Advanced Materials Research
ISSN: 1662-8985, Vols. 1010-1012, pp 1622-1625
doi:10.4028/www.scientific.net/AMR.1010-1012.1622
© 2014 Trans Tech Publications, Switzerland
Submitted: 2014-06-06
Accepted: 2014-06-08
Online: 2014-08-13
Review on the Mineral Processing-Metallurgy Combined Processes
Researches on Copper Oxide Ore
Yingbo Mao1, 2, a, Shuming Wen1, 2, b (Corresponding author), Jianjun Fang1, 2, c
1
Faculty of Land Resource Engineering, Kunming University of Science and Technology, Kunming,
Yunnan 650093, China
2
State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming, Yunnan
650093, China
a
email: [email protected], bemail: [email protected], cemail: [email protected]
Keywords: Copper Oxide Ore; Mineral processing; Metallurgy; Mineral-metallurgical combining
processing
Abstract. Methods used for mineral processing-metallurgy combined processes of copper oxide ore
were reviewed and the research directions of copper oxide ore were pointed out.
Introduction
The method of mineral processing-metallurgy combined processes of copper oxide ore
combines the mineral processing (mainly flotation) process with the metallurgy process (mainly a
"leaching-extraction-electrowinning" process) to deal with the copper oxide ore. These processes
are assembled in an optimized manner, which make the best use of their advantages and bypass
their disadvantages. They also have complementary advantages. The main applications of this
method are refractory copper oxide and oxide- sulfur mixed copper ore.
In recent years, a lot of researches have been conducted in order to efficiently recovery the
refractory copper ore. Among these investigations, the method of mineral processing - metallurgy
combined processes is an important aspect, which includes, leaching-sulfide precipitation-flotation
method, hydrothermal sulfide-flotation process, grinding-leaching-flotation treatment,
grinding-leaching-replacement-flotation process, chlorination roasting-flotation method, flotation tailings ammonia leaching treatment and ammonia leaching-residue flotation method.
Mineral Processing-Metallurgy Combined Processes of Copper Oxide Ore
2.1 Ammonia Leaching-Sulfide Precipitation - Flotation Process
The application of ammonia leaching process usually leads to the occurrence of many
problems, such as copper oxide scaring and solid-liquid separation difficulties. A solution to solve
these problems is to use ammonia leaching sulfide precipitation - flotation process [1] [2], in which,
firstly, the pulp and sulfur (sulfur element) is mixed; secondly, a pressure leaching process is
conducted in ammonia, carbon dioxide environment whereas copper oxides are transformed into the
copper ammonia complexes and sulfide ions during the leaching process react with the sulfide ions
of the copper ammonia complexes which leads them to precipitated as "synthetic copper sulfides";
finally, the precipitated "synthetic copper sulfides" and natural copper sulfides in the ore are
recovered by the conventional flotation method. This technology reduces the large solid-liquid
separation process, which significantly simplifies the processes. The complete processes are shown
in Fig.1. The main reactions occur in the leaching process are:
CuCO3·Cu(OH)+ NH3+NH4HCO3+S→Cu(NH3)42++CO32－+SO42－+S2Cu(NH3)42++S2－→CuS↓+4NH3↑
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Advanced Materials Research Vols. 1010-1012
1623
R a w O re
C r u s h in g a n d G r in d in g
N H 3、 C O
N H 3、 C O
2
2
s u lf u r P o w d e r A m m o n ia L e a c h in g S u lf id e P r e c ip ita tio n
S te a m
A gent
P u lp a u to c la v e d
F lo ta tio n
T a ilin g s
C o n c e n tr a te
Fig 1 Techology process of ammonia leaching sulfide precipitation - flotation
Compared to conventional sulfuration-floating process, technical indicators of the ammonia
leaching -sulfide precipitation-flotation process have been greatly improved, the recovery rates of
copper and high grade ore can reach 90.36% and 25.45%, respectively. During this process,
flotation is directly conducted after pulp ammonia, which reduces the solid-liquid separation
process and precious metals such as gold and silver can be effectively recovered. The problem of
distillation tower scaring can also be solved by changing ammonia brazing means. However, up to
now, the equipment specially designed for pulp ammonia remains to be further developed.
Especially, problems about serious abrasion of pipelines and valve equipments as well as the high
energy consumption during the whole processes all need to be solved. Therefore, it is difficult to
obtain better economic benefits to use this technology for treating low grade copper oxide ore, and
there is still a long distance for its wide application in industrial production.
2.2 Ammonia Leaching – Extraction-Electrowinning Processes
During the 90's in the last century, the "ammonia leaching-extraction electrowinning" process
was put forward in order to solve the distillation tower scaring problems in the ammonia leaching
process[3] [4] [5]. The leaching process used in this method was the same as that in the ammonia
pressure leaching process of ore, yet the copper ammonia solution leached was then experienced an
extraction process during which Cu2+ was converted into the organic phase; then a stripping process
was performed with sulfuric acid, finally the electrolytic copper would be achieved by
electrowinning of the copper rich liquid obtained in the stripping process. In 1990 October, a 5t/d
experimental study was carried out using this method. In that investigation, the recovery rate of
copper at the ammonia leaching stage was 75.64%, and 10.63% copper ore was obtained after
flotation of leached slag. At the extraction stage, the recovery rate of copper achieved 98.5%. After
the stripping process, cathodic copper of the first level with the purity ≥99.95% was achieved via
electrowinning of the copper rich liquid. An excellent index for the whole processes was obtained
as the theoretical recovery rate of 83.95%. The flow diagram for these processes is shown in Fig.2.
However, this technology still not solves the problem of high energy consumption and special
equipment requirements that are caused by pressure leaching. Therefore, it is difficult to obtain
better economic benefits to use this method to deal with treating low grade original ore, thus it is
not suitable for mass production.
1624
Environmental Protection and Resources Exploitation II
Raw Ore
Crushing and Grinding
CO2 、NH3
NH3 、CO2
CuO (Product)
Leaching
Distill
Rich
Liquor
Washing Water Solid-Liquid
Separation
Residual Liquid
Leaching Residue Dilute
Solution
Flotatong
Extraction
Raffinate
Rich Copper Liquid
Electro-Deposit
Copper
Electrodeposition
Electrolytic
Residue Fluid
Fig.2 Principle flowchart of crude ore roasting-ammonia Leaching-extraction-electrowinning
2.3 Concentrate Roasting-Ammonia Leaching-Electrowinning Processes
Concentrate "roasting-ammonia leaching-electrowinning" process [6], is used copper
concentrate as raw material, during which copper sulfide in the copper concentrate is converted to
oxide or sulfate and copper is transformed into the solution in the form of copper ammonia complex
form via the ammonia leaching process so that the purpose of ore and gangue separation is realized.
And then by extraction and striping, copper rich liquid is obtained; then an electrowinning process
is conducted on the copper rich liquid and the cathodic copper is finally reached. A small test has
conducted using this method to deal with the Dongchuan Tangdan copper concentrate. A leaching
rate of larger than 92% was reached for the ammonia leaching process, and a recovery rate of larger
than 99% was obtained when Lix54-100 was applied in the extraction process. However, in the
industrial test, leaching rate of ammonia leaching could only reach about 75% and copper in the
leaching slag could not be recovered in the flotation process. Therefore, from an economic point of
view, it is difficult to realize the large-scale production in the industry. The flow chart of this
method is shown in Fig.3.
C o p p e r C o n c e n tr a te
C o a l、 A ir
Sm oke
A b s o r p tio n
R o a s tin g
E m is s io n s
A m m o n ia W a te r
A m m o n ia L e a c h in g
L e a c h in g A g e n t
W a te r L e a c h in g R e s id u e
E x tr a c tio n
W a s h in g - u p
R a f f in a te
W a te r
L o a d e d O r g a n ic P h a s e
F in a l S la g
W a s te
E le c tr o ly te
W a s h in g - u p
W a s h in g L iq u o r
R ic h C o p p e r
L iq u id
E le c tr o d e p o s itio n
S tr ip p in g
R e n e w a b le
O r g a n ic P h a s e
P a r t o f th e D is tilla tio n E le c tr o ly tic
R e s id u e F lu id
E m is s io n s
Fig. 3 Principle flowchart of copper concentrate roasting - ammonia leaching–extraction-electrowinning
2.4 Ore Ammonia Leaching- Extraction-Electrowinning at Room Temperature and
Atmospheric Pressure and Slag Flotation Combined Processes
On account of that ammonia leaching at high temperature and high pressure is difficult to
operate and is too expensive for the economic consideration, combined processes as "ore ammonia
leaching -extraction-electrowinning at room temperature and atmospheric pressure and slag
Advanced Materials Research Vols. 1010-1012
1625
flotation" is proposed[7] [8]. For its easy operation properties and at the economic consideration,
this technology can be easily realized and has been scaled applied in Dongchuan. In 2005, an
industry with a 1500t/d ore processing capacity was built as the industrial demonstration plant,
which has continuously and stably produced for 18 months and the cumulative recovery rate of the
whole processes have reached 75%.
Conclusion
Mineral processing is the most commonly used method for treating copper oxide ore, and it is
difficult to separate the copper oxide ore highly using a solo process. Therefore, to develop an
efficient technology for mineral processing of copper oxide ore is an important aspect. Especially,
copper oxide ore resources can be effectively utilized in the mineral processing - metallurgy
combined processes, which is the main direction in the future research.
Acknowledgement
This study was supported by the National Natural Science Foundation of China (Grant No.
51364017) and the Analyze test fund of Kunming University of Science and Technology (Grant No.
20130536), and also the authors are grateful to Prof. Shuming Wen for his permission to publish
this paper.
References
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[4] Wei Yan. Ammoniacal Leaching of Compound Copper Ore Under High-Pressure [J],
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[5] Xiangyu Song. Experimental Research on Water-Heating Sulphidizing Flotation Process of A
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Environmental Protection and Resources Exploitation II
10.4028/www.scientific.net/AMR.1010-1012
Review on the Mineral Processing-Metallurgy Combined Processes Researches on Copper Oxide Ore
10.4028/www.scientific.net/AMR.1010-1012.1622