ISIJ International, Vol. 54 (2014), No. 3, pp.

543–547

Review

Pretreatment Process on Refractory Gold Ores with As

Xin-yuan NAN, Xin CAI* and Jun KONG

School of Electrical Engineering, Xinjiang University, 1230 Yan’an Road, Tianshan District, Urumqi, 830047 P. R. China.
(Received on August 30, 2013; accepted on October 17, 2013)

The problem of the refractory nature of gold bearing arsenide ores is described. The basic principle,
characteristics and application of pretreatment technique of arsenic-bearing gold ores are presented in
this paper. Several different classes of process options for pretreating refractory ores are considered.
These options include: roasting oxidation; wet chemical treatment; bacterial peroxidation; and other pre-
treatments such as: eliminating arsenic in vacuum, volatile smelting, segregation of roasting, electrochem-
ical oxidation. Its development tendency in the future is also looked ahead.

KEY WORDS: arsenic-bearing gold ore; pretreatment process; refractory gold ore.

flotation concentrate.4) The main chemical reactions are:

1. Introduction
12 FeAsS ( s ) + 29O2 ( g )
Gold ores are considered refractory if gold extractions
from a conventional cyanidation process are less than 80% = 4 Fe3 O 4 ( s ) + 3As4 O6 ( g ) + 12SO2 ( g ) .......... (1)
even after fine grinding.1) Arsenic-bearing refractory gold
ore has stones extremely difficult to deal with. In the stones, 2 FeAsS (s ) + 6O2 ( g ) = Fe 2 O3 (s ) + As2 O5 ( g ) + 2SO2 ( g )
gold is locked up in arsenic mineral matrix as the form of
.......................................... (2)
microscopic or submicroscopic lattice. If use conventional
cyanidation gold extraction process, the gold leaching rate In solidification roasting, solid sulphate and arsenate are
is very low. Because gold in such ores is very fine particle produced by oxidation of sulphur and arsenic with added
form wrapped with arsenic, the leach reagents are unable to limestone or dolomite decomposition in ores.
reach it in cyanide leaching process.2) The gold ores with As
2CaO + 2SO2 + O2 ( g ) = 2CaSO 4 ( s ) ............ (3)
must be broken or decomposed in the gold particles scales,
so that gold is fully exposed, and then extracted with the
3CaO + As2 O5 = Ca 3 ( AsO 4 )2 ( s ) .............. (4)
appropriate gold leaching agent. The process of crushing or
decomposition before gold leaching is called pretreatment It can dramatically improve gold cyanide leaching rate.
of refractory gold. Roasting has advantages of mature and reliable technology,
Statistics show that, in the world, about 2/3 gold resource simple operation, adaptability, etc. But it is easy to form sec-
belongs to the difficult processing ores, and about 1/3 total ondary wrapping to reduce leaching rate of gold in the roast-
output of world gold is produced from refractory gold. This ing process, and at the same time produces gases of SO2 and
proportion will further increase in future. Therefore, pre- As2O3 polluting environment seriously. In ores with a high
treatment of arsenic-bearing refractory gold has an extreme- sulphide content this treatment involves the production of
ly important significance.3) In recent years, researches are sulphuric acid. This is an undesirable feature, due to the
mainly about the refractory gold leaching easily through already saturated market for sulphuric acid. In ores with low
arsenic removal to expose gold, changing the composition, sulphide content it requires gas purification equipment. In
physic-chemical and electro-chemical properties of the ore. some cases, this method of preoxidation can result in a poor
Currently, there are four main methods of pretreatments of metal recovery. The process flow diagram is as show in Fig. 2.
refractory gold ores with As. Pretreatment options for deal- In order to solve under-burning, over-burning and envi-
ing with refractory gold ores are illustrated in Fig. 1 and ronmental pollutions and other defects, scientific and tech-
described in detail in the subsequent sections. nical workers have been researching to explore to improve
and develop the roasting process and equipment for many
years. For devices, they developed furnace from single to
2. Roasting Oxidation Pretreatment
multiple, roasting from fixed to fluidized bed up to flash
So far, the application of roasting oxidation pretreatment roasting. For technology, it developed from a roasting to
has a history of 70 years. The principle is to destroy the ores two, from air to oxygen-enriched roasting. In addition,
tissue to make gold exposed by the means of roasting the reduction roasting, chlorination roasting, salt sulfur fixation
* Corresponding author: E-mail: [email protected] and arsenic roasting are developed on the base of t-he tra-
DOI: http://dx.doi.org/10.2355/isijinternational.54.543 ditional process.

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 ISIJ International, Vol. 54 (2014), No. 3

Fig. 1. General process options for pretreating refractory gold ores.

Fig. 2. Block diagram of the two stage roasting process.

Roasting oxidation inevitably will emit a certain amount

of toxic and harmful gases in the process. Microwave roast-
ing is a new pretreatment to solve the problem. It uses min-
eral absorption properties to heat minerals. In this way, gold,
arsenic and sulfur can be separated from ores. The technical
advantages of microwave roasting are selectively heating
materials, fast heating rate and high heating efficiency.
Microwave heating has the effect of reducing the tempera-
ture of chemical reaction. So it can avoid generating gases
of SO2 and As2O3 by controlling the temperature appropri-
ately.5–7)
Kyuesi and Haque, etc. have studied the role of micro-
wave in the gold extraction process of arsenic-bearing
refractory gold ore.8,9) Haque K E used microwave to dis-
pose of arsenical pyrite and gold concentrate with pyrite, the
gold leaching rate reached 98%.10) Liu Quanjun etc. made a
test for a gold mine in Guizhou province. The ore without
micro-wave pretreatment could be hardly leached in cya- Fig. 3. Block diagram of the chemical leaching process.
nide. On the other hand the cyanide leaching of gold ore
increased to 86.53%.11) WeiMingan, Ma Shaojian, etc. also
researched microwave pretreatment of gold concentrate, and environmental concerns and development progress all con-
achieved good results. tribute to limiting the application of these techniques.12)
According to the different media, the pretreatment can be
divided into alkali-ne and acid leaching pretreatments.
3. Chemical Treatment
Depending on the reaction conditions, it can be divided into
Chemical treatment is another branch of ore pretreatment atmospheric pressure and hot pressure pretreatments.
and has the advantages roasting process doesn’t have. Those
are no difficult secondary leaching issues caused by under- 3.1. Alkaline Leaching Pretreatment
burning and over-burning, well-adapted and selecting differ- Alkaline leaching pretreatment is a chemical pretreatment
ent reagents according to different ores. The process of process which can oxidize and dispose of components of the
chemical treatment is as show in Fig. 3. ore through adding chemical reagents.
Reagent availability and cost, materials of construction, Meng Yuqun, Wu Minjie, etc. have researched to strengthen

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 ISIJ International, Vol. 54 (2014), No. 3

the alkaline leaching pretreatment on a gold concentrate are as follows:19)

with As at normal temperature and pressure. The gold con-
centrate has many metallic minerals with sulfides as major 3FeAsS + 8HNO3
ones. They are mainly pyrite, arsenopyrite, iron ore and so = 3Fe3+ + 3AsO 43− + 2S0 + 4H 2 O + 8NO ....... (10)
on. In the experiment, the ore is separated by physical and
chemical methods and is in ultrafine grinding. Then, use 6 FeS2 + 30HNO3
stirred tank to strengthen the alkaline leaching pretreatment = 3Fe 2 ( SO 4 )3 + 3H 2 SO 4 + 12H 2 O + 30 NO ......(11)
at normal temperature and pressure. Sulfur and arsenic
removal separates gold and sulfide fully. Finally, leach gold 2 FeS + 6HNO3 + H 2 SO 4 = Fe 2 ( SO 4 )3 + 4H 2 O + 6 NO
with cyanide and reach the purpose of gold extraction effi-
........................................ (12)
ciently. The main chemical reactions are:
HNO3 oxidation is an improving pretreatment technology.
3FeAsS + 9NaOH + 4O2 Cigna corporation has made experiments on gold ore of
= Na 3 AsS3 + 2 Na 3 AsO 4 + 3Fe ( OH )3 ........... (5) most deposit in the world.20) The result showed that the
effect on ore bearing sulphur of 1%–50% was good and time
4 FeAsS + 4FeS2 + 12NaOH + 3O2 + 6H 2 O of oxidation pretreatment was short. But it is not beyond the
scope of high temperature and pressure. And the problem of
= 4 Na 3 AsS3 + 8Fe ( OH )3 ....... (6)
nitric acid regeneration hasn’t been solved. The superiority
of technology hasn’t yet been confirmed by the practices of
2 FeAsS + 4 NaOH + 7O2 = 2FeAsO 4 + 2Na 2 SO 4 + 2H 2 O
industrialized production.21,22)
.......................................... (7)
2 FeAsS + 10 NaOH + 7O2 3.5. Pressure Oxidation
Pressure oxidation process is more mature. It oxidizes and
= 2 Fe ( OH )3 + 2 Na 3 AsO 4 + 2Na 2 SO 4 + 2H 2 O .... (8)
decomposes gold bearing sulfide to make gold exposed
2 FeS2 + 4 NaOH + 3O2 = 2 Na 2 S2 O3 + 2Fe ( OH )2 ... (9) from ores under conditions of high temperature and pres-
sure.23) The main chemical reactions are:
Under a certain condition, Na2S2O3 and Na3AsS3 are fur-
4 Fe2 AsS + 13O2 ( g ) + 6H 2 O = 4FeSO 4 + 4H 3 AsO 4 .... (13)
ther oxidized to Na2SO4 and Na3AsO4, Fe(OH)2 is oxidized
to Fe(OH)3, Fe(OH)3 decomposes to Fe2O3.
This method is environmental protection, simple process, 4 FeAsS + 7O2 ( g ) + 4H 2 SO 4 + 2H 2 O
short flow, small investment, etc.13–17) = 4 FeSO 4 + 4S ( l ) + 4H 3 AsO 4 .......... (14)

3.2. Acid Treatment

2S ( l ) + 3O2 ( g ) + 2H 2 O = 2H 2 SO 4 ( l ) ......... (15)
Atmospheric acid treatment usually uses permonosulfuri-
cacid to oxidize refractory gold ore with As. It’s said that the Sulphur may wrap releasing gold again in the reaction,
method is not suitable for all refractory gold ores, but has and is bad for cyanidation leaching. High temperature and
good results in dealing with symbiotic arsenopyrite gold ore. pressure are good for avoiding the generation of sulphur.
Because arsenopyrite is easily oxidized. The process can be carried on not only in acidic medium
Compared with roasting pretreatment and pressure oxida- but also in alkaline medium. It also deals with raw ores and
tion, acid treatment has low expense. Even so, this method concentrates. It has following advantages: first, soluble oxi-
has not yet been used in industrial applications because of dation product and completely decomposition reaction; sec-
some technology and equipment problems.18) ond, not releasing harmful gases; third, suitable for large
gold factory. The disadvantages are high requirements for
3.3. Wet Chlorination equipment and materials’ quality, security risks, careful
Wet chlorination uses chlorine (or chlorine oxidant) to operation and maintenance. When conditions are controlled
dispose of Arsenic-bearing refract-tory gold ore. It is an badly, it may produce sulfur, affect the process and reduce
effective method for the carbon refractory gold ore and is the gold’s recovery. The method is not appropriate for
used in preprocess of high arsenic gold ore. Beijing General refractory gold ore bearing organic carbon.
Research Institute of Mining and Metallurgy has studied a
refractory gold ore bearing high arsenic in Guizhou. It used
4. Bacterial Preoxidation
water chlorination to leach gold and gold leaching rate
reached 91.48%.17) High cost of chlorides and serious cor- The research of bacterial peroxidation is quite active. The
rosion of equipment are the key factors to restrict the appli- technology started to process ores in the 1950 s, and at first
cation of wet chlorination. leached to recovery copper from the low-grade copper ore
or marginal copper ore. In the mid-1980 s, the first commer-
3.4. HNO3 Catalyzing Oxidation Decomposition cial plant which applied bacterial oxidation to pretreat
Method refractory gold ores was built in South Africa. After bacte-
Nitric acid is the most efficient oxidant for pyrite, arse- rial oxidation, sulphide decomposition, arsenic comes into
nopyrite and nonferrous metal sulfide. In this method, nitric the solution, so as to remove arsenic. The process is showed
acid oxidizes spyrite and arsenical pyrite as a catalyst under in Fig. 4. The reactions are as follows:
the condition of low temperature and pressure. The reactions

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However, Bacterial oxidation process still has some

defects to be improved such as low pulp density, easy to cor-
rode the iron, requirements of temperature tolerance of bac-
teria, low processing speed.
A. D. Bailey, etc. have come up with a batch biooxidation24)
to increase pulp density. It made pulp density reached 40%
even 50%, was applied to refractory gold ore bearing lo-w
grade sulfide.
A. Mazuelos, etc. have designed a flooded packed bed
reactor.25) The reactor separates bacterial oxidation on Fe+2
from bacteria and ferric iron oxidation on refractory gold
ores, and improves the efficiency of bioreactor.
The institute of Microbiology of Chinese Academy of
Sciences has done many researches on bacterial oxidation.
In 1980, the institutdid tests on arsenic gold ore concentrate
to remove arsenic in Guangxi. On the condition of arsenic
content <6%, solid-to-liquid ratio of 1:5, temperature of 30–
35°C, ph=1.5–2.5, bacterial count greater than 1 085/ml, stir
pulp 5–6 day and night, use HCL to wash leached residue,
the elimination efficiency of As reaches 90%, recycle rate
of Au is over 90%.

5. Others
In addition to the above pretreatment processes, some
new type of pretreatments of refractory gold ore have been
developed such as eliminating arsenic in vacuum, volatile
Fig. 4. Block diagram of bacterial pre-oxidation.
smelting, segregation of roasting, electrochemical oxidation,
etc.
The process of eliminating arsenic in vacuum is that arse-
nopyrite is heat to decompose into As in vacuum. It is an
2 FeAsS + 7O2 ( g ) + H 2 SO 4 effective method to remove arsenic. If there is pyrite, sulfide
+ 2H 2 O T ⋅ F Fe 2 ( SO 4 )3 + 2H 3 AsO 4 ....... (16) or arsenide formed by precipitating S and As can be con-
gealed and deposited by condenser. So eliminated gas
Ferric sulphate is a strong oxidant produced in the reac- doesn’t need special purification.
tion, and reacts with arsenious sulfide. Volatile smelting removes As more completely and has
good technical and economic indicators. It has so large pro-
4 FeAsS + 4 Fe 2 ( SO 4 )3 + 5O2 ( g ) + 6H 2 O cessing capacity as to deal with different intermediate prod-
= 12 FeSO 4 + 4H 3 AsO 4 + 4S ...... (17) uct of smeltery. But smoke of the method contains much Au
to pollute environment seriously.
4 FeSO 4 + 2H 2 SO 4 + O2 = 2 Fe 2 ( SO 4 )3 + 2H 2 O ...... (18) Segregation roasting is to dead roast gold ore concentrate
with As to remove As. High concentration of flue gas gen-
2S + 3O2 + 2H 2 O T ⋅F 2H 2 SO 4 ........... (20) erated during the procedure should be recycled to further
process. The calcine of output makes separate-on with a cer-
The advantages are small investment, low cost, simple tain amount of reductant and chlorating agent. And separat-
method, easy operation, no environmental pollution, etc. ing product is selected to get high grade concentrate. The
Bacterial peroxidation can also be used in low grade ore advantage of the method is largely reducing energy con-
bearing arsenic, largely increase the leaching rate of heap sumption,26,27) but it is a big challenge for environment to
leaching. With the environmental pollution becoming handle the high con-centration of flue gas.
increasingly serious, today, bacterial oxidation is called Electrochemical oxidation28) uses electrodereaction to
‘green metallurgical process’ and is popular to become a oxidize gold ore bearing arsenide and sulfide in a certain
new hope of metallurgical engineering’s future. media. The dielectric system contains vitriol, nitric acid and
Bacterial oxidation process to leach gold is roughly divid- hydro-chloric acid, etc. The result of reaction is similar to
ed into three stages: (1) using bacteria culture medium to pressure oxidation. The process can change microstructure
cultivate thiobacillus ferroxidans, etc. and preparation for of refractory gold ore to improve porosity of ore. So it
sulfuric acid bacteria leaching solution of Ph=1.5–2.5; (2) becomes easily to leach gold. At the same time, peroxida-
bacteria catalyzing, oxidizing and re-moving arsenic and tion and leaching can be completed in one system.
sulfur; (3) the residue from pretreatment cyaniding (or other Compared with bacterial peroxidation of Harbuor Light, it
methods) to leach gold, solution of pretreatment can be is feasible to practice economically.29)
recycled after bacterial activation. The process flow diagram
is as follows.

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 ISIJ International, Vol. 54 (2014), No. 3

Acknowledgement
6. Prospect
The authors would like to acknowledge the support of the
The pretreatment technology of high arsenic gold ore is Provincial Na-tural Science Foundation of China (No.
becoming more and more appreciable and is an inevitable 2012211A004).
trend to gold development. Through the continuous efforts
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