西藏硫酸镁亚型盐湖原卤水吸附提锂中试研究

doi:10.19964/j.issn.1006-4990.2023-0142

Abstract

Abstract:

Taking a representative magnesium sulfate subtype salt-lake in Tibet as the research object，the world′s first pilot production line for lithium extraction from raw brine in the salt-lake was established using the manganese-based adsorbent as lithium carrier in the world.The adsorption/desorption operating parameters under pilot conditions were researched，and the optimal operating conditions obtained were：brine flow rate of 2.0 BV/h，brine volume of 12 BV，and pH adjuster mass fraction of 0.03%.The concentration of sulfuric acid used for desorption was 0.06 mol/L，the flow rate of dilute acid was 3.0 BV/h，and the volume of dilute acid was 5.5~6.0 BV.Under this condition，the total lithium recovery rate of brine was ≥90%，the average operating adsorption capacity of lithium ions was ≥4 mg/g，the average magnesium removal rate was ≥99.0%，and the dissolution loss rate of the adsorbent in each cycle was ≤0.05%.After three months of continuous operation，this pilot production line had produced over 50 t of industrial grade lithium carbonate.The production cost of lithium carbonate for the new lithium extraction process was 35 460 RMB/t，which was lower to the production cost of lithium carbonate by ore-based lithium extraction and lithium extraction using aluminum-based adsorbents.

Key words: adsorption, magnesium sulfate subtype salt lake, raw brine, lithium extraction, manganese-based adsorbent

CLC Number:

TQ131.1+1

LAI Xianrong, CHEN Zhouqin, SUN Hao, YANG Chao. Pilot study on lithium extraction by adsorption from raw brine of magnesium sulfate subtype salt lakes in Tibet[J]. Inorganic Chemicals Industry, 2023, 55(11): 86-92.

Figures/Tables 14

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References 16

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编号	解吸量Q_d/kg	吸附量q/kg	解吸率D_t/%
A	63.1	63.1	100.0
B	57.8	57.8	100.0
C	61.0	61.0	100.0

编号	卤水中离子质量浓度/（mg·L^-1）		吸附母液中离子质量浓度/（mg·L^-1）		吸附率/ %	吸附容量/ （mg·g^-1）	脱镁率/ %	解吸液中离子质量浓度/ （mg·L^-1）			解吸率/%	溶损率/%
编号	Li⁺	Mg²⁺	Li⁺	Mg²⁺	吸附率/ %	吸附容量/ （mg·g^-1）	脱镁率/ %	Li⁺	Mg²⁺	Mn²⁺	解吸率/%	溶损率/%
A塔	149.7	7.43	36.2	7.38	75.8	4.05	99.3	495.9	79.7	15.7	99.5	0.04
B塔	383.3	7.63	153.9	7.58	59.8	4.09	99.3	524.5	74.3	14.7	99.4	0.02
C塔	391.2	7.60	166.5	7.55	57.4	4.01	99.3	509.2	75.2	15.8	99.6	0.03

反渗透		体积/ m³	ρ（Li⁺）/ （mg·L^-1）	处理时间/h	处理效率/ （m³·h^-1）	浓缩倍数
批次一	进料	1 150	1 050	28.8	40	8.85
	产水	1 020	26.00
	浓缩	130	9 366
批次二	进料	1 470	884.2	36.8	40	9.13
	产水	1 310	18.00
	浓缩	160	8 200
批次三	进料	1 260	921.6	31.5	40	9.00
	产水	1 120	18.50
	浓缩	140	8 390

编号	ρ（Li⁺）/ （g·L^-1）	ρ（Mg²⁺）/ （mg·L^-1）	ρ（Ca²⁺）/ （mg·L^-1）	ρ（Mn²⁺）/ （mg·L^-1）
批次1	16.41	21.2	1.12	8.63
批次2	14.49	10.7	9.30	6.40
批次3	15.16	5.30	5.23	5.86
批次4	15.21	1.09	2.26	1.83

项目	样品检测值/（mg·L^-1）	质控测定值/（mg·L^-1）	相对偏差/%	质控要求/（mg·L^-1）	质控评价	检测方法
氨氮	0.067	0.065	1.5	＜2.0（二级）	合格	HJ 535—2009
化学需氧量	10	10	0.0	≤15（Ⅰ类）	合格	HJ/T 132—2003
总磷	0.04	0.04	0.0	＜0.1（Ⅱ类）	合格	GB 11893—1989
总氮	0.87	0.88	0.6	＜1.0（Ⅲ类）	合格	HJ 636—2012

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Pilot study on lithium extraction by adsorption from raw brine of magnesium sulfate subtype salt lakes in Tibet

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项目	名称	规格	单耗/ t	单价^* （万元·t^-1）	总价/ 万元	备注
原材料	原卤水	m³	670	—	—	—
	吸附剂	颗粒	0.01	35.0	0.350	含运费
	碳酸钠	工业一级	1.650	0.25	0.412	含运费
	硫酸	工业一级	1.500	0.20	0.300	含运费
	调节剂	工业一级	1.600	0.30	0.480	含运费
	地下水	—	300	0.000 1	0.030	当地
	包装袋	—	1	0.01	0.010	吨袋
	离子膜及其他	—	—	—	0.300	—
能耗	电	—	10 000度	0.80元/度	0.800	—
设备折旧	总设备投资3.0亿元，10年折旧期				0.300	—
财务成本人工费用管理销售	资金利息：5%/a，总投资6.0亿元				0.300	—
	120人，10 000元/（人·月）				0.144	西藏
	—				0.120	—
合计	—				3.546

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