影响离子型稀土矿浸出液H+浓度的因素

doi:10.16085/j.issn.1000-6613.2024-0786

化工进展 ›› 2025, Vol. 44 ›› Issue (7): 4267-4273.DOI: 10.16085/j.issn.1000-6613.2024-0786

• 资源与环境化工 • 上一篇

影响离子型稀土矿浸出液H⁺浓度的因素

胡思涛¹(), 秦磊¹(), 王观石¹, 蔡隆祥¹, 罗嗣海², 彭陈亮¹, 龙平¹

^1.江西理工大学土木与测绘工程学院，江西赣州 341000
^2.南昌大学工程建设学院，江西南昌 330031

收稿日期:2024-05-10 修回日期:2024-08-29 出版日期:2025-07-25 发布日期:2025-08-04
通讯作者: 秦磊
作者简介:胡思涛（2000—），男，硕士研究生，研究方向为离子型稀土资源绿色提取。E-mail：1344862821@qq.com。
基金资助:
国家自然科学基金(52164008);国家自然科学基金(52364015);江西省03专项及5G项目(20224ABC03A11);江西省“千人计划”科技创新高端人才项目(jxsq2023201013);江西省高等学校井冈学者特聘教授岗位资助项目(205201200003);江西省自然科学基金(20212BAB211012)

Factors affecting the concentration of H⁺ in the leaching solution of ionic rare earth ore

HU Sitao¹(), QIN Lei¹(), WANG Guanshi¹, CAI Longxiang¹, LUO Sihai², PENG Chenliang¹, LONG Ping¹

^1.School of Civil and Surveying & Mapping Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiangxi, China
^2.School of Infrastructure Engineering, Nanchang University, Nanchang 330031, Jiangxi, China

Received:2024-05-10 Revised:2024-08-29 Online:2025-07-25 Published:2025-08-04
Contact: QIN Lei

摘要/Abstract

摘要：

离子型稀土矿开采过程中H⁺浓度是影响浸出率的重要因素之一。为研究离子型稀土矿浸出液H⁺浓度的影响因素，本文通过柱浸实验，测试浸矿前和浸矿后溶液、矿土H⁺质量，分析溶液中H⁺浓度和矿土上H⁺浓度对浸出液H⁺浓度的影响。通过测试浸出液阳离子与H⁺浓度，分析浸出液阳离子和H⁺浓度的变化规律；使用正交实验极差法和方差法，分析酸性阳离子对浸出液H⁺浓度的影响程度；通过水解理论计算酸性阳离子水解产生H⁺浓度，验证酸性阳离子对浸出液H⁺浓度的影响程度。结果表明，浸矿后比浸矿前溶液中H⁺质量增加了10^-3.30g，矿土上H⁺质量增加了10^-3.40g，说明浸出液中H⁺不是矿土上H⁺解吸产生的；由极差法和方差法分析，影响浸出液H⁺浓度的主要因素是Al³⁺（R=6.225、F=519.07）水解，其次是NH₄⁺（R=1.093、F=16.45）水解、Re³⁺（R=1.020、F=14.14）水解，浸出液中H⁺是由矿土上的酸性阳离子水解产生的，Al³⁺水解占主要因素；浸出液中Al³⁺、NH₄⁺、Re³⁺三者浓度最高时水解产生H⁺浓度之比为932∶20∶1，验证得出影响稀土浸出液H⁺的主要因素是Al³⁺水解。

关键词: 离子型稀土, 极差分析, 方差分析, 水解反应, 酸碱度

Abstract:

During the extraction process of ion-adsorption type rare earth ore, the concentration of H⁺ is one of the critical factors influencing the leaching rate. To investigate the influencing factors of H⁺ concentration in the leaching solution of ion-adsorption type rare earth ore, this article conducted column leaching experiments. We tested the solutions and ore soil for H⁺ mass before and after leaching and analyzed the impact of H⁺ concentration in the solution and on the ore soil on the H⁺ concentration in the leaching solution. The cation concentration and H⁺ concentration in the leaching solution was also tested and the changing patterns of cation concentration and H⁺ concentration was analyzed. Using the orthogonal experimental range method and variance method, the influence degree of acidic cations on the H⁺ concentration in the leaching solution was analyzed. Through hydrolysis theory, the H⁺ concentration produced by acidic cation hydrolysis was calculated, and the extent of the impact of acidic cations on the H⁺ concentration in the leaching solution was verified. Results showed that, after leaching, the mass of H⁺ in the solution increases by 10^-3.30g and the mass of H⁺ on the ore soil increases by 10^-3.40g, compared to those before leaching, which indicated that the H⁺ in the leaching solution did not originate from the desorption of H⁺ on the ore soil. From the range method and variance analysis, the main factor affecting the H⁺ concentration in the leaching solution was the hydrolysis of Al³⁺ (R=6.225, F=519.07), followed by the hydrolysis of NH₄⁺ (R=1.093, F=16.45) and Re³⁺ (R=1.020, F=14.14). The H⁺ in the leaching solution was produced by the hydrolysis of acidic cations on the ore soil, with Al³⁺ hydrolysis being the predominant factor. When the concentrations of Al³⁺, NH₄⁺ and Re³⁺ in the leaching solution were at their highest, the ratio of H⁺ concentrations produced by hydrolysis was 932∶20∶1, confirming that the main factor affecting the H⁺ concentration in the rare earth leaching solution was the hydrolysis of Al³⁺.

Key words: ionic rare earth, range analysis, analysis of variance, hydrolysis reaction, pH

中图分类号:

TD865

胡思涛, 秦磊, 王观石, 蔡隆祥, 罗嗣海, 彭陈亮, 龙平. 影响离子型稀土矿浸出液H⁺浓度的因素[J]. 化工进展, 2025, 44(7): 4267-4273.

HU Sitao, QIN Lei, WANG Guanshi, CAI Longxiang, LUO Sihai, PENG Chenliang, LONG Ping. Factors affecting the concentration of H⁺ in the leaching solution of ionic rare earth ore[J]. Chemical Industry and Engineering Progress, 2025, 44(7): 4267-4273.

图/表 14

参考文献 25

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阳离子	含量/mg·g^-1
Re³⁺	0.37
Al³⁺	0.087
Na⁺	0.059
K⁺	0.061
Mg²⁺	0.043
Ca²⁺	1.47
NH₄⁺	0.12

阳离子	含量/mg·g^-1
Re³⁺	0.37
Al³⁺	0.087
Na⁺	0.059
K⁺	0.061
Mg²⁺	0.043
Ca²⁺	1.47
NH₄⁺	0.12

矿样稀土离子相	质量分数/%
Nd₂O₃	27.12
La₂O₃	29.99
Eu₂O₃	0.82
Dy₂O₃	2.58
Pr₆O₁₁	6.81
Gd₂O₃	3.29
Lu₂O₃	0.22
CeO₂	4.06
Er₂O₃	1.51
Sm₂O₃	5.91
Yb₂O₃	1.52
Tb₄O₇	0.59
Ho₂O₃	0.53
Tm₂O₃	0.22
Y₂O₃	14.82

矿样稀土离子相	质量分数/%
Nd₂O₃	27.12
La₂O₃	29.99
Eu₂O₃	0.82
Dy₂O₃	2.58
Pr₆O₁₁	6.81
Gd₂O₃	3.29
Lu₂O₃	0.22
CeO₂	4.06
Er₂O₃	1.51
Sm₂O₃	5.91
Yb₂O₃	1.52
Tb₄O₇	0.59
Ho₂O₃	0.53
Tm₂O₃	0.22
Y₂O₃	14.82

项目	硫酸铵浸矿前			硫酸镁浸矿前
项目	浸矿剂	顶水	矿土滞留水	浸矿剂	顶水	矿土滞留水
体积/L	0.335	8.154	0.669	0.587	8.111	0.669
H⁺浓度/g·L^-1	10^-5.30	10^-5	10^-6.80	10^-5.77	10^-5	10^-6.80
H⁺质量/g	10^-5.78	10^-4.09	10^-6.98	10^-6.00	10^-4.09	10^-6.98

影响离子型稀土矿浸出液H⁺浓度的因素

Factors affecting the concentration of H⁺ in the leaching solution of ionic rare earth ore

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样品编号	硫酸铵浸矿后		样品编号	硫酸镁浸矿后
样品编号	体积/L	H⁺浓度/g·L^-1	样品编号	体积/L	H⁺浓度/g·L^-1
A-1	0.052	10^-6.80	M-1	0.080	10^-6.79
A-2	0.056	10^-6.80	M-2	0.084	10^-6.70
︙	︙	︙	︙	︙	︙
A-88	0.079	10^-4.30	M-85	0.086	10^-4.68
矿土滞留水	1.927	10^-4.60	矿土滞留水	2.141	10^-4.50

样品编号	浸矿前矿土pH	硫酸铵浸矿后矿土pH	硫酸镁浸矿后矿土pH
K-1	5.4	4.1	4.5
K-2	5.4	4.4	4.3
K-3	5.1	4.4	4.6
K-4	5.4	4.2	4.4
K-5	5.2	4.4	4.2
平均值	5.3	4.3	4.4

试样号	A	B	C	pH
1	1	1	1	3.695
2	1	2	2	3.226
3	1	3	3	3.102
4	1	4	4	3.066
5	2	1	2	3.317
6	2	2	1	3.092
7	2	3	4	3.554
8	2	4	3	3.184
9	3	1	3	3.507
10	3	2	4	3.396
11	3	3	1	3.016
12	3	4	2	3.285
13	4	1	4	3.237
14	4	2	3	3.412
15	4	3	2	3.311
16	4	4	1	3.284

试样号	A	B	C
K₁	13.089	13.756	13.087
K₂	13.147	13.126	13.139
K₃	13.204	12.983	13.205
K₄	13.244	12.819	13.253
K₁²	171.322	189.228	171.270
K₂²	172.844	172.292	172.633
K₃²	174.346	168.558	174.372
K₄²	175.404	164.327	175.642
R	1.020	6.225	1.093

方差来源	平方和	自由度	均方	F	显著性
A	0.003	3	0.001	14.14	显著
B	0.126	3	0.042	519.07	特别显著
C	0.004	3	0.001	16.45	显著
误差	0.001	6	0.00008	—	—
总和	0.134	15	—	—	—

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试样号	A	B	C
1	500	50	500
2	800	200	800
3	1000	300	1000
4	1200	500	1200

试样号	A	B	C
1	500	50	500
2	800	200	800
3	1000	300	1000
4	1200	500	1200

样品编号	浓度/mol·L^-1			实际测量pH	理论计算pH	绝对值
样品编号	Re³⁺	Al³⁺	NH₄⁺	实际测量pH	理论计算pH	绝对值
A-42	0	0	0	6.70	7.00	0.30
A-46	14.53×10^-3	11.96×10^-3	18.61×10^-3	3.72	3.64	0.08
A-50	23.40×10^-3	19.48×10^-3	27.17×10^-3	3.51	3.56	0.05
A-51	21.84×10^-3	18.70×10^-3	49.17×10^-3	3.53	3.57	0.04
A-55	10.96×10^-3	12.04×10^-3	61.00×10^-3	3.64	3.63	0.01
A-60	0.55×10^-3	0.73×10^-3	33.33×10^-3	4.13	4.06	0.07

样品编号	浓度/mol·L^-1			实际测量pH	理论计算pH	绝对值
样品编号	Re³⁺	Al³⁺	NH₄⁺	实际测量pH	理论计算pH	绝对值
A-42	0	0	0	6.70	7.00	0.30
A-46	14.53×10^-3	11.96×10^-3	18.61×10^-3	3.72	3.64	0.08
A-50	23.40×10^-3	19.48×10^-3	27.17×10^-3	3.51	3.56	0.05
A-51	21.84×10^-3	18.70×10^-3	49.17×10^-3	3.53	3.57	0.04
A-55	10.96×10^-3	12.04×10^-3	61.00×10^-3	3.64	3.63	0.01
A-60	0.55×10^-3	0.73×10^-3	33.33×10^-3	4.13	4.06	0.07

影响离子型稀土矿浸出液H+浓度的因素

Factors affecting the concentration of H+ in the leaching solution of ionic rare earth ore

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影响离子型稀土矿浸出液H⁺浓度的因素

Factors affecting the concentration of H⁺ in the leaching solution of ionic rare earth ore