Thermal desorption of mercury from gold-loaded granule activated carbon and its

effect on gold elution

J.M. Hua
a, b,
, K.M. Wei
a
, Q. Zheng
a
a
College of Chemistry and Chemical Engineering, Fuzhou University, Xueyuan Road 2, University Town, Fuzhou 350108, Fujian, PR China
b
Zijin Research and Engineering Institute of Mining & Metallurgy, Zijin Mining Group Co. Ltd., Qingang Road 53, Shanghang, 364200, Fujian, PR China
a b s t r a c t a r t i c l e i n f o
Article history:
Received 22 September 2011
Received in revised form 10 February 2012
Accepted 13 February 2012
Available online 21 February 2012
Keywords:
Mercury removal
Gold-loaded GAC
Thermal desorption
Gold elution
The thermal desorption technique has been explored experimentally to remove mercury from the gold-
loaded granule activated carbon (GAC) co-adsorbed during heap leaching of gold ores bearing mercury.
The effects of treatment temperature, retention time and ow rate of steam used as purge gas on residual
mercury levels were investigated. Characterization techniques such as N
2
adsorptiondesorption, X-ray pow-
der diffraction and X-ray photoelectron spectroscopy, were employed to understand how thermal treatment
affects the gold elution in a caustic cyanide-free eluant from the treated GAC. The results showed that mer-
cury desorption was strongly affected by the treatment temperature and steamowrate. Treatment for 3 h at
550 C under steam atmosphere with 0.4 m
3
/h ow rate was allowed to remove more than 99.78% mercury
and the content of residual mercury in the treated GAC was decreased to 0.035 g/kg, likely reaching the
thresh level of mercury extraction during gold elution in a caustic cyanide eluant. Meanwhile, activated car-
bon was partially regenerated, with only 4.06% weight loss of carbon, mainly due to microporosity recovery.
However, it was observed that the thermal process would have heavily inuenced elution of gold from the
treated activated carbon in a caustic eluant without sodium cyanide. This phenomenon has been attributed
primarily to the change of chemical state of gold species and accumulation of highly dispersed gold species
and even formation of more stable gold nano-particles caused by a combination of promotion of high temper-
ature and steam oxidation. The elution of gold from the treated sample could be improved through introduc-
tion of NaCN into the caustic eluant. However only 83.84% of gold was eluted, probably because the elution
time was insufcient.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Many gold ores all over the world contain appreciable amounts of
mercury. The presence of mercury not only poses a severe health haz-
ard to plant workers and the local environment, but also affects the
overall economics of gold production process. This is due to volatiliza-
tion of mercury occurring during several stages of processing such as
carbon stripping, carbon regeneration and electrowinning, and that
mercury additionally consumes cyanide, decreases the gold-loading
capacity of the granule activated carbon (GAC) and even complicates
the re rening of cathodes (Misra et al., 1998; Tessele et al., 1998).
Therefore, a feasible and economical method for the removal of mer-
cury from gold processing streams is signicantly needed. Many in-
vestigators have been devoted to development of various methods
and/or precipitants aimed at remediating the problems (Atwood,
2002, 2003; Blue et al., 2010; Matlock et al., 2002a, 2002b; Tassel et
al., 1997). It is well known that the studied methods can be classied
as the two types, i.e. re and wet method. The former generally in-
volves retorting of the electrowon cathodes and thermal treatment
of gold-loaded GAC. However, the retort of mercury is in the nal
steps of the extraction process and mercury still is emitted into the
air as a vapor, meanwhile the thermal treatment is thought to be an
energy consuming method and the released gasses need to be treated
before being discharged. There are relatively few studies on thermal
desorption of mercury from gold-loaded GAC in the literature, al-
though the thermal treatment technology has been widely applied
to remove and/or recover mercury from mercury-containing/
contaminated materials, such as spent uorescent lamps (Jang et al.,
2005), soils (Navarro et al., 2009), dredging sludge (Lesa et al.,
2009), scrubber wastes (Hawk and Aulbaugh, 1998) and spent vari-
ous sorbents (Ho et al., 1998; Ozaki et al., 2008). The latter includes
selective precipitation of the mercury cyanide complexes and stabili-
zation of mercury through introduction of precipitant into the heap
during cyanidation. Presently, great attention is increasingly paid to
development of a newinexpensive, non-toxic, highly selective and ef-
fective precipitant to form a stable mercury precipitate, since Na
2
S,
CaS and other inorganic suldes and polysuldes have been proven
Hydrometallurgy 117-118 (2012) 8692
Corresponding author at: National Research Center of Chemical Fertilizer Catalysts,
Fuzhou University, Gongye Road 523, Fuzhou 350002, Fujian, PR China. Tel./fax: +86
591 83770818.
E-mail address: kinminghua@sina.com (J.M. Hua).
0304-386X/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2012.02.009
Contents lists available at SciVerse ScienceDirect
Hydrometallurgy
j our nal homepage: www. el sevi er . com/ l ocat e/ hydr omet
to be not very effective. Misra et al. (1998) utilized dimethyl dithio-
carbamates (DTC) as precipitating reagents for mercury removal
from gold cyanide solution, as well as stabilization of mercury in col-
umn/heap during cyanidation. Their results indicated that dimethyl
dithiocarbamates are efcient and have no deleterious effect on
gold adsorption by activated carbon. Tessele et al. (1998) examined
the suitability of dissolved air otation (DAF) for the removal of the
resultant precipitates from the aqueous solution by adding suitable
coagulants and occulants. Their results showed that almost com-
plete removal (>98%) of Hg from dilute solution and the process ef-
ciency was dependent on system solution and interfacial chemistry,
overall aggregation phenomena and operating parameters. However,
signicant problems with thiocarbonate and thiocarbamate ligands
have recently been reported, for example, unstable metalligand
complexes, high dosage ratios, ligands' decomposition to hazardous
materials, and so on (Matlock et al., 2002a, 2002b). Atwood (2002)
have designed and synthesized a new mercury precipitant, i.e. 1,3-
benzenediamidoethanethiol (BDTH
2
). They reported that the reagent
is economical, non-toxic, effective and capable of precipitating mer-
cury and other divalent metals such as Fe, Cu, Cd and Pb from acidic
or basic water and ethanolic solutions. BDTH
2
and closely related de-
rivatives is currently being sold by CTI Science, Inc. under the Trade-
name OSR#1 as a nutritional supplement (Blue et al., 2010).
Recently, we have applied the thermal technology to remove mer-
cury, employing nitrogen as purge gas, from gold-loaded GAC (Hua,
2007; Hua and Zou, 2009). The experimental results indicated that
the removal efciency of mercury was strongly affected by the purg-
ing way, desorption temperature, nitrogen ow rate and retention
time. The sweeping gas through the sample bed is more favorable
than over it. The efcient mercury removal could be achieved with
low weight loss of carbon. The consumption of nitrogen is relatively
higher and the production of a large quantity of nitrogen in remote
mining sites is uneconomical, although a nitrogen generator of large
capacity could be installed on the site. In this study, the removal ef-
ciency of mercury from gold-loaded GAC was investigated adopting
steam as purge gas instead of nitrogen. The untreated and treated
samples were characterized by N
2
adsorptiondesorption, X-ray
powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS),
with the aim to relate the effect of the thermal treatment on the elu-
tion of gold with the gold state and the microstructure and properties
of the activated carbon.
2. Experimental
2.1. Sampling and pretreatment
Field GAC samples used in this study were provided by an active
gold mining site at Caodi country in Sichuan province, China. In the
laboratory, these samples were solar-dried for several hours. The
test samples were obtained according to the conical quartering meth-
od. A typical analysis of the test sample is given as follows: rate of
water content (R) 22.43%, mercury content (M
Hg
) 13.833 g/kg, gold
content (M
Au
) 5.230 g/kg, iodine number (N
I
) 364 mg/g.
2.2. Thermal desorption of mercury
The apparatus used for the experiments on mercury desorption is
sketched in Fig. 1.
It includes a steam boiler, a steamow meter, a 50 mm (ID) stain-
less steel desorber enclosed in a tubular electric furnace, a thermo-
couple probe for measuring hearth temperature, and a clarier-
barrel for purication of the tail gas before being discharged into air
(Hua, 2007). The heating hearth is controlled by a programmed con-
troller with feedback through the setpoint thermocouple positioned
inside the furnace wall. In an experiment, a xed weight (M, equiva-
lent to 100.0 g) of the pretreated sample was placed in the desorber.
The left and right parts of the sample bed were both packed with the
same quartz granules. Prior to mercury desorption, the sample was
dried in dead air at 120 C for 1 h. The purge steamowed at a prede-
termined ow rate through the desorber, while the furnace was heat-
ed from room-temperature to the desired temperature in several
minutes and kept for designate time. The tail gas was dispersed by
means of perforated tube through a barrel containing 40 l of saturated
KMnO
4
aqueous solution acidied with 5% H
2
SO
4
to absorb the vapor-
ized mercury and other gaseous and/or particulate contaminants
prior to discharge. At the completion of the experiment, the steam
was shut off. After cooling naturally to room-temperature, the treated
sample was discharged for analysis of its weight (M), rate of water
content (R), mercury content (M
Hg
), gold content (M
Au
) and iodine
number (N
I
). In this study, the experimental parameters were de-
sorption temperature, retention time and steam ow rate, ranged
from 350 to 850 C, 1.05.0 h, and 0.11.8 m
3
/h, respectively. Ther-
mally treated samples were coded by Sample B and the pretreated
samples by Sample A hereafter.
2.3. Elution of gold
The pretreated and thermally treated sample was subjected to
gold stripping test aiming at investigating the effect of the thermal
treatment on it. Prior to gold elution, the pretreated sample was sub-
jected to the thermal treatment. The treatment temperature was set
at 550 C, while the retention time was 3 h. The steam ow rate of
the thermal process was 0.2 m
3
/h. Analysis of the treated sample is
as follows: R 12.17%, M
Hg
0.164 g/kg, M
Au
5.507 g/kg. Mercury re-
moval efciency was up to 98.993% with 4.06% weight loss of carbon.
The batch gold elution experiments were carried out in GSH-2 au-
toclave (2 l internal volume). In a cyanide-free elution experiment,
rstly, 100.0 g of the sample was placed into the autoclave and
(2)

(3)
(8)
(7)
(4)
(1)
(6)

(5)
P
Fig. 1. Sketch of the experimental apparatus: (1) steam generator; (2) ow meter; (3) electric furnace; (4) desorber; (5) thermocouple; (6) programmed controller; (7) clarier-
barrel; (8) perforated tube.
87 J.M. Hua et al. / Hydrometallurgy 117-118 (2012) 8692
contacted with the measured volume of 2% w/w sodium hydroxide
aqueous (600 ml) and then lled with oxygen gas from cylinder.
Then the interior temperature was raised to 130 C in an hour,
when the charged pressure reached to 0.48 MPa, and kept at the tem-
perature for an hour. At the completion of the rst stage experiment,
the power was shut off. After cooling naturally to room temperature,
the eluate was removed from the autoclave. The fresh sodium hy-
droxide aqueous was introduced and the second stage experiment
commenced, operating parameters remaining the same as above.
The third stage experiment was a duplication of the second stage ex-
periment. At the end of the experiment, the sample was washed with
tap water (500 ml) for 15 min and was dried at 110 C, then sent to
analyze its weight, content of water, gold (M
Au
) and mercury
(M
Hg
). The quantity of gold/mercury stripped from the sample was
calculated from the difference between the initial and nal gold/mer-
cury contents. In a cyanide-added elution experiment, the process is
almost the same as above except that some quantity of sodium cya-
nide is added to the eluant.
2.4. Data analysis
The removal efciency (R
M
) of mercury and the weight loss of car-
bon (L
C
) are calculated from the following Eqs. (1) and (2).
R
M
1M 1R M
Hg
= M 1R M
Hg
h o
100%
n
1
L
C
1M 1R 1M
Hg

= M 1R 1M
Hg
h i n o
100%
2
The percent regeneration (E
CR
) of activated carbon is given by
E
CR
N
I
=N
I
100%: 3
The elution efciency (E
G
) of gold and the extraction efciency
(E
M
) of residual mercury from the treated sample are dened as For-
mulas (4) and (5).
E
G
M
Au
M
Au
=M
Au
100% 4
E
M
M
Hg
M
Hg

=M
Hg
100% 5
For the pretreated sample, the M
Au
, M
Hg
in Eqs. (4) and (5) need
to be substituted as M
Au
, M
Hg
, respectively.
2.5. Sample characterization
Surface area and pore structure were determined using a Micro-
meritics OMNISORP100CX nitrogen adsorption apparatus. Prior to
analysis, the sample was degassed at 120 C until the vacuum inside
the sample tube was more than 110
5
MPa. The Brunauer
EmmettTeller (BET) specic surface area (S
BET
) was calculated
from N
2
adsorption data at relative pressures 0.05bP/P
0
b0.2. The
specic surface area of micro pore (S
m
) was calculated according to
the t-method. The total pore volume (V
p
) was calculated from the
adsorbed amount at P/P
0
=0.98. The total volume of micropores
(V
m
, widths smaller than 2 nm) was calculated from the statistical
thickness of adsorbed layers (t-method) and from the Dubinin
Radushkevich (DR) equation applied to N
2
adsorption data at
196 C. The mean pore size (R
av
) was evaluated from the
StoeckliBallerini equation. Pore size distribution was calculated
using BarrettJoynerHalenda (BJH) method while the micropore
size distribution was calculated according to the MP-method.
The XRD patterns were obtained on a Nihon Rigaku D/max-3C X-
ray powder diffractometer with Cu K radiation (30 mA, 40 kV)
over a 2 range of 5~90. The obtained patterns were used to
determine the phases present in the samples. The mean sizes of
gold crystallites were estimated using the Scherrer equation, which
employed the corrected full width at half maximum (FWHM).
The XPS analysis was performed with a ESCAIRB MKI spectropho-
tometer with Al K radiation (1486.6 eV). The samples were pressed
into pellets and these were transferred to a test chamber. The spectra
were collected with an analyzer pass energy of 25.5 eV and an elec-
tron take off angle of 45. The vacuum in the test chamber was main-
tained below 1.3310
7
Pa during the collection. Binding energies
were corrected for surface charging by referencing them to the ener-
gy of C1s peak of contaminant carbon at 284.8 eV.
3. Results and discussion
3.1. Mercury desorption
3.1.1. Effect of the desorption temperature
In Table 1 the experimental results of mercury desorption, held for
3 h under the steam ow rate of 0.2 m
3
/h, as a function of the treat-
ment temperature (T) are reported, in which mercury removal ef-
ciency and the weight loss of carbon are also presented. Table 2
shows the iodine number and the percent regeneration after the ther-
mal treatment of the sample as a function of treatment temperature.
As can be seen in Table 1, the percent of mercury removal in-
creased with the temperature during the thermal treatment. The
weight loss of carbon followed the same trend. The mercury content
of sample decreased to around 0.165 g/kg after 1 h roasting at 350,
450 and 550 C respectively, with a reduction of the mercury content
of approximately 98.99%. The weight loss of carbon was low, around
4%. When temperature was raised to 650 C, the mercury content fur-
ther decreased to 0.033 g/kg, with a mercury removal efciency of
99.81% and the carbon loss of 7.04%. However, the carbon loss became
highly serious, above 19.24%, although mercury removal would be
highly efcient (more than 99.99%) when temperature was higher
than 750 C. Moreover, the apparent increase of the gold content of
sample occurred, which was attributed to the partial weight loss of
the carbon due to being oxidized by oxygen originating from steam
pyrolysis because the gold adsorbed on the activated carbon could
not evaporate during the thermal process. In viewof mercury removal
efciency, weight loss of carbon, and energy consumption, the desorp-
tion temperature of 550 C was adopted in a follow up experiment.
In addition, the effect of thermal regeneration during the thermal
treatment can be seen from Table 2. It clearly demonstrates that the
iodine number of the treated sample increased gradually along with
increase of the treatment temperature. The percent regeneration of
the sample followed the same trend, implying that the activated car-
bon was partially regenerated during the thermal process. This fact is
to be expected since the method is indeed thermal regeneration of
spent activated carbon except for application of lower temperature.
Thermal regeneration processes typically involve heating the spent
carbon at high temperatures (typically between 800 and 1000 C)
under mildly oxidizing atmospheric conditions (usually steam or car-
bon dioxide or a mixture of both) (Miguel et al., 2003). Hence, the de-
velopment of surface area, porosity during the process may also be
expected, as it will be described and discussed below.
Table 1
Results of mercury desorption and mercury removal efciency as a function of treat-
ment temperature.
T (C) M (g) R (%) M
Hg
(g/kg) M
Au
(g/kg) R
M
(%) L
C
(%)
350 75.45 1.97 0.166 5.344 98.978 3.58
450 74.65 1.93 0.165 5.394 98.993 4.57
550 83.80 12.17 0.164 5.507 98.993 4.06
650 73.20 2.59 0.033 5.457 99.805 7.04
750 63.55 2.52 0.026 6.604 99.865 19.24
850 34.40 1.74 0.003 10.880 99.992 55.93
88 J.M. Hua et al. / Hydrometallurgy 117-118 (2012) 8692
3.1.2. Effect of the retention time
The effect of retention time (t) on mercury desorption was checked
under the following operating conditions, i.e. desorption temperature
550 C, steamowrate 0.2 m
3
/h. The results of mercury desorption as
a function of the retention time are collected in Table 3, together with
mercury removal efciency and the weight loss of carbon.
As shown in Table 3, the remnant mercury content of the sample
would increase, being above 0.211 g/kg, when the retention time
shortened from 3.0 h to below 1.5 h. However, when the retention
time prolonged from 3.0 h to more than 4.0 h, the residual mercury
further decreased, but the amplitude is not prominent. These results
imply that the retention time is less important than that of the de-
sorption temperature. Similarly, the weight loss of the sample is not
affected by retention time signicantly, which leads to slight variation
of gold content of the sample, except for the 5 h-treated sample. In
view of steam consumption and energy cost, the appropriate reten-
tion time is suggested as 23 h.
3.1.3. Effect of the steam ow rate
Table 4 summarizes the experimental results of mercury desorp-
tion, at 550 C for 3 h, as a function of the steam ow rate (R
S
),
along with mercury removal efciency and the weight loss of carbon.
As shown in Table 4, the mercury content of the treated sample
decreased to 0.210 and 0.164 g/kg after thermal treatment under
the steam atmosphere with ow rate being 0.1, 0.2 m
3
/h, achieving
mercury removal efciency 98.70% and 98.99%, respectively. When
steam ow rate was raised from 0.4 to 0.8 m
3
/h, the mercury content
was reduced from 0.035 to 0.003 g/kg, with mercury removal ef-
ciency increasing from 99.78% to 99.98%. When further raised to
1.2 m
3
/h or higher, the residual mercury would not further decline,
being around 0.002 g/kg. This implies that the removal of mercury
is also a strong function of the steam ow rate. The rate of mercury
removal is relatively fast at the initial stage of the treatment but
slows down and eventually levels off later. Moreover, the steam
ow rate seems to affect mercury removal more notably, compared
to the effect of desorption temperature. This can be satisfactorily
explained due to the fact that the boiling temperature of elemental
mercury is 357 C, far lower than the set desorption temperature
550 C (Jang et al., 2005). However, the effect of steam ow rate on
the weight loss of the sample is not signicant, thus the gold content
of the sample does not vary much. In consideration of the steam con-
sumption and energy cost, steam ow rate is suggested at 0.4 m
3
/h.
3.2. Gold elution
The results of gold and mercury elution from the pretreated and
thermally treated samples in a 2% w/w NaOH eluant at 130 C under
pressurized oxygen atmosphere are presented in Table 5. In case of
addition of NaCN to the eluant, the effect of varying NaCN concentra-
tion on gold and mercury elution is shown in Table 6.
As can be seen from Table 5, the elution efciency of gold from the
pretreated sample reached up to 82.47% and 50.70% of the mercury
was also extracted. For the thermally treated sample, less than 7%
gold was eluted and almost no mercury in the sample was extracted.
From these results it is evident that the thermal treatment for mercu-
ry desorption would drastically inuence gold elution from the load-
ed activated carbon in a cyanide-free eluant. However, the elution of
gold was signicantly improved by addition of NaCN to the caustic el-
uant and elution efciency of gold increased almost linearly along
with increase of NaCN concentration in the eluant, as observed from
Table 6. Of course, the extraction of the residual mercury was also en-
hanced signicantly due to the addition of NaCN. But the total quan-
tity of the extracted mercury from the treated sample would be low
since its content of the residual mercury was considerably low. It is
worth noting that the residual mercury level after elution process
would be around 0.035 g/kg, even if the concentration of the added
sodium cyanide up to 2% w/w. This value may be the thresh level of
mercury extraction during gold elution process, suggesting that
there is no need to eliminate all total mercury content (Busto et al.,
2011). Hence, the appropriate thermal treatment parameters are sug-
gested as follows: desorption temperature 550 C, retention time 3 h,
steam ow rate 0.4 m
3
/h. Thereby, the mercury pollution, originated
from its co-adsorption with gold onto GAC, in the followed-up pro-
cess such as gold elution, electrowinning and carbon regeneration
would be eliminated almost completely.
Evidently, there is a need to focus on the gold elution behavior
since both elution efciencies of gold, from the pretreated sample in
cyanide-free caustic eluant and from the thermally treated sample
with addition of NaCN up to 2% w/w, are not more than 84%. The rea-
son for this would be analyzed and explained below, in conjunction
with the results of structural characterization.
3.3. Surface area and porosity analysis
Surface area and porosity of the pretreated and thermally treated
samples are presented comparatively in Table 7. It is clearly seen
that after thermal treatment the micropore volumes apparently in-
creased (about 20%). The same happened with the pore volume and
surface area, but the average radius of pores remained unchanged at
~1.90 nm. This is mainly a result of the removal of adsorbed mercury
and cyanides within the pore systems of activated carbon. It is well
known that they can easily volatilize even at normal atmospheric
temperature. Of course, heating of carbon in a mildly oxidizing atmo-
sphere results in partial oxidation of its surface at the same time. This
Table 2
The iodine number and percent regeneration of the sample after thermal treatment as
a function of treatment temperature.
T (C) 350 500 550 600 650
N
I
(mg/g) 482 553 593 617 625
E
CR
(%) 45.90 52.67 56.48 58.76 59.52
Table 3
Results of mercury desorption and mercury removal efciency as a function of reten-
tion time.
t (h) M (g) R (%) M
Hg
(g/kg) M
Au
(g/kg) R
M
(%) L
C
(%)
1.0 89.30 17.93 0.251 5.556 98.464 4.47
1.5 74.00 1.01 0.211 5.526 98.714 4.52
2.0 85.40 14.52 0.168 5.465 98.980 4.84
3.0 83.80 12.17 0.164 5.507 98.993 4.06
4.0 74.00 0.95 0.142 5.607 99.130 4.45
5.0 74.40 1.08 0.110 5.262 99.328 4.06
Table 4
Results of mercury desorption and mercury removal efciency as a function of steam
ow rate.
R
S
(m
3
/h) M (g) R (%) M
Hg
(g/kg) M
Au
(g/kg) R
M
(%) L
C
(%)
0.1 86.80 14.53 0.210 5.479 98.702 3.35
0.2 83.80 12.17 0.164 5.507 98.993 4.06
0.4 74.00 0.68 0.035 5.480 99.783 4.18
0.8 73.80 0.07 0.003 5.504 99.980 3.85
1.2 76.00 2.96 0.002 5.560 99.987 3.85
1.8 73.80 0.07 0.002 5.401 99.987 3.85
Table 5
Results of gold and mercury elution in a 2% w/w NaOH eluant at 130 C under pressur-
ized oxygen atmosphere.
Sample M (g) R (%) M
Au
(g/kg) M
Hg
(g/kg) E
G
(%) E
M
(%)
A 82.75 8.88 0.917 6.820 82.467 50.698
B 78.80 4.57 5.148 0.164 6.519 0.000
89 J.M. Hua et al. / Hydrometallurgy 117-118 (2012) 8692
may have an effect on the pore structure. A detailed view of the
changes in porosity is presented in Figs. 24. It is found that there is
no evident difference in the meso- and macro-pore size distributions
between the pretreated and thermally treated samples. Moreover,
neither obvious difference was revealed in the desorption branch, in-
dicating that they have the pore structure with the same shape char-
acteristics, according to the type of the hysteresis loop (Wu et al.,
2008). However, their slight difference was clearly shown in the mi-
cropore size distributions, especially in the range of 0.30.5 nm, as il-
lustrated in Fig. 3. Hence it can be inferred that an increase in the
volume of micropore contributes to that of the total pore volume of
the thermally treated carbons. In addition, these results imply that
mercury and other metal cyanide impurities mainly adsorbed on the
surface of the micropores and that the micropore structure of the ac-
tivated carbon was partially regenerated during the thermal process,
leading to an increase of its iodine number.
3.4. XRD
XRD patterns of the pretreated and thermally treated samples are
reported in Fig. 5. This gure clearly shows that the pretreated sample
presents two broad peaks, indicating that it is mainly amorphous and
partly graphitic. Meanwhile, no peaks assigned to gold species were
observed, suggesting that the adsorbed gold species is in amorphous
and/or highly dispersed state. However, after thermal treatment, in-
tense reections of metallic gold were clearly presented, along with
several weak reections of graphite and even one of octa-carbon,
while that of amorphous carbon did not change appreciably. The av-
erage size of gold particles is 78 nm, estimated from the line-width
of the Au(111) reection peak by using the Scherrer equation. The re-
sults suggest that the treatment at high temperature promotes the
decomposition of dispersed gold cyanides to metallic gold followed
by gold clusters accumulation and gold nano-particles formation
while further graphitization and even partial crystallization of amor-
phous carbon occurs at the same time (Wu et al., 2008). The formed
larger gold nano-particles are more stable, leading to difcult elution
of gold even in a caustic cyanide solution under pressurized oxygen
atmosphere. Meanwhile, the further graphitization and partial crys-
tallization of the carbon is unfavorable for adsorption of gold. This
may account for the lower percent regeneration of the carbon during
the thermal process. It is noteworthy that the decomposition of
adsorbed mercury cyanides occurred initially, followed by the volatil-
ization of mercury. However, the previous results of mercury desorp-
tion under different temperature suggest that some mercury is still
retained on the carbon. This fact could be indicative of some Hg
chemisorption and some Hg/Au alloys probably existed on the carbon
surface. It is well known that the amalgamation between mercury
and gold occurs easily with formation of Hg/Au alloys (Kobiela et
al., 2003; Nowakowski et al., 1997). The Hg/Au alloys were not
detected directly by XRD, probably because it is highly dispersed
and its diffraction peaks become too broad, lost in the background
of the spectra (Kobiela et al., 2003). The presence of Hg/Au amalgam
would inhibit gold desorption from the thermal treated sample, al-
though its structure is not stable, changing with the temperature
and thermal decomposition would occur even at the temperature
slightly higher than 200 C (Izquierdo et al., 2011).
3.5. XPS
The XPS spectra in the Au4f region of the pretreated and thermally
treated samples are shown in Fig. 6. In this region, each gold species
shows two peaks, due to the Au4f
5/2
and Au4f
7/2
transitions. On the
pretreated sample, the two strong peaks are centered at 89.360.2
and 85.690.2 eV, respectively, suggesting that gold is mainly pre-
sent in ionic state. This is due to the fact that gold species adsorbs
on activated carbon most likely as Au(CN)
2

under industrial condi-

tions, as suggested by previous investigations (Ibrado and
Fuerstenau, 1995; Jia et al., 1998; Tan et al., 2005). After the thermal
treatment, the two peaks become broader and both shifted signi-
cantly towards to lower binding energy, their positions centered at
88.09 and 84.13 eV, respectively, suggesting that gold is partially in
Au
0
state (Somodi et al., 2008; Wang et al., 2009). This result is con-
sistent with the XRD result which showed that metallic gold clusters
Table 6
Effect of varying NaCN concentration on gold and mercury elution from the thermally
treated samples.
NaCN(wt%) M (g) R (%) M
Au
(g/kg) M
Hg
(g/kg) E
G
(%) E
M
(%)
0.5 90.00 6.68 1.169 0.053 78.772 67.683
1.0 82.90 20.23 1.084 0.039 80.316 76.220
2.0 86.00 22.84 0.890 0.032 83.839 80.488
Table 7
Surface area and porous data of the pretreated and thermally treated samples.
Sample S
BET
/
(m
2
g
1
)
S
m
/
(m
2
g
1
)
V
p
/
(cm
3
g
1
)
V
m
/
(cm
3
g
1
)
R
av
/
(nm)
A 699.20 585.20 0.33 0.27 1.906
B 842.95 698.23 0.40 0.32 1.909
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
B
d
V
/
d
H
R
(
c
m
3

g
-
1

n
m
-
1
)
HR (nm)
A
Fig. 3. Pore size distribution comparison of the pretreated (A) and thermally treated
(B) samples, determined following the MP method.
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85
0.000
0.002
0.004
0.006
0.008
0.010
0.012
B
d
V
/
d
W
(
c
m
3

g
-
1

n
m
-
1
)
Wp(nm)
A
Fig. 2. Pore size distribution comparison of the pretreated (A) and thermally treated
(B) samples, determined following the BJH method.
90 J.M. Hua et al. / Hydrometallurgy 117-118 (2012) 8692
or/and nano-particles are present on the surface of activated carbon.
However, two shoulder peaks can be observed clearly, which indi-
cates the co-existence of other oxidation states of gold. Deconvolu-
tion of the Au4f peak shows the second peaks at 89.18 eV (Au4f
5/2
)
and 85.01 eV (Au4f
7/2
), which could be assigned to positively charged
gold clusters (Au
n
+
). This can be attributed to a combination of two
factors: on the one hand, the decomposition of Au(CN)
2

to metallic
gold followed by the accumulation of gold clusters and even sintering
of gold nano-particles, both caused by the application of high temper-
ature and, on the other hand, their partial oxidation under mildly ox-
idizing atmosphere arising from the oxidative nature of steam (Cabal
et al., 2009; Miguel et al., 2003).
Additionally, the XPS comprehensive spectra of the pretreated and
thermally treated samples reveal that their surface elemental compo-
sition contains C, O, N, Na, Mg, Si, Fe, Au and Hg. The surface contents
of Nand Hg of the treated sample are observed to decrease apparently.
This is because of desorption and/or volatilization of cyanide and mer-
cury during the thermal process. However, the presence of the base
metals, especially Ca and Mg, has a detrimental effect on the elution
of gold from the loaded activated carbon, as suggested generally in
the literature (Jia, et al., 1998). Silica was also found to be able to ad-
sorb more gold cyanide per area than activated carbon, due to the che-
misorptive interactions between gold species and the silica surface
(Chen, et al., 2006; Petersen and Van Deventer, 1997). The further
graphitization and even partial crystallization of the carbon support
is unfavorable for adsorption of gold and would promote more gold
cyanide species to migrate to the silica surface. Thus part of gold spe-
cies are immobilized, even buried and/or coated in/by the silica net-
work. This may also retard the elution of gold fromthe treated sample.
On the base of the above elution, XRD and XPS results, some pos-
sible explanations on the elution behavior of gold from the pretreated
and thermally treated samples can be given as follows. For the pre-
treated sample, the adsorbed gold species could be easily eluted in a
2% w/w NaOH eluant at 130 C under pressurized oxygen atmo-
sphere. However, only 82.47% elution of gold was achieved in total
3 h. This may be because the elution time is not long enough to give
higher elution since desorption of gold from the loaded activated car-
bon is one of the slowest steps (Pyke et al., 1997). The elution time
used in industry is generally more than 8 h, such as 812 h in the
pressurized Zadra process, while it is only 3 h in total in our case. Of
course, it cannot be excluded that the presence of base metals and sil-
ica has an adverse effect on the gold elution, since the elution process
is very complex, inuenced by a large number of factors. For the ther-
mally treated sample, only 6.52% gold was eluted. It is inferred that
the dramatic decrease of gold elution efciency is mainly due to the
modication of chemical state of gold species and accumulation of
gold species and even formation of more stable gold nano-particles
during the thermal desorption of mercury, as evidenced directly by
the XRD and XPS spectra of the investigated samples. The elution of
gold from the thermally treated activated carbon could be improved
through introduction of NaCN into the caustic eluant. However, only
83.84% of the gold was eluted with increasing NaCN concentration
up to 2% w/w. As similar to the pretreated sample, the reason for
this may also be that the total elution time is too short and that the
presence of base metals and silica is likely to retard gold elution.
Moreover, other possible and important explanations can be given
as follows: (a) the formed larger gold nano-particles are more stable,
leading to difcult elution of gold, as revealed by XRD; (b) the further
graphitization of the carbon in conjunction with strong interactions
between gold and silica have a detrimental effect on the elution of
gold, as elucidated in the section of XPS result; (c) the possible pres-
ence of Hg/Au amalgam would also inhibit gold elution. Future work
will be directed to investigate these hypotheses, especially focused on
the inuence of time on the elution performance.
4. Conclusions
The thermal treatment using steam as purge gas was found to be
very effective to remove mercury from gold-loaded GAC. The experi-
mental results indicated that mercury desorption was strongly affected
0 10 20 30 40 50 60 70 80 90 100 110
&
&
&
#
#
2 /( )
@ -- amorphous carbon
# --- graphite
$ --- octacarbon
& -- metallic gold
#
@
$
&
B
A
Fig. 5. XRDpattern comparison of the pretreated (A) and thermally treated (B) samples.
98 96 94 92 90 88 86 84 82 80
Au
0
Au
n
+
Au
+
4f
7/2
4f
5/2
B
A
Binding Energy (eV)
Fig. 6. XPS of Au4f comparison of the pretreated (A) and thermally treated (B) samples
and peak tting of Au4f peaks.
-0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1
170
180
190
200
210
220
230
240
250
260
270
V
o
l
u
m
e

(
c
m
3

g
-
1
)
Relative Pressure (P/P
0
)
B
A
Fig. 4. Adsorptiondesorption isotherms comparison of the pretreated (A) and ther-
mally treated (B) samples.
91 J.M. Hua et al. / Hydrometallurgy 117-118 (2012) 8692
by desorption temperature and steam ow rate. Treatment for 3 h at
550 C under steam atmosphere with 0.4 m
3
/h ow rate was allowed
to remove more than 99.78% mercury. The content of residual mercury
in the treated GAC was decreased to 0.035 g/kg, likely reaching the
thresh level of mercury extraction during gold elution in a caustic cya-
nide eluant under pressurized oxygen atmosphere. Moreover, activated
carbon was partially regenerated at the same time with only about 4%
weight loss of carbon, mainly due to microporosity recovery. However,
further graphitization and even partial crystallization of amorphous
carbon also occurred simultaneously. Moreover, it was found that the
thermal process would have heavily inuenced elution of gold from
the treated activated carbon ina caustic eluant without sodiumcyanide.
This phenomenon has been attributed primarily to the modication of
chemical state of gold species and accumulation of gold species and
even formation of more stable gold nano-particles caused by a combi-
nation of promotion of high temperature and steam oxidation, as ob-
served using XRD and XPS analysis. The elution of gold from the
treated sample could be improved through introduction of NaCN into
the eluant. But only 83.84% of gold was eluted, probably due to lack of
enough elution time.
Acknowledgments
The authors would like to thank the nancial support of this study
by the Science and Technology Ofce of Fujian province with the
young scientist project no. 2006F3151. They are also grateful to pro-
fessor Shuiju Wang for his help in the XPS analysis and invaluable
comments (Xiamen University, Xiamen, China) and to vice researcher
Yihong Xiao and Yingying Zhan for their help in the surface area, po-
rosity and XRD analysis, respectively (Fuzhou University, Fuzhou,
China). They would also wish to thank technologist Tao Liu for his
participation in the experimentation (Zijin Research and Engineering
Institute of Mining & Metallurgy, Shanghang, China).
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