CN110560070B - 一种用含铁废料制备掺杂纳米铁酸锌的方法 - Google Patents
一种用含铁废料制备掺杂纳米铁酸锌的方法 Download PDFInfo
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Abstract
本发明公开了一种用含铁废料制备掺杂纳米铁酸锌的方法，属于光催化材料技术领域。其主要特征是以含铁废料为铁源，提取其中的铁以及其他有价元素，制备出光催化性能优于纯纳米铁酸锌的掺杂纳米铁酸锌；不仅解决了二次资源中有价金属元素的有效利用问题，而且制备方法简单、成本低廉，制备的掺杂铁酸锌可有效降解有机废水，达到以废治废的目的，具有很好的应用前景。
Description
技术领域
本发明涉及有机废水的光催化降解领域，尤其涉及一种用含铁废料制备掺杂纳米铁酸锌的方法。
背景技术
随着冶金矿产资源的日益减少，冶金二次资源的综合利用日益受重视。湿法炼锌回转窑渣中含有大量的铁及其少量的Al、Ti、Cu等有价金属元素，是一种很好的二次资源，若露天堆积容易导致土壤或水资源的重金属污染。目前对于这些含铁废料回收利用的研究，主要集中在如何回收其中的某一元素，如采用回转窑挥发的方式从高含锌量的布袋尘中回收锌；采用酸浸的方式从湿法炼锌回转窑渣中提取铜；这些研究或者技术的特点是回收废渣中的某一有价元素，而不能对废料中的有价元素进行综合回收。
目前，大量研究表明，通过在纳米铁酸锌中掺杂其他金属元素，可有效提高其光催化性能，但是，用于掺杂的试剂往往价格较高，从废料中提取铁的同时提取掺杂元素，可以有效降低经济成本。
发明内容
本发明的目的就在于为了解决上述问题而提供一种用含铁废料制备掺杂纳米铁酸锌的方法。以含铁废料为铁源，制备纳米铁酸锌，同时从其中提取其他元素进行掺杂，制备掺杂纳米铁酸锌，其光催化性能优于纯纳米铁酸锌。本发明所公开的方法，对含铁废料中的有价元素进行了综合回收利用，且用较低的成本制备出光催化性能优良的纳米铁酸锌粉末。
本发明通过以下技术方案来实现上述目的：
本发明用含铁废料制备光催化纳米铁酸锌的方法包括以下步骤：
(1)将工业含铁废料研磨成粒径为-200目以下的粉末，用稀硫酸、稀盐酸或稀硝酸在50～90℃下浸出1～3h，提取铁及废渣中的其他有价元素，过滤获得滤液，在滤液中加入适量双氧水使其中的Fe2+氧化为Fe3+；
(2)稀释浸出液控制其中的Fe3+浓度为0.01～0.1mol/L，用稀释氨水或者氢氧化钠或者氢氧化钾溶液调整pH为5～10，使稀释的浸出液沉淀出以Fe(OH)3为主的沉淀物，过滤并洗涤沉淀物；
(3)用有机酸溶液在60℃下溶解沉淀物，并同时加入一定量的工业氧化锌粉，待固体物料彻底溶解，在不超过60℃的温度下蒸发水分并形成胶状物质作为纳米铁酸锌制备的前驱体；
(4)将步骤(3)所获得的前驱体在500～700℃下煅烧1～3h，获得掺杂纳米铁酸锌粉。
步骤(1)中的含铁废料为湿法炼锌回转窑渣或高炉布袋尘，是含铁为主兼含有其他金属元素的废料。选择含铁废料作为铁源，可以降低成本。在提取含铁废料中铁的同时，提取其中的其他金属元素，作为掺杂元素，避免了价格较高的掺杂试剂的使用。
步骤(2)调整Fe3+浓度为0.01～0.1mol/L可辅助控制进入沉淀中除铁外其他金属元素的量。调整浸出液pH为5～10之间是控制掺杂元素种类的重要措施。当调整浸出液pH值低于5时，掺杂元素主要为Al，但是掺杂量较少，提升纳米铁酸锌光催化性能的效果不显著,甚至光催化效果略有降低；当调整浸出液pH值高于10时，掺杂元素涵盖了Al、Si、Ti、Zn、Cu、Ca、Mn等元素，虽然掺杂元素种类多，有利于协同作用，改善催化剂的光催化效果，但是在此pH值下，杂质元素掺入量过多，反而导致催化剂的光催化性能降低；当调整浸出液pH值在7～9之间时，掺杂元素主要为Al、Si、Ti、Zn、Cu，当调整浸出液pH值在9～10时，掺杂元素主要为Al、Si、Ti、Zn、Cu、Ca、Mn，此时杂质元素的掺入量较为适合，催化剂的光催化效果最佳。
步骤(3)中，由于浸出液中除了Fe3+外还含有其他金属离子，为充分溶解沉淀物，有机物酸与浸出液中Fe3+的摩尔比应在1.5以上，且适当提高有机酸与铁离子的摩尔比有利于细化纳米铁酸锌，增强其光催化性能。加入的工业氧化锌粉与浸出液中Fe3+的摩尔比为1:2，物料溶解过程中，加热至60℃有利于固体物溶解在有机酸中，加热温度过高时容易导致有机酸的分解，过低时，溶解速度慢，沉淀不易完全溶解。若沉淀不能完全溶解则会影响到纳米铁酸锌的粒度，使催化剂粒度变粗，光催化效果变差。在不超过60℃的温度下蒸发水分是为了防止水分蒸发过程中，有机物分解。
步骤(4)中，煅烧温度应保持在500～700℃，温度过低不利于纳米铁酸锌的形成，但是煅烧温度过高时容易导致晶粒长大，不利于纳米铁酸锌光催化性能的提高。
本发明的有益效果在于：
本发明是一种用含铁废料制备掺杂纳米铁酸锌的方法，与现有技术相比，本发明针对含铁废料作为一种二次资源，大量堆积造成浪费，且有些含铁废料中含有重金属离子污染环境，现有工艺不能有效利用其中有价元素的问题，以含铁废料为铁源，提取其中的铁以及其他有价元素，制备出光催化性能优于纯纳米铁酸锌的掺杂纳米铁酸锌，用于有机废水的光催化降解，达到以废治废的目的。大量研究表明，通过在纳米铁酸锌中掺杂其他金属元素，可有效提高其光催化效果，但是，用于掺杂的试剂往往价格较高，从废料中提取铁的同时提取掺杂元素，可以有效控制成本。
以含铁废料为铁源，同时提取其中的其他金属元素作为掺杂元素，可有效降低掺杂纳米铁酸锌的制备成本；
具有环保优势，首先，解决了含铁废料污染环境的问题；其次，此废料制备的纳米铁酸锌具有优良的光催化性能，可用于有机物的光催化降解；
掺杂元素的种类及掺入量可通过改变浸出液pH值的方式来调整，使所制备的掺杂纳米铁酸锌光催化性能达到最佳。
附图说明
图1为实施例1、2、3、4所制备的纳米铁酸锌粉的XRD图；
图2为实施例1、2、3、4所制备的纳米铁酸锌粉光催化降解甲基橙降解率。
具体实施方式
下面对本发明作进一步说明：
实施例1
取化学纯试剂氯化铁10g，用100毫升30％稀硫酸在80℃下浸出2h获得浸出液，加5ml双氧水氧化，用蒸馏水将其稀释至Fe3+浓度为0.01mol/L，过滤并用蒸馏水多次洗涤，获得沉淀物。用浓度为0.1mol/L的柠檬酸溶液在60℃下充分溶解所获得的沉淀物，并同时加入化学纯氧化锌，柠檬酸与沉淀物中的Fe3+摩尔比为3:1，化学纯氧化锌粉与沉淀物中的Fe3 +摩尔比为1:2。待物料充分溶解，将溶液在不高于60℃的温度下进行蒸发，获得黄褐色的凝胶。凝胶在500℃下煅烧2h，获得蓬松状物质，用研钵磨细，即为纳米铁酸锌，经检测为纯铁酸锌。该铁酸锌粉的XRD图谱如附图1所示。催化剂用量为0.01g，双氧水用量为3ml，在300nm紫外光催化下降解100ml浓度为20mg/l的甲基橙溶液，其降解率如附图2所示。
实施例2
某湿法炼锌回转窑渣，其成分如下表所示：
表1回转窑渣元素含量(wt％)
取回转窑渣10g，用100毫升1:1的盐酸在50℃下浸出2h获得浸出液，加5ml双氧水氧化，用蒸馏水将其稀释至Fe3+浓度为0.01mol/L，取稀释后的浸出液500ml，缓慢加入1:1的氨水，调整pH为4，过滤并用蒸馏水多次洗涤，获得沉淀物。用浓度为0.1mol/L的柠檬酸溶液在60℃下充分溶解所获得的沉淀物，并同时加入工业氧化锌，柠檬酸与沉淀物中的Fe3+摩尔比为3:1，工业氧化锌粉与沉淀物中的Fe3+摩尔比为1:2。待物料充分溶解，将溶液在不高于60℃的温度下进行蒸发，获得黄褐色的凝胶。凝胶在500℃下煅烧2h，获得蓬松状物质，用研钵磨细，即为掺杂纳米铁酸锌，经检测为铁酸锌，其XRD图谱如附图1所示。如附表1所示，掺杂粉末与纯纳米铁酸锌相比，晶峰发生偏移，这是掺杂元素导致的，且掺杂粉末晶粒度变细。催化剂用量为0.01g，双氧水用量为3ml，在300nm紫外光催化下降解100ml浓度为20mg/l的甲基橙溶液，如附图2所示，该掺杂粉末与纯纳米铁酸锌相比，催化效果略差于纯铁酸锌粉末。
实施例3
某湿法炼锌回转窑渣，其成分如下表所示：
表2回转窑渣元素含量(wt％)
取回转窑渣10g，用100毫升30％稀硫酸在80℃下浸出2h获得浸出液，加5ml双氧水氧化，用蒸馏水将其稀释至Fe3+浓度为0.01mol/L，取稀释后的浸出液500ml，缓慢加入1:1的氨水，调整pH为7，过滤并用蒸馏水多次洗涤，获得沉淀物。用浓度为0.1mol/L的柠檬酸溶液在60℃下充分溶解所获得的沉淀物，并同时加入工业氧化锌，柠檬酸与沉淀物中的Fe3+摩尔比为3:1，工业氧化锌粉与沉淀物中的Fe3+摩尔比为1:2。待物料充分溶解，将溶液在不高于60℃的温度下进行蒸发，获得黄褐色的凝胶。凝胶在500℃下煅烧2h，获得蓬松状物质，用研钵磨细，即为掺杂纳米铁酸锌，经检测为铁酸锌，其XRD图谱如附图1所示。如附表1所示，掺杂粉末与纯纳米铁酸锌相比，晶峰发生偏移，这是掺杂元素导致的，且掺杂粉末晶粒度变细。催化剂用量为0.01g，双氧水用量为3ml，在300nm紫外光催化下降解100ml浓度为20mg/l的甲基橙溶液，如附图2所示，该掺杂粉末与纯纳米铁酸锌相比，催化效果明显优于纯铁酸锌粉末。
实施例4
某湿法炼锌回转窑渣，其成分如下表所示：
表3回转窑渣元素含量(wt％)
取回转窑渣10g，用100毫升30％稀硫酸在80℃下浸出2h获得浸出液，加5ml双氧水氧化，用蒸馏水将其稀释至Fe3+浓度为0.01mol/L，取稀释后的浸出液500ml，缓慢加入1:1的氨水，调整pH为10，过滤并用蒸馏水多次洗涤，获得沉淀物。用浓度为0.1mol/L的柠檬酸溶液在60℃下充分溶解所获得的沉淀物，并同时加入工业氧化锌，柠檬酸与沉淀物中的Fe3+摩尔比为3:1，工业氧化锌粉与沉淀物中的Fe3+摩尔比为1:2。待物料充分溶解，将溶液在不高于60℃的温度下进行蒸发，获得黄褐色的凝胶。凝胶在500℃下煅烧2h，获得蓬松状物质，用研钵磨细，即为掺杂纳米铁酸锌，经检测为铁酸锌，其中含有Si、Al、Cu、Zn、Mn、Ca等掺杂元素。如附表1所示，掺杂粉末与纯纳米铁酸锌相比，晶峰发生偏移，这是掺杂元素导致的，且掺杂粉末晶粒度变细。催化剂用量为0.01g，双氧水用量为3ml，在300nm紫外光催化下降解100ml浓度为20mg/l的甲基橙溶液，如附图2所示，该掺杂粉末与纯纳米铁酸锌相比，催化效果明显优于纯铁酸锌粉末。
附表1纳米铁酸锌晶体参数
附表1为实施例1、2、3、4所制备的纳米铁酸锌粉的晶粒参数
以上显示和描述了本发明的基本原理和主要特征及本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (2)
1.一种用含铁废料制备掺杂纳米铁酸锌的方法，其特征在于：包括以下步骤：
（1）将湿法炼锌回转窑渣研磨成粒径为200目以下的粉末，用稀硫酸、稀盐酸或稀硝酸在50~90℃下浸出1~3h，提取铁及废渣中的其他有价元素，过滤获得滤液，在滤液中加入适量双氧水使其中的Fe2+氧化为Fe3+；
（2）稀释浸出液，控制其中的Fe3+浓度为0.01~0.1mol/L，掺杂元素的种类及掺杂量通过改变浸出液的pH值来调整，用稀释氨水或者氢氧化钠或者氢氧化钾溶液调整浸出液pH值为7~10之间，使稀释的浸出液沉淀出以Fe(OH)3为主的沉淀物，过滤并洗涤沉淀物；
（3）用有机酸溶液在60℃下溶解沉淀物，并同时加入一定量的氧化锌粉，待固体物料彻底溶解，在不超过60℃的温度下蒸发水分并形成胶状物质作为纳米铁酸锌制备的前驱体；
（4）将步骤(3)所获得的前驱体在500~700℃下煅烧1~3h，获得掺杂纳米铁酸锌粉；
所述的有机酸为柠檬酸、酒石酸有机酸，有机酸与浸出液中Fe3+的摩尔比为1.5~4:1。
2.根据权利要求1所述的用含铁废料制备掺杂纳米铁酸锌的方法，其特征在于：所述的氧化锌为工业氧化锌，氧化锌与浸出液中Fe3+的摩尔比为1:2。
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