碳化法制备电池级碳酸锂工艺优化研究

doi:10.11962/1006-4990.2019-0230

Abstract

Abstract:

The carbonization method of lithium carbonate is characterized by its high reaction efficiency and simple process.It has become the mainstream process for battery-grade lithium carbonate production.However,in the process of preparing battery-grade lithium carbonate by carbonization method and with salt lake lithium concentrate as raw material,there are still problems such as low carbon dioxide utilization in the carbonization process,poor removal of impurities in the carbonized liquid and low lithium yield.With salt lake lithium concentrate as raw material,process optimization experiments were carried out from three main links：carbonization,purification and pyrolysis,that is,changing from atmospheric carbonization to pressurized carbonization,and using a combination of chemical purification and ion exchange resin adsorption to remove carbonization.Impurities in the liquid were changed from conventional pyrolysis to pressure pyrolysis,which can increase the carbon dioxide utilization rate in the carbonization processed to 87.4%,the removal rate of calcium and magnesium in the purification processed to 97.92% and 96.09%,and the direct yield of lithium in the whole processed to 82.27%.

Key words: salt lake lithium, carbonization method, battery grade lithium carbonate, purification, pyrolysis

CLC Number:

TQ131.11

Zhang Yan,Zhao Zhenzhong,Ma Zhaohui,Zhao Yancai,Chen Zhiyu,Ma Zhengqiang. Optimization of process for preparation of battery grade lithium carbonate by carbonization[J]. Inorganic Chemicals Industry, 2020, 52(3): 68-71.

Figures/Tables 8

References 10

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主要成分	质量分数/%	主要成分	质量分数/%
Li₂CO₃	62.1	Pb	0.004 7
Ca	0.42	Mn	0.001 4
Mg	0.40	Ni	0.004 8
B	0.097	Al	0.004 8
K	1.70	Si	2.55
Na	8.14	Cl^-	9.15
Fe	0.069	SO₄^2-	0.96
Cu	0.000 1	H₂O	13.44

物料名称	洗涤渣主要成分质量分数/%					锂损失率/%	渣率/ %
物料名称	Li₂CO₃	K	Ca	Na	Mg	锂损失率/%	渣率/ %
洗涤渣	91.47	0.27	0.56	0.15	0.46	1.27	65.4

平均粒度/ μm	粒度分布（体积分数）/%
平均粒度/ μm	0.1~1 μm	1~10 μm	10~100 μm	100~1 000 μm
17.68	12.54	45.54	40.06	1.83

序号	碳化渣主要成分质量分数/%					碳化率/ %	CO₂利用率/%
序号	Li₂CO₃	Na	K	Ca	Mg	碳化率/ %	CO₂利用率/%
1	43.50	0.015	0.58	0.16	3.37	95.46	65.5
2	53.61	0.016	0.47	0.25	2.85	94.82	67.2
3	46.06	0.014	0.56	0.19	2.94	95.05	58.4
4	48.24	0.011	0.54	0.22	3.13	93.74	62.8
5	54.48	0.018	0.44	0.17	2.60	93.61	62.3
序号	碳化液主要成分质量浓度/（g·L^-1）
序号	Li	Na	K	Ca	Mg
1	8.26	0.37	0.27	0.13	0.11
2	8.19	0.09	0.18	0.09	0.10
3	7.98	0.15	0.26	0.15	0.09
4	7.84	0.18	0.22	0.20	0.18
5	8.06	0.24	0.25	0.17	0.16

序号	CO₂分压/MPa	液固质量比	温度/ ℃	反应时间/min	碳化率/ %	CO₂利用率/%
1	0.1	20∶1	20	40	94.82	81.6
2	0.1	10∶1	20	40	94.02	79.2
3	0.2	20∶1	20	30	96.20	87.4
4	0.2	10∶1	20	30	93.64	82.5

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Optimization of process for preparation of battery grade lithium carbonate by carbonization

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净化方式	序号	净化液主要成分质量浓度/（g·L^-1）					除钙率/%	除镁率/%
净化方式	序号	Li	Na	K	Ca	Mg	除钙率/%	除镁率/%
化学净化	1	9.75	0.24	0.19	0.034	0.046	77.3	61.6
	2	9.66	0.16	0.10	0.025	0.037	83.3	69.1
	3	9.15	0.18	0.16	0.028	0.041	81.3	65.8
	4	9.48	0.21	0.09	0.032	0.035	78.6	70.8
	5	9.52	0.23	0.11	0.036	0.038	76.0	68.3
离子交换树脂净化	1	9.45	0.10	0.12	0.001 5	0.002 4	95.5	94.7
	2	9.12	0.15	0.073	0.002 7	0.004 3	89.2	88.3
	3	9.31	0.11	0.085	0.002 0	0.002 1	92.8	94.8
	4	9.41	0.08	0.11	0.002 4	0.002 9	92.5	91.7
	5	9.43	0.09	0.10	0.002 1	0.001 9	94.1	95.0

热解方式	序号	热解液成分质量浓度/（g·L^-1）						热解率/%
热解方式	序号	Li	K	Ca	Na	Mg	Cl	热解率/%
常规热解	1	2.7	0.15	0.006 4	0.72	0.007 2	0.73	71.1
	2	3.3	0.23	0.010 0	1.05	0.006 8	0.68	64.6
	3	2.5	0.11	0.005 4	0.55	0.008 5	0.43	73.2
	4	3.1	0.21	0.007 6	0.64	0.011 0	0.37	66.8
	5	2.9	0.17	0.009 2	0.42	0.010 0	0.31	68.9
加压热解	1	1.4	0.12	0.004 6	0.20	0.002 0	0.38	85.0
	2	1.5	0.21	0.003 7	0.26	0.004 2	0.28	83.9
	3	1.2	0.14	0.004 4	0.15	0.003 7	0.35	87.1
	4	1.4	0.16	0.004 2	0.24	0.003 4	0.32	85.0
	5	1.6	0.15	0.003 8	0.22	0.004 1	0.28	82.8

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