CN111185139A - 一种亲水性球形复合锂离子筛吸附剂的制备方法 - Google Patents
一种亲水性球形复合锂离子筛吸附剂的制备方法 Download PDFInfo
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Abstract
本发明公开了一种亲水性球形复合锂离子筛吸附剂的制备方法,主要步骤包括:将锂离子筛与壳聚糖溶液混合均匀,获得复合水凝胶。然后将其滴入到碱溶液中形成凝胶小球,再对凝胶小球进行交联处理,经洗涤和干燥后,获得亲水性球形复合锂离子筛吸附剂。本发明制备的亲水性球形复合锂离子筛吸附剂的制备方法简单、稳定性好,不但解决了粉末锂离子筛渗透率低的问题,还解决了亲水性壳聚糖稳定性差等问题,有利于材料的工业化生产和应用。
Description
技术领域
本发明属于锂提取技术领域,涉及吸附剂的制备技术,尤其是一种亲水性球形复合锂离子筛吸附剂的制备方法。
背景技术
锂及其衍生品广泛应用于玻璃、催化剂、铝生产、橡胶合成、医药和锂离子电池等众多领域,尤其随着锂离子电池的飞速发展,使得全球对锂资源的需求呈直线增长。
目前,锂的提取主要来源于固体锂矿资源,但随着锂需求的不断增加,固体锂矿资源在未来将不再满足需求。卤水等液体锂矿中包含大量的锂资源,相比于其他提锂方法,吸附法是从这类液体锂矿中提锂的较理想方法。锂离子筛对锂具有较高的吸附选择性,但其粉末形式限制了在工业中的运用。尽管造粒方式可解决该问题,但传统的粘结剂都是一些疏水性材料,如聚氯乙烯、聚丙烯腈等,造粒成型后会导致吸附速率、吸附容量的降低。
尽管专利CN106140076A公开了一种用于吸附金属离子的壳聚糖复合吸附剂,但该吸附剂以MnO2为内核,主要用于吸附Cu、Co、Ni、Cd、Cr等金属离子。且在制备过程中,以硫代卡巴肼为交联剂,并涉及与金属离子形成配合物等复杂过程。专利CN103316623A公开了以壳聚糖等多糖为粘结剂,制备球形锂离子筛吸附剂的方法。但是,该法以锂锰氧化物(Li1.6Mn1.6O4、LiMn2O4等)为内核,经包覆后再进行Li+洗脱。相对于脱Li+后再进行包覆,其对Li+的吸附容量相对较低。此外,在球形材料制备过程中,采用高温热溶和溶剂转相法成型,过程较为繁琐,且交联后需采用甲苯、丙酮等毒性有机试剂进行洗涤,因而存在环保等方面的问题。
鉴于此,开发一种制备过程简单、环保的高性能亲水性锂吸附剂,对于锂资源的开发具有重大意义。
发明内容
本发明的目的在于,针对液体锂矿中锂的分离提取,开发一种制备方法简单、制备过程绿色环保的亲水性、高稳定性和高吸附性能球形锂离子筛复合吸附剂。
一种亲水性球形复合锂离子筛吸附剂的制备方法,步骤如下:
1)将壳聚糖溶解于乙酸溶液中获得壳聚糖溶液,然后加入锂离子筛并混合搅拌均匀,获得含锂离子筛的复合水凝胶;
2)将步骤1)中获得的复合水凝胶滴入到NaOH溶液中,形成含壳聚糖/锂离子筛的复合凝胶小球,然后用去离子水冲洗至中性;
3)将步骤2)中获得的复合凝胶小球置于烧瓶中,向烧瓶中加入交联剂进行交联,然后用乙醇和去离子水冲洗除去未反应的交联剂;
4)将步骤3)中获得的材料进行干燥,即得亲水性球形复合锂离子筛吸附剂。
而且,所述锂离子筛为HMn2O4、H1.66Mn1.66O4、H4Mn5O12、H2TiO3、H4Ti5O12中的一种或两种以上的混合物。
而且,步骤1)中壳聚糖与锂离子筛的质量比为1:4~4:1。优选3:2。
而且,步骤1)中壳聚糖浓度为1~5wt%,乙酸浓度为1~4%。
而且,步骤1)中NaOH的浓度为0.5~2mol/L。
而且,步骤3)中所述交联剂为乙二醇缩水甘油醚,壳聚糖与交联剂的质量比为1:1~1:2,交联温度40~60℃,交联时间3~9h。
而且,所述步骤4)中所述的干燥为真空干燥或冷冻干燥。
本发明的优点和积极效果:
本发明吸附剂的制备方法简单,所制备的材料稳定性好,不仅解决了粉末离子筛渗透率低的问题,还解决了亲水性壳聚糖稳定性差等问题,有利于材料的工业化生产和应用。
附图说明
图1为本发明亲水性球形复合锂离子筛吸附剂的制备工艺流程图;
图2为实施例1制备过程中获得的壳聚糖/离子筛复合凝胶小球照片;
图3为不同H4Mn5O12离子筛包覆量下材料的稳定性变化图;
图4是实施例1中材料交联前后在0.25mol/L HCl中的稳定性对比图;
图5a是实施例1中所制备的亲水性球形复合锂离子筛吸附剂实物图;
图5b是实施例1中所制备的亲水性球形复合锂离子筛吸附剂SEM图;
图6是实施例1中所制备材料吸附锂实验结果图;
图7a是实施例2制备过程中所得水凝胶颗粒照片;
图7b是实施例2制备过程中所得水凝胶颗粒干燥后的交联CTS/HMn2O4吸附剂照片;
图8a是实施例3制备过程中所得水凝胶颗粒照片;
图8b是实施例3制备过程中所得水凝胶颗粒干燥后的交联CTS/H1.66Mn1.66O4吸附剂照片;
图9a是实施例4制备过程中所得水凝胶颗粒照片;
图9b是实施例4制备过程中所得水凝胶颗粒干燥后的交联CTS/H2TiO3吸附剂照片;
图10a是实施例5制备过程中所得水凝胶颗粒照片;
图10b是实施例5制备过程中所得水凝胶颗粒干燥后的交联CTS/H4Ti5O12吸附剂照片。
具体实施方式
下面结合附图和具体实施例对本发明做进一步说明。
实施例1:交联壳聚糖包覆H4Mn5O12吸附剂(制备流程见图1)
称取3g壳聚糖于烧杯中,向烧杯中加入97mL 4%的乙酸,使用磁力搅拌器持续搅拌,直至壳聚糖溶解完全。
将2gH4Mn5O12离子筛加入到上述壳聚糖溶液中,充分混合搅拌均匀,然后使用超声振荡,使离子筛粉末均匀分布于壳聚糖溶液中。
将壳聚糖/锂离子筛复合水凝胶滴入到1mol/LNaOH溶液中,形成含壳聚糖/锂离子筛的复合凝胶小球,然后用去离子水冲洗至中性。所得的凝胶小球见图2。
不同离子筛包覆量下,材料的稳定性见图3。当离子筛在材料中的占比在20%~80%范围时,包覆效果较好。
将复合凝胶小球放入烧瓶中,然后加入乙二醇缩水甘油醚,其中壳聚糖与交联剂的质量比为1:1,在45℃下交联9h。当壳聚糖与H4Mn5O12的质量比为3:2时,交联前后材料在0.25mol/LHCl中的稳定性对比见图4。
交联完成后,用乙醇和去离子水冲洗5次,除去未反应的交联剂。交联后的复合凝胶小球用冷冻干燥除去水分,即得亲水性多孔球形复合锂离子筛吸附剂。当壳聚糖与H4Mn5O12的质量比为3:2时,所得干燥后的材料见图5。该材料在Li+浓度为25.78mg/L的地热水中吸附性能见图6。
实施例2:交联壳聚糖包覆HMn2O4吸附剂
制备方法与实施例1相似,其中HMn2O4占材料质量的80%,所用NaOH的浓度为2mol/L,壳聚糖与交联剂的质量比为1:2,反应温度和时间分别为60℃和9h。制备过程中所得水凝胶颗粒及干燥后的交联CTS/HMn2O4吸附剂见图7。
实施例3:交联壳聚糖包覆H1.66Mn1.66O4吸附剂
制备方法与实施例1相似,其中H1.66Mn1.66O4占材料质量的20%,所用NaOH的浓度为0.5mol/L,壳聚糖与交联剂的质量比为1:1,反应温度和时间分别为40℃和3h。制备过程中所得水凝胶颗粒及干燥后的交联CTS/H1.66Mn1.66O4吸附剂见图8。
实施例4:交联壳聚糖包覆H2TiO3吸附剂
制备方法与实施例1相似,其中H2TiO3占材料质量的45%,所用NaOH的浓度为1.5mol/L,壳聚糖与交联剂的质量比为1:1.5,反应温度和时间分别为50℃和4.5h。制备过程中所得水凝胶颗粒及干燥后的交联CTS/H2TiO3吸附剂见图9。
实施例5:交联壳聚糖包覆H4Ti5O12吸附剂
制备方法与实施例1相似,其中H4Ti5O12占材料质量的40%,所用NaOH的浓度为1.0mol/L,壳聚糖与交联剂的质量比为1:1,反应温度和时间分别为45℃和9h。制备过程中所得水凝胶颗粒及干燥后的交联CTS/H4Ti5O12吸附剂见图10。
以上显示和描述了本发明的实施例,对于本技术领域的普通技术人员来说,还可以根据上述说明加以改进或变换,所有这些改进和变换都应属于本发明所附权利要求的保护范围。
Claims (8)
1.一种亲水性球形复合锂离子筛吸附剂的制备方法,其特征在于:步骤如下:
1)将壳聚糖溶解于乙酸溶液中获得壳聚糖溶液,然后加入锂离子筛并混合搅拌均匀,获得含锂离子筛的复合水凝胶;
2)将步骤1)中获得的复合水凝胶滴入到NaOH溶液中,形成含壳聚糖/锂离子筛的复合凝胶小球,然后用去离子水冲洗至中性;
3)将步骤2)中获得的复合凝胶小球置于烧瓶中,向烧瓶中加入交联剂进行交联,然后用乙醇和去离子水冲洗除去未反应的交联剂;
4)将步骤3)中获得的材料进行干燥,即得亲水性球形复合锂离子筛吸附剂。
2.根据权利要求1所述的亲水性球形复合锂离子筛吸附剂的制备方法,其特征在于:所述锂离子筛为HMn2O4、H1.66Mn1.66O4、H4Mn5O12、H2TiO3、H4Ti5O12中的一种或两种以上的混合物。
3.根据权利要求1或2所述的亲水性球形复合锂离子筛吸附剂的制备方法,其特征在于:步骤1)中壳聚糖与锂离子筛的质量比为1:4~4:1。
4.根据权利要求3所述的亲水性球形复合锂离子筛吸附剂的制备方法,其特征在于:步骤1)中壳聚糖与锂离子筛的质量比为3:2。
5.根据权利要求1或2所述的亲水性球形复合锂离子筛吸附剂的制备方法,其特征在于:步骤1)中壳聚糖浓度为1~5wt%,乙酸浓度为1~4%。
6.根据权利要求1或2所述的亲水性球形复合锂离子筛吸附剂的制备方法,其特征在于:步骤1)中NaOH的浓度为0.5~2mol/L。
7.根据权利要求1或2所述的亲水性球形复合锂离子筛吸附剂的制备方法,其特征在于:步骤3)中所述交联剂为乙二醇缩水甘油醚,壳聚糖与交联剂的质量比为1:1~1:2,交联温度40~60℃,交联时间3~9h。
8.根据权利要求1所述的亲水性球形复合锂离子筛吸附剂的制备方法,其特征在于:所述步骤4)中所述的干燥为真空干燥或冷冻干燥。
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