CN107282013A - 一种粒径可控的多孔磁性壳聚糖凝胶微球及制备方法 - Google Patents
一种粒径可控的多孔磁性壳聚糖凝胶微球及制备方法 Download PDFInfo
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Abstract
本发明提供了一种基于原位共沉淀原理的粒径可控的多孔磁性壳聚糖凝胶微球及制备方法，包括以下主要步骤：1、Fe2+、Fe3+与壳聚糖混合溶液络合反应配制前驱诱导预溶胶；2、将预溶胶逐滴滴加到含有NaOH、柠檬酸钠等的碱性浸泡液中共沉淀生成纳米Fe3O4；3、预溶胶发生交联反应并固化，交联后的壳聚糖凝胶微球呈多孔网状结构，Fe3O4均匀分布在其中。通过调节蠕动泵转速和溶液浓度控制壳聚糖凝胶微球粒径大小。该方法制得的壳聚糖凝胶微球孔隙丰富、比表面积大、吸附性和耐酸性强，具有制备方法简单、材料来源广泛、成本低廉、易分离回收、无二次污染等特点。本发明可用于矿山、冶炼厂、电子厂、电镀厂废水以及放射性废水中金属的富集回收和污染修复。
Description
技术领域
本发明属于环境功能材料领域，涉及一种粒径可控的多孔磁性壳聚糖凝胶微球及制备方法。
背景技术
重金属具有毒性大、难降解且易在生物体内富集等特点，对生态环境和人体健康造成了极大的危害[1]。目前，重金属废水处理方法主要有化学法、物理化学法、生物法[2]。其中，化学法和物理化学法处理效率较高，应用较为广泛[3]，但其存在二次污染且对低浓度重金属废水处理效果较差的局限。相比之下，生物吸附法以其处理效率高、反应彻底、无二次污染等优势逐渐受到研究人员关注[4]。利用壳聚糖等天然生物质材料富集去除水中低浓度重金属研究日趋活跃[5]。
壳聚糖(Chitosan)是由自然界广泛存在的甲壳素经过脱乙酰作用所得到的产物，化学名称为聚葡萄糖胺(1-4)-2-氨基-B-D葡萄糖，是目前发现的唯一一种天然碱性多糖，也是自然界中仅次于纤维素的第二大可再生资源[6]。具有来源广泛、环境友好、易降解等优点[7]，在医药、食品、化工、环境等领域得到了广泛的应用[8]。作为典型的天然生物高分子，壳聚糖分子中大量氨基（C2位）、羟基（C6位）等活性基团，能通过螯合、离子交换或形成离子对等方式吸附富集水中的重金属[9]。由于壳聚糖在酸性溶液中易被质子化，形成的游离态氨基会失去对重金属的配位能力，直接影响壳聚糖对重金属的吸附效果。因此，研究人员尝试在特定条件下将壳聚糖进行分子内或分子间交联改性。壳聚糖交联产物不仅可以提高对重金属离子的吸附能力，也可明显改善壳聚糖自身的机械性能和酸溶性[10]，还可提高抗降解性，增强分子稳定性[11]。为了达到循环再利用的目的，提高吸附剂机械强度，近年磁性壳聚糖微球作为一种新型多功能复合材料已经被广泛应用到各个领域[12]。
目前，磁性壳聚糖微球制备方法主要有简单包埋法、悬浮聚合法、乳液聚合法和分散共聚反应法等。这些方法大多对反应制备条件要求极高[13]，或需经过复杂制备流程完成凝胶微球的制备[14]，不仅制备成本高，而且在制备过程中需要用到的乳化剂、交联剂、引发剂等有毒有害的化学试剂[15]对环境存在着二次污染的潜在危害[16]。同时在实际应用中受吸附剂的形态限制，特定尺寸的吸附剂只适用于特定情况处理，并且由于耐酸性较差，不适于对酸性废水的处理，在应用中存在一定局限性。因此，选择一种对环境潜在危害小，成本低廉的方法制备出一种性能稳定、耐酸性较强、适用范围广、粒径可控的磁性壳聚糖凝胶微球是在天然生物质吸附剂制备领域亟需解决的重点和难点问题。
参考文献：
[1]胡曼,王香兰. 改性壳聚糖对铅的吸附性能研究[J] 安徽农业科学,2012,07:4208-4209+4212.
[2]张军丽,张燕,潘庆才. 合成壳聚糖/DNS杂化材料及吸附重金属Pb~(2+)的性能研究[J] 应用化工,2011,02: 225-228.
[3]化学工业部环境保护设计技术中心站, 化工环境保护设计手册[M],第6卷.1998:北京：化学工业出版社.
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发明内容
本发明所解决的技术问题在于提供一种粒径可控多孔磁性壳聚糖凝胶微球制备方法。该凝胶微球可以作为废水中重金属离子吸附剂，其内部多孔结构明显，耐酸性强，制备与处理成本低，再生性能良好，处理效果理想。
本发明通过以下技术方案予以实现：以Fe2+，Fe3+掺杂壳聚糖溶液制备前驱诱导预凝胶；借助壳聚糖与金属离子的螯合作用使Fe2+、Fe3+均匀分散，然后经碱化处理后壳聚糖发生固化，利用原位共沉淀原理形成纳米级Fe3O4；同时离子型交联剂柠檬酸钠与壳聚糖发生交联反应，形成多孔结构。所述多孔磁性壳聚糖凝胶球，纳米级Fe3O4均匀分散在壳聚糖凝胶微球的网状结构中，使其具有良好的磁感应强度，并且交联后的壳聚糖凝胶球耐酸性明显提高。所述多孔磁性壳聚糖凝胶球的粒径可根据实际需要控制在100~5000μm范围内。
所述多孔磁性壳聚糖凝胶微球的制备方法包括以下步骤。
1）将一定质量壳聚糖溶于2%的乙酸溶于中，配制质量分数为1wt%~5wt%的壳聚糖溶胶。
2）配制Fe2+（0.005~0.02M），Fe3+（0.0025~0.01M）的混合溶液，加入壳聚糖溶胶中，用磁力搅拌器充分搅拌上述混合溶液从亮黄色变为暗红色，络合反应完全后，前驱诱导预溶胶配制完成。
3）将上述前驱诱导预溶胶用蠕动泵滴入预先配好的碱性溶液中进行浸泡，根据实际需求，控制滴速以控制微球粒径，微球在固化成球的同时完成原位共沉淀反应与交联反应。
4）将所得的多孔磁性壳聚糖凝胶微球通过外加磁场收集分离后，用去离子水冲洗至中性后，在去离子水中浸泡储存备用。
步骤1）中所述壳聚糖的质量分数为3.0×105g/mol-1，脱乙酰度为80%~95%；
步骤1）中壳聚糖溶胶浓度为1wt%~6wt%；
步骤2）中含Fe2+的化合物可为Fe(NO3)2、FeCl2·4H2O、FeSO4等含亚铁盐中的至少一种；所述含Fe3+的化合物可为Fe(NO3)3、FeCl3·6H2O、Fe2(SO4)3等含铁盐中的至少一种；
步骤2）所配制的混合溶液中Fe2+（0.1~0.5M）与Fe3+（0.2~1M）的摩尔比为0.1~2.0；
步骤3）中所述碱性浸泡液中主要成分为NaOH、柠檬酸钠和去离子水；
步骤3）中碱性浸泡液中NaOH浓度为1~5M，柠檬酸钠浓度0.01~1M；
步骤3）中蠕动本液滴滴速根据实际需要控制在0.5~10ml/min.
本发明制备方法特点主要在于
制备方法简单，制备成本低廉。
绿色环保，制备过程中无有毒有害试剂的使用，无二次污染的产生。
所制得凝胶微球可通过外加磁场进行回收，粒径可控，多孔结构明显，具有良好的吸附性和耐酸性。
附图说明
附图1为多孔磁性壳聚糖凝胶微球照片。
附图2为普通壳聚糖微球和磁性多孔壳聚糖凝胶微球的傅里叶红外光谱对比图。
附图3为普通壳聚糖微球（A）与多孔磁性壳聚糖凝胶微球（B）外观扫描电镜对比图。
附图4多孔磁性壳聚糖内部结构扫描电子显微镜（SEM）照片。
具体实施方式
下面结合具体实施例1、实施例2及说明书附图进一步说明本发明。
实例1：在烧杯中加入0.4g壳聚糖，加入10~20ml的2%的醋酸溶液，用磁力搅拌器溶解搅拌30min（3000r/min），配制同时含有Fe2+（0.5~1M）、Fe3+(1~2M)的混合溶液（摩尔比为0.1~2.0），加入壳聚糖溶液继续搅拌30min（3000r/min），溶液从亮黄色变为暗红色。用去离子水配制碱性浸泡溶液，称取一定质量的氢氧化钠和柠檬酸钠，使溶解后的溶液中其浓度分别为1~5M和0.01~1M。用蠕动泵将壳聚糖溶液逐滴滴入上述碱性浸泡溶液中，浸泡24h后，外加磁场将磁性壳聚糖凝胶微球分离，用去离子水多次冲洗直至中性，所获得的磁性壳聚糖凝胶微球浸泡在去离子水中储存待用。通过傅立叶红外光谱，SEM和光学显微镜对吸附剂官能团及内部结构进行表征分析（表征结果见附图2、附图3、附图4）。
实例2：取1mmol/L的Pb2+溶液3ml，加入0.15g磁性壳聚糖凝胶微球作为吸附剂，吸附12h后，通过火焰原子吸收光谱法测定溶液中铅剩余浓度，根据公式①计算其去除率。通过扫描电镜对吸附剂吸附前后进行对比（表征结果见附图4C，附图4D）。
公式①：去除率=(Co-Ce)*V/Co*100%
其中Co为初始浓度，Ce为吸附平衡浓度，V为铅溶液体积。
经计算得，该吸附剂对1mmol/L的Pb2+溶液的去除率达到90%以上。
附图1中各图均为反映多孔磁性壳聚糖凝胶微球不同性质的光学照片，附图1A图中凝胶微球在无外加磁场作用下散落在烧杯底部，附图1B图中加入外加磁场后，凝胶微球迅速被吸附到烧杯的一侧，表明该吸附剂具有良好的磁感应强度，因此在实际应用过程中可以通过外加磁场对小球达到回收目的。附图1C图为普通壳聚糖微球和磁性壳聚糖凝胶球在相同作用力下挤压后所发生的形变情况。普通壳聚糖凝胶球完全破碎，多孔磁性壳聚糖凝胶球形态保持完整。附图1D图为不同粒径的多孔磁性壳聚糖微球光学照片，在实际应用中可根据不同需求调节改变其粒径尺寸以适应实际处理需求。附图1E图为磁性壳聚糖凝胶球光学显微镜下的内部孔隙结构图。附图1F图为磁性壳聚糖凝胶微球干燥前后粒径分布柱状图和形态变化对比照片。
附图2为傅里叶红外光谱对比图，红外光谱在574cm-1处为Fe-O震动峰，B，C在此处出现峰值表明了Fe3O4的存在。1078cm-1处是一级羟基的震动峰。1382cm-1处为伯醇吸收峰，A，B在此处变化不大，证明Fe3O4的引入并未明显影响到壳聚糖此处的活性官能团，C在此处变化较大，证明了铅离子与活性基团发生螯合作用。1419cm-1处为C-N震动峰，A，B在此处变化不大，但C在此处变化较大，是由于Pb2+在氨基上的吸附引起了位移。A中1594cm-1处是C=O的震动峰，1643cm-1为氨基的震动峰，B中分别位移至1598cm-1和1639cm-1，是由于柠檬酸根起了交联作用引起的位移，并且B中氨基峰减弱，羰基峰增强，证明了交联剂在氨基处发生了作用，减少了部分氨基，但柠檬酸根同时引入了更多的羧酸根，同样可以作为吸附官能团，C中这两个位置的吸收峰均有减弱，证明了吸附的发生。2877cm-1和2923cm-1属于-CH和-CH2的吸收峰，A中3430cm-1处为-OH和-NH的吸收峰，B中在此处发生了位移，也证明了交联反应的发生。
附图3中A图为使用相同方法制备出的无Fe3O4存在的普通壳聚糖凝胶微球，B图为多孔磁性壳聚糖凝胶微球，由于磁性壳聚糖凝胶微球内具有优于普通壳聚糖凝胶微球的特殊多孔结构，明显可以看出A图凝胶微球表面光滑，而B图由于内部孔隙较多，导致表面凹凸不平。
附图4中A、B分别45倍和80倍放大下的凝胶微球剖面扫描电镜照片，C图为900倍放大下多孔磁性壳聚糖凝胶微球的内部网状结构扫描电镜图，D图为放大1200倍后吸附了铅离子后的壳聚糖凝胶微球光学显微镜图，图中可见微球多孔结构被明显堵塞，并且表面附着大量的团聚物，与火焰原子吸收及红外光谱分析结果相结合，进一步的确定了吸附反应的发生。
Claims (10)
1.一种粒径可控的多孔磁性壳聚糖凝胶微球及其制备方法，其特征在于以壳聚糖为基材，以柠檬酸钠为离子型交联剂，通过原位共沉淀法形成Fe3O4并均匀的分布于壳聚糖网络结构中；所述壳聚糖凝胶微球具有良好的磁感应强度与明显的多孔结构，其粒径可以根据需要控制在100~5000μm。
2.如权利1所述，基于多孔磁性壳聚糖凝胶微球的制备方法，其特征在于包括如下步骤：
（1）室温常压下，将壳聚糖溶于2wt%醋酸溶液中，充分搅拌30min；
（2）配制一定摩尔比的Fe2+和Fe3+混合溶液，加入到壳聚糖溶液中持续搅拌30min制备前驱诱导溶胶；
（3）将步骤（2）中混合溶液用蠕动泵逐滴滴入碱性浸泡溶液中，共沉淀生成Fe3O4，溶胶固化与交联反应同时发生，生成壳聚糖凝胶微球；
（4）通过外加磁场分离磁性凝胶微球，用去离子水冲洗至pH6~7，储存于超纯水中备用。
3.如权利要求2中制备方法所述，其特征在于，步骤（1）中优选质量分数大于3.0×105g/mol-1、脱乙酰度为大于80%的壳聚糖。
4.如权利要求2中制备方法所述，其特征在于，步骤（1）中壳聚糖溶液浓度为1wt%~6wt%。
5.如权利要求2中制备方法所述，其特征在于，步骤（2）Fe2+（0.005~0.02M），Fe3+（0.0025~0.01M），Fe2+与Fe3+的摩尔比为0.1~2.0。
6.如权利要求2中制备方法所述，其特征在于，步骤（3）中前驱诱导溶胶在碱性溶液中浸泡时间为12~24h。
7.如权利要求2中制备方法所述，其特征在于，步骤（3）中碱性浸泡液中含有NaOH和柠檬酸钠。
8.如权利要求2中制备方法所述，其特征在于，步骤（3）中可通过控制蠕动泵的转速和液体浓度控制成多孔磁性壳聚糖凝胶微球粒径大小，粒径范围在100~5000μm。
9.如权利要求7所述，其特征在于NaOH浓度为1~5M，柠檬酸钠浓度为0.01~1M。
10.如权利要求1所述的多孔磁性壳聚糖凝胶微球内部具有大量天然空隙，可以用于矿山、冶炼厂、电子厂、电镀厂废水以及放射性等废水中金属离子富集回收和污染修复。
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| CN109603765A (zh) * | 2018-12-14 | 2019-04-12 | 陕西师范大学 | 一种低聚壳聚糖磁珠的、制备方法及其应用 |
| CN109603765B (zh) * | 2018-12-14 | 2021-07-16 | 陕西师范大学 | 一种低聚壳聚糖磁珠的、制备方法及其应用 |
| CN109894097A (zh) * | 2019-04-09 | 2019-06-18 | 合肥工业大学 | 一种去除水体中四环素类抗生素的方法 |
| CN110117009A (zh) * | 2019-05-27 | 2019-08-13 | 武汉大学 | 一种铁氮共掺杂磁性多孔石墨化纳米碳气凝胶的制备方法 |
| CN111659353A (zh) * | 2020-05-26 | 2020-09-15 | 广西大学 | 一种原位季铵化磁性壳聚糖微球的制备方法 |
| CN113230987A (zh) * | 2021-05-24 | 2021-08-10 | 南京工业大学 | 一种简易的磁性壳聚糖气凝胶的制备方法 |
| CN113413881A (zh) * | 2021-06-17 | 2021-09-21 | 兰州大学 | 一种BWO/Fe3O4@cBC壳聚糖凝胶小球的制备方法及应用 |
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