盐湖铝系提锂吸附剂成型条件的影响研究

doi:10.11949/0438-1157.20211079

摘要/Abstract

摘要：

铝系锂吸附剂成型颗粒在盐湖卤水提锂工业应用过程中存在吸附容量低、吸附速率慢和吸附剂粉末脱落等问题。基于现有反溶剂法挤压成型工艺，对盐湖铝系提锂吸附剂成型条件的影响进行了系统性研究。实验结果显示吸附剂成型颗粒粒径越小，达到吸附平衡越快，当颗粒直径d<1 mm时，吸附剂颗粒可在24 h左右达到吸附平衡；降低黏结剂浓度可有效加快吸附剂颗粒的吸附速率，但黏结剂浓度过低会导致其对粉末的包裹性下降；吸附剂颗粒的吸附速率与致孔剂添加比例成正比，当致孔剂添加比例为20%时，吸附剂颗粒能在4 h内完成快速吸附阶段，吸附平衡时对察尔汗高镁锂比盐湖卤水中锂的吸附容量可达4.97 mg·g^-1。

关键词: 盐湖卤水, 铝系吸附剂, 锂吸附, 成型造粒

Abstract:

The aluminum-based adsorbent is an effective adsorbent for lithium recovery from brines with an ultrahigh Mg/Li ratio. And the granulated Li/Al-LDHs adsorbent has been widely used in the salt lake lithium extraction industry, but low adsorption capacity, slow adsorption rate and powder loss are the common problems in industrial. In this work, the anti-solvent method is used to granulate the Li/Al-LDHs adsorbent powder with high hydrophilicity and the effects of granulating conditions are also investigated comprehensively. The experimental results show that, the smaller the diameter of the adsorbent particles, the faster the adsorption equilibrium is reached. When particle diameter <1 mm, the adsorbent can reach adsorption equilibrium in about 24 h. Diluting the binder concentration can effectively accelerate the adsorption rate of the adsorbent, but would increase the powder loss in the adsorbent particles. Adding NaCl as a porogen can shorten the time for the adsorbent reaching equilibrium, specially, the adsorbent particles can accomplish the rapid adsorption in about 4 h and the lithium adsorption capacity at equilibrium can reach 4.97 mg·g^-1 with 20% of the NaCl addition ratio in the Qarham old brine with a high Mg²⁺/Li⁺ ratio.

Key words: ultrahigh Mg/Li ratio brine, Li/Al-LDHs adsorbent, lithium adsorption, granulation

中图分类号:

TQ 133.1

张瑞, 钟静, 林森, 于建国. 盐湖铝系提锂吸附剂成型条件的影响研究[J]. 化工学报, 2021, 72(12): 6291-6297.

Rui ZHANG, Jing ZHONG, Sen LIN, Jianguo YU. Study on the influence of granulation conditions on Li/Al-LDHs for lithium recovery from low grade brine[J]. CIESC Journal, 2021, 72(12): 6291-6297.

图/表 10

图1 不同颗粒粒径吸附剂小球的锂吸附动力学曲线

Fig.1 Lithium adsorption kinetic curves of granulated Li/Al-LDHs with different particle diameters

图2 不同黏结剂浓度下吸附剂小球的锂吸附动力学曲线

Fig.2 Lithium adsorption kinetic curves of granulated Li/Al-LDHs with different adhesive concentrations

图3 77 K下不同黏结剂浓度下吸附剂小球的N2吸附/解吸等温线(a)和孔径分布(b)

Fig.3 N2 adsorption/desorption isotherm (a) and pore size distributions (b) of granulated Li/Al-LDHs with different adhesive concentrations at 77 K

表1 不同黏结剂浓度下铝系吸附剂小球的孔结构参数

Table 1 Pore structure parameters of granulated Li/Al-LDHs with different adhesive concentrations

黏结剂DMF浓度/(g·ml^-1)	比表面积/(m²·g^-1)	孔容/(cm³·g^-1)	平均孔径/nm
0.070	36.85	0.12	8.22
0.052	40.55	0.14	7.94
0.047	45.31	0.14	7.84

图4 不同黏结剂浓度吸附剂小球在水中的接触角

Fig.4 Contact angles of granulated Li/Al-LDHs with different adhesive concentrations

图5 吸附剂小球在摇瓶实验中的粉末损失情况（1为直接黏结成型；2~4为反溶剂法成型，黏结剂浓度分别为0.047、0.052、0.070 g·ml-1）

Fig.5 Powder loss of granulated Li/Al-LDHs in shake flask experiment(1 is direct bonding granulation; 2,3,4 are anti-solvent granulation with the adhesive concentrations of 0.047,0.052 and 0.070 g·ml-1）

图6 不同NaCl含量下吸附剂小球的锂吸附动力学曲线

Fig.6 Lithium adsorption kinetic curves of granulated Li/Al-LDHs with different NaCl contents

图7 77K下不同致孔剂NaCl含量下吸附剂小球的N2吸附-解吸等温线(a)和孔径分布(b)

Fig.7 N2 adsorption/desorption isotherm (a) and pore size distributions (b) of granulated Li/Al-LDHs with different NaCl contents at 77K

表2 不同致孔剂NaCl含量下吸附剂小球的孔结构参数

Table 2 Pore structure parameters of granulated Li/Al-LDHs with different NaCl contents

NaCl含量/%	比表面积/(m²·g^-1)	孔容/(cm³·g^-1)	平均孔径/nm
0	36.85	0.12	8.22
5	36.84	0.12	8.75
10	33.18	0.12	8.64
20	28.44	0.11	9.29

图8 不同致孔剂NaCl含量吸附剂小球在水中的接触角

Fig.8 Contact angles of granulated Li/Al-LDHs with different NaCl contents

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