Extraction of Cerium (Ⅳ) by Primary Amine N1923 from Sulfuric Acid Medium Containing Fluorine

doi:10.19894/j.issn.1000-0518.210088

Chinese Journal of Applied Chemistry ›› 2022, Vol. 39 ›› Issue (02): 307-314.DOI: 10.19894/j.issn.1000-0518.210088

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Extraction of Cerium (Ⅳ) by Primary Amine N1923 from Sulfuric Acid Medium Containing Fluorine

Yu-Fei YAN¹^,², Ji CHEN¹^,²(), Kai LI¹, Dan ZOU¹, De-Qian LI¹

^1.State Key Laboratory of Rare Earth Resources Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
^2.University of Chinese Academy of Sciences, Beijing 100039, China

Received:2021-03-02 Accepted:2021-04-28 Published:2022-02-10 Online:2022-02-09
Contact: Ji CHEN
Supported by:
National Natural Science Foundation of China(51174184)

Abstract

Abstract:

Cerium (Ce) usually exists in minerals with accompany of multiple elements, such as fluorine (F). To develop technologies and provide theoretical foundations for comprehensive recovery of Ce and F, the extraction and stripping process of Ce (Ⅳ) by primary amine N1923 in sulfuric acid medium containing fluorine was investigated. The effects of H₂SO₄acidity, extractant concentration, fluorine ion concentration and temperature on the extraction process were comprehensively investigated, meanwhile the extraction mechanism was discussed. It is shown that Ce (Ⅳ) and F^-can be extracted by primary amine N1923 in sulfuric acid medium at the same time, while the H₂SO₄acidity has no significant effect on the extraction. The extraction efficiency of Ce (Ⅳ) increases with the increase of F^-concentration in the aqueous phase and the extraction process conforms to the addition mechanism. Through investigating the extraction performance at varied temperatures, the reaction equilibrium constant and thermodynamic parameter are calculated, revealing that the extraction process is an exothermic reaction driven by both entropy and enthalpy. In the fluorine-containing system, the saturation loading capacity of N1923 (volume fraction 15%) is 18.85 g/L for Ce (Ⅳ) and 2.00 g/L for F^-. Fourier transform infrared (FT-IR) transmission spectroscopy and nuclear magnetic resonance (NMR) spectra of extracted complexes indicate that the complexes are partially polymerized and is bidentatally coordinated in the equilibrium extraction compound. In addition, Ce (Ⅳ) and F^-in the loaded organic phase can be effectively stripped using HNO₃containing H₂O₂as a stripping agent. The stripping rate of Ce (Ⅳ) can reach 90% and the F^-can be almost stripped thoroughly.

Key words: Primary amine N1923, Cerium (Ⅳ), Fluorine, Solvent extraction

CLC Number:

O616

Yu-Fei YAN, Ji CHEN, Kai LI, Dan ZOU, De-Qian LI. Extraction of Cerium (Ⅳ) by Primary Amine N1923 from Sulfuric Acid Medium Containing Fluorine[J]. Chinese Journal of Applied Chemistry, 2022, 39(02): 307-314.

Figures/Tables 12

Fig.1 The effect of concentration of H2SO4on the extraction of Ce（Ⅳ）and F－by primary amine N1923c（N1923）＝0.1 mol／L；c（Ce（Ⅳ））＝0.045 mol／L；c（F－）＝0.09 mol／L

Fig.2 The effect of concentration of fluorine ion on the extraction of Ce（Ⅳ）by primary amine N1923c（N1923）＝0.1 mol／L；c（Ce（Ⅳ））＝0.045 mol／L；c（H2SO4）＝1.0 mol／L

Fig.3 The effect of concentration of primary amine N1923 on the extraction of Ce（Ⅳ）and F－c（H2SO4）＝1.0 mol／L；c（Ce（Ⅳ））＝0.045 mol／L；c（F－）＝0.09 mol／L

Fig.4 The effect of concentration of on the extraction of Ce（Ⅳ）by N1923 in F－containing H2SO4mediumc（N1923）＝0.1 mol／L；c（Ce（Ⅳ））＝0.045 mol／L；c（F－）＝0.09 mol／L；c（H2SO4）＝1.0 mol／L

Fig.5 The effect of temperature on the extraction of Ce（Ⅳ）by primary amine N1923 in F－-containing H2SO4mediumc（N1923）＝0.1 mol／L；c（Ce（Ⅳ））＝0.045 mol／L；c（F－）＝0.09 mol／L；c（H2SO4）＝1.0 mol／L

Table 1 Thermodynamic parameters of Ce（Ⅳ）extraction by N1923 in H2SO4media with fluorine

温度	反应平衡常数对数值	吉布斯自由能	熵变	焓变
T／K	log K_ex	ΔG／（kJ·mol^－1）	ΔS／（J·mol^－1·K^－1）	ΔH／（kJ·mol^－1）
293	1.71	－9.60	4.92	－8.16
298	1.69	－9.66	5.02
303	1.67	－9.71	5.11
308	1.65	－9.73	5.09
313	1.63	－9.75	5.09
318	1.60	－9.74	4.97

Fig.6 The loading capacity of Ce（Ⅳ）and F－by primary amine N1923 with／without fluorine in H2SO4 mediaφ（N1923）＝15%；c（H2SO4）＝1.0 mol／L；c（Ce（Ⅳ））＝0.045 mol／L；c（F－）＝0.09 mol／L

Fig.7 FT-IR spectra of N1923 extracted complexes for different systemin H2SO4medium

Table 2 Characteristic FT-IR peaks of N1923 extracted complexes for different system in H2SO4medium

特征峰	伯胺N1923	硫酸酸化N1923	酸化N1923的F萃合物	酸化N1923的Ce（Ⅳ）-F萃合物	酸化N1923的Ce（Ⅳ）-F萃合物
Assignment	N1923	N1923 sulfate	N1923-H₂SO₄-F	N1923-Ce（Ⅳ）	N1923-Ce（Ⅳ）
NH₂伸缩振动	3303，3369	／	／	／	／
ν（NH₂）	3303，3369	／	／	／	／
+NH₃伸缩振动	／	.3020，3423	3063，3462	3085，3140，3462	3087，3141，3461
ν（+NH₃）	／	.3020，3423	3063，3462	3085，3140，3462	3087，3141，3461
NH₂变形振动	800，1612	／	／	／	／
δ（NH₂）	800，1612	／	／	／	／
+NH₃变形振动	／	1505，1600	1525，1625	1524，1623	1524，1622
δ（+NH₃）	／	1505，1600	1525，1625	1524，1623	1524，1622
C—N伸缩振动	1140	1127	1123	1121	1121
ν（C—N）	1140	1127	1123	1121	1121
CH₂弯曲振动	722	722	722	722	722
γ（CH₂）	722	722	722	722	722
伸缩振动	／	641	／	633，648	635，648
ν（）	／	641	／	633，648	635，648
伸缩振动1	／	／	／	945，972	946，971
ν₁（）	／	／	／	945，972	946，971
伸缩振动2	／	447	437	437	438
ν₂（）	／	447	437	437	438
伸缩振动3	／	1056，1197，1221	1041，1174	1034，1090，1168，1222	1034，1090，1168，1222
ν₃（）	／	1056，1197，1221	1041，1174	1034，1090，1168，1222	1034，1090，1168，1222
伸缩振动4	／	590	586	597，617	598，618
ν₄（）	／	590	586	597，617	598，618

Fig.8 1H NMR spectra of Ce（Ⅳ）-F loaded extracted complexes of N1923

Table 3 1H NMR spectra peaks of N1923 extracted complexes for different system in H2SO4medium

结构官能团	伯胺N1923	硫酸酸化N1923	酸化N1923的F萃合物	酸化N1923的Ce（Ⅳ）萃合物	酸化N1923的Ce（Ⅳ）-F萃合物
Structure	N1923	N1923 sulfate	N1923-H₂SO₄-F	N1923-Ce（Ⅳ）	N1923-Ce（Ⅳ）-F
—NH₂	1.03～1.04	Disappear	Disappear	Disappear	appearDis
—NH⁺　3	／	7.34	7.41	6.78～6.89	6.80～6.90
—CH₃	0.85～0.88	0.86～0.88	0.86～0.89	0.85～0.89	0.85～0.89
—CH₂—	1.25	1.25～1.35	1.25～1.36	1.25	1.22～1.25
—CH—NH₂	2.64～2.65	1.61～1.64	1.60～1.66	1.67～1.70	1.67～1.78
H₂SO₄	／	5.60	Disappear	Disappear	Disappear
	／	3.12	3.10	3.29	3.29

Fig.9 Effect of H+concentration on the stripping of Ce（Ⅳ）（solid line）and F－（dotted line）from Ce（Ⅳ）-F loaded N1923φ（N1923）＝15%；ρ（loaded-Ce（Ⅳ）in N1923）＝18.62 g／L；ρ（loaded-F in N1923）＝1.95 g／L；Vo∶Va＝1∶2

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Extraction of Cerium (Ⅳ) by Primary Amine N1923 from Sulfuric Acid Medium Containing Fluorine

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