Selective Extraction and Recovery of Copper from the Leaching of Low-grade Copper Ore by H2SO4-NaCl Solution Using Cextrant 230

doi:10.19894/j.issn.1000-0518.230002

Chinese Journal of Applied Chemistry ›› 2023, Vol. 40 ›› Issue (5): 758-768.DOI: 10.19894/j.issn.1000-0518.230002

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Selective Extraction and Recovery of Copper from the Leaching of Low-grade Copper Ore by H₂SO₄-NaCl Solution Using Cextrant 230

Yu FANG¹^,², Wang-Qiang KUANG², Sheng-Ting KUANG²^,³(), Wu-Ping LIAO¹^,²^,³()

^1.School of Chemistry and Chemical Engineering，Nanchang University，Nanchang 330031，China
^2.Institute of Material and Chemistry，Ganjiang Innovation Academy，Chinese Academy of Sciences，Ganzhou 341000，China
^3.State Key Laboratory of Rare Earth Resource Utilization，Changchun Institute of Applied Chemistry，Chinese Academy of Sciences，Changchun 130022，China

Received:2023-01-08 Accepted:2023-03-27 Published:2023-05-01 Online:2023-05-26
Contact: Sheng-Ting KUANG,Wu-Ping LIAO
About author:wpliao@gia.cas.cn
stkwong@gia.cas.cn
Supported by:
Ganjiang Innovation Academy Chinese Academy of Sciences （No.?E055C002）, Jiangxi Province Natural Science Foundation(20212BAB213033);Jiangxi “Double Thousand Plan”(Jxsq.2020101005)

Abstract

Abstract:

The aid-leaching reagent NaCl can improve the leaching efficiency of copper from low-grade complex copper ore at ambient temperature and pressure， which gives a leach solution containing mixed acids. The extraction of Cu²⁺， Fe³⁺， Co²⁺， Mg²⁺ and Al³⁺ from the mixed H₂SO₄-HCl solutions using di（2-ethylhexyl）［N-（2-ethylhexyl） amino methyl］ phosphonate （Cextrant 230） is studied here. Cextrant 230 has better extraction ability and selectivity towards Cu²⁺ and Fe³⁺ than Co²⁺， Mg²⁺ and Al³⁺ in the mixed acid solutions. The extraction of Cu²⁺can be facilitated by Cl^- while it is restrained by SO $4 2 -$ and HSO $4 -$ . The extraction reaction of Cu²⁺ is an exothermic process. The loading capacity of 0.60 mol/L Cextrant 230 for Cu²⁺ is determined to be 13.1 g/L at an initial pH of 1.16 with 20 g/L Cl^-. The loaded Cu（Ⅱ） can be stripped completely by H₂SO₄. By 2 stages of extraction， the content of iron in the mixed acid solution is decreased from 0.65 g/L to 32 mg/L and only 1.5% copper is co-extracted. After iron removal， the copper product with the purity of 99.7% and the yield of 98.5% can be obtained by 4 stages of extraction， 1 stage of scrubbing and 3 stages of stripping.

Key words: Copper, Cextrant 230, Mixed acid solution, Solvent extraction, Recovery

CLC Number:

O658.2

Yu FANG, Wang-Qiang KUANG, Sheng-Ting KUANG, Wu-Ping LIAO. Selective Extraction and Recovery of Copper from the Leaching of Low-grade Copper Ore by H₂SO₄-NaCl Solution Using Cextrant 230[J]. Chinese Journal of Applied Chemistry, 2023, 40(5): 758-768.

Figures/Tables 11

Fig.1 Effect of the equilibrium pH on the extraction of Cu2+， Fe3+， Co2+， Mg2+and Al3+ from the single solutions （A） and mixed solutions （B）Note:c(Cextrant 230)=0.10 mol/L, ρ(Cl－)=20 g/L; A. c(Mn+)=0.01 mol/L; B. c(Mn+)=0.002 mol/L

Table 1 Separation factors （β） between copper and other metal cations at different acidities

pH_e	β
pH_e	$D (F e 3 +) / D (C u 2 +)$	$D (C u 2 +) / D (M g 2 +)$	$D (C u 2 +) / D (C o 2 +)$
0.66	8.44	2.78	2.29
1.41	4.00	1.17	2.38
2.34	14.3	1.08	2.89
2.52	7.53	4.25	2.20
2.86	16.6	61.2	6.75

Table 1 Separation factors （β） between copper and other metal cations at different acidities

pH_e	β
pH_e	$D (F e 3 +) / D (C u 2 +)$	$D (C u 2 +) / D (M g 2 +)$	$D (C u 2 +) / D (C o 2 +)$
0.66	8.44	2.78	2.29
1.41	4.00	1.17	2.38
2.34	14.3	1.08	2.89
2.52	7.53	4.25	2.20
2.86	16.6	61.2	6.75

Fig.2 Effect of the Cl- （A）， SO42- and HSO4- （B） concentration on the extraction of metal cationsNote:c(Cextrant 230)=0.10 mol/L, initial pH=1.16; A: c(Mn+)=0.002 mol/L; B: c(Cu2+)=0.01 mol/L, ρ(Cl-)=20 g/L

Table 2 Separation factors （β） between copper and other metal cations at different chloride concentrations

ρ（Cl^-）/（g·L^-1）	β
ρ（Cl^-）/（g·L^-1）	$D (F e 3 +) / D (C u 2 +)$	$D (C u 2 +) / D (M g 2 +)$	$D (C u 2 +) / D (C o 2 +)$
10	33.3	4.62	8.53
20	18.8	7.21	12.3
30	12.8	12.7	16.1

Table 2 Separation factors （β） between copper and other metal cations at different chloride concentrations

ρ（Cl^-）/（g·L^-1）	β
ρ（Cl^-）/（g·L^-1）	$D (F e 3 +) / D (C u 2 +)$	$D (C u 2 +) / D (M g 2 +)$	$D (C u 2 +) / D (C o 2 +)$
10	33.3	4.62	8.53
20	18.8	7.21	12.3
30	12.8	12.7	16.1

Fig.3 Effect of the Cextrant 230 concentration on the extraction of metal cationsNote:c(Mn+)=0.002 mol/L, ρ(Cl-)=20 g/L, initial pH=1.16; A. V(Organic phase)∶V(Aqueous phase)=1∶1; B. c(Cextrant 230)=0.10 mol/L

Table 3 Separation factors （β） between copper and other mixed metal ions at different organic/aqueous phase ratios

Organic phase/Aqueous phase	β
Organic phase/Aqueous phase	$D (F e 3 +) / D (C u 2 +)$	$D (C u 2 +) / D (M g 2 +)$	$D (C u 2 +) / D (C o 2 +)$
3/1	59.2	19.9	137
2/1	14.5	10.0	68.4
1/1	6.43	4.13	20.6

Table 3 Separation factors （β） between copper and other mixed metal ions at different organic/aqueous phase ratios

Organic phase/Aqueous phase	β
Organic phase/Aqueous phase	$D (F e 3 +) / D (C u 2 +)$	$D (C u 2 +) / D (M g 2 +)$	$D (C u 2 +) / D (C o 2 +)$
3/1	59.2	19.9	137
2/1	14.5	10.0	68.4
1/1	6.43	4.13	20.6

Fig.4 Effect of temperature on extraction of Cu2+Note：c（Cextrant 230）=0.10 mol/L， c（Cu2+）=0.01 mol/L， ρ（Cl－）=20 g/L， initial pH=1.16

Table 4 Thermodynamic parameters of Cu2+ extraction with Cextrant 230

T/K	E/%	lg K_ex	ΔG/（kJ·mol^-1）	ΔH/（kJ·mol^-1）	ΔS/（J·mol^-1·K^-1）
298	89.2	7.91	-45.2	-39.8±0.07	17.9
303	86.7	7.81	-45.3		18.1
308	82.6	7.68	-45.3		17.8
313	78.5	7.56	-45.3		17.6
318	74.4	7.46	-45.4		17.6
323	70.7	7.38	-45.7		18.0

Fig.5 Loading capacity of Cu2+ by Cextrant 230 （A） and stripping of the loaded Cu2+ by different inorganic acidsNote: A. c(Cextrant 230)=0.60 mol/L, c(Cu2+)=0.21 mol/L, ρ(Cl－)=20 g/L, initial pH=1.16; B. 0.60 mol/L Cextrant 230 loaded 13.1 g/L Cu2+

Table 5 The composition of the mixed solutions before and after extraction

Element	Feed （F₁）/（mg·L^-1）	Raffinate after removing Fe （F₂）/（mg·L^-1）	Raffinate after extracting Cu （R）/（mg·L^-1）
Cu（Ⅱ）	17 961	17 690	0.2
Co（Ⅱ）	4 480	4 380	3 170
Mg（Ⅱ）	2 190	2 100	1 570
Al（Ⅲ）	550	540	0.1
Fe（Ⅲ）	650	32	＜0.1

Table 6 The parameters for the extraction and separation of copper from mixed solution

System	Parameters
Organic phase （S₁）	0.80 mol/L Cextrant 230
Feed （F₁）	given in table 5
Organic phase （S₂）	0.20 mol/L Cextrant 230
Feed （F₂）	given in table 5
Scrubbing regent （W）	2.7 mol/L NaCl
Strippant （St）	8.5 % Na₂CO₃（mass percent）
Volume ratio （S₂∶F₂∶W∶St）	10∶2.5∶1∶10
Extraction stages	4
Scrubbing stages	1
Stripping stages	3

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Selective Extraction and Recovery of Copper from the Leaching of Low-grade Copper Ore by H₂SO₄-NaCl Solution Using Cextrant 230

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