CN113413886A - 一种高分子吸附材料及其制备方法与应用 - Google Patents
一种高分子吸附材料及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种高分子吸附材料及其制备方法与应用,其制备方法包括以下步骤:以Fe3O4@SiO2,丙烯酸、丙烯酰胺、对苯乙烯磺酸钠或者Fe3O4@SiO2,丙烯酸、丙烯酰胺、苯乙烯为原料,聚乙烯醇为分散剂,十六烷为制孔剂,制备磁性复合水凝胶,再经硫醇改性制备改性磁性复合水凝胶P(AA/AM/SSS)/Fe3O4@SiO2或P(AA/AM/S)/Fe3O4@SiO2。本发明能够有效地减缓纳米Fe3O4的团聚现象,提高材料的比表面积,增加吸附鏊和基团,有效的提高了吸附能力。
Description
技术领域
本发明涉及磁性水凝胶的制备以及在工业中的应用,属于高分子复合材料吸附剂领域。
背景技术
大多数重金属离子,即使浓度很低,也具有毒性并且不会被生物降解。重金属离子有极大的毒性,不易排出体外;如若不慎摄入人体,可能会致癌、致畸,甚者产生生命危险。工业中产生的废水中常含有大量铅离子Pb(Ⅱ)、镉离子Cd(Ⅱ)等重金属离子,若不加处理直接排放到环境水系中,会导致严重的水污染事件发生。处理这些重金属离子废水常用化学沉淀法、离子交换法、电化学法和吸附法。其中,吸附法是目前处理重金属离子废水的有效方法之一,其具有操作简单灵活、高去除率、多数吸附材料易回收、成本低等优点。于此同时,对吸附法所用新型吸附材料的要求日益增高,既要求具有高吸附量、易回收、重复利用性好等优良性能,又需要易制备、低成本,于环境无害。
水凝胶吸附剂因其经济效益而被广泛关注,特别是磁性水凝胶,不仅具有良好的吸附能力且易于回收。以Fe3O4纳米颗粒作为水凝胶的一种原料时,虽然水凝胶对重金属离子具有良好的吸附效果,但是由于纳米Fe3O4粒子之间存在范德华力以及自身的磁力作用,容易发生团聚现象,这将会减小水凝胶的比表面积并降低其吸附重金属能力。
发明内容
本发明的目的是提供一种高分子吸附材料及其制备方法与应用,以解决Fe3O4纳米颗粒作为水凝胶的一种原料时存在团聚,从而复合不均匀,不稳定问题,并提高水凝胶三维网状结构和比表面积,从而解决吸附能力低的问题。
为实现上述目的,本发明采用如下技术方案:
一种高分子吸附材料的制备方法,其特征在于:包括以下步骤:
(1)将Fe3O4纳米颗粒分散到水中,加入乙醇、氨水和硅酸乙酯,制备得到 Fe3O4@SiO2磁性纳米粒子;
(2)以Fe3O4@SiO2磁性纳米粒子、丙烯酸、丙烯酰胺和对苯乙烯磺酸钠或者 Fe3O4@SiO2磁性纳米粒子、丙烯酸、丙烯酰胺和苯乙烯为原料,并加入分散剂和制孔剂,制备磁性复合水凝胶P(AA/AM/SSS)/Fe3O4@SiO2或P(AA/AM/S)/Fe3O4@SiO2;
(3)将步骤(3)得到到磁性复合水凝胶改性,将其羟基变为硫醇基,得到所述高分子吸附材料。
所述步骤(2)中,以聚乙烯醇为分散剂,将丙烯酸加入氢氧化钠水溶液中和,再加入丙烯酰胺和对苯乙烯磺酸钠或丙烯酰胺和苯乙烯,同时加入Fe3O4@SiO2纳米粒子,然后加入过硫酸钾作为引发剂,N,N’-亚甲基双丙烯酰胺为交联剂,同时加入十六烷作为制孔剂,,搅拌,制得磁性复合水凝胶。
所述步骤(2)中,各原料混合后,升温至50℃-80℃,然后搅拌至黏稠,放入烘箱干燥,得到磁性复合水凝胶。
所述步骤(2)中,AA/AM/SSS与Fe3O4@SiO2磁性纳米粒子的质量比为(5~10): 1,AA/AM/S与Fe3O4@SiO2磁性纳米粒子的质量比(10~5):1,分散剂的用量占原料总质量的5-20%,制孔剂的用量占原料总质量的1-10%。
所述步骤(3)中,将磁性复合水凝胶放在质量浓度为14%的氢氧化钠溶液中,加入二硫化碳,搅拌处理24h,然后用去离子水将改性后的产物冲洗至中性,在70℃下干燥12h,得到硫醇基改性磁性复合水凝胶。
一种用于所述的高分子吸附材料的制备方法的装置,包括依次连接的反应釜、双钢带冷却结片机、破碎机,所述双钢带冷却结片机的前半部分设置有一个保温室,保温室下方通入导热油,双钢带冷却结片机的后半部分下方通入冷凝水。
一种由所述的方法制备得到的复合高分子吸附材料。
所述的高分子吸附材料作为吸附剂在吸附工业废水中的重金属离子或化工染料中的应用。
所述重金属离子为Pb2+、Cu2+、Co2+、Cd2+和Ni2+的一种或多种。
所述化工染料为亚甲基蓝、甲基橙、孔雀绿和碱性藏花红的一种或多种。
吸附重金属离子的条件是:温度20~45℃,pH值为3~6;吸附化工染料的条件是:温度20~45℃,pH值为1~8。有益效果:相比于现有技术,本发明具有以下优点:
(1)较于Fe3O4纳米颗粒作为水凝胶时,Fe3O4@SiO2其吸附性能更强。介孔SiO2因其具有均匀的孔结构,较大的比表面积和良好的孔径特性,被广泛应用于吸附分离领域。本发明将SiO2包裹在纳米Fe3O4外层制备得到Fe3O4@SiO2,能够有效地减缓纳米 Fe3O4的团聚现象,并提高磁性介孔微球对重金属的吸附能力。
(2)加入聚乙烯醇作为分散剂,十六烷为制孔剂,显著提高三维网状结构和孔洞结构,提高比表面积,从而提高吸附能力。
(3)印染行业废水总排放量占染料和重金属离子废水总排放量的1/3,平均废水回用率仅为7%左右,本发明所制备的磁性水凝胶水凝胶具有清晰的三维网状结构,能够通过其表面的羧基和氨基与亚甲基蓝(MB)和孔雀石绿(MG)相互作用,对MB,MG 的吸附较好。
(4)本发明所制备的磁性水凝胶作为吸附剂具有广泛的适用性,对污水中的铅、镍、镉、铜等重金属均有显著的吸附效果,尤其是对铅离子选择性好,最大吸附量达到4975mg/g,高效的再生和金属离子回收能力,对铅、镍、镉、铜等吸附能力没有损失,可以重复使用。
(5)本发明所制备的磁性水凝胶具有较好的再生能力。
附图说明
图1为实施例1中磁性水凝胶的合成示意图;
图2a为实施例1中磁性水凝胶红外光谱;
图2b为实施例1中磁性水凝胶的XRD分析曲线;
图2c为实施例1中磁性水凝胶的热重图谱;
图3为实施例1中不同pH值时磁性水凝胶对典型重金属离子的吸附曲线;
图4为实施例1中的吸附时间与吸附量的关系;
图5为实施例1中磁性水凝胶的重复利用性测试;
图6为实施例1中的中试生产工艺流程图;
图7为实施例1中的中试生产设备图;
图8为实施例1中的中试生产DCS图;
图9为实施例2中磁性复合水凝胶的红外光谱图;
图10为实施例2中磁性复合水凝胶的拉曼图;
图11为实施例2中磁性复合水凝胶的X射线衍射图;
图12为实施例2中磁性复合水凝胶的热重曲线;
图13为实施例2中pH值与吸附量的关系;
图14为实施例2中吸附时间与吸附量的关系;
图15为实施例2中吸附次数对吸附量的影响。
具体实施方式
下面结合实施例对本发明做更进一步的解释。
实施例1
磁性水凝胶P(AA/AM/S)/Fe3O4@SiO2的制备
(1)实验室小试
(1.1)磁性水凝胶制备
如图1所示,将Fe3O4纳米颗粒分散到水中,加入乙醇、氨水和硅酸乙酯制备得到Fe3O4@SiO2磁性复合纳米粒子。以0.3g聚乙烯醇为分散剂,将3.14mL丙烯酸加入氢氧化钠水溶液中和,再加入1.11g丙烯酰胺和0.61mL苯乙烯,同时加入Fe3O4@SiO2纳米粒子,然后加入0.10g过硫酸钾作为引发剂,0.027g N,N’-亚甲基双丙烯酰胺为交联剂,同时加入十六烷作为制孔剂,升温至80℃,然后搅拌8h至黏稠,用清水洗涤,放入烘箱干燥24h,粉碎得约200目的磁性复合水凝胶P(AA/AM/S)/Fe3O4@SiO2。其中, AA/AM/S与Fe3O4@SiO2磁性纳米粒子的质量比为5:1。
将P(AA/AM/S)/Fe3O4@SiO2,转移至100mL质量浓度为14.0%的氢氧化钠溶液中,加入1mL的二硫化碳,用磁力搅拌处理24h,用去离子水将改性后的产物冲洗至中性,也在70℃下干燥12h,获得硫醇基改性磁性水凝胶。
(1.2)磁性水凝胶形态与结构表征
图2a所示为改性磁性水凝胶与P(AA/AM/S)水凝胶的红外光谱图。由图可知,在3429 cm-1和3439cm-1处出现的是-NH与-OH的伸缩振动峰。-CH2-的伸缩振动吸收峰在2960cm-1和2940cm-1处出现,苯环的伸缩振动峰则在1596cm-1和1531cm-1处出现。1392cm-1和1393cm-1两处峰表明两种水凝胶中都有-COONa中的-C=O-的对称伸缩振动峰。而776cm-1处出现了Si-O的对称伸缩振动峰,620cm-1附近出现了Fe3O4上的Fe-O的伸缩振动吸收峰。
图2b为XRD分析曲线,磁性水凝胶30.5°,35.4°,43.3°,54.5°,57.5°和63.1°处出现的特准衍射峰分别归属于反尖晶石结构Fe3O4[220],[311],[400],[422],[511] 和[440]的晶面。由上述两个方面可知形成了P(AA/AM/S)/Fe3O4@SiO2
图2c为磁性水凝胶的热重曲线,当温度低于340℃时,磁性水凝胶的质量损失率为12.5%;在340~422℃时磁性水凝胶的质量损失率为30.5%,水凝胶中一些低聚物和水凝胶链上较为稳定的基团断裂分解;422℃之后,磁性水凝胶的质量损失率在缓慢降低。磁性水凝胶的热分解温度(重量损失5%)达到205℃,说明磁性水凝胶具有较为良好的热稳定性。通过BET测试法得到磁性水凝胶比表面积、孔体积、平均孔直径分别为700-900m/g、90-120cm3/g、315-30nm,属于介孔材料。
(1.3)pH对磁性水凝胶吸附金属离子的影响
不同pH的铅离子溶液,对水凝胶吸附铅离子有着很重要的影响。由于铅离子溶液pH值的不同,水凝胶对铅离子的吸附性能会有所不同。本次测试在其他条件相同的情况下,以金属离子溶液的pH作为唯一变量,测试重金属离子溶液pH值对水凝胶吸附铅离子性能的影响。取5份质量为0.10g的磁性水凝胶粉末分别装入装有浓度为1000mg/L,体积为50mL的重金属离子溶液的锥形瓶中。将重金属离子溶液的pH分别调至2、3、4、 5、6,30℃条件下搅拌120min。静置沉淀后取上清液吸收适量稀释。以原子吸收分光光度计测试其浓度。
由图3可知,当pH值区于1和2之间,磁性水凝胶吸附的重金属离子的量较小;当pH值在2~4之间时,吸附量上升;而当pH值位于4~6时,吸附量仍呈现上升趋势,相对比之前较慢。可能原因是pH低时水凝胶中的NH3 +会因为-NH2进行质子化而大量溢出,对重金属离子产生静电排斥,最终降低磁性水凝胶对重金属离子的吸附性能,因此,在后续的实验中铅离子溶液的PH值控制在5左右。
(1.4)磁性水凝胶不同吸附时间的分析
对比其他几种重金属离子,磁性水凝胶对Pb(Ⅱ)的吸附效果较为显著,以下选择50ml 1000mg/L Pb(Ⅱ)溶液为对象研究磁性水凝胶的吸附性能,图4为磁性水凝胶随吸附时间吸附量的变化曲线,在吸附开始的一段时间里吸附容量迅速增加,随吸附时间变化,吸附量趋于平缓,在180min达到饱和。这主要是因为随反应进行磁性水凝胶吸附位点逐渐被Pb(Ⅱ)占据,达到478mg/g。
表1磁性水凝胶对Pb(Ⅱ)吸附的准一级和准二级动力学模型拟合参数与颗粒扩散模型拟合参数
磁性水凝胶吸附动力学拟合结果见表1。所得准二级动力学的相关系数(R2>0.999) 高于准一级动力学;对比实验所得的吸附容量和理论吸附容量,准二级动力学所得的理论吸附容量更接近于实验所得的吸附容量,因此,磁性水凝胶对Pb(Ⅱ)的吸附动力学更加符合准二级动力学模型,,吸附方式为化学吸附。
(1.5)竞争吸附分析
称取4份0.2磁性水凝胶粉末,分别加入到重金属离子Pb(Ⅱ)/Cd(Ⅱ)、 Pb(Ⅱ)/Ni(Ⅱ)、Pb(Ⅱ)/Cu(Ⅱ)、Pb(Ⅱ)/Cd(Ⅱ)/Cu(Ⅱ)/Ni(Ⅱ)四个体系溶液。在200 r/min下恒温25℃震荡2h后,采用原子吸收分光光度计测量Pb(Ⅱ)的含量。
对磁性水凝胶进行竞争吸附实验。在Pb(Ⅱ)/Cd(Ⅱ)/Cu(Ⅱ)/Ni(Ⅱ)、 Pb(Ⅱ)/Cd(Ⅱ)、Pb(Ⅱ)/Ni(Ⅱ)、Pb(Ⅱ)/Cu(Ⅱ)这四个体系中,铅离子的竞争吸附量受影响较小,仍可达到466、456、465、454mg/g,说明磁性水凝胶对Pb(Ⅱ)的亲和力较大。
(1.6)再生吸附分析
对于吸附剂而言,除了要对材料的吸附性能是否高效进行考察以外,还要对其循环再生性能进行测试,重复利用性能是衡量一个吸附材料其实际应用性能的一个重要标准。主要是以Pb2+为实验对象,对其进行吸附解吸附实验分析,从而检测磁性水凝胶的重复利用性能。向50mL 1 000mg/L的Pb(Ⅱ)溶液中加入0.20g磁性水凝胶粉末,在 200r/min下恒温25℃震荡2h,静置沉降,取上清液,测定溶液中Pb(Ⅱ)的含量。用浓盐酸进行解吸附。重复吸附解吸附实验十次,同时平行三次上述实验。计算水凝胶的对应的吸附量。
由图5可知,随着吸附次数的增加,水凝胶对Pb(Ⅱ)的吸附量微微下降。十次吸附中仍能对铅离子溶液有418mg/g的吸附量,这说明磁性水凝胶具有优异再生能力。
(2)工厂中试
生产流程如图6所示,将原料207Kg丙烯酸、35Kg苯乙烯和100Kg丙烯酰胺;加入分散剂聚乙烯醇,引发剂过硫酸钾约0.5~0.7Kg;N,N’-亚甲基双丙烯酰胺交联剂,制孔剂十六烷;Fe3O4@SiO2(35~70Kg)投入到500L的反应釜中。加入NaOH溶液调节体系 pH值为6~7,温度控制在50℃~80℃,搅拌速率控制在40~70转/分钟,反应7~9 小时以后,停止反应。
生产设备图见图7,包括依次连接的反应釜1、双钢带冷却结片机2、破碎机3,双钢带冷却结片机2的前半部分设置有一个保温室4,保温室下方通入导热油,双钢带冷却结片机的后半部分下方通入冷凝水。生产DCS图见图8。
完成聚合后的产物从反应釜底流出,流入双钢带冷却结片机,结片机前半部分是一个保温室,在保温室下方通入导热油,对产物进行恒热干燥,结片机后半部分需要在下方通冷凝水对干燥后的产物进行冷却,接着使用破碎机进行粉碎,硫醇基改性,干燥,最后称重装袋。
(2.1)吸附性能测试
在30℃,PH值为5的条件下,取0.1g磁性水凝胶粉末分别装入装有浓度为1000mg/L,体积为50mL的重金属离子溶液的锥形瓶中,搅拌120min,测得磁性水凝胶对铅离子的吸附最好,吸附量最大可达396mg/g;
温度20~40℃,PH为4~6,制备的磁性水凝胶对铅离子的吸附量为390mg/g;
温度20~40℃,PH为5~6,制备的磁性水凝胶对铜离子的吸附量为283mg/g;
温度20~40℃,PH为4~5,制备的磁性水凝胶对镉离子的吸附量为284mg/g;
温度20~40℃,PH为5~6,制备的磁性水凝胶对镍离子的吸附量为198mg/g。对于化工染料的吸附测试结果如下:
在温度为20~40℃,PH在4~6,制备的磁性水凝胶对初始浓度为1000mg/g的亚甲基蓝(MB)的最大吸附量为397mg/g,对初始浓度为800mg/g的孔雀石绿(MG)最的大吸附量为379mg/g;
在温度为20~40℃下,PH为1~3,制备的磁性水凝胶对初始浓度为300mg/L的甲基橙的最大吸附量为288mg/g;
在温度为20~40℃,PH为3~7,制备的磁性水凝胶对初始浓度为1000mg/L的碱性藏红花的最大吸附量为432mg/g,当吸附时间为50min时,吸附达到平衡。
综上,本实施例制备的磁性水凝胶是一种吸附性能优良的复合材料,可以有效的去除工业废水中的重金属离子铅、镍、镉、铜等。除了对重金属离子具有吸附作用外,其对化工染料也有较好的吸附性能,尤其是对亚甲基蓝,甲基橙,孔雀绿,碱性藏花红等
实施例2
磁性水凝胶P(AA/AM/SSS)/Fe3O4@SiO2的制备及应用
(1)实验室小试
(1.1)磁性水凝胶制备
将Fe3O4纳米颗粒分散到水中,加入乙醇、氨水和硅酸乙酯制备得到Fe3O4@SiO2磁性复合纳米粒子。以0.3g聚乙烯醇为分散剂,将3.14mL丙烯酸加入氢氧化钠水溶液中和,再加入1.11g丙烯酰胺和0.61g对苯乙烯磺酸钠,同时加入Fe3O4@SiO2纳米粒子,然后加入0.10g过硫酸钾作为引发剂,0.027g N,N’-亚甲基双丙烯酰胺为交联剂,同时加入十六烷作为制孔剂,升温至50℃,然后搅拌至黏稠,用清水洗涤,放入烘箱干燥,得到磁性水凝胶P(AA/AM/SSS)/Fe3O4@SiO2。其中,AA/AM/SSS与Fe3O4@SiO2的质量比为5:1。
将磁性水凝胶P(AA/AM/SSS)/Fe3O4@SiO2,转移至100mL质量浓度为14.0%的氢氧化钠溶液中,加入1mL的二硫化碳,用磁力搅拌处理24h,用去离子水将改性后的产物冲洗至中性,在70℃下干燥12h,获得硫醇基改性磁性水凝胶。
(1.2)磁性水凝胶形态与结构表征
图9为三元共聚水凝胶与磁性水凝胶的红外光谱图,在3507cm-1、1541cm-1、1393cm-1处分别为-CH2-的不对称伸缩峰、C=O的伸缩振动峰、C-H的伸缩振动峰,在575cm-1、806cm-1、1198cm-1处的峰分别为Fe3O4的Fe-O振动峰、SiO2的Si-O对称伸缩振动峰、 Si-O-Si对称吸收峰。图10为三元共聚水凝胶与磁性水凝胶的拉曼光谱图,在226cm-1、 292cm-1、410cm-1、497cm-1、611cm-1处显示的是Fe3O4的对称振动峰。图11为磁性水凝胶的X射线衍射图,图中显示出了Fe3O4衍射峰(2θ=29.9°、35.2°、43.0°、53.3°、 56.8°、62.4°),以上三种测试分析结果共同说明了Fe3O4@SiO2与三元共聚水凝胶成功复合。
图12为磁性水凝胶的热重曲线(TG)和热重微分曲线(DTG)。当温度低于372℃时失重率为9%,这主要是水凝胶表面官能团的降解过程;在356℃~471℃有较高的质量损失,这是由于水凝胶中一些低聚物和水凝胶链上较为稳定的基团的断裂分解所致;在471℃之后,水凝胶的质量损失趋于平缓,这与水凝胶内部的热稳定性有关。此外,比表面积及孔径分布测试结果显示:制备得到的磁性水凝胶比表面积为700-900m/g、 90-120cm3/g、315-30nm,是一种优良的介孔材料。
(1.3)pH值对磁性水凝胶吸附重金属离子的影响
在不同的pH值条件下,磁性水凝胶对重金属离子的吸附效果也不同。将0.1g磁性水凝胶,分别加入到1g/L的Pb2+、Cu2+、Co2+、Cd2+、Ni2+离子溶液中;调节溶液pH 值为2、3、4、5、6,充分搅拌2h。静置后取样,用原子吸收分光光度计测试重金属离子的浓度,计算其吸附量。
图13为pH值与吸附量的关系图,当pH值在2~4时,对金属离子的吸附量逐渐增加,pH值达到4以后,吸附量增加缓慢甚至出现降低。以吸附效果最好的Pb2+为例,当pH值为4~5时,水凝胶对其吸附量达到最大值497mg/g;当pH值继续增大,吸附效果减弱,这主要是因为水凝胶中的-NH2会质子化从而产生大量的-NH3 +,-NH3 +会对溶液中的金属离子产生排斥作用。
(1.4)吸附时间对磁性水凝胶吸附重金属离子的影响
在pH值为4的Pb2+溶液中加入0.1g磁性水凝胶粉末,振荡4h,在不同时间点取样测试。根据实验得到的数据,分别拟定拟一级动力学方程,拟二级动力学方程和颗粒扩散方程。图12为不同时间磁性水凝胶对Pb2+的吸附量。在吸附初期,水凝胶内吸附点位充足,吸附量上升较快。当时间在40~50min时,吸附量上升缓慢,并逐渐达到平衡,在50min以后,吸附量几乎无法再升高,逐渐达到一个饱和的状态,此时水凝胶内吸附点位基本被填满,水凝胶的吸附率达到99%,具有较好的吸附效果。
表2吸附动力学拟合参数
表2为磁性水凝胶的吸附动力学拟合参数。表中数据显示:对于Pb2+的吸附过程不符合一阶动力学模型和颗粒扩散模型(R2<0.9000),然而很好地拟合了拟二级动力学模型(R2>0.9950),根据此方程推算出的理论吸附量502.44mg/g与实验得到的结果相近,这说明拟二级动力学方程能更好地描述磁性水凝胶对Pb2+的吸附过程,其吸附过程是一种化学吸附。
(1.5)竞争吸附分析
称取5份0.2g磁性水凝胶粉末,分别加入到重金属离子混合溶液中(Pb2+/Cd2+、 Pb2 +/Ni2+、Pb2+/Co2+、Pb2+/Cu2+、Pb2+/Cd2+/Co2+/Cu2+/Ni2+),振荡2h,取样测量溶液中 Pb2+浓度。表3为磁性水凝胶在混合体系中对Pb2+的吸附量和去除率。在单组分体系中,水凝胶对Pb2+的吸附量最大达到497mg/g。在混合体系中,水凝胶对Pb2+的吸附量均有所下降,这是由于水凝胶上的吸附点位是一定的,而活性吸附点不能被重复占据并且各个金属离子的初始浓度都较大所致。但是,磁性水凝胶在混合体系中对Pb2+的去除率仍然能够达到90%左右,说明磁性水凝胶对Pb2+有较高的选择性。
表3混合体系中磁性水凝胶对Pb2+的吸附量和去除率
(1.6)磁性水凝胶可重复利用性分析
为了实现磁性水凝胶的再生,将吸附完的磁性水凝胶加入到0.5mol/L的HCl溶液中,在室温下恒温振荡,进行解吸附,用去离子水洗至中性,再对Pb2+进行吸附实验。如图13所示,循环7次吸附解吸附实验以后,磁性水凝胶对Pb2+的吸附量仍有265mg/g,是初始值(497mg/g)的53%,这说明磁性水凝胶具有较好的再生性能。
(2)工厂中试:
(2.1)生产流程类似于图6所示,将原料105Kg丙烯酸、66Kg丙烯酰胺和174Kg 对苯乙烯磺酸钠,加入分散剂聚乙烯醇,;引发剂过硫酸钾约0.5~0.7Kg;N,N’-亚甲基双丙烯酰胺交联剂;Fe3O4@SiO2(35~70Kg)投入到500L的反应釜中,制孔剂十六烷。加入NaOH溶液调节体系pH值为6~7,温度控制在50℃~80℃,搅拌速率控制在40~70转/分钟,反应7~9小时以后,终止反应。
生产设备图见图7,包括依次连接的反应釜1、双钢带冷却结片机2、破碎机3,双钢带冷却结片机2的前半部分设置有一个保温室4,保温室下方通入导热油,双钢带冷却结片机的后半部分下方通入冷凝水。生产DCS图见图8。
完成聚合后的产物从反应釜底流出,流入双钢带冷却结片机,结片机前半部分是一个保温室,在保温室下方通入导热油,对产物进行恒热干燥,结片机后半部分需要在下方通冷凝水对干燥后的产物进行冷却,接着使用破碎机进行粉碎,硫醇基改性,干燥,最后称重装袋。
(2.2)吸附性能测试
在30℃,pH值为5的条件下,取0.1g磁性水凝胶粉末,加入到50mL,1g/L的Pb2+离子溶液中,搅拌振荡45分钟,测得磁性水凝胶对Pb2+吸附效果最好,吸附量最大可达373mg/g,去除率可达74%。
以同样的方法测得在20~45℃,pH值为5~6,对Cu2+的最大吸附量313mg/g。
在20~45℃,pH值为3~5,对Co2+的最大吸附量276mg/g。
在20~45℃,pH值为5~6,对Cd2+的最大吸附量130mg/g。
在20~45℃,pH值为4~6,对Ni2+的最大吸附量279mg/g。
对于化工染料的吸附测试结果如下:
在20~45℃,pH值在4~5,磁性水凝胶对初始浓度为350mg/L的亚甲基蓝的最大吸附量为368mg/g。
在20~45℃,pH值在1~3,磁性水凝胶对初始浓度为300mg/L的甲基橙的最大吸附量为270mg/g。
在20~45℃,pH值在3~4,磁性水凝胶对初始浓度为1000mg/L的孔雀石绿的最大吸附量为365mg/g。
在20~45℃,pH值在6~8,磁性水凝胶对初始浓度为1000mg/L的碱性藏花红的最大吸附量为405mg/g。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种高分子吸附材料的制备方法,其特征在于:包括以下步骤:
(1)将Fe3O4纳米颗粒分散到水中,加入乙醇、氨水和硅酸乙酯,制备得到Fe3O4@SiO2磁性纳米粒子;
(2)以Fe3O4@SiO2磁性纳米粒子、丙烯酸、丙烯酰胺和对苯乙烯磺酸钠或者Fe3O4@SiO2磁性纳米粒子、丙烯酸、丙烯酰胺和苯乙烯为原料,并加入分散剂和制孔剂,制备磁性复合水凝胶P(AA/AM/SSS)/Fe3O4@SiO2或P(AA/AM/S)/Fe3O4@SiO2;
(3)将步骤(3)得到到磁性复合水凝胶改性,将其羟基变为硫醇基,得到所述高分子吸附材料。
2.根据权利要求1所述的高分子吸附材料的制备方法,其特征在于:所述步骤(2)中,以聚乙烯醇为分散剂,将丙烯酸加入氢氧化钠水溶液中和,再加入丙烯酰胺和对苯乙烯磺酸钠或丙烯酰胺和苯乙烯,同时加入Fe3O4@SiO2纳米粒子,然后加入过硫酸钾作为引发剂,N,N’-亚甲基双丙烯酰胺为交联剂,同时加入十六烷作为制孔剂,搅拌,制得磁性复合水凝胶。
3.根据权利要求2所述的高分子吸附材料的制备方法,其特征在于:所述步骤(2)中,各原料混合后,升温至50℃-80℃,然后搅拌至黏稠,放入烘箱干燥,得到磁性复合水凝胶。
4.根据权利要求1或2所述的高分子吸附材料的制备方法,其特征在于:所述步骤(2)中,AA/AM/SSS与Fe3O4@SiO2磁性纳米粒子的质量比为(5~10):1,AA/AM/S与Fe3O4@SiO2磁性纳米粒子的质量比(10~5):1,分散剂的用量占原料总质量的5-20%,制孔剂的用量占原料总质量的1-10%。
5.根据权利要求1所述的高分子吸附材料的制备方法,其特征在于:所述步骤(3)中,将磁性复合水凝胶放在质量浓度为14%的氢氧化钠溶液中,加入二硫化碳,搅拌处理24h,然后用去离子水将改性后的产物冲洗至中性,在70℃下干燥12h,得到硫醇基改性磁性复合水凝胶。
6.一种用于实现权利要求1所述的高分子吸附材料的制备方法的装置,其特征在于:包括依次连接的反应釜、双钢带冷却结片机、破碎机,所述双钢带冷却结片机的前半部分设置有一个保温室,保温室下方通入导热油,双钢带冷却结片机的后半部分下方通入冷凝水。
7.一种由权利要求1所述的方法制备得到的复合高分子吸附材料。
8.权利要求7所述的高分子吸附材料作为吸附剂在吸附工业废水中的重金属离子或化工染料中的应用。
9.根据权利要求8所述的应用,其特征在于:所述重金属离子为Pb2+、Cu2+、Co2+、Cd2+和Ni2+的一种或多种;所述化工染料为亚甲基蓝、甲基橙、孔雀绿和碱性藏花红的一种或多种。
10.根据权利要求8所述的应用,其特征在于:吸附重金属离子的条件是:温度20~45℃,pH值为3~6;吸附化工染料的条件是:温度20~45℃,pH值为1~8。
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