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New Hydrometallurgical Process for Gold Recovery

Article · January 2008

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 Buletinul Ştiinţific al Universităţii “Politehnica” din Timisoara, ROMÂNIA
Seria CHIMIE ŞI INGINERIA MEDIULUI
Chem. Bull. "POLITEHNICA" Univ. (Timişoara) Volume 53(67), 1-2, 2008

New Hydrometallurgical Process for Gold Recovery

R. Radulescu, A. Filcenco-Olteanu, E. Panţuru, L. Grigoraş

Research and Development National Institute for Metals and Radioactive Resources
B-dul Carol I, nr. 70, sector 2, 020917 Bucharest – ROMANIA,
Phone: (+40) 21–315.23.41, Fax: (+40) 21–313.12.58, E-Mail: icpmrr@icpmrr.ro, http://www.icpmrr.ro

Abstract: A new hydrometallurgical process has been developed for recovery of gold from secondary sources such as
gravitational concentrates from alluvial sands. The method consist in leaching the gold with chlorine resulted from NaClO
decomposition in hydrochloric acid medium, [AuCl4]- selective recovery from hydrochloric solutions by adsorption on
non-ionic polymeric resin type Amberlite XAD-7, gold elution with a mixture of organic solvent – hydrochloric acid and
its reduction with an organic reducer. The gold powder is melt obtaining thus high grade (999,6 ‰) gold with a recovery
yield over 98 %. The influence of the main parameters for the aqueous chlorination, the extraction and stripping data and
the method for the recovery of gold from upgrade strip liquor are presented. A flow sheet based on this process is also
presented.

Keywords: gold, secondary sources, hydrometallurgy.

1. Introduction Amberlite XAD-7 is characterized by weak ester

The more restrictive regulations for controlling the
environmental pollution by cyanide bearing streams and
materials have given an impetus to the researches aiming
the discovery of some new, more ecological methods for
gold dissolving [1-2] and more efficient methods for gold
separation and refinement [3-4]
The recent developments promote alternative
approaches to the cyanidation process such as thiourea,
chlorine, bromine, thiosulphate, iodine, aqua regia leaching
followed by recovery step.
Chlorine leaching has a few advantages due to the
higher dissolution rate of gold, low price of leaching
reagents and non-polluting character.
Dissolution of metallic gold was studied [5] by
generating chlorine « in situ » from the reaction between
commercial sodium hypochlorite and hydrochloric acid :
NaClO + NaCl + 2 HCl → 2 NaCl + Cl2 + H2O (1)
The following equilibriums are established:
Cl2 + H2O = H+ + Cl- + HClO- Kh(298)= 3,94 x 10-4 (2)
HClO = H+ + ClO- Kd(298)= 7 x 10-9 (3)
Cl2 + Cl- = Cl3- Kat(298)= 1,95 x 10-1 (4)
The dissolution reaction of gold is:
Au(s) + Cl-(aq) + 3/2 Cl2(aq) → AuCl4-(aq) (5)
The gold dissolved as [AuCl4]- can be extracted from
chloride matrix by very weak bases (having a carbon-
oxygen bond as active group) such as ether and butyl
diglyme (diethylene glycol dibutyl ether).
groups and hence the adsorption of gold is successful.
The objective of this paper is to present a procedure for
gold recovery from gravity concentrates obtained from
alluvial sands.
At the first stage the gold is leached with chlorine
generated « in situ » by reaction of NaClO and HCl, and
the optimum conditions corresponding to a yield of 99%
for gold solubility was investigated. At the second stage the
parameters for separation, concentration and refinement of
dissolved gold by adsorption on non-ionic polymeric
Amberlite XAD-7 resin are presented.
The final stage is the recovery of the high grade (>
999,6 ‰) gold from strip liquor. The flow sheet produces
the optimum get parameters, the recovery yield of gold is
over 98 %.
2. Materials and experimental procedure
The materials used in the experiments are the gravity
concentrates obtained from different alluvial sands. The
gold contents in these materials range from 6.9 g/t to
1197.5 g/t and all amount is free gold. Gangue minerals are
silica , ilmenit ,zircon ,magnetit and other heavy minerals.
Leaching experiments were performed in a glass reactor of
2 or 6 litter capacity immersed in a thermostatically
controlled water bath equipped with a constant temperature
circulator. Mixing was provided by a glass stirrer with
controlled speed electric motor. At the end of the leach, the
slurry was filtered .Both filtered and residue were
chemically analysed. Filtrates were volumetrically analysed
for acid concentration. The filtrates obtained were used for
the ion exchange study.
The adsorption experiments of gold on Amberlite
XAD-7 were performed using two different gold solutions:

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Chem. Bull. "POLITEHNICA" Univ. (Timişoara) Volume 53(67), 1-2, 2008

synthetic solutions for the experiments made for the study

of influence of acid concentration on gold distribution on
resin; leach solutions generated from different gold
concentrates.
The adsorption-elution experiments of gold were made
in dynamically conditions, glass columns containing
Amberlite XAD-7 resin with a glass-wood plug over they
stop-cock were used . The columns diameter and the
amount of resin were chosen taking into account the
experiments made.
Amberlite XAD-7 was commercial type from ROHM Figure 1. The influence of reaction time on gold dissolution at different
& HAAS. All other reagents used were of reagent or temperatures .Experimental conditions: S:L ratio 1:1.5, conc.of HCl: 3N
commercial grade. ,conc.of NaClO :0,150 l/kg conc.
After each test, the gold content in the solutions and The acid consumption is small because only a small
residues was determined by atomic absorption part of the mass is reacting with the hydrochloric acid (the
spectrometry (AAS) by means of calibration curves. major part of the concentrate remaining inert). Up to a pH
Amberlite XAD-7 was commercial type from ROHM & of 1,5 the rate of leaching was not affected by pH. Because
HAAS. All other reagents used were of reagent or the minimum free acidity required for the subsequent
commercial grade. After each test, the gold content in the reparation step of gold, from solutions, by ion exchange, is
solutions and residues was determined by atomic 2,2 – 2,8 N HCl, the free acidity needed in leaching
absorption spectrometry (AAS) by means of calibration process, for avoiding a supplementary dilution of the leach
curves. is 3 N HCl.
After Viñals (1995) the rate of the aqueous
3. Results and discussion chlorination is determined by the concentration of the
trichloride ion. The correlation between the mixed
3.1. Leaching studies potentials and the trichloride and chloride ion
concentrations is presented in Fig. 2.
Taking into account the physic – chemical
characteristics of the hydro-gravitational gold concentrates,
meaning the presence of gold grains lens-like and granular,
with sizes from a few microns till several milimetters,
dissipated into a mineral mass with a relative chemical
inertia, there were studied the following dissolution
factors :
- solid : liquid ratio ;
- temperature ;
- time ;
- stirring speed ;
- chlorine and chloride ion concentration ;
- redox potential.
Because the gangue materials have a chemical inertia
v.s. leaching conditions and so the consumption of reagents
are small ,the optimum solid : liquid ratio means the ratio
proving a homogenous reaction mass allowing the intimate Figure 2 . The mixed potential as function of the trichloride and
contact of dissolution agent with the grains of gold. The chloride ion concentration( after Viñals, 1995)
satisfactory solid-liquid ration, experimentally proved is 1 :
1,5. The potential required for a rapid leaching rate and for
The rate of dissolution is given by the correlated action avoiding the reduction of gold is 900 mV
of both temperature and time. The experimental results are (vs AgCl/Ag(KCl sat)).
shown in the Figure 1. The sodium hypochlorite (commercial grade) optimum
After 3 hours of reaction at 50-70°C, the dissolution concentration for ensuring both the gold dissolution (fig. 3)
yields for gold are > 98,5 %, and after 4 hours, at 50°C and the maintenance of an oxidant redox potential for
temperature, the dissolution yield is > 99 %.In the reactor avoiding the reduction of the dissolute gold (fig. 4) were
used the concentrates become well suspended at minimum determined experimentally. The amount of
800 min-1 stirring speed, the specific rate is practically 0.150 L NaClO/kg conc. realized the both conditions.
independent of the agitation intensity in conditions of full The optimum conditions for the dissolution yield of
suspension. gold are:

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Chem. Bull. "POLITEHNICA" Univ. (Timişoara) Volume 53(67), 1-2, 2008

- solid:liquid ratio 1:1.5 3.2. The separation, concentration and refinement of

- temperature 50o C gold from hydrochloric solutions
- time 4h
- stirring speed 800 min-1
- hydrochloric acid concentration 3N The auriferous solutions contain the gold as (AuCl4)-,
- sodium hypochlorite concentration 0.150 l/kg conc. have 2,2 – 2,8 N HCl free acidity and the main impurities
- redox potential 900 mV(v.s.AgCl/Ag(KCl sat.)) are iron (III), silver (I) and small amounts of Ti, Zr, Cr, Ni,
Si, Te, Pb.
The experimental results are presented in Table l. For the separation of gold from these solutions the ion
The average recovery of gold is more than 99 %. exchanging method was chosen on a polymeric adsorptive
resin type Amberlite XAD-7. It is a non-ionic aliphatic
acrylic polymer that derives its adsorptive properties from
its macro-reticular structure containing both a continuous
polymer phase and a continuous pore phase. The material
has the ester groups (CO2 R) as functional groups.

The characteristics of the Amberlite XAD-7 resin are :

- chemical nature: methyl metha - acrylate, aliphatic
(moderately polar);
- porosity volume: 55%
- humide density : 1.05 g/cm3
- surface area: 450 m2/g
- average pore diameter :80Å
- pore volume: 1.14 cm3/g
Figure 3 .The influence of NaClO concentration on gold dissolution yield.
Experimental conditions: s/l ratio 1:1.5 conc. of HCl 3 N, temp. 50o, time - granulometry : 20 -50 mesh
4 hours.
The pore dimensions and the presence of the estheric
1200 groups as functional groups are the two factors that confer
mV (v.s. AgCl / Ag(KCl sat.))

1000 a significant selectivity for the (AuCl4)- ions.

The adsorbent has the pores diameter sufficient that the
800
(AuCl4)- can migrate through the pores until to the
600 adsorbent surface. Amberlite XAD-7 is characterized by a
400 weak ester groups and hence the adsorption of gold is
analogous to the extraction of oxygenated compounds, the
200
presumed mechanism is of solvatation [6]
0
0 50 100 150 200 250 R-CO2 + (AuCl4)- → R-CO2 . AuCl3 + Cl- (6)
ml. NaClO / kg conc.
But also the adsorption of gold on to resin XAD-7 can
Figure 4. The potential of leach as function of NaClO concentration. be attributed to the polarisation force between the anionic
Experimental conditions: s/l ratio 1:1.5 conc. of HCl 3 N, temp. 50o,
time 4 hours
gold species and the charged resin site [7].
Some researches was made, viewing the establishment
TABLE 1. Experimental results obtain in the dissolution step of the optimum adsorption parameters for the complex
(AuCl4)-, searching the influence of the solution free
Feed , Leach , Steril, Yield, acidity and the loading kinetic of resin. The experiments
Sample
g/t mg/L g/t %
made for establish the influence of free acidity on gold
1 6.9 4.1 0.05 99.2
distribution on Amberlite XAD-7 were made with synthetic
2 81.0 55.0 0.1 99.8
solutions. The results are presented in Fig.5
3 44.7 29.7 0.1 99.7
In the free acidity range 2-4 N HCl the resin loading is
4 197.7 130.8 0.2 99.8
maximum. The possible explanation would be that at a
5 994.6 609.0 0.2 99.9
lower acid concentration the resin is incompletely
6 186.3 123.8 0.05 99.9 protonated, whereas at higher than 4 N HCl, the
7 214.1 142.7 0.2 99.9 competition with chloride ions becomes significant. The
8 115.7 76.8 0.2 99.8 presence of Cl2 do not affect the adsorption of gold species.
9 1197.5 790.3 0.1 99.9 The real solutions, used in the adsorption step of gold had
10 153.0 105.1 0.2 99.8 2,2 – 2,8 N HCl free acidity.

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Chem. Bull. "POLITEHNICA" Univ. (Timişoara) Volume 53(67), 1-2, 2008

If the resin is loaded at its maximum capacity, during

18 the washing step, the gold strip descends, thus occurr a
16 significant loss of gold in the washing water.
14 The loaded and washed resin was eluted with an mixture of
organic solvent (acetone) and hydrochloric acid at a ratio of
Au, g/L of resin

12
10 2,5 : 1. The elution curve is presented in Fig. 7.
8
6
4
2
0
0 2 4 6 8 10
HCl, N

Figure 5. The gold distribution on Amberlite XAD-7 at different acid

conc.

For establishing the resin loading kinetic it is taken

account the fact that the effective capacity decreases during
the loading in fixed bed with the feeding rate increasing
because the influence of mass transfer on the breakthrough
curve slope. The condition of almost importance for the
adsorption process is the avoiding of gold loss in effluent;
so, the working feed-flow was between 3 and 5 BEV/h.
Figure 7. Elution curve of gold from Amberlite XAD-7
The resin work capacity for real solution is 20 g Au/l,
lower than the maximum capacity (30 g Au/l) obtained; the
gold concentration of effluent was bellow 1 mg/l. The The eluant flow rate through the column was
experimental results are presented in fig.6. maintained at 1 BEV/h, total elution occures at 1,5 BEV
eluant volume.

The eluted resin was regenerated by washing with HCl

1 N, and was reintroduced in the adsorption stage.
The optimum conditions established for adsorption -
elution step are:
-free acidity for feed solution:2.2-2.8 N HCl
-feed flow:3-5 BEV/h
-work capacity of resin:20 g/l resin
-gold concentration in effluent :max.1 mg/l
-washing solution :HCl 3N
-eluant: : acetone +hydrochloric acid (2.5+1)
-eluant flow : 1 BEV/h

The experimental results of gold adsorption-elution

-
Figure 6. Loading isotherms of AuCl4 adsorption by Amberlite XAD-7 steps are presented in table 2. The feed solutions were
(conc. of gold : 0,6 g/l) obtained by leaching different gold concentrates.

TABLE 2.The experimental results of gold adsorption - elution steps

Feed Effluent Wash Adsorption Elute Elution

No.
Au, mg/L Au, mg/L Au, mg/L yield, % Au, mg/L Yield , %
1 55.0 0.5 0.2 99.0 4710 99.7
2 35.0 0.5 0.3 99.5 2500 98 .8
3 122.0 0.8 0.2 99.3 8845 99.6
4 119.0 0.9 0.2 99.2 7033 99.3
5 145.0 1.0 0.4 99.3 8625 99.8
6 147.0 0.7 0.4 99.5 7790 99.8
7 125.0 0.5 0.3 99.5 9880 99.2
8 54.0 0.5 0.2 99.0 5305 99.1
9 930.0 0.4 0.4 99.9 10730 99.8
10 120.0 0.3 0.6 99.7 7168 99.8

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Chem. Bull. "POLITEHNICA" Univ. (Timişoara) Volume 53(67), 1-2, 2008

3.3. Fine gold preparation 4. Conclusions

Actually, the auriferous elute is a solution of
tetrachloro-auric acid in a mixture of acetone and
hydrochloric acid. The AAS analysis of elutes sample
proved that the main accompanying elements (Fe, Ag, Ti,
Zr, Si) were lower than 5 ppm concentrations.
The recovery of gold from these solutions was made with
conventional method of reduction.
The reducer used was hydrochinone:
2H(AuCl4)+3C6H4(OH)2→2Au+C6H4O2+8HCl
The selection of hydroquinone was made because the
reduction rate and the filterability of reduced gold powder.
The hydroquinone consumption is given by the reaction
stoichiometry (1 g hydroquinone for 1 g Au) plus an excess
of about 3 times hydroqinone to obtain the maximum yield.
The mother liquor had maximum 0,5 mg Au/l. The reaction
take place at 40-50°C in 20 minutes.
The reduced gold was filtered, washed, dried and melt
in pots from bones flour, at 1060°C, thus obtaining fine
gold (min. 999,6 ‰). The purity of metallic gold was
determined by spectral analysis ( table 3).
TABLE 3. The purity of metallic gold
Impurities Ag Cu Pb
Content 2.0 0.1 bdl*
Impurities Ni Si Na
Content bdl* 5.0 bdl*
*bdl –billow detection limit (0.05ppm)
The main operations for recovery of fine gold from
alluvial concentrates [8] are presented in Fig.8
Auriferous concentrate
In this work, the application of aqueous chlorination of
native gold from gravimetric concentrates from alluvial
sands and the obtaining of fine gold from hydrochloric
solutions by ion exchange procedure using Amberlite
XAD-7 non ionic resin was demonstrate.
The dissolution of native gold takes place in a HCl/Cl2
medium, the chlorine being generated « in situ » by the
reaction of NaClO and HCl. The dissolution time is 4h at
50°C and 900 mV (vs. AgCl/Ag(KCl sat.)) potential, at a
(7) solid : liquid ratio 1 : 1,5. Under optimal leaching
conditions, the dissolution yield of gold is higher than
99 %.
The separation, concentration and refinement of gold
from hydrochloric solutions is made by adsorption into the
polymeric macroporous Amberlite XAD-7 non-ionic resin.
The elution of gold is made with a mixture of acetone and
hydrochloric acid. In the optimum conditions the recovery
of gold in adsorption-elution step is 98 %.
From elute the gold is recovered by reduction with
hydroquinone, and the gold powder is melt at 1060°C to
obtain the fine metallic gold of high purity (min. 999,6 ‰).
Non-toxic technique according to the conventional
cyanidation, high yield of recovering (95 %), high purity
of obtained gold (min. 999,6 ‰) and low capital
Zn Fe
investment are the major reasons for development of this
2.0 bdl* processes.
Mg Ca The procedure was experienced on other raw materials
2.0 bdl* too (chlorous sludge from pyrites ash processing, anode
mud from copper electrolysis, slag and auriferous dust
resulted by metallic gold processing) obtaining the same
good results [9-10]

HCl REFERENCES
NaClO Gold Solubilization

Phases separation Residue

1. Pesic, B., Sergent, R.H., Reaction mechanism of gold dissolution with
Auriferous solution
HCl
Washing
Residue
bromine, Metall.Trans.B, 1993, 24, pp. 419.
2. Michel, D., Frenay, J., Integration of amino acid in to thiosulphat gold
Auriferous solution
Resin
Gold Adsorption leaching process, Randol Gold and Silver Forum ’99, Denver, Colorado.
1999.
HCl Washing
3. Els, E.R., Lorenzen, L., Aldrich, C., The adsorption of precious metals
Resin Washing
solution
and base metals on a quaternary ammonium group ion exchange resin,
Loaded resin Minerals Engeneering, 2000, 13(4), pp. 401.
HCl
4. Jung, R.S., Preparation, Proprieties and sorption behaviour of
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Natl. Sci. Counc. ROC (A), 1999, 23(3), pp. 353.
5. Viñals, J., Nuñez, C., Herreros, O., Kinetics of the aqueous chlorination
Auriferous eluate
Resin
of gold suspended particles, Hydrometallurgy, 1995, vol. 38, pp. 125-147.
Washing /
regeneration
HCl Hydroquinone Gold reduction 6. Edwards, R.I., Haines, A.K., Tekiele, W.A.M., The separation of gold
from acid leach liquors with Amberlite XAD-7, Proc. Int. Conf.«The
Filtration theory and practice of ion Exchange »,Cambridge, 1976, 40.1.
7. Feng, D., Aldrich, C., Elution of ion exchange resin by use of
ultrasonication, Hydrometallurgy, 2000, 55, pp. 201-212.
Gold precipitate Mother liquour 8. Radulescu, R., Filip, Gh., Procedeu hidrometalurgic de recuperare a
To water treatment
aurului native din concentrate» Patent RO 112296B, 1997.
Melting
station 9. Radulescu, R., Georgescu, D., Filip, G., Procedeu hidrometalurgic de
Fine Gold
recuperare a aurului şi argintului din nămolurile cloroase, Patent RO
118664, 2004.
10. Radulescu, R., Georgescu, D., Filip, G., Tomus, N., Munteanu, C.,
Figure 8. The main operation of the experimented method for gold
Benoniu, I., Procedeu de recuperare a aurului, argintului şi cuprului din
recovery
zguri. Patent RO 120079, 2006.

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