压釜加热至200℃反应9小时,之后将其冷却至室内温度,形成黑色溶液;
(4)经过滤后,用蒸馏水/乙醇(V:V,1:1)冲洗沉淀物,在真空73℃下使其干燥,最后获得四氧化三铁/改性膨润土纳米复合物。
以实施例1相同的催化性能实验对其进行测试,结果显示,其20min达到平衡,甲基橙溶液脱色率仅为97.23%。
对比例5
一种膨润土芬顿磁性催化剂的制备方法,包括以下步骤:
(1)2.16克的六水合三氯化铁、5.76克的乙酸钠以及1.6克的聚乙二醇200的混合物在60毫升的乙二醇里被均匀搅拌18分钟;
(2)0.5克的改性膨润土和1毫升的环氧氯丙烷被添加入均匀溶液里;在43℃下,新的混合物被不断搅拌长达1.5小时;
(3)混合物被转移至一个100毫升的高压釜加热至200℃反应12小时,之后将其冷却至室内温度,形成黑色溶液;
(4)经过滤后,用蒸馏水/乙醇(V:V,1:1)冲洗沉淀物,在真空73℃下使其干燥,最后获得四氧化三铁/改性膨润土纳米复合物。
以实施例1相同的催化性能实验对其进行测试,结果显示,其20min达到平衡,甲基橙溶液脱色率仅为94.55%。
对比例6
一种膨润土芬顿磁性催化剂的制备方法,包括以下步骤:
(1)2.16克的六水合三氯化铁、5.76克的乙酸钠以及1.6克的聚乙二醇200的混合物在60毫升的乙二醇里被均匀搅拌18分钟;
(2)0.5克的改性膨润土和1毫升的环氧氯丙烷被添加入均匀溶液里;在43℃下,新的混合物被不断搅拌长达1.5小时;
(3)混合物被转移至一个100毫升的高压釜加热至200℃反应9小时,之后将其冷却至室内温度,形成黑色溶液;
(4)经过滤后,用蒸馏水/乙醇(V:V,1:1)冲洗沉淀物,在真空80℃下使其干燥,最后获得四氧化三铁/改性膨润土纳米复合物。
以实施例1相同的催化性能实验对其进行测试,结果显示,其20min达到平衡,甲基橙溶液脱色率仅为98.98%。
本发明对膨润土芬顿磁性催化剂的制备条件进行了研究,对比例2-6显示,本发明所采用的工艺参数下制备的膨润土芬顿磁性催化剂具有最好的甲基橙溶液脱色率,而改变其任一工艺参数均会对其催化剂效果产生不良影响。
以上所述的实施例仅是对本发明的优选方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案做出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。
Claims (5)
1.一种膨润土芬顿磁性催化剂,其特征在于,以改性膨润土为负载基体,负载磁性四氧化三铁纳米颗粒,所述四氧化三铁纳米颗粒负载于所述改性膨润土的层间和孔隙。
2.根据权利要求1所述的膨润土芬顿磁性催化剂,其特征在于,所述膨润土芬顿磁性催化剂的层间距为1.35-1.58nm,孔径为6.25-6.85nm,孔容为0.48-0.52cm3/g,在300-700℃可保持较好的热稳定性;饱和磁化强度值在25.34-34.28emu/g,在外加磁场作用下2-4s可实现固液分离,在强酸、强碱中微溶。
3.一种如权利要求1或2所述的膨润土芬顿磁性催化剂的制备方法,其特征在于,采用水热反应用以合成四氧化三铁/改性膨润土。
4.根据权利要求3所述的膨润土芬顿磁性催化剂的制备方法,其特征在于,包括以下步骤:
将六水合三氯化铁、乙酸钠以及聚乙二醇200的混合物在乙二醇里均匀搅拌,形成均匀溶液;
改性膨润土和环氧氯丙烷被添加入均匀溶液里,不断搅拌;
混合物加热反应,之后将其冷却至室内温度,形成黑色溶液;
经过滤后,用蒸馏水/乙醇冲洗沉淀物,干燥,最后获得膨润土芬顿磁性催化剂。
5.根据权利要求4所述的膨润土芬顿磁性催化剂的制备方法,其特征在于,包括以下步骤:
(1)将2.16克的六水合三氯化铁、5.76克的乙酸钠以及1.6克的聚乙二醇200的混合物在60毫升的乙二醇里被均匀搅拌18分钟,形成均匀溶液;
(2)将0.5克的改性膨润土和1毫升的环氧氯丙烷添加入均匀溶液里;
在43℃下,搅拌1.5小时;
(3)将混合物转移至一个100毫升的高压釜加热至200℃反应9小时,之后将其冷却至室内温度,形成黑色溶液;
(4)经过滤后,用蒸馏水/乙醇(V:V,1:1)冲洗沉淀物,在真空73℃下使其干燥,最后获得膨润土芬顿磁性催化剂。
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