Accepted Manuscript

Title: Selective recovery of mercury from high

mercury-containing smelting wastes using an iodide solution
system

Authors: Zhilou Liu, Dongli Wang, Shu Yang, Hui Liu, Cao
Liu, Xiaofeng Xie, Zhifeng Xu

PII: S0304-3894(18)30788-X
DOI: https://doi.org/10.1016/j.jhazmat.2018.09.001
Reference: HAZMAT 19725

To appear in: Journal of Hazardous Materials

Received date: 1-6-2018

Revised date: 2-8-2018
Accepted date: 1-9-2018

Please cite this article as: Liu Z, Wang D, Yang S, Liu H, Liu C, Xie X,
Xu Z, Selective recovery of mercury from high mercury-containing smelting
wastes using an iodide solution system, Journal of Hazardous Materials (2018),
https://doi.org/10.1016/j.jhazmat.2018.09.001

This is a PDF file of an unedited manuscript that has been accepted for publication.
As a service to our customers we are providing this early version of the manuscript.
The manuscript will undergo copyediting, typesetting, and review of the resulting proof
before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that
apply to the journal pertain.
Selective recovery of mercury from high mercury-containing
smelting wastes using an iodide solution system

Zhilou Liu,1,# Dongli Wang,2,# Shu Yang,2 Hui Liu,2 Cao Liu,2 Xiaofeng

Xie,2 Zhifeng Xu,1,*

T
1
School of Metallurgy and Chemical Engineering, JiangXi University of Science and

IP
Technology, 86 Hongqi Road, Ganzhou 341000, China

R
2
School of Metallurgy and Environment, Central South University, 93 Lushan Road,

SC
Changsha 410083, China

#
U
Both authors contributed equally to this work and share senior authorship
N
* Corresponding author. Postal address: School of Metallurgy and Chemical
A
M

Engineering, JiangXi University of Science and Technology, 86 Hongqi Road, Ganzhou

341000, China. Tel: +86-797-8312412. Fax: +86-797-8312204. E-mail:

ED

xzf_1@163.com
PT

Graphical Abstract
E
CC
A

1
 T
R IP
SC
Highlights U
N
 ► A novel technique for mercury recovery from mercury-containing smelting wastes
A
was proposed.
M

 ► The leachate after electrolysis can be recycled for mercury leaching.

 ► Mercury leaching kinetics follows the shrinking core diffusion model.
 ► Mercury leaching rate depended on the distribution of mercury species in waste.
ED

Abstract:
PT

The mercury resources recovery and safe disposal of mercury-containing waste is

E

an urgent problem. In this study, a new method using an iodide solution system was
CC

proposed to selectively recover mercury from high mercury-containing smelting

wastes. The mercury leaching efficiency, yields, leaching kinetics and

A

thermodynamics were researched. The major factors which affect mercury leaching

efficiency including iodide concentration, oxidant, pH and temperature were

evaluated. Over 97% and 93% of mercury can be efficiently leached from wastewater

2
treatment sludge (W-S) and acid sludge (A-S). After leaching, the mercury

concentration during leaching toxicity test is under the limits set for hazardous

waste. Additionally, the electrolytic technology can efficiently recover mercury from

leachate in the form of elemental mercury, and the leachate after electrolytic can be

reused for mercury leaching. The mercury leaching kinetics follows the shrinking

T
core diffusion model and is controlled by solid product diffusion. The mechanism

IP
research shows the leaching efficiency was strongly dependent on the distribution of

R
mercury species in smelting waste. The consequence on mercury leaching and

SC
recovery could provide nonferrous smelters with a practical and yet easy-to-adopt

U
perspective to reduce the risk of mercury contamination and selectively recover
N
mercury resources from mercury-containing smelting wastes.
A
M

Keywords: Smelting waste; Selective leaching; Mercury recovery; Mercury species

1. Introduction
ED

Mercury is known as one of the most harmful elements in the world on account
PT

of the characteristics of toxicity, volatility and bioaccumulation along the trophic

E

chain [1, 2], and is listed as a priority pollutant by the US Environment Protection
CC

Agency. Due to the affinity between mercury and sulfide, mercury usually occurs in

the form of HgS [3], and is concentrated in mineral ores. Therefore, nonferrous
A

smelting production is identified as one of the largest anthropogenic sources for

mercury release and emission [4-6].

3
 During the high temperature smelting process, nearly all of mercury in the raw

materials is transferred to the flue gas [7, 8]. Then, the mercury in the flue gas finally

enriches in the dusts or precipitates in the flue gas purification process such as

electrostatic precipitation and wet dust collection, leading to the formation of

mercury-containing wastes [7, 9, 10]. According to the recent research [11], the total

T
mercury amount in smelting wastes is over 700 tons each year. Generally, mercury-

IP
containing waste from nonferrous smelting industry is landfilled and would pose a

R
great threat to ground water. Although several researches [12, 13] are developing

SC
some adsorbent materials to adsorb mercury ions in ground water, the best way to

U
decrease mercury pollution of smelting wastes is reduce the transformation of
N
mercury from waste to ground water. The stabilization/solidification techniques
A

have become the most common method for mercury-containing wastes disposal due
M

to the low cost and high efficiency [14, 15].However, this technique could not recycle
ED

metal mercury and cause huge waste of mercury resources, especially for high

mercury-containing smelting wastes. Additionally, the production of primary

PT

mercury will be forbidden in the future according to the requirements of the

E

Minamata Convention. Hence the mercury recovery from smelting wastes will
CC

become a main way to meet the demand for mercury. From the perspective of

reducing mercury contamination and recycling mercury resources, some other

A

techniques that focus on the recovery of mercury from high mercury-containing

smelting wastes should been adopted.

4
 Thermal desorption technology is the most common strategy to recover mercury

from mercury-containing wastes [16-18]. Lee et al. [19] developed a vacuum thermal

desorption system to recycle mercury in the form of gaseous elemental mercury

from industrial fly ash and sludge. The mercury recovery efficiency was over 96%

after vacuum heating at 400 oC for 3 h. Despite high recovery efficiency, this method

T
has not been widely used for mercury-containing smelting wastes. Many volatile

IP
components such as selenium, arsenic and chlorine widely exist in mercury-

R
containing smelting wastes [20, 21]. These volatile elements would go into the gas

SC
phase with mercury during heating process. Then, these volatile components would

U
react with gaseous elemental mercury, leading to the formation of nonvolatile
N
mercury compounds which reduce mercury recovery efficiency. Compared with
A

thermal desorption technology, the leaching-extraction is quite attractive for

M

mercury recovery from smelting wastes because the mercury can be separated by
ED

changing the solvent and extractant [22]. For example, Roselaine et al. [23] proposed

an aqueous two-phase system to recovery mercury after acid leaching. Although the
PT

extraction process could avoid the effect of impurities in leaching liquor such as zinc,
E

lead and copper, the use of organic solvents is not environmentally safe. Therefore, a
CC

technology realizing selective leaching without the presence of organic solvents

becomes a development tendency for the mercury recovery from mercury-

A

containing smelting wastes.

In this study, a novel method was proposed to selectively separate and recover

mercury from high mercury-containing smelting wastes. The whole process consists

5
of two stages, the leaching process using iodide solution and the electrolysis process.

Several important parameters including iodide concentration, oxidant, solution

temperature and pH were investigated. In addition, the mercury recovery rate was

evaluated to elucidate the optimal conditions, and the mechanism of selective

leaching was proposed.

T
IP
2. Material and methods

R
2.1 Mercury-containing smelting wastes

SC
Two typical mercury-containing smelting wastes, wastewater treatment sludge

U
(W-S) and acid sludge (A-S), were from a lead smelter using oxygen bottom-blown
N
smelting technology and selected as raw materials for mercury recovery in this
A
study. Fig. S1 shows the route and source of W-S and A-S in the nonferrous smelting
M

flue gas purification process. The W-S was collected from the waste acid purification
ED

process where some chemical reagents such as lime and limestone were added to

remove heavy metal ions including mercury ion, while the A-S was collected from the
PT

electrostatic-demister process installed at wet smelting flue gas scrubbing system.

E

The collected wastes were air-dried for 7 days and then fully grinded using an agate
CC

mortar and sieved using a standard mesh (ASTM E100).

2.2 Experimental system for mercury leaching and recovery

A

A schematic diagram of experimental apparatus is shown in Fig. S2. The mercury

recovery apparatus consisted of a thermostatic water bath, filter flask and

electrolysis device. The pH of leaching solution was determined by a pH instrument

6
(Mettler-S220, Seven Compact, Switzerland), where diluted sulfuric acid or sodium

hydroxide was used to adjust pH value. The leaching solution was prepared by

dissolving compounds such as KI in purified water. The main experimental process

for mercury leaching and electrolysis included mainly the following three steps: (1)

25 g of mercury-containing smelting wastes were added to 100 mL of leaching

T
solution with constant temperature, and the stirring rate was 500 rpm for all the

IP
selective leaching of Hg; (2) The smelting waste were filtered from liquid-solid

R
mixture (the filter was 10 kDa-0.45 μm). After filtering, the smelting wastes were

SC
cleaned using 20 mL of deionized water at least twice to ensure all the mercury ions

U
entered into leachate; (3) The three electrode system was applied where graphite
N
electrode, mercurous chloride electrode and copper electrode were applied as
A

counter electrode, reference electrode and working electrode, respectively. The

M

electrode couple (length 25mm, width 25mm, thickness 1mm) was connected to a
ED

constant-voltage power supply. During electrolytic process, the copper sheet was

used as cathode and the electrolysis voltage was -0.5 V (calomel electrode as
PT

reference). The volume of electrolyte was 100mL and the stirring speed was 300 rpm
E

during each experiment. After the above steps, the mercury in smelting wastes could
CC

be recovered in the form of elemental mercury.

A

2.3 Analysis and characterization method

2.3.1 Metal content analysis

7
 The mercury concentration in W-S samples was analyzed with a Lumex 915M +

Pyro attachment with a detection limit of 0.5 ppb. The mercury-containing waste

was heated in Pyro attachment to 800 °C to guarantee the complete volatilization of

mercury in the form of elemental mercury and then elemental mercury was

determined by Lumex 915M. Because the mercury concentration in the A-S samples

T
exceeded its detecting range, the US EPA method 7471B was used. 5 g of smelting

IP
wastes were digested with 20 mL of aqua regia at 80 °C (HNO3:HCl = 1:3, v:v). Then,

R
the digested solution was diluted to a required concentration. The mercury content

SC
in leachate and electrolyte was measured with Cold-vapor atomic absorption

U
spectrometry (CVAAS; S-H-22, Themo Jarrell Ash Corporation, USA). Other metal
N
contents in solution such as Pb and Zn were determined by ICP-OES (Optima 7300
A

DV, PerkinElmer Inc., Waltham, USA).

M

2.3.2 Hg-TPD analysis

ED

Mercury-thermal programmed desorption technique (Hg-TPD) has been

PT

extensively demonstrated to be a useful technique for identifying the mercury

species in various wastes [24, 25]. In this study, the mercury-containing smelting
E
CC

wastes were heated from 20 °C to 650 °C at a heating rate of 5 °C/min with a N2

volume flow rate of 0.6 L/min. The mercury concentration in the gas was monitored
A

in real time by an on-line RA-915 analyzer. Origin 8.5 software was used during data

fitting for evaluating the proportion of various mercury compounds.

2.3.3 Leaching toxicity analysis

8
 The leaching toxicity tests were performed based on the china standard leaching

test (CSLT) method and the toxicity characteristic leaching procedure (TCLP) method

which are described in standard document and EPA Test Method 1311 [26, 27],

respectively. In the CSLT tests, the solution pH was adjusted to 3.20 using mixed

solution of H2SO4 and HNO3 (the mass ratio of H2SO4 and HNO3 is 2).Then, 10 g waste

T
was added to 100 mL of prepared solution. The mixtures were tumbled for 18 hours

IP
at the speed of 30 rpm to simulate an extended leaching time in the ground, and

R
then filtered through a glass fiber filter (pore size is 0.6~0.8 mm). In the TCLP test,

SC
the solution pH was adjusted to 2.88 with acetic acid. Then, 5 g of waste was added

U
to 100 mL of prepared solution. The follow-up steps are same with CSLT. At last, the
N
leaching solution was quantified using ICP-OES.
A
M

2.3.4 Characterization method

The chemical composition of the mercury-containing smelting wastes was

ED

confirmed by X-ray fluorescence spectrometry (XRF; Bruker AXS Corporation, S4-

PT

Pionner, Germany). The phase composition of wastes was analyzed by X-ray

diffraction (XRD; Rigaku TTR, AX III θ/θ, Japan). The step scanning procedure was
E
CC

used with a sweep speed of 10 °/min in the 2θ range from 10° to 80°. The surface

microform and element content was characterized by scanning electron microscopy

A

(SEM, Nova Nano230, USA) and energy dispersive X-ray spectrometry (EDS, Oxford

X-act, UK).

2.4 Calculation

9
 In this paper, the mercury leaching efficiency ( L % ) and recovery efficiency

( R % ) are calculated as follows:

C le a c h a te V le a c h a te
 L (% )   100% (1)
C in itia l M in itia l
 C fin a l M fin a l

M r c o v e ry
 C fin a l M fin a l
 M add
 R (% )   100% (2)

T
C in itia l M in itia l

IP
where C le a c h a te and V le a c h a te are the mercury concentration and the volume of

R
leachate, respectively; C in itia l and C fin a l are the mercury concentrations in smelting

SC
wastes before and after leaching process, respectively; M in itia l
and M fin a l
are the

total mass of wastes before and after leaching process, respectively;

U M re c o v e ry
and
N
M add
are the mercury recovery mass and mercury addition mass, respectively.
A

3. Results and discussions

M

3.1 Characterization of mercury-containing smelting wastes

ED

3.1.1 XRF analysis

PT

The elemental composition of the wastewater treatment sludge (W-S) and the
E

acid sludge (A-S) was determined by XRF. The results shown in Table 1 indicate that
CC

the major elements in the W-S are Ca and S, and in the A-S are Pb, Hg and Se. The

mass fraction of mercury in the W-S and A-S is 0.52% and 22.06%, respectively. This
A

result is similar to the individual test results using Lumex 915M + Pyro attachment

and Cold-vapor atomic absorption spectrometry. The mercury concentration in W-S

and A-S is higher than the average mercury content which is between 0.3% and 0.5%

10
in primary mercury mines. Therefore, both W-S and A-S are becoming important

resources for mercury recovery.

3.1.2 XRD and Hg-TPD analyses

The XRD pattern (Fig. 1a) reveals that the W-S was composed of gypsum

T
(CaSO4·2H2O), while the A-S was mainly composed of metacinnabar (HgS), mercury

IP
selenite (HgSe), selenium (Se) and anglesite (PbSO4) (see Fig. 1b). The volatile matter

R
in flue gas such as Hg, Se and S can react with each other with the decrease of flue

SC
gas temperature during purification process, leading to the formation of HgSe and

HgS in the A-S. The reason that mercury species in the W-S was not been detected by
U
N
XRD might be due to low content or amorphous state. Therefore, Hg-TPD technique
A
was used to determine mercury speciation in the W-S and the results are shown in
M

Fig. S3. The desorption temperatures of different pure reference mercury

compounds are summarized in Table S1. The results indicate that Hg2Cl2, HgS and
ED

HgSO4 are mercury species present in the W-S. The presence of Hg2Cl2 and HgSO4
PT

might come from the reactions between HgCl2 and Hg0 according to reaction 3 and 4.

In addition, some researches [7, 10] indicate that Hg2+ might disproportionately
E
CC

catalyse sulphite to generate sulphate and sulphide. Then the generated sulphide

could react with Hg2+ to form insoluble HgS in the wastewater treatment process.
A

The reactions involving the formation of mercury speciation in the W-S are as

follows:

H g C l 2 (a q )  H g (g )  H g 2 C l 2 (s ) 
0
(3)

11
 2 2
Hg (aq )  S O 4 (a q )  H g S O 4 (s )  (4)

4 H g S O 3 (a q )  H g S (s )   3 H g S O 4 (a q ) (5)

3.2 Mercury leaching test

3.2.1 Effect of iodide concentration

T
For the sake of investigating the impact of iodide concentration on the mercury

IP
leaching efficiency of two different types of smelting wastes, two set of experiments

R
were carried out in parallel. It can be seen from the Fig. 2 that the mercury leaching

SC
efficiencies of the W-S and A-S increase with iodide concentration. As the iodide

U
content increases from 0.02 to 0.1 mol/L, the mercury leaching efficiencies increase
N
from 61.89% to 81.22% and from 41.43% to 58.22% corresponding to W-S and A-S,
A

respectively. However, mercury leaching efficiencies have a little change by a further

M

increase in the iodide concentration. Therefore, the optimum concentration of

ED

iodide for mercury leaching is 0.1 mol/L. What is noteworthy is that the mercury

leaching efficiencies between the W-S and A-S differ greatly. This consequence might
PT

be explained by the reason that the leaching rate or leaching behavior of different
E

mercury phases is different during the leaching process using iodide solution for
CC

example the percentage of HgS in the W-S is comparatively higher than A-S. This will

be studied in details in the following sections.

A

3.2.2 Effect of oxidant

From the above results, the leaching residues contain significant amounts of

mercury where the mercury mass fraction in the A-S residue can still reach about
12
10.56% even after the leaching process using a high iodide concentration solution.

To improve the mercury leaching efficiency, three kinds of oxidants, Fe(NO3)3, H2O2

and NaClO were tested in this study and the results are in Fig. 3. As the

concentration of oxidant increase from 0 to 0.06 mol/L, the mercury leaching

efficiencies of the W-S and A-S sharply rise from 81.22% to over 99% and from

T
58.24% to over 96%, respectively. This illustrates that the addition of oxidants can

IP
significantly promote the leaching efficiency of mercury. Among the three oxidants,

R
the NaClO is the best for mercury leaching under the same concentration. However,

SC
other impurities such as Pb2+ and Cd2+ in leachate are also the highest (the date of

U
main impurity ions concentration in leachate is shown in Table S2). For example, the
N
concentration of Pb2+ and Cd2+ in A-S leachate can reach up to 15.32 and 35.72 mg/L
A

at 0.06 mol/L NaClO. The presence of Cl-, as oxidative product of NaClO, facilitates
M

the leaching of Pb2+ and Cd2+ due to an affinity between them. The stability
ED

constants logβ of PbCl3- and CdCl42- are 3.23 and 2.8 respectively. The concentration

of impurities in leachate when H2O2 was used as oxidant is also higher than Fe(NO3)3.
PT

It is quite clear that the Fe(NO3)3 are the best oxidant and the corresponding content
E

is 0.04mol/L after comprehensively considering the selectivity and leaching

CC

efficiency.
A

3.2.3 Effect of solution pH and temperature

The mercury leaching efficiencies under the condition of 0.1 mol/L iodide ions and

0.04 mol/L Fe(NO3)3 in solution as a function of the solution pH and temperature are

shown in Fig. 4. According to Fig. 4a, mercury leaching is favored at lower solution
13
pH in the range of 2 to 5. This phenomenon might be illuminated by the following

reasons: 1) the oxidizing capacity of Fe3+ becomes strong with the decrease of pH; 2)

the formation of colloidal Fe(OH)3 when the pH is over 3 reduce the activity of Fe3+.

From the experiment results on solution temperature (Fig. 4b), it can be

concluded that the mercury leaching efficiency depends on temperature when the

T
IP
solution temperature rises from 20 to 40 °C, but begins to remain stable as the

temperature rises continually. More energy could be provided at high temperatures

R
SC
which enhances the reaction rate. Therefore, the increase of reaction activity is the

major cause for the increase of mercury leaching efficiency when the temperature is

U
below 40 °C. A significant phenomenon is that the mercury leaching efficiency for A-
N
S is always lower than for W-S with the increase of solution pH and temperature. It
A
M

could be mainly due to the difference in the mercury phase compositions for

example the primary phase in the W-S and A-S is HgS and HgSe, respectively.
ED

3.3 Mercury recovery test

PT

After mercury leaching, the average concentration of mercury is 643.41 mg/L in

E

W-S leachate and 7246.87 mg/L in A-S leachate (the composition of leachate is
CC

shown in Table S3). The mercury species in leachate should be HgI42- based on the

theory of chemical equilibrium, because the iodide concentrations in leachate are

A

several orders of magnitudes higher than mercury concentrations. To separate

mercury from leachate, the constant voltage electrolysis technology was used in this

study. Fig. 5 shows the changes of mercury recovery efficiency and current efficiency

14
with time. The results indicate that over 98% of mercury could be recovered when

the electrolysis time exceeds 300 min. Fig. S4 shows the microstructure of cathode at

different electrolysis time. Obviously, a layer on the cathode surface was formed

over time. The date of EDS shows that layer was composed of elemental mercury

(see Table S4). These results demonstrate the feasibility of electrolysis technology

T
for mercury recovery. However, the current efficiency is only less than 35%, which is

IP
much lower than those reported in the literatures [25, 26]. The oxidation and

R
reduction of I-/I2 and Fe2+/Fe3+ between anode and cathode may be major causes of

SC
low current efficiency. In the future, diaphragm electrolysis could be investigated to

U
avoid the reduction of I2 and Fe3+ on the cathode. The chemical reaction in the
N
electrolysis process can be expressed as below.
A

2 
M

H gI4  2e  H g
0
 4I (6)


2I  2e  I2 (7)
ED

2 3
Fe  e  Fe (8)
PT

The solution after mercury recovery by electrolysis was returned to leaching

E

processes, and the effect of regenerated leachate on mercury leaching efficiency was
CC

evaluated. Fig. 5b shows that the leaching efficiency of mercury kept in above 96%

for W-S and 93% for A-S during five cycles of leaching and electrolysis. This suggests
A

that the mercury leaching efficiency did not decrease remarkably after the five

cycles. The performance of cycle experiments indicates the iodide ions could be

reused, which is very meaningful to lowering operating costs.

15
3.4 Leaching characteristics of W-S and A-S

CSLT and TCLP method were applied simultaneously to assess the potential release

of smelting wastes in this study. The leaching toxicity of W-S and A-S before and

after leaching is presented in Table S5. The concentrations of mercury in leachate for

the W-S and A-S before leaching obviously exceed the Hg content in the standard of

T
IP
CSLT and TCLP. After leaching, the leachable of mercury level from W-S and A-S is

lower than that of hazardous waste limits. This means that the potassium iodide

R
SC
leaching process is contribute to reducing the hazards of smelting wastes to

environment. A remarkable fact is that the concentration of Se in A-S leachate

U
increase from 49.79 mg/L after leaching to 7.64 mg/L before leaching. This may be
N
caused by the decomposition of HgSe during mercury leaching process, resulting in
A
M

the formation of unstable selenium compounds. The A-S after mercury leaching

could be used as raw materials for the recycle of valuable Se and Pb.
ED

3.5 Kinetic analysis of mercury leaching from the W-S and A-S
PT

The kinetic analyses for mercury leaching from smelting wastes were studied using
E

shrinking core mode [28]. The kinetic data for mercury leaching at 0.1 mol/L I- (see
CC

Fig. 6) indicate that the best kinetic model with high regression coefficient is solid

product diffusion. The regression coefficient for mercury leaching from W-S and A-S
A

are over 0.98 and 0.99, respectively. The apparent activation energy (Ea) can be

calculated by the slope in Fig. S5 according to Arrhenius equation. The Ea values of

mercury leaching are 8.83 and 15.47 kJ/mol for W-S and A-S, respectively. The Ea for

16
W-S again supports the leaching of mercury follows solid product diffusion, while the

Ea value determined for A-S is higher for a diffusion process and under mixed control

by solid product diffusion and chemical reaction. Some studies have been reported

that the dissolution rate of HgSe is inferior to HgS in the iodine solution [29, 30]. This

may be the reason why the kinetic mode for A-S follows the mixed control by solid

T
product diffusion and chemical reaction.

R IP
3.6 Mechanism of mercury leaching

SC
3.6.1 Mercury leaching rate for different mercury species

U
From section 3.21, the leaching rates of different mercury species have great
N
difference. To deeply understand the leaching behavior of mercury, the W-S and A-S
A
samples disposed by different solutions were characterized by Hg-TPD, and the
M

results are presented in Fig. 7. The HgSO4 peak in Fig. 7a at about 558 °C disappear
ED

after leaching process using iodide solution, indicating HgSO4 phase in W-S could

dissolve completely even without the addition of oxidants. The proportions of

PT

dissolved Hg2Cl2 (the peak at about 118 °C) and HgS (the peak at 195 and 316 °C)
E

calculated by peak areas are 87.64% and 68.73%, respectively. After adding iron ions
CC

as oxidant, the rest of HgS could be efficiently leached from residual. The chemical

reaction can be listed as follows:

A

 2 2
H gSO 4  4I  H gI4  SO 4 (9)

  2 
2 H g 2C l2  16 I  O 2  4H  4 H gI 4  4C l  2 H 2O (10)

17
 Compared Fig. 7a with Fig. 7b, there are a major difference in mercury species

distribution between W-S and A-S. Fig. S3 illustrates that HgSe, HgS and HgSO4 were

the mercury species in the A-S and accounted for 92.23%, 6.24%, and 1.53% of the

total, respectively. Obviously, HgSe is the primary mercury species in the A-S, which

is consistent with the XRD result in Figure 1b. The leaching efficiency of HgSe, only

T
less than 30%, is lower than HgS in the absence of Fe3+. Hence, the dissolution rate of

IP
HgSe is lower than HgS. From the above results, the orders of dissolution rate in

R
iodide solution are HgSe<HgS<Hg2Cl2<HgSO4. The surface morphology of A-S residue

SC
was characterized by SEM-EDS and the results are shown in Fig. S6. It shows that

U
some selenium and sulfur particles which are the decomposition product of HgSe
N
and HgS appeared on the surface of unreacted HgSe and HgS particles during
A

leaching process. Therefore, the dissolution process in the presence of potassium

M

iodide and iron nitrate can be explained by reaction 11 and 12:

ED

 3 2 2
H gS  4I  2Fe  H gI4  2Fe S (11)
PT

 3 2 2
H gSe  4I  2Fe  H gI4  2Fe  Se (12)
E

3.6.2 Selective leaching of mercury

CC

The common impurities such as Pb, Zn, Cu and Cd in mercury-containing smelting

wastes are in the form of insoluble sulfate or sulfide. The standard free energy
A

changes of possible chemical reactions during leaching process are evaluated by

using HSC 6.0 software. The corresponding chemical equations and thermodynamic

results are shown in Table S6 and Fig. S7. It can be seen that the standard free

18
energies of mercury leaching reactions are all negative, which confirmed again the

feasibility of mercury leaching. The PbSO4 cannot dissolve in leachate due to positive

standard free energies. According to previous literature [31, 32], the actual

dissolution rate of ZnS and CdS in acid solution is very slow although it is feasibility in

thermodynamics. The oxidative product of CuS in potassium iodide solution is CuI

T
which has a low solubility. Hence, it can be concluded that the metal elements, Pd,

IP
Cu, Zn and Cd, retain in leaching residues. The difference between mercury and

R
other metal elements in dissolution rate or behavior is the key factor for mercury

SC
selective leaching.

4. Conclusions U
N
A
In this study, we proposed a new method to recover mercury from high mercury-
M

containing smelting wastes. The mercury in wastes could be selectively leached using

an iodide solution system. The results show that high iodide concentration, ferric
ED

irons as oxidant, low pH and high temperature are helpful for efficient leaching of
PT

mercury. The mercury in leachate could be recovered in the form of elemental

mercury using electrolytic technology, and the leachate after electrolytic can be
E
CC

recycled for mercury leaching. Additionally, the leaching behavior and rate are

strongly dependent on the distribution of mercury species in smelting waste, and the
A

orders of dissolution rate in iodide solution are HgSe<HgS<Hg2Cl2<HgSO4. The results

of thermodynamic calculation supported mercury could be selectively dissolved in

mixed solution of iodide and iron ions. The new leaching system using an iodide

19
solution provides a feasible method to reduce the risk of mercury contamination and

recover mercury resources from mercury-containing smelting wastes.

References

[1] J.P. Coelho, M.E. Pereira, A. Duarte, M.A. Pardal, Macroalgae response to a mercury contamination
gradient in a temperate coastal lagoon (Ria de Aveiro, Portugal), Estuar. Coast. Shelf S. 65 (2005) 492-
500.

T
[2] B. Henriques, L.S. Rocha, C.B. Lopes, P. Figueira, R.J.R. Monteiro, A.C. Duarte, M.A. Pardal, E.

IP
Pereira, Study on bioaccumulation and biosorption of mercury by living marine macroalgae: Prospecting
for a new remediation biotechnology applied to saline waters, Chem. Eng. J. 281 (2015) 759-770.

R
[3] H. Biester, M. Gosar, G. Müller, Mercury speciation in tailings of the Idrija mercury mine, J.
Geochem. Explor. 65 (1999) 195-204.

SC
[4] L.D. Hylander, R.B. Herbert, Global emission and production of mercury during the
pyrometallurgical extraction of nonferrous sulfide ores, Environ. Sci. Technol. 42 (2008) 5971-5977.
[5] X. Ye, D. Hu, H. Wang, L. Chen, H. Xie, W. Zhang, C. Deng, X. Wang, Atmospheric mercury

U
emissions from China's primary nonferrous metal (Zn, Pb and Cu) smelting during 1949–2010, Atmos.
Environ. 103 (2015) 331-338.
N
[6] L. Zhang, S. Wang, L. Wang, Y. Wu, L. Duan, Q. Wu, F. Wang, M. Yang, H. Yang, J. Hao, X. Liu,
Updated Emission Inventories for Speciated Atmospheric Mercury from Anthropogenic Sources in
A
China, Environ. Sci. Technol. 49 (2015) 3185-3194.
M

[7] Z. Liu, D. Wang, B. Peng, L. Chai, H. Liu, S. Yang, B. Yang, K. Xiang, C. Liu, Transport and
transformation of mercury during wet flue gas cleaning process of nonferrous metal smelting, Environ.
Sci. Pollut. Res.24 (2017) 22494-22502.
ED

[8] Z. Liu, D. Wang, B. Peng, L. Chai, S. Yang, C. Liu, C. Zhang, X. Xie, H. Liu, Mercury re-emission
in the smelting flue gas cleaning process: the influence of arsenite, Energy Fuel. 31 (2017) 11053-11059.
[9] R. Meij, The fate of mercury in coal-fired power plants and the influence of wet flue-gas
PT

desulphurization, Water Air Soil Poll. 56 (1991) 21-33.

[10] Z. Liu, B. Peng, L. Chai, H. Liu, S. Yang, B. Yang, K. Xiang, C. Liu, D. Wang, Selective Removal
of Elemental Mercury from High-Concentration SO2 Flue Gas by Thiourea Solution and Investigation
E

of Mechanism, Ind. Eng. Chem. Res. 56 (2017) 4281-4287.

[11] Q. Wu, S. Wang, L. Zhang, M. Hui, F. Wang, J. Hao, Flow Analysis of the Mercury Associated with
CC

Nonferrous Ore Concentrates: Implications on Mercury Emissions and Recovery in China, Environ. Sci.
Technol. 50 (2016) 1796-1803.
[12] D. Chandra, S.K. Das, A. Bhaumik, A fluorophore grafted 2D-hexagonal mesoporous organosilica:
A

Excellent ion-exchanger for the removal of heavy metal ions from wastewater, Microporous Mesoporous
Mater. 128 (2010) 34-40.
[13] T. Zou, C. Wang, R. Tan, W. Song, Y. Cheng, Preparation of pompon-like ZnO-PANI heterostructure
and its applications for the treatment of typical water pollutants under visible light, J. Hazard. Mater. 338
(2017) 276-286.
[14] X.-Y. Zhang, Q.-C. Wang, S.-Q. Zhang, X.-J. Sun, Z.-S. Zhang, Stabilization/solidification (S/S) of
mercury-contaminated hazardous wastes using thiol-functionalized zeolite and Portland cement, J.

20
Hazard. Mater. 168 (2009) 1575-1580.
[15] J.H. Cho, Y. Eom, T.G. Lee, Stabilization/solidification of mercury-contaminated waste ash using
calcium sodium phosphate (CNP) and magnesium potassium phosphate (MKP) processes, J. Hazard.
Mater. 278 (2014) 474-482.
[16] O. Rodríguez, I. Padilla, H. Tayibi, A. López-Delgado, Concerns on liquid mercury and mercury-
containing wastes: A review of the treatment technologies for the safe storage, J. Environ. Manage. 101
(2012) 197-205.
[17] M. Jang, S.M. Hong, J.K. Park, Characterization and recovery of mercury from spent fluorescent
lamps, Waste Manage. 25 (2005) 5-14.
[18] T.C. Chang, J.H. Yen, On-site mercury-contaminated soils remediation by using thermal desorption

T
technology, J. Hazard. Mater. 128 (2006) 208-217.

IP
[19] W.R. Lee, Y. Eom, T.G. Lee, Mercury recovery from mercury-containing wastes using a vacuum
thermal desorption system, Waste Manage. 60 (2017) 546-551.

R
[20] P. Xing, B. Ma, C. Wang, Y. Chen, Cleaning of lead smelting flue gas scrubber sludge and recovery
of lead, selenium and mercury by the hydrometallurgical route, Environ. Technol. (2017) 1-9.

SC
[21] Z. Zhou, D. Dreisinger, An investigation of mercury stabilization techniques through hypochlorite
leaching and thiosulfate/selenosulfate precipitation, Hydrometallurgy, 169 (2017) 468-477.
[22] J.H. Cho, Y. Eom, J.-M. Park, S.-B. Lee, J.-H. Hong, T.G. Lee, Mercury leaching characteristics of

U
waste treatment residues generated from various sources in Korea, Waste Manage. 33 (2013) 1675-1681.
[23] R.C. da Cunha, P.R. Patrício, S.J.R. Vargas, L.H.M. da Silva, M.C.H. da Silva, Green recovery of
N
mercury from domestic and industrial waste, J. Hazard. Mater. 304 (2016) 417-424.
[24] H. Xu, Y. Ma, W. Huang, J. Mei, S. Zhao, Z. Qu, N. Yan, Stabilization of mercury over Mn-based
A
oxides: Speciation and reactivity by temperature programmed desorption analysis, J. Hazard. Mater. 324
M

321 (2017) 745-752.

[25] M. Rumayor, J.R. Gallego, E. Rodríguez-Valdés, M. Díaz-Somoano, An assessment of the
environmental fate of mercury species in highly polluted brownfields by means of thermal desorption, J.
ED

Hazard. Mater. 324 325 (2017) 1-7.

[26] China, Identification standard for hazardous wastes-Identification for leaching toxicity, 2007.
[27] S.o.t.C.o.A.R.o.t.A. Chemical, Toxicity Characteristic Leaching Procedure (TCLP) Test Method
PT

1311 in U.S. Environmental Protection Agency, 1992.

[28] M. Sethurajan, D. Huguenot, R. Jain, P.N.L. Lens, H.A. Horn, L.H.A. Figueiredo, E.D. van
Hullebusch, Leaching and selective zinc recovery from acidic leachates of zinc metallurgical leach
E

residues, J. Hazard. Mater. 324 (2017) 71-82.

[29] C. Han, W. Wang, F. Xie, T.a. Zhang, Mechanism and kinetics of mercuric sulfide leaching with
CC

cuprous-thiosulfate solutions, Sep. Purif. Technol. 177 (2017) 223-232.

[30] J. Falandysz, M. Drewnowska, Cooking can decrease mercury contamination of a mushroom meal:
Cantharellus cibarius and Amanita fulva, Environ. Sci. Pollut. Res. 24 (2017) 13352-13357.
A

[31] V.V. Zhukov, A. Laari, M. Lampinen, T. Koiranen, A mechanistic kinetic model for direct pressure
leaching of iron containing sphalerite concentrate, Chem. Eng. Res. Des. 118 (2017) 131-141.
[32] M. Lampinen, A. Laari, I. Turunen, Kinetic model for direct leaching of zinc sulfide concentrates at
high slurry and solute concentration, Hydrometallurgy 153 (2015) 160-169.

Table 1. Elemental analysis of the W-S and A-S.

Elements composition (%)

21
 Hg Pb Zn Cu Cd Ca As Se S Cl
W-S 0.52 0.18 2.45 0.09 0.18 23.23 0.11 0.43 20.54 0.03
A-S 22.06 21.26 6.16 0.54 0.23 0.04 0.075 27.67 6.98 0.12

4000
 a
3000
Counts

2000

T
IP
1000 

 

R
 
0
10 20 30 40 50 60 70 80

SC
2 Theta/deg.

1500

1200



U b
N
900
Counts

A

600  
  
M


 
300   
 
  






 
0
ED

10 20 30 40 50 60 70 80
2 Theta/deg.
PT

Fig. 1. XRD diagrams of the wastewater treatment sludge (a) and the acid sludge (b). (α
E

CaSO4·2H2O, gypsum, PDF#33-0311; β HgS, metacinnabar, PDF#06-0261; χ HgSe, mercury

CC

selenide, PDF#08-0469; δ Se, selenium, PDF#06-0362; ε PbSO4, anglesite, PDF#36-1461).

A

22
 100
W-S

Mercury leaching efficiency (%)

80 A-S

60

40

20

T
0
0.02 0.06 0.10 0.14 0.18

IP
Iodide concentration (mol/L)

R
Fig. 2. Effect of iodide concentrations on mercury leaching efficiency of W-S (a) and A-S (b).

SC
Experimental conditions: liquid-solid ratio = 4; solution temperature = 30 oC; pH = 2.5;

reaction time = 60 min; stirring speed = 500 rpm.

U
N
A
100
100 a b
Mercury leaching efficiency (%)

Mercury leaching efficiency (%)

M

90
95

80
90 Fe(NO3)3 Fe(NO3)3
ED

H2O2 H2O2
70
85 NaClO NaClO

60
80
PT

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.00 0.01 0.02 0.03 0.04 0.05 0.06
Oxidant concentration (mol/L) Oxidant concentration (mol/L)
E

Fig. 3. Effect of different oxidants on mercury leaching efficiency of W-S (a) and A-S (b).
CC

Experimental conditions: iodide concentration = 0.1 mol/L; liquid-solid ratio = 4; solution

A

temperature = 40 oC; pH = 1.0; reaction time = 60 min; stirring speed = 500 rpm.

23
 105 105

a W-S b W-S
Mercury leaching efficiency (%)

Mercury leaching efficiency (%)

100
A-S A-S
100
95

90 95

85
90
80

T
75 85
2.0 2.5 3.0 3.5 4.0 4.5 5.0 20 25 30 35 o
40 45 50
Solution pH Temperature ( C)

R IP
Fig. 4. Effects of solution pH (a) and temperature (b) on mercury leaching efficiency of W-S

SC
and A-S. Experimental conditions: iodide concentration = 0.1 mol/L; ferric ion concentration

= 0.04 mol/L; solution temperature = 40 oC (if it's not a variable); pH = 1.0 (if it's not a

variable); the other conditions were same with above leaching experiment. U
N
100
A
100
a b W-S A-S
M Mercury leaching efficiency (%)

80 95
Efficiency (%)

Mercury recovery efficiency

60
Current efficiency 90
ED

40

20 85
PT

0
80
0 100 200 300 400 500
Time (min) Run 1 Run 2 Run 3 Run 4 Run 5
E

Fig. 5. (a) Changes of mercury recovery efficiency and current efficiency over time. (b)
CC

Mercury leaching efficiency by iodide solution during five cycles of leaching and electrolysis.
A

Experimental conditions: (a) electrolysis voltage = -0.5 V, stirring speed = 300 rpm,

electrolyte volume = 100 mL, electrode spacing = 3 cm, electrolytic area = 8 cm2; (b) iodide

concentration = 0.1 mol/L; ferric ion concentration = 0.04 mol/L; solution temperature = 40

o
C; pH = 1.0; the other conditions were same with above leaching experiment.

24
 140 140
a b
2 2
Liquid film diffusion model R =0.8785 Liquid film diffusion model R =0.9552
120 2 120 2
Chemical reaction model R =0.9614 Chemical reaction model R =0.9843
2 2
100 Solid product model R =0.9849 100 Solid product model R =0.9939

80 80

%
%

60
60
40
40
20

T
20
0

IP
0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)

R
Fig. 6. Kinetic model fits of W-S (a) and A-S to experimental results of mercury leaching

SC
where the liquid film diffusion model, chemical reaction model and solid product diffusion

model, could be expressed by the linear relationship between 1-(1-x)2/3, 1-(1-x)1/3 and 1-3(1-
U
N
x)2/3+2(1-x) against time, respectively. Experimental conditions: iodide concentration = 0.1
A

mol/L, Fe(NO3)3 concentration = 0.04 mol/L, initial solution pH = 2.5, solution temperature =
M

40 °C, stirring rate = 500 r/min, mass ratio of solid to liquid = 1/4.
ED
PT

80 HgS black Before leaching

-
a 800 Before leaching
Leaching with I
- b
Leaching with I 700
E

- 3+
Hg2Cl2 -
Leaching with I and Fe
3+ HgSe Leaching with I and Fe
60 600
Mercury signal

Mercury sigal
CC

HgS red 500

HgSO4
40 400

300 HgS red

20 200 HgSO4
A

100
0 0
0 100 200 300 400 500 600 700 0 100 200 300 400 500 600 700
o o
Temperature( C) Temperature( C)

25
Fig. 7. Mercury thermal decomposition profiles of W-S (a) and A-S (b) disposed by different

processes.

T
R IP
SC
U
N
A
M
ED
E PT
CC
A

26