CN116159540A - 一种Zn-Al水滑石薄膜及其制备方法和在回收镓中的应用 - Google Patents
一种Zn-Al水滑石薄膜及其制备方法和在回收镓中的应用 Download PDFInfo
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Abstract
本发明提供了一种Zn‑Al水滑石薄膜及其制备方法和在回收镓中的应用，属于吸附材料制备和水处理技术领域。制备方法包括如下步骤：将六水合氯化铝和氯化锌溶于去离子水中，搅拌；调节溶液pH至碱性，搅拌；将所得混合体系转移到反应釜中，进行水热反应，冷却，离心，洗涤，干燥后，得到水滑石粉体材料；将得到的水滑石粉体材料溶解于甲酰胺中超声粉碎，向混合溶液中加入PVA和SA混合搅拌，每次取混合溶液抽膜，形成的膜置于CaCl2中浸泡，置于烘箱中烘干，水滑石薄膜可自然脱落。在pH＝3时对镓的最大饱和吸附量为118.84mg·g‑1，可实现稀散金属Ga(III)的有效分离。
Description
技术领域
本发明提供了一种Zn-Al水滑石薄膜及其制备方法和在回收镓中的应用，属于吸附材料制备和水处理技术领域。
背景技术
国内外现在对于水滑石粉体的研究逐渐深入，开拓了不同金属水滑石的不同特点以及用途，国内有相关文献采用SA/水滑石/石墨烯凝胶球作为吸附材料，海藻酸钠(SA)插层水滑石吸附剂，SA/壳聚糖/水滑石材料多为常见，国外也有相应对于SA/水滑石的研究，如图所示。但将水滑石制成水滑石/SA/聚乙烯醇(PVA)膜状材料是一项未成熟的探索，而膜材料相较于粉体材料与吸附球体材料相比，膜材料具有质地均匀等更多优势，是当下研究的发展趋势。
镓是一种重要的稀有分散元素，因为其数量小，在地壳中的含量很少，倾向于Al(OH)3。随着科学技术的不断发展和镓及其化合物需求量的逐渐增加，许多工业催化过程使用昂贵和稀有的过渡金属。镓的物理性质与铟、铊相似。镓的主要生产来自铝土矿中获得铝的过程以及锌生产中产生的废料中获得铝的过程。铝土矿中镓的平均含量为50mg·kg-1，锌矿床的含量也可能与铝土矿相当利用的镓量却相当少。其他镓储量较大矿为磷酸盐矿，当磷通过电热法从磷镓在铝土矿和铅锌矿中虽然含量相对较高，但目前从矿中可以开发态伴生存在。
发明内容
为解决上述技术问题，本发明的目的在于提供一种Zn-Al水滑石薄膜的制备方法，本发明的方法相较于传统技术相比，具有分离效率高，无污染，高效低能耗等优点，成膜后的水滑石类化合物柔软性、耐挤压性好，具有强韧性以及透水性，可实现对Ga(III)的高效吸附分离，具有很高的实用价值。
为达到上述目的，本发明采用的技术方案如下：
一种Zn-Al水滑石薄膜，制备方法包括如下步骤：
1)Zn-Al水滑石粉体的制备：
将六水合氯化铝和氯化锌溶于去离子水中，搅拌；调节溶液pH至碱性，搅拌；将所得混合体系转移到反应釜中，进行水热反应，冷却，离心，洗涤，干燥后，得到水滑石粉体材料；
2)Zn-Al水滑石薄膜的制备：
将得到的水滑石粉体材料溶解于甲酰胺中超声粉碎，向混合溶液中加入PVA和SA混合搅拌，每次取混合溶液抽膜，形成的膜置于CaCl2中浸泡，置于烘箱中烘干，水滑石薄膜可自然脱落。
上述的一种Zn-Al水滑石薄膜，步骤1)中，按摩尔比，六水合氯化铝：氯化锌＝1：3。
上述的一种Zn-Al水滑石薄膜，步骤1)中，所述的搅拌是在303K下搅拌1h。
上述的一种Zn-Al水滑石薄膜，步骤1)中，调节pH至碱性是缓慢滴加氢氧化钠溶液调节溶液pH至10。
上述的一种Zn-Al水滑石薄膜，步骤1)中，所述的水热反应是在383K的条件下反应24h。
上述的一种Zn-Al水滑石薄膜，步骤2)中，按质量比，水滑石粉体材料：PVA：SA＝240:1:1。
上述的一种Zn-Al水滑石薄膜，步骤2)中，在CaCl2中浸泡是在0.1mol/L CaCl2中浸泡10s。
上述的一种Zn-Al水滑石薄膜作为吸附剂在吸附镓中的应用。
上述的应用，方法如下：取上述的一种Zn-Al水滑石薄膜置于振荡瓶中，加入含Ga(III)金属离子的溶液，密封摇匀后，振荡吸附。
上述的应用，包括洗脱步骤，向固体物中加入洗脱剂进行洗脱，在25℃条件下振荡24h后，过滤，所述洗脱剂为浓度为0.25mol L-1～2.0mol L-1，所述洗脱剂为NaOH、NH3H2O、HCl。
本发明的有益效果是：
1)本项目的特殊之处在于水滑石材料自身为粉体材料，通过SA的稳定性以及PVA的粘合性，以甲酰胺作为溶剂，通过超声，抽滤，烘干使其形成极具韧性的膜状结构。单纯的水滑石材料难以形成膜状结构，需借助SA表面具有不饱和离子和具有孤电子对的羧基、羟基等化学基团，一方面SA的不饱和离子与镓离子发生离子交换反应；另一方面SA表面的羧基、羟基等基团与镓离子发生络合作用起到黏附的作用，并且和金属有配位，发生沉积，变成不是粉体的材料，以及PVA材料的粘附性得以制成膜材料。
2)膜结构在21世纪多数工业中，扮演重要角色，且发展前景广阔，相较于传统技术相比，具有分离效率高，无污染，高效低能耗等优点，成膜后的水滑石类化合物柔软性、耐挤压性好，具有强韧性以及透水性。粉体材料在使用过程中难以控制其上粉的均均匀程度，且粉体材料易被污染，浮游粉尘亦会有着火爆炸的危险，而制成膜质材料在抽膜过程中抽膜溶液均匀分布于滤纸表面，所得到的膜薄厚均匀，则可解决此类难题。
3)本发明制备的Zn-Al水滑石薄膜类化合物，对溶液中的镓均有较大的吸附量，并在pH＝3时，对镓的最大吸附量为118.84mg·g-1。
综上所述，本发明制备的Zn-Al水滑石薄膜类化合物可以有效的吸附镓离子，而且制备过程简便绿色，吸附率高，易携带，具有实际的实用性。
附图说明
图1是水滑石/SA/PVA类化合物复合膜的合成示意图。
图2是水滑石/SA/PVA类化合物复合膜(4LDHs-0.5SA-0.5PVA)的扫描电镜图。
图3是水滑石/SA/PVA类化合物复合膜(4LDHs-0.5SA-0.5PVA)的O(A)、Zn(B)、Al(C)、C(D)元素面扫图和EDS含量图(E)以及EDS中各元素数据分析结果。
图4是水滑石/SA/PVA类化合物复合膜(4LDHs-0.5SA-0.5PVA)在pH＝1、2、3、10对镓的吸附性能对比图。
图5是水滑石/SA/PVA类化合物复合膜(4LDHs-0.5SA-0.5PVA)在pH＝3对镓的吸附等温线拟合图。
图6是不同吸附材料(LDHs，0LDHs-0.5SA-0.5PVA，1LDHs-0.5SA-0.5PVA，2LDHs-0.5SA-0.5PVA，4LDHs-0.5SA-0.5PVA)的热重曲线图。
具体实施方式
下面通过具体实施例对本发明做进一步阐述，但并不限制本发明。
实施例1不同的水滑石粉体材料的加入量下制备的水滑石/SA/PVA类化合物复合膜1、水滑石/SA/PVA类化合物复合膜(水滑石：SA：PVA＝1:0.5:0.5，1LDHs-0.5SA-0.5PVA)
将4.83g六水合氯化铝4.83g和8.18g氯化锌溶于25mL去离子水中，所得混合物在303K下搅拌1h；完全溶解后，缓慢滴加氢氧化钠溶液调节溶液pH至10，继续搅拌3h；将所得混合体系转移到反应釜中，在500W，383K的条件下反应24h。冷却，离心，洗涤，干燥后，得到12g水滑石粉体材料。将制得的0.1g水滑石粉体材料溶解于10mL甲酰胺中超声粉碎1h，向混合溶液中加入0.05g PVA和0.05g SA混合搅拌，完全溶解后，每次取3mL混合溶液抽膜，形成的膜置于100mL 0.1mol/LCaCl2溶液中浸泡10s后，置于50℃烘箱中烘干，水滑石薄膜可自然脱落，命名为1LDHs-0.5SA-0.5PVA。合成过程如图1所示。
2、水滑石/SA/PVA类化合物复合膜(水滑石：SA：PVA＝2:0.5:0.5，2LDHs-0.5SA-0.5PVA)
按1中所述方法制备，不同点在于，以0.2g水滑石粉体材料替代1中的0.1g水滑石粉体，命名为2LDHs-0.5SA-0.5PVA。
3、水滑石/SA/PVA类化合物复合膜(水滑石：SA：PVA＝3:0.5:0.5，3LDHs-0.5SA-0.5PVA)
按1中所述方法制备，不同点在于，以0.3g水滑石粉体材料替代1中的0.1g水滑石粉体，命名为3LDHs-0.5SA-0.5PVA。
4、水滑石/SA/PVA类化合物复合膜(水滑石：SA：PVA＝4:0.5:0.5，4LDHs-0.5SA-0.5PVA)
按1中所述方法制备，不同点在于，以0.4g水滑石粉体材料替代1中的0.1g水滑石粉体，命名为4LDHs-0.5SA-0.5PVA。
5、水滑石/SA/PVA类化合物复合膜(水滑石：SA：PVA＝5:0.5:0.5，5LDHs-0.5SA-0.5PVA)
按1中所述方法制备，不同点在于，以0.5g水滑石粉体材料替代1中的0.1g水滑石粉体，命名为5LDHs-0.5SA-0.5PVA。
随水滑石用量增多，薄膜变厚变白，直至海藻酸钠:SA:PVA＝5：0.5：0.5无法成膜，膜在揭下时会破损，则4LDHs-0.5SA-0.5PVA为最佳和成比例复合膜。
实施例2不同的SA和PVA的加入量下制备的水滑石/SA/PVA类化合物复合膜1.水滑石/SA/PVA类化合物复合膜(水滑石：SA：PVA＝1:0.7:0.3，1LDHs-0.7SA-0.3PVA)
将六水合氯化铝(4.83g)和氯化锌(8.18g)溶于去离子水(25mL)中，所得混合物在303K下搅拌1h；完全溶解后，缓慢滴加氢氧化钠溶液调节溶液pH至10，继续搅拌3h；将所得混合体系转移到反应釜中，在500W，383K的条件下反应24h。冷却，离心，洗涤，干燥后，得到水滑石粉体材料(12.00g)。将制得的水滑石粉体材料(0.10g)溶解于甲酰胺(10.00mL)中超声粉碎1h，向混合溶液中加入PVA(0.03g)和SA(0.07g)混合搅拌，完全溶解后，每次取混合溶液(3mL)抽膜，形成的膜置于0.1mol/L CaCl2溶液(100mL)中浸泡10s后，置于50℃烘箱中烘干，水滑石薄膜可自然脱落，命名为1LDHs-0.7SA-0.3PVA。
2.水滑石/SA/PVA类化合物复合膜(水滑石：SA：PVA＝1:0.5:0.5，1LDHs-0.5SA-0.5PVA)
按1中所述方法制备，不同点在于，以0.05gPVA,0.05gSA替代1中的0.03gPVA,0.07gSA，命名为1LDHs-0.5SA-0.5PVA。
3.水滑石/SA/PVA类化合物复合膜(水滑石：SA：PVA＝1:0.3:0.7，1LDHs-0.3SA-0.7PVA)
按1中所述方法制备，不同点在于，以0.07g PVA,0.03gSA替代1中的0.03g PVA,0.07gSA，命名为1LDHs-0.3SA-0.7PVA。
实验选取0.1MPa作为进水压力，将不同复合膜过滤镓溶液，一段时间后测水通量。结果表明，水滑石/SA/PVA类化合物复合膜(水滑石：SA：PVA＝1:0.7:0.3)较于水滑石/SA/PVA类化合物复合膜(水滑石：SA：PVA＝1:0.3:0.7)透水性更好，吸附效果更加，随PVA含量增加，生成膜更为致密，水通量几乎为零。
表征
1、图2是4LDHs-0.5SA-0.5PVA的扫描电镜图。由图2可以看出，4LDHs-0.5SA-0.5PVA的表面粗糙，制得的膜具有典型的水滑石层片状结构，从图3的EDS和元素面扫图的结果表明，已经检测到Zn、Al元素。
2、图6是4LDHs-0.5SA-0.5PVA的热重曲线。由图6可以看出，五种材料中水滑石受热几乎不分解，较为稳定；在水滑石中仅加入PVA与SA和在水滑石中加入PVA和SA大部分被分解。生物质的SA和具有羟基结构的PVA具有亲水性，因此在200℃以下失重率高于锌铝水滑石，并且在200到300℃时，SA/PVA复合膜失重率高达60％以上，由于水滑石的热稳定性较好，在温度高达800℃时，失重率不足10％。随着水滑石含量的增加，复合膜在800℃时失重率减少，由此说明，复合膜制备成功。
实施例3水滑石/SA/PVA类化合物复合膜作为吸附剂在吸附Ga(III)中的应用(一)水滑石/SA/PVA类化合物复合膜在不同酸度条件下对Ga(III)的吸附性能测试
方法如下：准确称取10mg吸附剂分别置于震荡瓶中，加入10mL不同酸度的20mg·L-1镓溶液后摇匀，将震荡瓶放在恒温震荡箱中，转速为180rpm，30℃下震荡24h，过滤，用原子吸收法测定吸附前后溶液中镓离子的浓度。结果如图4所示。
由图4可以看出，随着溶液pH为1、2、3、10时，吸附剂对镓的吸附量仅在pH＝3时稳定，pH＝1、2、10时吸附量极低。当水滑石的加入量从1.0g(1LDHs-0.5SA-0.5PVA)增加到4.0g(4LDHs-0.5SA-0.5PVA)时，在pH＝3条件下，对镓的吸附率从38.26％提高到86.94％。在pH＝3时对镓的最大饱和吸附量为118.84mg·g-1。
(二)水滑石/SA/PVA类化合物复合膜(4LDHs-0.5SA-0.5PVA)吸附Ga(III)的吸附等温线
方法：分别取浓度为20mg·L-1，80mg·L-1，100mg·L-1，150mg·L-1，200mg·L-1，300mg·L-1，400mg·L-1，500mg·L-1，800mg·L-1的Ga(III)溶液，调节pH为3。分别加入20mg实施例1制备的3LDHs-0.5SA-0.5PVA，在30℃，180r/min的振荡箱中振荡24h。结果如图5。
由酸度实验研究发现在pH＝3时，水滑石/SA/PVA类化合物复合膜(水滑石：SA：PVA＝3:0.5:0.5)吸附效果最佳，因此在pH＝3时，测定了吸附剂的饱和吸附量，并对实验数据进行了Langmuir，Freundlich，Temkin，和Dubinin-Radushkevich吸附等温线模型拟合。拟合结果如图5所示，四种模型的拟合值R2分别为0.991，0.957，0.898，0.974。由此说明4LDHs-0.5SA-0.5PVA对Ga(III)的吸附等温线更符合Langmuir模型，且对Ga(III)的最大吸附量为118.84mg·g-1，这表明吸附材料对Ga(III)的吸附为单分子层吸附过程，吸附剂的吸附位点均匀分散于吸附剂表面。
(三)不同解析剂对吸附镓的水滑石/SA/PVA类化合物复合膜的洗脱效果
方法：称取10份10mg水滑石/SA/PVA类化合物复合膜(4LDHs-0.5SA-0.5PVA)，加入10mL pH＝3，浓度为20ppm Ga(III)溶液，放入震荡箱，设置温度为30℃，转速为180rmin-1震荡24h。将溶液过滤，收集吸附后的吸附剂干燥。将每份干燥后的吸附剂加入到10mL的解析液(不同浓度HCl、NaOH和NH3 H2O)中进行解析，在303K下恒温震荡12h后，测定解析液中镓离子的浓度。通过计算得到解析率，结果如表1所示。
表1不同洗脱液对镓离子的洗脱效果
由表1可知，HCl、NaOH、NH3·H2O对于水滑石/SA/PVA类化合物复合膜均具有较好的洗脱效果，而NaOH洗脱效果最好，当浓度为1mol·L-1和2mol·L-1洗脱率均可达到100.00％。由此看出，水滑石/SA/PVA类化合物复合膜可用于镓的回收再利用，是一种较有应用前景的吸附材料。
Claims (10)
1.一种Zn-Al水滑石薄膜，其特征在于，制备方法包括如下步骤：
1)Zn-Al水滑石粉体的制备：
将六水合氯化铝和氯化锌溶于去离子水中，搅拌；调节溶液pH至碱性，搅拌；将所得混合体系转移到反应釜中，进行水热反应，冷却，离心，洗涤，干燥后，得到水滑石粉体材料；
2)Zn-Al水滑石薄膜的制备：
将得到的水滑石粉体材料溶解于甲酰胺中超声粉碎，向混合溶液中加入PVA和SA混合搅拌，每次取混合溶液抽膜，形成的膜置于CaCl2中浸泡，置于烘箱中烘干，水滑石薄膜可自然脱落。
2.根据权利要求1所述的一种Zn-Al水滑石薄膜，其特征在于，步骤1)中，按摩尔比，六水合氯化铝：氯化锌＝1：3。
3.根据权利要求1所述的一种Zn-Al水滑石薄膜，其特征在于，步骤1)中，所述的搅拌是在303K下搅拌1h。
4.根据权利要求1所述的一种Zn-Al水滑石薄膜，其特征在于，步骤1)中，调节pH至碱性是缓慢滴加氢氧化钠溶液调节溶液pH至10。
5.根据权利要求1所述的一种Zn-Al水滑石薄膜，其特征在于，步骤1)中，所述的水热反应是在383K的条件下反应24h。
6.根据权利要求1所述的一种Zn-Al水滑石薄膜，其特征在于，步骤2)中，按质量比，水滑石粉体材料：PVA：SA＝1-2：1：1。
7.根据权利要求1所述的一种Zn-Al水滑石薄膜，其特征在于，步骤2)中，在CaCl2中浸泡是在0.1mol/L CaCl2中浸泡10s。
8.权利要求1所述的一种Zn-Al水滑石薄膜作为吸附剂在吸附镓中的应用。
9.根据权利要求8所述的应用，其特征在于，方法如下：取权利要求1所述的一种Zn-Al水滑石薄膜置于振荡瓶中，加入含Ga(III)金属离子的溶液，密封摇匀后，振荡吸附。
10.根据权利要求8所述的应用，其特征在于，包括洗脱步骤，向固体物中加入洗脱剂进行洗脱，在25℃条件下振荡24h后，过滤，所述洗脱剂为浓度为0.25mol L-1～2.0mol L-1，所述洗脱剂为NaOH、NH3 H2O、HCl。
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