磁性交联壳聚糖微球的制备及其吸附U（Ⅵ）的试验研究
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摘要
高分子材料的发展趋势是高性能化和多功能化,越来越多的人们开始广泛地研究性质特殊的高分子复合微球。本文系统地研究了制备工艺参数与表面活性剂对水基磁流体稳定性和颗粒磁性的影响,利用均匀试验设计研究了不同交联剂作用下磁性壳聚糖微球的制备。最后考察了改性壳聚糖磁性微球对铀的吸附效果,并对改性壳聚糖磁性微球的形貌和结构进行了表征,研究结果表明:
水基磁流体制备过程中,改变各种试验因素对磁流体的制备有很大的影响。由正交试验得出制备吐温修饰的磁流体的理化影响因素主次顺序为:加热温度>N Fe2+/NFe3+>反应时间>pH>搅拌速度>超声分散时间。最佳试验水平组合为:温度45℃,pH为9,NFe2+/NFe3+为1:2,反应时间为30min,超声分散时间为30min,搅拌速度2000rpm。三种水基磁流体的X射线衍射图显示,三种水基磁流体的磁性粒子为纯净的Fe3O4粒子,制备过程中三种表面活性剂的加入并不对Fe3O4粒子的晶形造成破坏性影响。根据Scherrer方程计算,估算出Fe3O4粒子的平均粒径D为28nm。
磁性微球的制备试验采用均匀设计的方法,并由DPS专业数据处理软件分析得到各组中各个因素的最佳水平。
改性壳聚糖磁性微球对铀的吸附试验研究表明改性壳聚糖磁性微球对铀具有吸附速度快、去除速率高的特点,对浓度为10mg/L、50mg/L、100mg/L的铀溶液分别在2分钟、8分钟、10分钟后去除率达到99%、98%和98%以上。通过正交试验得到了改性壳聚糖磁性微球吸附铀试验的影响因素主次顺序为:铀初始浓度>pH>投加量>温度,最佳试验水平组合为:pH值为4,U(VI)初始浓度200mg/L,投加量0.7g,温度为40℃。
吸附后的改性壳聚糖磁性微球用0.1mol/L NaOH、0.5mol/L NaOH、0.1mol/LEDTA三种解吸剂解吸再生4次后,对铀的去除率仍可达90%以上,说明该磁性微球具有良好的重复使用性,为实际应用提供了可能。由改性壳聚糖磁性微球SEM图可以看出其粒径属于微米级,并且其表面疏松,凹凸不平,呈现出许多微小的空隙。红外光谱图中在1649cm-1处出现了新的碱键(C=N)特征吸收峰,表明交联剂D参加了交联反应。从XRD图可以看出改性壳聚糖磁性微球在包裹Fe3O4后在30.0°,35.5°,62.5°均出现了Fe3O4的衍射峰,证明Fe3O4乳化交联过程中其尖晶石结构没有改变,也表明改性壳聚糖磁性微球中包裹了Fe3O4。
In recent years, the development of polymer materials trends to be high- performance ,multi-function.Specialpropertiesofpolymercompositemicro-sphereshaveattractedmoreand more people to research it. The high polymer compound materials, particularlymagnetic high polymer materials, have attracted more attention in nanometer magneticmaterials domains. This paper systematically studied the influence of preparationprocessing parameters and surfactant on stability of water-based magnetic particles, andstudied the preparation of magnetic chitosan microsphere crosslinked by differentcrosslinkingagent usinguniform designmethod..Finallyweinspectedadsorptioneffect ofmagneticmicrospheres touranium,andthestructureandmorphologyof magneticchitosanmicrosphere were detected by scanning electron microscope (SEM), X-ray diffraction(XRD)andinfraredspectra(IR),theresultsareasfollowing:
In water-based magnetic fluid preparation process, reaction temperature, pH, stirringspeed, ultrasonic dispersing time, reaction time, NFe2+ /NFe3+and different surfactants havetremendous influence on the properties of magnetic fluid. The order of factors influencingon the properties of magnetic fluid are heating temperature > NFe2+/ NFe3+ > reaction time>pH > stirring speed > ultrasonic dispersing time according to the orthogonal experiment.And the optimum conditions are: temperature 45℃, pH 9, NFe2+/ NFe3+ 1:2, the reactiontime 30min, ultrasonic dispersing time 30min, stirring speed 2000rpm. The resultsmeasured by X-raydiffractometer demonstrate that Fe3O4 is the main part of the magneticfluid.The Fe3O4 crystalline forms of magnetic fluid don’t change, which are modified bydifferent surfactant. According to the Scherrer equation, the average diameter of Fe3O4is28nm.
The preparation of magnetic microspheres was designed by uniform design method,andtheoptimumlevel offactorsineachgroupwasobtainedbythespecial dataprocessingsoftware.
The results of modified magnetic microspheres adsorption to uranium indicated thatthis process had the advantage of fast adsorption and high removal efficiency. For 10mg/Luranium solution, the removal rate is 99% after 2 minutes. The removal efficiency of50mg/L uranium solution can be up to 98% 8 minutes later, and the rate of 100mg/Luranium solution achieved more than 98% after 10 minutes. The sequence of factors influencingonadsorptionis:Uraniuminitialdensity>pH>biosorbentdose>temperature.And the optimum conditions are: pH 4, Uranium initial density 200mg/l, biosorbent dose0.7g,temperature40℃.
The modified magnetic microspheres can be eluted with 0.1mol/L NaOH, 0.5mol/LNaOH, 0.1mol/L EDTA. After desorption 4 times, the removal efficiency can still reachemore than 90%, which can explained the modified magnetic microspheres have goodavailability of reusing and provided the possibility for practical application. The particalsize of modified magnetic microspheres measured by SEM belonged to micrometer level.Its surface was porous and presents many small holes. IR-spectrum of modified magneticmicrospheres existedtheC=Ncharacteristicabsorptionpeakat 1649cm-1,whichindicatedthat crosslinking agent D reacted with chitosan.Bythe phase analysis in the XRD patternswe could see that the Fe3O4 diffraction peak appeared at 30.0℃, 35.5℃and 62.5℃, Itproved that the spinel structure of Fe3O4, existed in modified magnetic microspheres, didnot change. The result also indicated that the modified magnetic microspheres hadwrappedFe3O4successfully.
水基磁流体制备过程中,改变各种试验因素对磁流体的制备有很大的影响。由正交试验得出制备吐温修饰的磁流体的理化影响因素主次顺序为:加热温度>N Fe2+/NFe3+>反应时间>pH>搅拌速度>超声分散时间。最佳试验水平组合为:温度45℃,pH为9,NFe2+/NFe3+为1:2,反应时间为30min,超声分散时间为30min,搅拌速度2000rpm。三种水基磁流体的X射线衍射图显示,三种水基磁流体的磁性粒子为纯净的Fe3O4粒子,制备过程中三种表面活性剂的加入并不对Fe3O4粒子的晶形造成破坏性影响。根据Scherrer方程计算,估算出Fe3O4粒子的平均粒径D为28nm。
磁性微球的制备试验采用均匀设计的方法,并由DPS专业数据处理软件分析得到各组中各个因素的最佳水平。
改性壳聚糖磁性微球对铀的吸附试验研究表明改性壳聚糖磁性微球对铀具有吸附速度快、去除速率高的特点,对浓度为10mg/L、50mg/L、100mg/L的铀溶液分别在2分钟、8分钟、10分钟后去除率达到99%、98%和98%以上。通过正交试验得到了改性壳聚糖磁性微球吸附铀试验的影响因素主次顺序为:铀初始浓度>pH>投加量>温度,最佳试验水平组合为:pH值为4,U(VI)初始浓度200mg/L,投加量0.7g,温度为40℃。
吸附后的改性壳聚糖磁性微球用0.1mol/L NaOH、0.5mol/L NaOH、0.1mol/LEDTA三种解吸剂解吸再生4次后,对铀的去除率仍可达90%以上,说明该磁性微球具有良好的重复使用性,为实际应用提供了可能。由改性壳聚糖磁性微球SEM图可以看出其粒径属于微米级,并且其表面疏松,凹凸不平,呈现出许多微小的空隙。红外光谱图中在1649cm-1处出现了新的碱键(C=N)特征吸收峰,表明交联剂D参加了交联反应。从XRD图可以看出改性壳聚糖磁性微球在包裹Fe3O4后在30.0°,35.5°,62.5°均出现了Fe3O4的衍射峰,证明Fe3O4乳化交联过程中其尖晶石结构没有改变,也表明改性壳聚糖磁性微球中包裹了Fe3O4。
In recent years, the development of polymer materials trends to be high- performance ,multi-function.Specialpropertiesofpolymercompositemicro-sphereshaveattractedmoreand more people to research it. The high polymer compound materials, particularlymagnetic high polymer materials, have attracted more attention in nanometer magneticmaterials domains. This paper systematically studied the influence of preparationprocessing parameters and surfactant on stability of water-based magnetic particles, andstudied the preparation of magnetic chitosan microsphere crosslinked by differentcrosslinkingagent usinguniform designmethod..Finallyweinspectedadsorptioneffect ofmagneticmicrospheres touranium,andthestructureandmorphologyof magneticchitosanmicrosphere were detected by scanning electron microscope (SEM), X-ray diffraction(XRD)andinfraredspectra(IR),theresultsareasfollowing:
In water-based magnetic fluid preparation process, reaction temperature, pH, stirringspeed, ultrasonic dispersing time, reaction time, NFe2+ /NFe3+and different surfactants havetremendous influence on the properties of magnetic fluid. The order of factors influencingon the properties of magnetic fluid are heating temperature > NFe2+/ NFe3+ > reaction time>pH > stirring speed > ultrasonic dispersing time according to the orthogonal experiment.And the optimum conditions are: temperature 45℃, pH 9, NFe2+/ NFe3+ 1:2, the reactiontime 30min, ultrasonic dispersing time 30min, stirring speed 2000rpm. The resultsmeasured by X-raydiffractometer demonstrate that Fe3O4 is the main part of the magneticfluid.The Fe3O4 crystalline forms of magnetic fluid don’t change, which are modified bydifferent surfactant. According to the Scherrer equation, the average diameter of Fe3O4is28nm.
The preparation of magnetic microspheres was designed by uniform design method,andtheoptimumlevel offactorsineachgroupwasobtainedbythespecial dataprocessingsoftware.
The results of modified magnetic microspheres adsorption to uranium indicated thatthis process had the advantage of fast adsorption and high removal efficiency. For 10mg/Luranium solution, the removal rate is 99% after 2 minutes. The removal efficiency of50mg/L uranium solution can be up to 98% 8 minutes later, and the rate of 100mg/Luranium solution achieved more than 98% after 10 minutes. The sequence of factors influencingonadsorptionis:Uraniuminitialdensity>pH>biosorbentdose>temperature.And the optimum conditions are: pH 4, Uranium initial density 200mg/l, biosorbent dose0.7g,temperature40℃.
The modified magnetic microspheres can be eluted with 0.1mol/L NaOH, 0.5mol/LNaOH, 0.1mol/L EDTA. After desorption 4 times, the removal efficiency can still reachemore than 90%, which can explained the modified magnetic microspheres have goodavailability of reusing and provided the possibility for practical application. The particalsize of modified magnetic microspheres measured by SEM belonged to micrometer level.Its surface was porous and presents many small holes. IR-spectrum of modified magneticmicrospheres existedtheC=Ncharacteristicabsorptionpeakat 1649cm-1,whichindicatedthat crosslinking agent D reacted with chitosan.Bythe phase analysis in the XRD patternswe could see that the Fe3O4 diffraction peak appeared at 30.0℃, 35.5℃and 62.5℃, Itproved that the spinel structure of Fe3O4, existed in modified magnetic microspheres, didnot change. The result also indicated that the modified magnetic microspheres hadwrappedFe3O4successfully.
引文
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