CN109513419B - 一种磁性镁锰层状双金属氧化物复合材料及制备与应用 - Google Patents
一种磁性镁锰层状双金属氧化物复合材料及制备与应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 25
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 23
- 150000002696 manganese Chemical class 0.000 claims abstract description 21
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 19
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- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 13
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- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 6
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 6
- 239000011565 manganese chloride Substances 0.000 claims description 6
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- 239000002243 precursor Substances 0.000 claims description 6
- 229910001385 heavy metal Inorganic materials 0.000 claims description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- -1 manganese salt compound Chemical class 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
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- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
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Abstract
本发明属于吸附材料技术领域，公开了一种磁性镁锰层状双金属氧化物复合材料及制备与应用。将可溶性的镁盐和锰盐溶于水中得到镁盐与锰盐复合液，将可溶性的碳酸盐和氢氧化物溶于水中，得到碳酸盐与氢氧化物复合液；将四氧化三铁粉末加入到碳酸盐与氢氧化物复合液中，加入乙醇超声分散得到分散液，然后加入镁盐与锰盐复合液，陈化，离心，洗涤，干燥，研磨过筛，250～550℃煅烧，得到磁性镁锰层状双金属氧化物复合材料。本发明复合材料对Cd的去除具有较强的磁性，具有吸附效率高、吸附速度快和稳定的特点。不仅能将Cd高效固定，而且可利用磁铁分离回收材料。
Description
技术领域
本发明属于吸附材料技术领域，具体涉及一种磁性镁锰层状双金属氧化物复合材料及制备与应用。
背景技术
镉能够在动物、植物和人体内大量积累，人体内的镉主要是通过食物、水和空气而进入人体被积蓄下来；镉进入人体后会与人体内含有的羟基、硫基、氨基的蛋白质分子形成镉蛋白，通过血液到达全身，并有选择性的在肾、肝中蓄积。其中肾脏是镉中毒的靶器官，将近三分之一的镉会蓄积在肾脏中，会对人体造成严重的危害。而吸附法是目前应用很广泛的去除废水中重金属的方法，该方法具有操作简单、经济有效等特点。其中金属氧化物去除效率较高，但通常主要以超细粉体形式存在，直接应用于常规的柱吸附系统时存在压降大或难以分离等工程技术瓶颈。如何开发一种既可以高效固定Cd且易于分离的材料，已成为人们研究的重点之一。
发明内容
针对以上现有技术存在的缺点和不足之处，本发明的首要目的在于提供一种磁性镁锰层状双金属氧化物复合材料的制备方法。
本发明的另一目的在于提供一种通过上述方法制备得到的磁性镁锰层状双金属氧化物复合材料。所述磁性镁锰层状双金属氧化物复合材料具有较强的磁性、吸附和稳定性。
本发明的再一目的在于提供上述磁性镁锰层状双金属氧化物复合材料在重金属镉污染处理中的应用。
本发明目的通过以下技术方案实现：
一种磁性镁锰层状双金属氧化物复合材料的制备方法，包括如下制备步骤：
(1)将可溶性的镁盐和锰盐溶于水中得到镁盐与锰盐复合液，将可溶性的碳酸盐和氢氧化物溶于水中，得到碳酸盐与氢氧化物复合液；
(2)将四氧化三铁粉末加入到碳酸盐与氢氧化物复合液中，加入乙醇超声分散，得到分散液；
(3)将镁盐与锰盐复合液加入到步骤(2)的分散液中，陈化，离心，洗涤，干燥，研磨过筛，得到前驱体粉末；
(4)将步骤(3)所得前驱体粉末在250～550℃煅烧，得到磁性镁锰层状双金属氧化物复合材料。
优选地，步骤(1)中所述镁盐为氯化镁、硝酸镁或硫酸镁，更优选为氯化镁；所述锰盐为氯化锰、硝酸锰或硫酸锰，更优选为氯化锰；所述碳酸盐为碳酸钠或碳酸钾，更优选为碳酸钠；所述氢氧化物为氢氧化钠或氢氧化钾，更优选为氢氧化钠。
优选地，步骤(1)中所述镁盐:锰盐:碳酸盐:氢氧化物的摩尔比为(5～60):(5～40):(2～30):(5～60)，更优选为(10～30):(10～20):(4～15):(10～30)。
优选地，步骤(1)中所述镁盐与锰盐复合液中，镁盐的浓度为0.03～0.09mol/L，锰盐的浓度为0.01～0.045mol/L；所述碳酸盐与氢氧化物复合液中，碳酸盐的浓度为0.005～0.2mol/L，氢氧化物的浓度为0.005～0.4mol/L。
优选地，步骤(2)中所述四氧化三铁与碳酸盐的质量摩尔比为(0.5～5)g:(0.01～1)mol。
优选地，步骤(2)中所述乙醇的加入量为碳酸钠与氢氧化钠复合液体积的0.1～2倍；所述超声分散的时间为10～60min。
优选地，步骤(3)中所述镁盐与锰盐复合液采用滴加方式加入到分散液中，滴加速度为0.1～5mL/min。
优选地，步骤(3)中所述陈化时间为12～36h，所述干燥是指在50～80℃干燥12～36h，所述研磨过筛是指研磨过100～500目筛。
优选地，步骤(4)中所述煅烧时间为1～5h。
一种磁性镁锰层状双金属氧化物复合材料，通过上述方法制备得到。
上述磁性镁锰层状双金属氧化物复合材料在重金属镉污染处理中的应用。
本发明的制备方法及所得到的产物具有如下优点及有益效果：
(1)本发明的材料是基于镁锰层状双金属氧化物对镉的高固定性能与四氧化三铁的强磁性而制备的磁性镁锰层状双金属氧化物复合材料，该复合材料对Cd的去除具有较强的磁性，具有吸附效率高、吸附速度快和稳定的特点。
(2)本发明的材料不仅能将Cd高效固定，而且可利用磁铁分离回收材料。
(3)本发明所用镁锰盐和四氧化三铁所含元素为自然界的组成成分，具有价格低廉，来源广泛，无环境污染等特点。
(4)本发明的制备方法简单，反应条件温和，低耗能，产率高，应用前景广阔。
附图说明
图1为实施例1制备的磁性镁锰层状双金属氧化物复合材料的SEM图；
图2为实施例1制备的磁性镁锰层状双金属氧化物复合材料的TEM图；
图3为实施例1制备的磁性镁锰层状双金属氧化物复合材料的XRD图；
图4为实施例1制备的磁性镁锰层状双金属氧化物复合材料在不同时间下Cd吸附量曲线图；
图5为实施例1制备的磁性镁锰层状双金属氧化物复合材料在不同Cd初始浓度下的Cd吸附量曲线图；
图6为实施例1中吸附Cd后的磁性镁锰层状双金属氧化物复合材料(右)与四氧化三铁(左)的磁分离效果对比图。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
本实施例的一种用于处理环境中镉污染的磁性镁锰层状双金属氧化物复合材料的制备方法，具体制备步骤如下：
(1)准确称取0.026mol氯化镁和0.013mol氯化锰采用500mL去离子水进行溶解得到镁盐与锰盐复合液，将0.01mol碳酸钠和0.02mol氢氧化钠采用250mL去离子水进行溶解得到碳酸盐与氢氧化物复合液；
(2)将0.25g四氧化三铁粉末加入到碳酸盐与氢氧化物复合液并加入250mL无水乙醇，超声分散30min，得到分散液；
(3)将镁盐与锰盐复合液以滴加速度1mL/min缓慢滴入步骤(2)的分散液中，陈化24h，以4000r/min离心5min后去除上清液，用去离子水冲洗数次，在60℃温度下干燥24h，研磨过200目筛，得到前驱体粉末。
(4)将步骤(3)的前驱体粉末于马弗炉中350℃下煅烧3h，得到磁性镁锰层状双金属氧化物复合材料。
所制备的磁性镁锰层状双金属氧化物复合材料的形貌和结构表征如图1、图2和3所示。其中图1为SEM图、图2为TEM和图3为XRD图。从图1中可知，磁性镁锰层状双金属氧化物复合材料中四氧化三铁均匀地分布在镁锰双金属氧化物片层上；由图2材料的TEM，可清晰地看出薄片上较为均匀地分布小颗粒，这与SEM的结果相一致，所以可以得到结论四氧化三铁均匀地分布在镁锰双金属氧化物上。由图3可知，磁性镁锰层状双金属氧化物复合材料的XRD谱图上具备四氧化三铁的特征峰，说明为四氧化三铁与镁锰双金属氧化物相互作用，形成了磁性镁锰层状双金属氧化物复合材料。
所得磁性镁锰层状双金属氧化物复合材料在重金属镉污染处理中的应用效果测试：
(1)准确称取多份0.005g磁性镁锰层状双金属氧化物复合材料分别置于50ml离心管中，分别向离心管中移取25mL配制好的12mg·L-1Cd溶液，充分混合后置于30±1℃水浴振荡器上震荡，震荡时间为2,4,6,8,10,15,20，25,30,60,90,120min后，取溶液过0.45μm滤膜，原子吸收分光光度计测定溶液中Cd的浓度，测试结果如4所示。从图4可知，磁性镁锰层状双金属氧化物复合材料对Cd吸附几乎在10分钟内就可以达到吸附平衡，之后Cd的吸附随着时间的变化不大，说明磁性镁锰层状双金属氧化物复合材料能快速的对Cd进行固定去除，且吸附量高达59mg g-1，对应去除率几乎为100％。
(2)准确称取多份0.005g磁性镁锰层状双金属氧化物复合材料分别置于50ml离心管中，分别向离心管中移取25mL配制好的不同初始浓度的Cd溶液(初始浓度Cd设置为50mgL-1，100mg L-1,150mg L-1,200mg L-1,250mg L-1,300mg L-1，350mg L-1)，充分混合后置于30±1℃水浴振荡器上震荡24h后，取上清液过0.45μm滤膜，原子吸收分光光度计测定溶液中Cd的浓度。测试结果如图5所示。从图5中可以看出，Freundlich吸附方程能较好的描述磁性镁锰层状双金属氧化物复合材料对Cd的吸附特征，这说明磁性镁锰层状双金属氧化物复合材料对Cd的吸附属于多分子层吸附，Langmuir拟合可知磁性镁锰层状双金属氧化物复合材料对Cd最大吸附量高达436mg g-1，说明了材料的高效性。
(3)准确称取多份0.005g磁性镁锰层状双金属氧化物复合材料分别置于50ml离心管中，分别向离心管中移取25mL配制好的12mg·L-1Cd溶液，充分混合后置于30±1℃水浴振荡器上震荡，震荡时间为30min后，利用磁铁分离吸附后的材料，并用四氧化三铁的磁分离效果作为对比，结果如图6所示。从图6可以看出，左边为四氧化三铁的磁分离效果，右边为磁性镁锰层状双金属氧化物复合材料固定Cd后的磁分离效果，可以看出，磁性镁锰层状双金属氧化物复合材料具有与四氧化三铁相当的磁分离效果，说明本发明研发的材料磁性较强，易于实现磁分离。
实施例2
一种用于处理环境中镉污染问题的磁性镁锰层状双金属氧化物复合材料的制备方法，包括以下步骤：
(1)准确称取0.026mol氯化镁和0.013mol氯化锰采用500mL去离子水进行溶解得到镁盐溶液与锰盐复合液、0.01mol碳酸钠和0.02mol氢氧化钠采用250mL去离子水进行溶解得到碳酸盐溶液与氢氧化物复合液；
(2)将0.25g四氧化三铁粉末加入到碳酸盐溶液与氢氧化物复合液并加入250mL无水乙醇，超声分散30min；
(3)将镁盐溶液与锰盐复合液以滴加速度1mL/min缓慢滴入步骤(2)的分散液中，陈化24h，以4000r/min离心5min后去除上清液，用去离子水冲洗数次，在60℃温度下干燥24h，研磨过200目筛。
(4)将步骤(3)的粉末于马弗炉中250℃下煅烧5h，得到磁性镁锰层状双金属氧化物复合材料。
所制备的磁性镁锰层状双金属氧化物复合材料的形貌和结构表征结果显示四氧化三铁均匀地分布在镁锰双金属氧化物片层上，形成了磁性镁锰层状双金属氧化物复合材料。
实施例3
一种用于处理环境中镉污染问题的磁性镁锰层状双金属氧化物复合材料的制备方法，包括以下步骤：
(1)准确称取0.026mol氯化镁和0.013mol氯化锰采用500mL去离子水进行溶解得到镁盐溶液与锰盐复合液、0.01mol碳酸钠和0.02mol氢氧化钠采用250mL去离子水进行溶解得到碳酸盐溶液与氢氧化物复合液；
(2)将0.25g四氧化三铁粉末加入到碳酸盐溶液与氢氧化物复合液并加入250mL无水乙醇，超声分散30min；
(3)将镁盐溶液与锰盐复合液以滴加速度1mL/min缓慢滴入步骤(2)的分散液中，陈化24h，以4000r/min离心5min后去除上清液，用去离子水冲洗数次，在60℃温度下干燥24h，研磨过200目筛。
(4)将步骤(3)的粉末于马弗炉中550℃下煅烧1h，得到磁性镁锰层状双金属氧化物复合材料。
所制备的磁性镁锰层状双金属氧化物复合材料的形貌和结构表征结果显示四氧化三铁均匀地分布在镁锰双金属氧化物片层上，形成了磁性镁锰层状双金属氧化物复合材料。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (8)
1.一种磁性镁锰层状双金属氧化物复合材料在重金属镉污染处理中的应用，其特征在于，所述磁性镁锰层状双金属氧化物复合材料的制备包括如下步骤：
(1)将可溶性的镁盐和锰盐溶于水中得到镁盐与锰盐复合液，将可溶性的碳酸盐和氢氧化物溶于水中，得到碳酸盐与氢氧化物复合液；
(2)将四氧化三铁粉末加入到碳酸盐与氢氧化物复合液中，加入乙醇超声分散，得到分散液；
(3)将镁盐与锰盐复合液加入到步骤(2)的分散液中，陈化，离心，洗涤，干燥，研磨过筛，得到前驱体粉末；
(4)将步骤(3)所得前驱体粉末在250～550℃煅烧，得到磁性镁锰层状双金属氧化物复合材料。
2.根据权利要求1所述的应用，其特征在于：步骤(1)中所述镁盐为氯化镁、硝酸镁或硫酸镁；所述锰盐为氯化锰、硝酸锰或硫酸锰；所述碳酸盐为碳酸钠或碳酸钾；所述氢氧化物为氢氧化钠或氢氧化钾。
3.根据权利要求1所述的应用，其特征在于：步骤(1)中所述镁盐:锰盐:碳酸盐:氢氧化物的摩尔比为(5～60):(5～40):(2～30):(5～60)。
4.根据权利要求1所述的应用，其特征在于：步骤(1)中所述镁盐与锰盐复合液中，镁盐的浓度为0 .03～0 .09mol/L，锰盐的浓度为0 .01～0 .045mol/L；所述碳酸盐与氢氧化物复合液中，碳酸盐的浓度为0 .005～0 .2mol/L，氢氧化物的浓度为0 .005～0 .4mol/L。
5.根据权利要求1所述的应用，其特征在于：步骤(2)中所述四氧化三铁与碳酸盐的质量摩尔比为(0 .5～5)g:(0 .01～1)mol。
6.根据权利要求1所述的应用，其特征在于：步骤(2)中所述乙醇的加入量为碳酸钠与氢氧化钠复合液体积的0 .1～2倍；所述超声分散的时间为10～60min。
7.根据权利要求1所述的应用，其特征在于：步骤(3)中所述镁盐与锰盐复合液采用滴加方式加入到分散液中，滴加速度为0 .1～5mL/min；所述陈化时间为12～36h，所述干燥是指在50～80℃干燥12～36h，所述研磨过筛是指研磨过100～500目筛。
8.根据权利要求1所述的应用，其特征在于：步骤(4)中所述煅烧时间为1～5h。
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