CN112619621B - 一种多孔纺丝复合材料的制备方法及其提锂应用 - Google Patents

一种多孔纺丝复合材料的制备方法及其提锂应用 Download PDF

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CN112619621B
CN112619621B CN202011524295.4A CN202011524295A CN112619621B CN 112619621 B CN112619621 B CN 112619621B CN 202011524295 A CN202011524295 A CN 202011524295A CN 112619621 B CN112619621 B CN 112619621B
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lithium
spinning
porous
composite material
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CN112619621A (zh
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邓天龙
赵凯宇
余晓平
李明礼
多吉
郭亚飞
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Central Laboratory Of Tibet Autonomous Region Geological And Mineral Exploration And Development Bureau
Tianjin University of Science and Technology
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Tianjin University of Science and Technology
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Abstract

本发明公开了一种多孔纺丝复合材料的方法及其提锂应用，方法包括如下步骤：(1)将高分子聚合物与有机溶剂混合加热搅拌，使其充分溶解，并静置脱泡；(2)向该混合溶液中加入锂离子筛粉末及水溶性致孔剂，充分搅拌混合均匀；(3)利用湿法纺丝设备将混合溶液喷丝至凝固浴中相转化成型；(4)通过牵伸水洗，烘干固化后得到多孔纺丝复合吸附材料。将获得的多孔纺丝复合吸附材料应用于液体锂矿中锂的提取。本发明不仅有效地解决了粉体材料的流动性和循环稳定性差的问题，而且相对于粒状、棒状等吸附材料而言，其吸附速率和吸附容量得到了极大的提升，因而在盐湖卤水、地下卤水、地热水等中锂资源的开发利用方面具有良好的应用前景。

Description

一种多孔纺丝复合材料的制备方法及其提锂应用
技术领域
本发明属于材料化工领域，涉及锂离子吸附材料，尤其是一种多孔纺丝复合材料的方法。
背景技术
锂，作为最轻的金属，广泛的应用于航空航天、锂离子电池、核工业、陶瓷、电子器件等领域，被誉为21世纪的“战略性能源金属”。随着现代高新科技的不断发展，人们对锂的需求量日益剧增。锂的来源主要分为两类：一是以锂云母、锂辉石、透锂长石等为主的固体锂矿资源，二是以盐湖卤水、浓海水、地热水、地下卤水等为主的液体锂矿资源。但随着固体锂矿资源的日益枯竭及提取时较高的能耗，人们逐渐将目光转向了储量丰富、成本较低的液体锂矿资源。
目前，在液体锂矿中提取锂的方法主要有沉淀法、电化学法、萃取法、吸附法等，其中吸附法具有成本低、工艺简单、绿色高效的优势，逐渐成为最具有应用前景的提锂方法。该技术的关键是制备吸附性能优异的锂吸附剂，而锂离子筛型氧化物因其具有较高的吸附容量和锂离子选择性，逐渐成为研究的热点。但锂离子筛型氧化物大多以超细粉末形式存在，较差的流动性和循环稳定性极大的限制了其在工业上的应用，解决该问题的关键是制备一种吸附容量高、吸附速率快、循环稳定性好、成本低的复合锂离子筛吸附剂。
通过检索，发现如下相关专利文献报道：
1、专利CN101898113A公开了一种以聚氯乙烯为粘结剂，锰系锂离子筛(LMO：LiMn2O4、Li1.6Mn1.6O4、Li4Mn5O12)为内核材料的球形锂离子复合吸附剂，虽然流动性差的问题得到了改善，但经包覆后的锂离子筛吸附速率下降明显。
2、专利CN106902781B公开了一种负载HMO的介孔空心硅球，其拥有较大的比表面积和吸附速率，但应用时锂离子筛直接暴露于空心硅球表面与溶液接触，因此循环稳定性较差。
3、专利CN102211012A公开了一种以聚偏氟乙烯为粘结剂，N,N-二甲基乙酰胺为溶剂、Li1.6Mn1.6O4为内核材料的锂离子筛混合基质膜用于海水提锂，然而单位质量的内核材料负载量少，吸附平衡时间长(以12小时计)，提锂效率较低。
4、专利CN109225121A公开了一种以聚丙烯腈为粘结剂，H1.6Mn1.6O4为内核材料的中空纤维膜，虽然提锂效率得到了进一步提升，但在盐酸洗脱时由于歧化反应造成锰溶损较为严重，循环稳定性较差，且相应配套膜组件易被污染，膜设备维护费用昂贵，不利于规模化工业操作。
由于地热水锂矿矿化度低，一般仅1～10g/L、含锂浓度低(5～30mg/L)，其绿色高效提取困难；另一方面，对于低矿化度的盐湖湖表卤水，由于锰系锂离子筛溶损，既易造污染，且循环稳定性差，上述专利提到的吸附材料不适用于地热水和低矿化度的盐湖湖表卤水提取锂。
为实现从液体锂矿中绿色高效的提取锂，需开发一种制备工艺简单、性能稳定、吸附效率高、易于工业化操作的多孔纺丝复合吸附剂。
发明内容
本发明目的在于提供一种制备流程简单、吸附容量高、吸附速度快、易于规模化制备和工业化操作的纤维状纺丝复合吸附材料，实现含锂浓度低(5～30mg/L)和低矿化度的液体锂矿资源中高效的分离回收锂，为多孔纺丝复合吸附材料的工业化应用奠定基础。
一种多孔纺丝复合材料的制备方法，步骤如下：
(1)将高分子聚合物加热搅拌溶解于有机溶剂中，并将混合溶液在室温下静置脱泡；
(2)向步骤(1)中获得的混合溶液中加入一定量的锂离子筛粉末及水溶性致孔剂，并充分搅拌混合均匀，获得高分子聚合物/锂离子筛的复合纺丝原液；
(3)将步骤(2)中获得的复合纺丝原液加入湿法纺丝设备的原料罐中，通过喷丝头将纺丝原液喷入凝固浴中进行相转化成型，获得多孔复合原丝；
(4)将步骤(3)中凝固成型的复合原丝进行牵伸洗涤，经固化后获得多孔复合锂离子筛纺丝纤维。
(5)将步骤(4)中获得的多孔复合锂离子筛纺丝纤维应用于液体锂矿中锂的提取。
而且所述高分子聚合物为聚乙烯、聚丙烯、聚氯乙烯、聚偏氟乙烯、聚四氟乙烯、聚苯乙烯、聚丙烯腈、聚酰胺、聚砜、磺化聚砜、聚芳砜、聚醚砜中的一种或两种以上的混合物。
而且所述有机溶剂为二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、N-甲基吡咯烷酮、四氢呋喃、二氯甲烷、四氯甲烷中的一种或两种以上的混合物。
而且所述锂离子筛粉末为所述锂离子筛粉末为LiTi2O4、Li2TiO3、Li4Ti5O12，或其酸洗后H型产物中一种或两种以上的混合物。
而且所述水溶性致孔剂为LiCl、KCl、NaHCO3、(NH4)2CO3、NH4HCO3、聚乙二醇-200/400/600/800/1000、聚乙烯吡咯烷酮中的一种或两种以上的混合物。
而且所述致孔剂的添加量为混合溶液总质量的2～10％，此条件下可较大程度提高复合纤维的孔隙率，且保证锂离子筛粉末材料不发生泄露。
而且所述高分子聚合物与锂离子筛的质量比为1:4～4:1。
而且所述湿法纺丝设备喷丝头孔数为20-60孔，喷丝孔直径为0.05～0.5mm，喷丝速度为2-20m/min，收卷机速度为2-30m/min。
而且所述凝固浴为含有机溶剂二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、N-甲基吡咯烷酮、四氢呋喃、二氯甲烷中一种或两中以上的混合水溶液，其质量分数为5～25％，此条件下可使多孔复合锂离子筛纺丝纤维快速成型。
本发明还保护多孔纺丝复合材料在液体锂矿中提取锂中的应用。
所述的液体锂矿为地热水，其矿化度TDS为1～10g/L、含锂浓度为5～30mg/L，多孔纺丝复合材料在地热水提取锂时的pH控制为7-13；
所述的液体锂矿为低矿化度的盐湖湖表卤水，多孔纺丝复合材料在低矿化度的盐湖湖表卤水提取锂时的pH控制为7-13。
所述多孔纺丝所述液体锂矿还包括盐湖卤水、地下卤水、井矿卤水、地热水、海水、海底热液矿。
复合材料在液体锂矿中提取锂时所用的方法包括吸附柱、吸附床和吸附塔式操作。
本发明的优点和积极效果是：
(1)本发明的一种多孔纺丝复合材料不仅制备工艺流程简单、成本低，而且配套设备成熟，易于材料的规模化生产和应用。
(2)本发明的一种多孔纺丝复合材料有效地解决了锂离子筛粉末材料流动性差、成型困难、稳定性差、难以回收利用和规模化生产困难的问题。
(3)本发明的一种多孔纺丝复合材料对于锂离子具有很好的选择性，具有较高的吸附容量、吸附速率和循环稳定性，可广泛的应用于不同类型液体锂矿，尤其是地热水中锂的分离提取，且配套提锂方法易于实现连续工业化操作。
附图说明
图1(a)为本发明实施例1中制备的聚砜-H2TiO3多孔纺丝复合材料的实物图；
图1(b)为本发明实施例1中制备的聚砜-H2TiO3多孔纺丝复合材料的偏光显微镜放大图；
图2(a)为本发明实施例1中制备的聚砜-H2TiO3多孔纺丝复合材料与粉末H2TiO3在相同条件下吸附锂的吸附容量对比图；
图2(b)为本发明实施例1中制备的聚砜-H2TiO3多孔纺丝复合材料与粉末H2TiO3在相同条件下吸附锂的循环稳定性对比图；
图3(a)为本发明实施例2中制备的聚丙烯腈-H4Ti5O12多孔纺丝复合材料的实物图；
图3(b)为本发明实施例2中制备的聚丙烯腈-H4Ti5O12多孔纺丝复合材料的偏光显微镜放大图；
图4(a)为本发明实施例3中制备的聚丙烯腈-Li2TiO3多孔纺丝复合材料的实物图；
图4(b)为本发明实施例3中制备的聚丙烯腈-Li2TiO3多孔纺丝复合材料的偏光显微镜放大图。
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：聚砜-H2TiO3多孔纺丝复合材料的制备及其地热水提锂
称取10g聚砜颗粒于烧杯中，向烧杯中加入90g的N-甲基吡咯烷酮，使用恒温水浴磁力搅拌器加热搅拌，直至聚砜颗粒完全溶解。
称取10g H2TiO3粉末及8g水溶性致孔剂PEG-400加入到上述聚砜混合溶液中，充分混合搅拌均匀，使H型锂离子筛粉末H2TiO3均匀分散于聚砜混合溶液中。
将聚砜/H2TiO3复合纺丝原液加至湿法纺丝设备的原料罐中，调节喷丝头孔数为40，喷丝孔直径为0.07mm，喷丝速度为13m/min，牵伸收卷速度为16m/min，通过喷丝头喷丝到凝固浴中，经转相成型，牵伸水洗，获得多孔聚砜-H2TiO3复合纺丝材料。此条件下获得的复合纺丝材料形貌完整，粗细均匀，吸附性能优异，相比于相同条件下喷丝孔直径为0.1mm获得的复合纺丝材料，吸附容量提升13.69％，吸附速率提升30％。
将制备的多孔聚砜-H2TiO3复合纺丝材料应用于锂离子初始浓度为26.5895mg·L-1的地热水中进行提锂，调节地热水pH为12.1，在1L地热水加入1g聚砜-H2TiO3多孔纺丝复合材料进行吸附。
所制备材料的实物图和偏光显微镜放大图见图1(a)及图1(b)，与粉末H2TiO3在相同条件下吸附锂的吸附容量对比及循环稳定性见图2(a)及图2(b)。可见，经纺丝纤维包覆成型后的锂离子筛粉末，仍可保持较高的吸附容量和速率，与粉末材料相比无明显降低。
本实施例中制备的纤维状纺丝复合吸附材料相对于粒状、膜状等吸附材料而言，其吸附速率和吸附容量得到了极大的提升。例如专利CN101898113A中公开的PVC-LiMn2O4粒状复合吸附剂和专利CN102211012A中公开的PVC-Li1.6Mn1.6O4膜状复合吸附剂，其在常温下达到吸附平衡的时间分别为120小时和8小时，而本实施例中制备的多孔聚砜-H2TiO3纺丝复合材料在常温下仅需要1小时即可达到吸附平衡。例如文献“ACSAppliedMaterials&Interfaces，2019，11(29)，26364-26372”中报道的多孔PVC-PEG-H2TiO3复合微球，虽吸附速率得到了进一步提升，3小时即可达到吸附平衡，但吸附容量较低，仅为7mg·g-1，而本实施例中制备的多孔聚砜-H2TiO3纺丝复合可达23.39mg·g-1，且吸附平衡时间仅40分钟，各项吸附性能均得到显著提升。
实施例2：聚丙烯腈-H4Ti5O12纺丝复合材料的制备及其地热水提锂
称取10g聚丙烯腈粉末于烧杯中，向烧杯中加入90g的二甲基甲酰胺，使用恒温水浴磁力搅拌器加热搅拌，直至聚丙烯腈粉末完全溶解。
称取5g H4Ti5O12粉末加入到上述聚丙烯腈混合溶液中，充分混合搅拌均匀，使锂离子筛粉末均匀分散于聚丙烯腈混合溶液中。
将聚丙烯腈/H4Ti5O12复合纺丝原液加至湿法纺丝设备的原料罐中，调节喷丝头孔数为50，喷丝孔直径为0.05mm，喷丝速度为10m/min，牵伸收卷速度为110m/min，通过喷丝头喷丝到凝固浴中，经转相成型，牵伸水洗，获得聚丙烯腈-H4Ti5O12纺丝复合材料。所得材料的实物图及偏光显微镜放大图见图3(a)及图3(b)。
将制备的聚丙烯腈/H4Ti5O12纺丝复合材料应用于地热水提锂，调节地热水pH为11.8，在1.5L地热水加入1g聚砜-H2TiO3多孔纺丝复合材料进行吸附，吸附容量可达20.07mg/g，50分钟即可达到吸附平衡。
实施例3：聚丙烯腈-Li2TiO3纺丝复合材料的制备及其地热水提锂
称取10.5g聚丙烯腈粉末于烧杯中，向烧杯中加入90g的二甲基甲酰胺，使用恒温水浴磁力搅拌器加热搅拌，直至聚丙烯腈粉末完全溶解。
称取10g Li2TiO3粉末加入到上述聚丙烯腈混合溶液中，充分混合搅拌均匀，使锂离子筛粉末均匀分散于聚丙烯腈混合溶液中。
将聚丙烯腈/Li2TiO3复合纺丝原液加至湿法纺丝设备的原料罐中，调节喷丝头孔数为40，喷丝孔直径为0.07mm，喷丝速度为10m/min，牵伸收卷速度为10m/min，通过喷丝头喷丝到凝固浴中，经转相成型，牵伸水洗，获得聚丙烯腈-Li2TiO3纺丝复合材料，并经进一步酸洗后获得聚丙烯腈-H2TiO3纺丝复合材料。并在上述地热水中进行吸附，控制吸附pH为12，吸附柱的半径为5cm，柱高为50cm，流速为20ml·min-1。所得材料的实物图及偏光显微镜放大图见图4(a)及图4(b)。
本实施例中制备的聚丙烯腈-Li2TiO3纺丝复合材料相比于聚丙烯腈-Li2TiO3静电纺丝纳米纤维膜吸附速率得到了显著提升。例如文献“Journal ofIndustrial andEngineering Chemistry，2019，70，124-135”中报道的聚丙烯腈-Li2TiO3静电纺丝纳米纤维膜，其在初始锂离子初始浓度为70mg·L-1的氯化锂溶液中，常温下12小时达到吸附平衡，平衡吸附容量为28mg·g-1。而本实施例中聚丙烯腈-Li2TiO3纺丝复合材料，在相同吸附条件下，其柱床动态吸附容量达29.8mg·g-1，且吸附平衡时间仅1小时，效率提高12倍；同时，纺丝复合材料比纳米纤维膜更易加工，强度大、易于工程化应用。
以上显示和描述了本发明的实施例，均体现了本发明的制备简单、原料廉价易得等优点。应当理解的是，优选实施例对本发明的技术方案进行的详细说明是示意性而非限制性的，本领域技术人员在阅读本发明说明书的基础上，可以根据上述说明加以改进或变换，例如在材料制备过程中无需添加制孔剂，获得强度更高的吸附材料，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 (3)

1.一种用于液体锂矿中提取锂的多孔纺丝复合材料的制备方法，其特征在于，步骤如下：
(1) 将高分子聚合物加热搅拌溶解于有机溶剂中，并将混合溶液在室温下静置脱泡，所述高分子聚合物为聚丙烯腈或聚砜；
(2) 向步骤(1)中获得的混合溶液中加入一定量的锂离子筛粉末及水溶性致孔剂，并充分搅拌混合均匀，获得高分子聚合物/锂离子筛的复合纺丝原液，所述锂离子筛粉末为LiTi2O4、Li2TiO3、Li4Ti5O12，或其酸洗后H型产物中一种或两种以上的混合物，所述水溶性致孔剂为聚乙二醇-400；
(3) 将步骤(2)中获得的复合纺丝原液加入湿法纺丝设备的原料罐中，通过喷丝头将纺丝原液喷入凝固浴中进行相转化成型，获得多孔纺丝复合原材料；所述湿法纺丝设备喷丝头孔数为20-60孔，喷丝孔直径为0.07 mm，喷丝速度为2-20 m/min，收卷机速度为2-30m/min；
(4) 将步骤(3)中凝固成型的复合原丝进行牵伸洗涤，经固化后获得多孔纺丝复合材料；
所述致孔剂的添加量为混合溶液总质量的2~10 %，所述高分子聚合物与锂离子筛的质量比为1:4~4:1；
所述的液体锂矿为地热水，其矿化度TDS为1~10 g/L、含锂浓度为5 ~ 30 mg/L，多孔纺丝复合材料在地热水提取锂时的pH控制为12-13；或所述的液体锂矿为低矿化度的盐湖湖表卤水，多孔纺丝复合材料在低矿化度的盐湖湖表卤水提取锂时的pH控制为7-13。
2.根据权利要求1所述的方法，其特征在于：所述有机溶剂为二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、N-甲基吡咯烷酮、四氢呋喃、二氯甲烷中的一种或两种以上的混合物。
3.根据权利要求1所述的方法，其特征在于：所述凝固浴为含有机溶剂二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、N-甲基吡咯烷酮、四氢呋喃、二氯甲烷中一种或两种以上的混合水溶液，其质量分数为5~25 %。
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CN109289754A (zh) * 2018-11-14 2019-02-01 天津科技大学 一种磷钼酸铵复合凝胶吸附材料的制备方法
CN110975795A (zh) * 2019-12-20 2020-04-10 南京工业大学 一种提锂吸附剂的合成方法

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