硝酸锂改性钛系离子筛的制备及其吸附性能

doi:10.11949/0438-1157.20191484

摘要/Abstract

摘要：

钛系锂离子筛具有较高的锂吸附容量和稳定性，对其制备工艺及性能进行改进研究具有重要意义。使用硝酸锂和碳酸锂混合物作为锂源，与二氧化钛在500℃下进行固相反应，生成层状钛酸锂；使用0.2 mol·L ^-1盐酸对其酸洗24 h，得到了锂离子筛吸附剂；采用X射线衍射、扫描电镜、粒度分析、N ₂吸附-脱附方法等，对其性能进行了表征；通过锂离子的吸附实验，确定了吸附和再生性能；探究了该新型吸附剂的锂离子吸附机理。结果表明：吸附过程是单分子层化学吸附；经过改性，离子筛颗粒更加细小，孔体积和比表面积更大，结构完整；在70 mg·L ^-1的Li ⁺溶液中，吸附量为25.01 mg·g ^-1，准二级吸附速率常数为0.2762 g·(mg·h) ^-1，吸附速率较之未改性提高了54.56%；该离子筛对浓度为11.6 mg·L ^-1的Li ⁺溶液，其锂去除率可以达到99.77%。

关键词: 吸附剂, 动力学模型, 颗粒, 锂离子筛, 固相反应, 硝酸锂

Abstract:

Titanium based lithium ion sieves have excellent lithium adsorption capacity and stability, and the improvement studies on its preparation and character are of great importance. A mixture of LiNO ₃ and Li ₂CO ₃was used as the lithium source to synthesize laminar Li ₂TiO ₃ through the solid state reaction at 500℃, and lithium ion sieves were prepared after being put it in 0.2 mol·L ^-1 hydrochloric acid pickling solution for 24 h. Physicochemical properties of the ion sieves were characterized by X-ray diffraction (XRD), scanning electronmicroscopy (SEM), particle size distribution analysis and nitrogen adsorption-desorption measurements. Adsorption, regeneration properties of the ion sieves and adsorption mechanism were investigated. It is revealed that adsorption process conforms to the monomolecular and chemical adsorption. Furthermore, micro-scale particles with higher pore volume and higher specific area were obtained after modification. Adsorption capacity and pseudo-second-order kinetic constant of 25.01 mg·g ^-1 and 0.2762 g·(mg·h) ^-1, respectively, were obtained by pouring the lithium ion sieves in the solution of 70 mg·L ^-1 for 24 h. Hence, the increase in adsorption rate of 54.56% was observed. The removal rate of Li ⁺ (99.77%) can be reached using this ion sieves in the solution of concentration of 11.6 mg·L ^-1.

Key words: adsorbents, kinetic modeling, particle, lithium ion sieve, solid state reaction, LiNO ₃

中图分类号:

TQ 131.1

郭佳明, 刘明言, 吴强, 马永丽. 硝酸锂改性钛系离子筛的制备及其吸附性能[J]. 化工学报, 2020, 71(2): 879-888.

Jiaming GUO, Mingyan LIU, Qiang WU, Yongli MA. Preparation and adsorption performance of titanium based lithium ion sieve improved by LiNO ₃[J]. CIESC Journal, 2020, 71(2): 879-888.

图/表 14

图1 改性前后原料的热重曲线

Fig.1 TG-DTA curves of material before and after modification

图2 离子筛和前体的XRD谱图

Fig.2 XRD patterns of ion sieves and ion sieve precursors

图3 改性前后离子筛SEM图

Fig.3 SEM images of ion sieves before and after modification

图4 改性前后离子筛粒径分布

Fig.4 Particle size distribution of ion sieves before and after modification

图5 改性前后离子筛的N 2吸附-脱附等温线和孔径分布曲线

Fig.5 N 2 adsorption-desorption isotherms and pore size distribution curves of ion sieves before and after modification

图6 锂钛的洗脱率随酸浓度的变化

Fig.6 Li + uptake and Ti 4+ loss in pickling solution with different acid concentrations

图7 硝酸锂添加比例对锂离子筛吸附量的影响

Fig.7 Lithium adsorption capacity of ion sieves varies with adding ratio of lithium nitrate

图8 改性前后离子筛吸附量随吸附时间的变化

Fig.8 Lithium adsorption capacity of ion sieves varies with adsorption time

表1 改性前后离子筛动力学参数

Table 1 Kinetics parameters of ion sieves before and after modification

离子筛

一级动力学

二级动力学

k₁/h

q_e1/

(mg·g ^-1)

R²

k₂/

g·(mg·h) ^-1

q_e2/

(mg·g ^-1)

R²

图9 吸附量随平衡浓度的变化

Fig.9 Adsorption capacity of ion sieves varies with equilibrium concentration

表2 改性前后离子筛吸附等温线参数

Table 2 Adsorption isotherms parameters of ion sieves before and after modification

离子筛

Langmuir模型

Freundlich模型

q_m/

(mg·g ^-1)

R²

K_f/

(mg·g ^-1)

R²

图10 改性后离子筛在多种阳离子共存时的吸附选择性

Fig.10 Adsorption selectivity of modified ion sieves in presence of other cations

图11 改性后离子筛的循环性能

Fig.11 Cycle performance of modified ion sieves

图12 离子筛前体（a）、离子筛（b）、吸附后的离子筛（c）的晶体结构示意图

Fig.12 Crystal structure of ion sieve precursors(a), ion sieves(b) and ion sieves after adsorption (c)

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