CN111672479B - 一种海藻酸基金属光催化还原材料、制备方法及应用 - Google Patents
一种海藻酸基金属光催化还原材料、制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种海藻酸基金属光催化还原材料、制备方法及应用,N‑氨基胍官能团经过环氧氯丙烷嫁接在海藻酸钠高分子上,再经过氯化钙进行固化交联形成水凝胶状材料,最后,通过尿素渗透及水解制孔方法在水凝胶中加入孔结构以提高其对金属离子的吸附效率和光催化活性。通过此方法制备出的海藻酸基材料在酸性条件下对三价金离子有优良的吸附能力。本发明制备的海藻酸基光催化还原材料相较传统的光催化材料价格低廉,金属离子吸附容量大,可以处理较高浓度的金离子溶液,其光催化还原的特性亦可延伸到重金属离子污染方向,如六价铬、五价砷等重金属的废水处理。本发明为有机光催化材料的工业应用及金属离子废液的处理提供可行途径。
Description
技术领域
本发明涉及一种金属离子吸附光催化还原材料,具体涉及一种海藻酸基金属光催化还原材料的制备方法及应用。
背景技术
重金属污染是指由重金属及其化合物造成的环境污染,在工业开采、冶炼、加工过程中会产生大量的重金属,可以在藻类和污泥中累积,难以自然降解,并可以通过鱼类和贝壳进入食物链,造成严重的危害。这些重金属的处理和回收再利用一直是一个重要的研究问题。目前对于该类工业废水的传统处理工艺主要是化学还原法,存在药剂消耗大,重金属去除不彻底,易造成二次污染等问题。光催化原理是基于光催化剂在光照条件下激发的电子和空穴进行氧化还原反应,目前主要应用在净化污染物、物质合成和转化等方面。近年来,光催化由于其反应迅速,不产生二次污染的特性,在重金属去除领域受到一定关注。然而常见的光催化材料均为无机材料,对于金属离子吸附能力较弱,从而导致对较高浓度的金属离子废水处理能力受限。海藻酸钠,作为自然见中常见的生物质,大量存在于各种藻类植物中,其含有的大量羧基和羟基官能团有较好的金属离子吸附能力,被广泛的应用于金属离子吸附剂的制备中。
发明内容
本发明所要解决的技术问题在于:如何解决现有的技术,对于金属离子吸附能力较弱,从而导致对较高浓度的金属离子废水处理能力受限的问题,提供了一种海藻酸基金属光催化还原材料的制备方法及应用。
原料说明:
本发明中所使用的原料——海藻酸钠(SA)是一种可从藻类中提取的天然多糖,易溶于水溶液中形成凝胶,在褐藻中含量约为30~40%,是一类丰富的可再生资源。海藻酸钠是一种线性的阴离子聚合物,由α-L-甘露糖醛酸(M单元)、β-D-古罗糖醛酸(G单元)两种单体通过1,4糖苷键交替连接所形成,分子结构如1所示,其分子链上M和G单元的含量不同、位置变化等都会影响其凝胶性,当G单元含量较高时,形成的水凝胶硬度大且易碎;当M单元含量较高时,形成的水凝胶弹性好,因此可以通过控制M、G单元的比例,来制备不同强度的凝胶。在本发明中可选用不同M/G比的SA,以期提高制备出凝胶珠的稳定性和吸附性能,增加海藻酸基金属光催化还原材料在金属离子吸附过程中的循环使用次数,降低工业使用成本和实现生态资源循环使用的理念。
本发明是通过以下技术方案解决上述技术问题的,本发明包括以下步骤:
包括以下步骤:
(1)将1~4g N-氨基胍溶于100mL去离子水中,再加入3~8mL环氧氯丙烷,升温到65℃~75℃℃,搅拌条件下反应5~7h,向反应后的液体中加入2~3g海藻酸钠,保持60℃~70℃反应7~8h;
(2)将步骤(1)中得到的液体逐滴滴入到质量分数为1~5%氯化钙溶液中固化10~12h,将所得水凝胶过滤洗净;
(3)将步骤(2)中得到的水凝胶浸泡于含2~5%尿素的乙醇溶液中20~24h,再将浸泡后的水凝胶置于70~90℃热水中反应5~6h,生成海藻酸基材料;
(4)将步骤(3)中得到的海藻酸基材料用去离子水洗净,常温干燥得到最终产品,即海藻酸基金属光催化还原材料。
由多组探索实验结果可知,步骤(1)中N-氨基胍的最优选质量为2g,环氧氯丙烷的最优选体积为5ml,最优选温度为70℃,最优选搅拌时间为6h,海藻酸钠的最优选质量为2g,后续反应的最优选时间和温度分别为8h,70℃。
由多组探索实验结果可知,步骤(2)中氯化钙的最优选质量分数和固化时间分别为2%,12h。
由多组探索实验结果可知,步骤(3)中尿素的最优选质量分数为4%,在尿素和热水重浸泡最优选时间分别为24h和6h,最优选温度为80℃。
由多组探索实验结果可知,步骤(4)中海藻酸基材料用去离子水的最优选清洗次数为3次以上。
一种所述的制备方法制得的海藻酸基金属光催化还原材料。
一种海藻酸基金属光催化还原材料在重金属废水中应用。
优选的,所述海藻酸基金属光催化还原材料在酸碱性为酸性或中性的废水中高效吸附贵金属或重金属离子,并对三价金、六价铬、五价砷等高价金属离子具有光催化还原的能力。
所述海藻酸基金属光催化还原材料在酸性及中性的含重金属离子废水中可以较好的吸附各种常见重金属离子。
所述海藻酸基金属光催化还原材料在酸性及中性的含重金属离子废水中,在紫外光照或自然光照的条件下,光催化还原三价金,六价铬,五价砷等高价金属离子。
所述海藻酸基金属光催化还原材料在酸性条件下对重金属离子的络合物吸附以静电吸附为主。在该条件下金、铂、铬离子以络合物形式在溶液中带负电荷,而吸附剂表面为正电荷,从而发生静电吸引,对于铅、镉、铜、锌等重金属,吸附以络合为主,通过海藻酸钠高分子表面的羟基和羧基,与重金属离子形成络合物发生吸附。在紫外光或自然光照条件下,制备材料表面激发出电子,促使吸附在其表面的高价金属离子发生还原反应。
本发明相比现有技术具有以下优点:本发明通过N-氨基胍官能团经过环氧氯丙烷嫁接在海藻酸钠高分子上,再经过氯化钙进行固化交联形成水凝胶状材料,最后,通过尿素渗透及水解制孔方法在水凝胶中加入孔结构以提高其对金属离子的吸附效率和光催化活性,通过此方法制备出的海藻酸基材料在酸性条件下对三价金离子有优良的吸附能力。
本发明相比现有技术具有以下优点:本发明制备的海藻酸基金属光催化还原材料为有机光催化材料,相较传统的无机材料价格低廉,对金属离子吸附容量大,可以处理较高浓度的重金属离子废水。此外,通过表面改性和制孔,可以增加材料对可见光的吸收,提高光能利用率,其光催化还原的特性亦可延伸到重金属离子污染方向,如六价铬、五价砷等重金属的废水处理。
附图说明
图1是本发明材料表面的扫描电镜图;
图2是本发明材料在紫外光照下对金离子废水处理后表面的扫描电镜图;
图3是本发明材料的EDS面扫描能谱图;
图4是本发明材料的紫外漫反射光谱图。
具体实施方式
下面对本发明的实施例作详细说明,本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
实施例1
本实施例的一种海藻酸基金属光催化还原材料的制备方法,包括以下步骤:
(1)将1g N-氨基胍溶于100mL去离子水中,再加入3mL环氧氯丙烷,升温到70℃,搅拌条件下反应6h,向反应后的液体中加入2g海藻酸钠,保持70℃反应8h;
(2)将步骤(1)中得到的液体逐滴滴入到质量分数为2%氯化钙溶液中固化12h,将所得水凝胶过滤洗净;
(3)将步骤(2)中得到的水凝胶浸泡于含2%尿素的乙醇溶液中24h,再将浸泡后的水凝胶置于70℃热水中反应6h;
(4)将步骤(3)中得到的海藻酸基材料用去离子水洗净,常温干燥得到最终产品,即海藻酸基金属光催化还原材料。
实施例2
本实施例的一种海藻酸基金属光催化还原材料的制备方法,包括以下步骤:
(1)将2g N-氨基胍溶于100mL去离子水中,再加入5mL环氧氯丙烷,升温到70℃,搅拌条件下反应6h,向反应后的液体中加入2g海藻酸钠,保持70℃反应8h;
(2)将步骤(1)中得到的液体逐滴滴入到质量分数为2%氯化钙溶液中固化12h,将所得水凝胶过滤洗净;
(3)将步骤(2)中得到的水凝胶浸泡于含4%尿素的乙醇溶液中24h,再将浸泡后的水凝胶置于80℃热水中反应6h;
(4)将步骤(3)中得到的海藻酸基材料用去离子水洗净,常温干燥得到最终产品,即海藻酸基金属光催化还原材料。
实施例3
本实施例的一种海藻酸基金属光催化还原材料的制备方法,包括以下步骤:
(1)将4g N-氨基胍溶于100mL去离子水中,再加入8mL环氧氯丙烷,升温到70℃,搅拌条件下反应6h,向反应后的液体中加入3g海藻酸钠,保持70℃反应8h;
(2)将步骤(1)中得到的液体逐滴滴入到质量分数为2%氯化钙溶液中固化12h,将所得水凝胶过滤洗净;
(3)将步骤(2)中得到的水凝胶浸泡于含3%尿素的乙醇溶液中24h,再将浸泡后的水凝胶置于90℃热水中反应6h;
(4)将步骤(3)中得到的海藻酸基材料用去离子水洗净,常温干燥得到最终产品,即海藻酸基金属光催化还原材料。
吸附试验:制备两种不同pH值条件下(pH=1和3)的Au(III)离子溶液标记为a和b,浓度为1mmol/L。取上述三种实例中制备的吸附剂各600mg分别置于两种不同的模拟金属离子溶液中,分别标记为a1/a2/a3/b1/b2/b3,每组模拟金属离子溶液为200mL,吸附24h。
解吸试验:将上述各组吸附试验中吸附后的吸附剂各取出300mg,用100ml含1%N-氨基胍的pH=1的盐酸进行解吸附试验,每隔12h换一次解吸溶液,进行三次解吸附,分别标记为A1/A2/A3/B1/B2/B3。
检测分析:将做完吸附和脱附试验后的吸附剂,取出形貌规则的吸附剂做SEM形貌表征且做元素映射分析,各组样干燥后磨成粉末状后测FT-IR,取出吸附后的吸附剂做紫外光照射后送SEM。
对上述试验结果分析后可知a1与a3实例的吸附剂在pH为1时做完吸附试验后,出现明显的溶解且对目标金属离子的吸附容量较差,远不及a2;而b1/b2/b3虽然在pH为3时进行吸附和脱附试验时,吸附剂稳定性良好,但相比于在pH为1时其吸附效率及性能显著较差,则如图1所示,图1是实施例2扫描电镜照片;由图1可以看出制得的材料表面为球状;
通过对不同实施例的吸附剂稳定性及吸附性能进行分析后发现,a2组对Au(III)离子的吸附性能最好,将实例2备选为最优型制备方案,且对吸附后的a2组吸附剂进行紫外光照射后发现图2是实施例2的制备得到海藻酸基金属光催化还原材料在紫外光照下对金离子废水处理后表面的扫描电镜照片,可以观察到明显的金离子还原为金单质的现象;
对实施例2中吸附完成后的吸附剂进行元素映射(做N、O、Cl)分析后知图3第三张图中N元素分布密度较大,且其结果与FT-IR分析后基本相符合,由此知图3是实施例2的制备得到海藻酸基金属光催化还原材料EDS面扫描能谱图,可以发现N元素成功的嫁接在材料表面,提升其吸附能力;
图4是本发明的紫外漫反射光谱,可以发现通过改性可以提高材料对200~400nm波段光的响应能力,提高光催化效率。
由此可见,通过此方法制备的复合材料,在酸性及中性的含重金属离子废水中,在紫外光照或自然光照的条件下,光催化还原三价金,六价铬,五价砷等高价金属离子,在贵金属回收和降低重金属污染方面都有应用的意义。
尽管上面已经示出和描述了本发明的实施例,可以理解的是,上述实施例是示例性的,不能理解为对本发明的限制,本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。
Claims (6)
1.一种海藻酸基金属光催化还原材料的制备方法,其特征在于,包括以下步骤:
(1)将1~4 g N-氨基胍溶于100 mL去离子水中,再加入3~8 mL环氧氯丙烷,升温到65℃~75℃,搅拌条件下反应5~7 h,向反应后的液体中加入2~3 g海藻酸钠,保持60℃~70℃反应7~8 h;
(2)将步骤(1)中得到的液体逐滴滴入到质量分数为1~5%氯化钙溶液中固化10~12h,将所得水凝胶过滤洗净;
(3)将步骤(2)中得到的水凝胶浸泡于含2~5%尿素的乙醇溶液中20~24 h,再将浸泡后的水凝胶置于70~90℃热水中反应5~6 h,生成海藻酸基材料;
(4)将步骤(3)中得到的海藻酸基材料用去离子水洗净,常温干燥得到最终产品,即海藻酸基金属光催化还原材料。
2.一种如权利要求1所述的制备方法制得的海藻酸基金属光催化还原材料。
3.一种如权利要求2所述海藻酸基金属光催化还原材料在重金属废水中吸附重金属的应用。
4.根据权利要求3所述的一种海藻酸基金属光催化还原材料在重金属废水中吸附重金属的应用,其特征在于:所述海藻酸基金属光催化还原材料在酸性或中性的废水中,吸附重金属离子。
5.根据权利要求3所述海藻酸基金属光催化还原材料在重金属废水中吸附重金属的应用,其特征在于:所述海藻酸基金属光催化还原材料在酸性及中性的含重金属离子废水中,在紫外光照或自然光照的条件下,光催化还原三价金,六价铬,五价砷高价金属离子。
6.根据权利要求3所述海藻酸基金属光催化还原材料在重金属废水中吸附重金属的应用,其特征在于:所述海藻酸基金属光催化还原材料在酸性条件下,静电吸附重金属离子的络合物。
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