First-principles calculation of adsorption mechanism of hydrochloric acid on chalcopyrite surface

doi:10.12034/j.issn.1009-606X.220175

Abstract

Abstract:

The leaching of chalcopyrite has always been the core of copper sulfide hydrometallurgy, but chalcopyrite is a sulfide mineral that is difficult to be oxidized and decomposed. At present, a large number of macroscopic phenomena are obtained by focusing on experimental research, and the mechanism is mostly inferred. However, the lack of information on atomic or molecular level hinders the clear and effective explanation to these macroscopic phenomena. Therefore, it is necessary to study the surface interaction between liquid medium and chalcopyrite and the influence of medium on the formation of surface products by means of atomic or molecular level calculation and analysis, which are of great significance to reveal the reaction mechanism of leaching process and improve or develop a green hydrometallurgical technology of chalcopyrite. As a common leaching agent, hydrochloric acid can be used in the leaching of chalcopyrite, and it has been widely studied because of its advantages of recyclable leaching agent, high solubility of metal ions, good oxidation reduction performance and fast leaching rate. In this work, the adsorption and reaction mechanism of hydrochloric acid on different sites of chalcopyrite surface were studied with first-principles calculation. It was shown that the reconstructed sulfur terminated chalcopyrite (001) surface [labeled as (001)-S surface] led to the formation of disulphide S₂^2-. Hydrochloric acid was adsorbed on the sulfur terminated surface (001)-S of chalcopyrite in the form of dissociation. In the process of leaching, the adsorption of H⁺ on sulfur terminated surface (001)-S of chalcopyrite destroyed the S₂^2- formed on the surface. The surface structure of chalcopyrite (001)-S was destroyed by adsorption of chloride ion Cl^-. During the adsorption process, the chemical reactions between H⁺ and Cl^- with the surface of chalcopyrite produce the FeCl₂ and H₂S, which were both beneficial to the leaching of chalcopyrite. The results can provide a theoretical basis and guidance for future research.

Key words: chalcopyrite, hydrochloric acid, surface adsorption, first-principles

摘要：

采用第一性原理对盐酸在黄铜矿表面不同位点的吸附及反应机理进行研究。结果表明，黄铜矿(001)-S表面重构后形成了二硫化物S₂^2-。盐酸以解离形式在黄铜矿的(001)硫终止面(001)-S上吸附，浸出过程中H⁺在黄铜矿(001)-S表面上S位点的吸附都会破坏黄铜矿表面所形成的S₂^2-。Cl^-的吸附对黄铜矿(001)-S表面结构也会造成一定的破坏，吸附过程中H⁺和Cl^-与黄铜矿表面发生化学反应生成了FeCl₂和H₂S，这些都有利于黄铜矿的浸出。

关键词: 黄铜矿, 盐酸, 表面吸附, 第一性原理

CLC Number:

TF811

Xiaoliang LI, Guocai TIAN. First-principles calculation of adsorption mechanism of hydrochloric acid on chalcopyrite surface[J]. The Chinese Journal of Process Engineering, 2021, 21(7): 836-846.

李小亮, 田国才. 盐酸在黄铜矿表面吸附机制的第一性原理计算[J]. 过程工程学报, 2021, 21(7): 836-846.

Figures/Tables 16

Fig.1 The optimized unit of chalcopyrite (unit: °)

Table 1 Geometrical parameters of the chalcopyrite bulk after optimized

Parameter	This work	PWscf^[32]	VASP^[33]	Siesta^[29]	Experimental values^[12]
a=b	0.5256	0.5263	0.5279	0.5277	0.5289
c	1.0395	1.0362	1.0364	1.0447	1.0423
Fe-S	0.2229	0.2241	0.2257	0.2250	0.2257
Cu-S	0.2307	0.2293	0.2287	0.2300	0.2302
Fe-Fe	0.3696	0.3693	-	-	0.3713
Cu-Cu	0.3696	0.3693	-	-	0.3713
Fe-Cu	0.3716	0.3721	-	-	0.3740
S-S	0.3622	0.3659	-	-	0.3685

Fig.2 The chalcopyrite (001)-S surface (unit: nm)

Table 2 Reconstructed chalcopyrite (001)-S surface

Parameter	This work	Siesta^[29]	VASP^[33]	PWscf^[32]
S-S	0.220	0.223	0.2242	0.2158
Fe-S	0.214	0.224	0.2182	0.2319
Cu-S	0.235	0.230	0.2359	0.2326

Fig.3 The electron density of chalcopyrite (001)-S surface

Fig.4 The adsorption sites of chalcopyrite (001)-S surface (unit: nm)

Fig.5 Density of states of chalcopyrite (001)-S surface

Fig.6 Partial density of states of Fe and S atoms on chalcopyrite (001)-S surface

Table 3 The adsorption energy and Fe-Cl bond length considering different adsorption sites for H+ in the dissociation of hydrochloric acid

Adsorption site for H⁺	ΔΕ/(kcal/mol)	Distance of Fe-Cl/nm	Siesta^[30]
1	-19.4	0.232	-19.2
2	-19.5	0.231	-19.3
3	-14.4	0.227	-14.5
4	-12.8	0.230	-11.9
5	-20.9	0.230	-21.2
6	-20.0	0.232	-21.0
7	-13.5	0.230	-14.6
8	-10.6	0.229	-

Fig.7 The most stable configuration with dissociative adsorption of hydrochloric acid on chalcopyrite (001)-S surface (unit: nm)

Fig.8 The optimized configuration with Cl- migrated on the adsorption site (unit: nm)

Fig.9 The most stable configuration of two hydrochloric acid molecules dissociated and adsorbed on chalcopyrite (001)-S surface and H2S molecule and FeCl2 crystal optimized (unit: nm)

Fig.10 The electron density of two hydrochloric acid molecules dissociated and adsorbed on chalcopyrite (001)-S surface

Fig.11 PDOS analysis of Fe and S atoms before and after two hydrochloric acid molecules dissociative adsorption on chalcopyrite (001)-S surface (the dash lines represent Fermi level)

Fig.12 PDOS analysis of hydrochloric acid before and after dissociative adsorption on chalcopyrite (001)-S surface and the H2S molecule and FeCl2 crystal optimized

Table 4 Mulliken charge population of atoms before and after dissociative adsorption of hydrochloric acid on chalcopyrite (001)-S surface

Atom	Adsorption	S orbital, s/e	P orbital, p/e	D orbital, d/e	Total	Charge/e
H	Before	0.66	0.00	0.00	0.66	0.34
H	After	0.91	0.00	0.00	0.91	0.09
Cl	Before	1.93	5.41	0.00	7.34	-0.34
Cl	After	1.95	5.35	0.00	7.29	-0.29
S5	Before	1.87	4.27	0.00	6.14	-0.14
S5	After	1.85	4.38	0.00	6.23	-0.23
Fe	Before	0.36	0.50	6.94	7.79	0.21
Fe	After	0.37	0.50	6.91	7.77	0.23

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