Hydrometallurgy 125126 (2012) 115124

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Hydrometallurgy
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Recovery of gallium from Bayer liquor: A review

Zhuo Zhao a,, Yongxiang Yang b, Yanping Xiao b, Youqi Fan a
a
School of Metallurgy and Resource, Anhui University of Technology, 243002 Maanshan, PR China
b
Department of Materials Science and Engineering, Delft University of Technology, Mekelweg 2, 2628 CD, Delft, The Netherlands

a r t i c l e i n f o a b s t r a c t

Article history: Bayer liquor is the biggest raw material resource for gallium production. Four kinds of methods have been
Received 4 November 2011 developed to recover gallium from Bayer solutions, including fractional precipitation, electrochemical depo-
Received in revised form 24 May 2012 sition, solvent extraction, and ion exchange. The fractional precipitation method is based on AlGa precipita-
Accepted 5 June 2012
tion with CO2 and subsequent separation of Al and Ga with lime milk or sodium aluminate solutions. This
Available online 13 June 2012
approach is more environmentally friendly and with low cost, but the process is complicated. The electro-
Keywords:
chemical method includes both mercury cathode electrolysis and cementation. The electrolysis with mercury
Gallium recovery cathode has been prohibited in most countries because of high toxicity of mercury. Cementation is an elec-
Bayer liquor trochemical process realized by a displacement reaction between gallium and reductants, such as sodium
Electrolysis amalgam, aluminum and aluminumgallium alloy. Solvent extraction is an efcient method and by using
Solvent extraction Kelex 100 system about 80% of the gallium in Bayer liquor can be extracted. However, the kinetics of the ex-
Ion exchange traction process has been proved to be very slow, which generally requires several hours. Ion exchange is the
main method applied in industry for gallium recovery from Bayer liquor. Duolite ES-346 and DHG586 exhibit
good extracting properties for gallium, and are used as industrial resins. Unfortunately, the co-extraction of
vanadium and the degradation of the amidoxime groups still remain as the main problems during industrial
application. In order to recover gallium from Bayer liquor efciently, further research and development are
necessary.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Gallium is a metallic element in Group IIIA of the periodic table. It
was discovered in 1875 by a French chemist Paul-mile Lecoq de
Boisbaudran (Moskalyk, 2003). This soft and silvery-blue metal has
an atomic weight of 69.723, a hardness of 1.5 mohs, and a specic
gravity (i.e., density) of 5.904 and 6.905 g/cm 3 for the solid and liquid,
respectively. A solid piece of gallium will liquefy when being placed in
one's hand. It exhibits an unusually large liquid range due to its low
melting point of 302.98 K and high boiling point of 2676 K. Solid gal-
lium has an orthorhombic crystal structure and displays a conchoidal
fracture similar to glass. Gallium can exist in the form of six isotopes
of which only two, 69Ga (60.4%) and 71Ga (39.6%), are stable. Gallium
can form many substances such as bromides, chlorides, hydrides,
iodides, nitrides, oxides, selenides, sulphides and tellurides. Gallium
has the oxidation states of +1 and + 3 valences. Although the ele-
ment is stable with water it reacts vigorously with halogens even at
low temperatures. The element rapidly dissolves in either aquaregia
or concentrated sodium hydroxide in an aqueous medium. It also re-
acts with strong oxidants. The element is suited to readily form alloys
Corresponding author at: School of Metallurgy and Resource, Anhui University of
Technology, Maanshan, PR China. Tel.: + 86 138 5550 5238.
E-mail address: zhaozhuo1018@163.com (Z. Zhao).
(e.g., eutectic alloys) with most metals in conjunction with being a
component in low-melting alloys.
Since the 1970s gallium metal has attracted a lot of interests. Galli-
um combined with elements of group 15 displayed semiconducting
properties (Chou et al., 2008; Gupta et al., 2007), such as gallium arse-
nide (GaAs) and gallium nitride (GaN). They are valuable compounds
employed in advanced semiconductors for microwave transceivers,
DVD's, laser diodes in compact discs and other electronic applications
(Font et al., 2007). The supply and demand of gallium-bearing products
have gradually increased during the past decade. Hence, it is important
to nd out an effective method of extraction of gallium.
Gallium is a very widespread trace element. Its content in the litho-
sphere is about 10 ppm. Gallium is a cryptomorphic element whose aver-
age clarkes (geochemical density indicators) in the lithosphere are
relatively high. Due to the practical inability to form its own minerals in
natural conditions, it is considered quite rare (Poledniok, 2008). Given
the geochemical afnity between Al and Ga, the latter occurs mainly con-
centrated in bauxites and hosted by diaspore, various aluminosilicates
(such as clays), apatite, nepheline and frequently alunite. Ga also has a
chalcophile afnity, and thus, may occur as gallite (CuGaS2), and is
frequently substituted for Zn and Cu in sulphides, mainly in sphalerite
(ZnS), germanite (Cu26Fe4Ge4S32), and chalcopyrite (CuFeS2) (Font et
al., 2007). It is therefore not economical to mine any minerals for merely
recovering gallium. Generally, gallium is recovered as by-product mainly
from the production of alumina, and to a lesser extent from zinc

0304-386X/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2012.06.002
116 Z. Zhao et al. / Hydrometallurgy 125126 (2012) 115124

production (Dutrizac and Chen, 2000; Flamini et al., 2007; Xu et al., 2007). spent liquor
Other alternative potential sources of gallium are coal y ash, which can st
CO2 1 total carbonation
contain as much as 100 ppm of the metal (Dumortier et al., 2005; Fang
and Gesser, 1996), and the recycling of industrial electronic scrap (Lee
separation & washing filtrate
and Nam, 1998; Sturgill et al., 2000).
Bayer liquor obtained during alumina production from bauxite is
residue
the most important source of gallium. It was estimated that about
90% of world primary gallium is produced from Bayer liquor (Lu et lime milk dealumination
al., 2008). Gallium concentration in the bauxite ores is in a range
from 20 to 80 ppm. In the Bayer process about 70% of the gallium is separation & washing calcium aluminate residue
leached from the bauxite and follows the aluminum into the caustic
soda solution, and the remaining 30% is disposed with the red mud. filtrate
Gallium accumulates in the Bayer liquor due to several successive cir-
culations, reaching a concentration of 100300 mg/l (Figueiredo et al., CO2
nd
2 total carbonation
2002).
Many methods have been developed to extract gallium from Bayer separation & washing
liquor, however, only few of them are realized in industrial application.
This paper reviews all of the methods for the extraction of gallium from
gallium concentrates
Bayer liquor. Based on the specic process features of each method, the
research priority for recovering gallium from Bayer liquor in future is NaOH
dissolution
proposed. Na2S
filtration PbS
2. Recovery methods
filtrate
2.1. Fractional precipitation
electrolysis
The fractional precipitation method is based on AlGa co-precipitation
by using lime or CO2, continued with treatment with several successive purification HCl
steps resulting in an aluminum hydroxide richer in gallium, and followed
with a subsequent NaOH re-dissolution of gallium. gallium

Fig. 1. Flowsheet of lime method.

2.1.1. Lime method
AlGa separation is the key step for gallium recovery from Bayer
liquor. The idea of employing lime to achieve the separation was
rstly proposed by Aluminum Company of America (Alcoa) (Frary
and Oakmont, 1952). In 1957, a gallium recovery process, known as
lime method, was developed and applied to produce 2 tons of galli-
um by Shandong alumina renery (China). Actually, the lime method
was developed based on Sintering Process which was employed by
Shandong alumina renery at that time, and the feed solution was
not Bayer liquor but the spent liquor from carbonation precipitation
of Sintering Process. Gallium can also be extracted from Bayer process
liquor with this method, but it will cause some problems, which will
be explained later.
In the lime method, the circulating liquor is rst treated by a total
carbonation precipitation using CO2 gas to obtain gallium-enriched
precipitate. This precipitate is then dissolved by using lime milk for
separating gallium from aluminum. Finally gallium is recovered
from the NaGa(OH)4NaAl(OH)4 solution by a second carbonation
precipitation and the gallium concentrate is re-dissolved with NaOH
solution for gallium electrowinning after purication. Fig. 1 shows
the typical owsheet of the lime method.
After normal precipitation, the sodium aluminate solution (known
as spent liquor containing 0.030.05 g/l Ga) is subjected to the 1st
total carbonation precipitation to precipitate gallium, resulting in a
gallium-enriched residue. This procedure should be carried out at
low temperature (~80 C), until that the NaHCO3 concentration in
the liquor reaches about 60 g/l. The precipitation ratio of gallium
can reach up to 90%, but gallium cannot be completely precipitated
due to the high solubility of gallium in Na2CO3\NaHCO3 solution.
The solution should be cooled gradually with continuous agitation
during precipitation to reduce the gallium loss.
The precipitate obtained by 1st total carbonation precipitation
mainly consists of Al(OH)3 and dawsonite (Na2OAl2O32CO2nH2O).
Gallium is present in the dawsonite due to isomorphic substitution
for Al. Generally, this precipitate contains 0.10.2% of gallium. Inevita-
bly, impurities such as SiO2 and Fe2O3 still remain in the precipitate.
For aluminum and gallium separation by introducing lime milk,
major reactions are as follows:
NaAlGaOOHHCO3 s H2 O NaHCO3 AlGaOH3 s 1
2NaHCO3 CaOH2 Na2 CO3 CaCO3 s 2H2 O 2
2GaOH3 s Na2 CO3 CaOH2 2NaGaOH4 CaCO3 s 3
Dawsonite is decomposed to Al(OH)3, Ga(OH)3 and CaCO3, of which
Ga(OH)3 dissolves in Na2CO3 solution, while almost all of Al(OH)3 still
remains in precipitate. However, with the increase of lime milk dosage,
the Na2CO3 in solution will be causticized in Eq. (4):
Na2 CO3 CaOH2 2NaOH CaCO3 4
Both Al(OH)3 and Ga(OH)3 will dissolve into the formed NaOH solu-
tion, resulting in poor separation of aluminum and gallium, as shown in
Eq. (5):
AlGaOH3 NaOH NaAlGaOH4  5
In order to ensure a complete AlGa separation with minimal gallium
loss, lime milk should be added in two steps. For the rst step, the objec-
tive is to causticize Na2CO3 singly, making gallium and aluminum dis-
solved. The operation conditions of this process include: lime dosage
with CaO/CO2 =1/1 (molar ratio), liquid solid ratio 3, temperature
9095 C, and treatment time 1 h. As a result, about 3040% of aluminum
and 85% of gallium dissolve into solution. The purpose of the second step
 Z. Zhao et al. / Hydrometallurgy 125126 (2012) 115124
is to precipitate most of aluminum as 3CaOAl2O36H2O. Simultaneously
gallium remains in solution because gallium concentration is lower than
the CaOGa2O3 solubility. The operation conditions of this step include:
lime dosage with CaO/CO2 = 3/1 (molar ratio) and treatment time
12 h. It should be noted that too much lime dosage will lead to the
increase of gallium loss.
After the AlGa separation the obtained gallium-bearing solution
is then treated by the 2nd total carbonation precipitation, to make
further enrichment of gallium, which is benecial to subsequent elec-
trolysis process. In this step, the gallium precipitation ratio is more than
95%, and a gallium-enriched precipitate with 1% gallium can be prepared.
The concentrate is then dissolved with caustic alkali solution, simulta-
neously sodium sulde is added to remove heavy metal impurities such
as lead and zinc, ensuring a high-quality electrolyte. After purication,
the solution contains 210 g/l of gallium. Optimum conditions for elec-
trolysis process include: electric current density 400600 A/m2, tempera-
ture 6070 C and Na2O concentration 140160 g/l. The materials for
cathode and anode are stainless steel and nickel, respectively. During
electrolysis, gallium deposits on the cathode, accompanied by hydrogen
evolution. The deposited gallium will be in a liquid state because the elec-
trolysis temperature is higher than its melting point (29.8 C). After puri-
cation with hydrochloric acid at higher temperature to leach out other
impurities, gallium with 99.99% of purity can be produced.
Lime method has several advantages such as cheaper raw mate-
rials and high product quality. The key step of lime method, AlGa sep-
aration by using lime, is based on the reaction difference between
aluminum and gallium with Ca(OH)2. As a result, the aluminum in the
circulated liquor was nally transformed to 3CaOAl2O36H2O. Generally,
the Al2O3/Ga mass ratio in the cycled liquor is about 450, therefore 7 tons
of 3CaOAl2O36H2O will be generated when 1 kg gallium is produced
(calculated based on gallium recovery 50%). The treatment for the large
quantities of 3CaOAl2O36H2O residues is one of the key problems for
lime method. Furthermore, during the rst step of total carbonation the
composition of circulating liquor is considerably changed to contain
about 60 g/l of NaHCO3. This spoiled solution cannot be reintroduced
into the production cycle without further treatment, which interferes
with the normal sequence of the operations during the production of
alumina. In total about 4.4 tons of CO2 are needed for the production of
1 kg gallium including both the rst and the second carbonation steps.
For Bayer process it is extremely difcult to solve these problems; while
for Sintering Process, the 3CaOAl2O36H2O residues can return to the
sintering step to recover aluminum. Plenty of CO2 can be provided by
Sintering Process because in this process special limekiln is equipped to
produce CO2 for carbonation precipitation procedure. To summarize, the
lime method was originally developed for Sintering Process, which was
employed by Shandong alumina renery at that time. However, Sintering
Process for alumina production has almost been phased out due to its
high energy consumption. Therefore, lime method has also been phased
out in practice nowadays. Since the 1990s Shandong alumina renery
has changed its gallium recovery process to ion exchange which is
much more efcient.
2.1.2. Carbonation method
The rst substance used for AlGa separation to extract gallium
from Bayer liquor is CO2, which was discovered and patented in
1947 by Pechiney Compagnie of France (Beja, 1947). However, the
patent only proposed to prepare a mixture of alumina and gallium
oxide, a further treatment for pure gallium production was not men-
tioned. Based on the patent, carbonation method for metallic gallium
recovery was developed and subsequently employed by many alumi-
na reneries.
Fig. 2 illustrates a typical carbonation method. Upon treating the sodi-
um aluminate solution containing gallium with CO2 slowly (i.e. selective
carbonation precipitation) in the presence of aluminum hydroxide
seeds, about 90% aluminum hydroxide rst precipitates out; meanwhile
gallium remains unchanged resulting in increasing the liquor's gallium
117
Bayer liquor
CO2 selective carbonation Al(OH)3
liquor
CO2 total carbonation
residue
NaAl(OH)4 solution dissolution
solution
purification
purified solution
electrolysis
gallium
Fig. 2. Flowsheet of carbonation method.
concentration. It has been discovered that in strong basic solution alumi-
num hydroxide precipitates at a pH value of 10.6 while gallium hydroxide
at 9.49.7 (Xu and Xu, 2002). When CO2 is blown slowly through Bayer
liquor, it will cause a gradual decrease of the solution pH due to the reac-
tion between CO2 and NaOH (Eqs. (6) and (7)). When the solution pH
drops to 10.6 aluminum hydroxide begins to precipitate out according
to Eq. (8). The NaOH generated by Eq. (8) is continuously neutralized
by CO2 keeping the solution pH stable at about 10.6. Consequently, alumi-
num hydroxide deposits little by little while leaving gallium un-
precipitated.
CO2 2NaOH Na2 CO3 H2 O 6
CO2 Na2 CO3 H2 O 2NaHCO3 7
NaAlOH4 AlOH3 NaOH 8
After primary AlGa separation, the solution is treated by total
carbonation precipitation to transform all the gallium into an alumi-
num hydroxide richer in gallium. The enriched material is selectively
dissolved in appropriate amounts of sodium aluminate solution (k,
i.e. the molar ratio between Na2Ok and Al2O3 in solution, 2.53.0).
In this step, the volumes of sodium aluminate solution are carefully
controlled to dissolve gallium singly while leaving most of aluminum
undissolved in the solid. A purication procedure is used to remove the
impurities such as organics and heavy metals. An electrolytic technique is
applied to the resulting solution of sodium gallate and sodium aluminate
to produce pure gallium (Font et al., 2007; Moskalyk, 2003).
This method is an environment-friendly process. Compared with
lime method, the process is shortened by introducing one total car-
bonation precipitation. The liquor from the total carbonation precipi-
tation step can be recycled to partially replace CO2 in the slow
carbonation precipitation. The key issues of optimization of gallium
recovery and alumina production have basically been solved. The
main problem of this method is the proper treatment of large quanti-
ties of aluminum hydroxide with poor quality generated by the slow
carbonation precipitation. According to calculation, producing 1 kg
gallium generates about 1.5 tons of aluminum hydroxide with poor
quality. Practically the controlled slow carbonation to precipitate
118 Z. Zhao et al. / Hydrometallurgy 125126 (2012) 115124
aluminum singly is quite difcult to realize. Apart from many precip-
itation steps, the process is labor intensive. This method had been
widely used in 1970s by many alumina reneries worldwide, such
as Pechiney Compagnie (France), Ajka Timfoldgyar Alumina Co. Ltd.
(Hungary) and Guizhou alumina renery (China). However, with
the continuous development of the technologies these alumina ren-
eries have changed their gallium recovery method to more effective
methods.
2.2. Electrochemical methods
2.2.1. Mercury cathode electrolysis
Mercury cathode electrolysis was discovered by Bereteque (1955).
It employs liquid mercury as the cathode thereby allowing the possi-
ble precipitation of gallium during the electrolysis process. A typical
process known as Alusuisse process is shown in Fig. 3.
Theoretically, gallium cannot deposit on cathode when gallium-
containing aqueous solution is electrolyzed because gallium belongs to
more electronegativity metal than hydrogen with a standard electrode
potential of 0.521 V. Fortunately, the hydrogen overvoltage at mercury
is very high, and additionally the deposition potential of gallium can be
reduced by the formation of amalgam between mercury and deposited
gallium. Consequently, gallium ions can discharge at mercury cathode
to generate metallic gallium, even if the gallium concentration is low in
Bayer liquor.
Generally, this approach consists mainly of a sequence of three
procedures. The rst step is electrolyzing the sodium aluminate solu-
tion with a cathode formed by stirred liquid mercury and an anode
made from a metal which is insoluble under the conditions of the
electrolysis. As a result the gallium is deposited in the metallic state
at the cathode.
A low circulation of the mercury of the cathode will not make the
process effective. It needs a rather strong stirring, which acts chiey
on the surface of the mercury but without rupturing the continuity
of the surface. In other words, it must be avoided to pulverize the
mercury with a formation of droplets and to create a gyratory motion
causing an interruption in continuity at the surface of the cathode. If
the stirring is not sufciently strong, the objectives of the process
are not reached. The variation of the number of revolutions of the stir-
rer from the single to the double or inversely may cause a variation of
the yield from one to ten or inversely. Without the stirring, the gallium
deposit is insignicant. In Alusuisse process, an electrolytic cell with a
rotary mercury cathode is adopted to guarantee moderate stirring.
This apparatus can also signicantly reduce the mercury consumption
liquor
filtration
solution vanadium
residue NaOH
return to alumina solution
production process
Na2S/H2S
Fig. 3. Flowsheet of mercury cathode electrolysis method.
at the cathode. The anode can be made of nickel, which is particularly
advantageous because of its low oxygen-evolved overvoltage.
Vanadium, chromium and iron contained in electrolyte are quite
harmful for the electrolysis. After 4 or 5 h duration of the electrolysis,
all these elements deposit at the cathode. Furthermore, the increase
of the vanadium concentration leads to a remarkable decrease of
the hydrogen overvoltage. Purication is needed before the electroly-
sis if the electrolyte contains excess vanadium or other impurities.
In order to ensure the deposit of gallium, the terminal voltage (overall
voltage) must be at least 3.0 V, the cathodic potential at least 1.6 V, and
the current density at the cathode at least 35 A/m2 during the electrolysis.
Industrial electrolysis applies preferably a terminal voltage of 3.84.2 V, a
cathodic potential of 1.92.2 V, a current density of 45 A/m2, a tempera-
ture of 4550 C, and a duration of 1824 h.
The second step is extracting the gallium in the mercury with a
content of 0.31% by using a caustic alkali solution, for instance, the
caustic soda solution. The extraction is favored by a temperature in-
crease. At room temperature the attack is very slow. In industrial
practice, this step is carried out at a temperature of higher than
100 C with a strong stirring. If the gallium content in the mercury
is very low, the little amount of sodium which has deposited at the
cathode may be sufcient to dissolve the gallium after having reacted
with the water. It is advantageous to extract the gallium in a vessel
made from stainless steel. The catalysis by stainless steel takes place
at the wall of the vessel and the stainless steel is not corroded. Ac-
cordingly, the stainless steel tank is adopted for the extraction in
practice. At the end a sodium gallate (NaGa(OH)4) solution con-
taining 20 g/l of gallium is obtained. The separated mercury is reused
for electrolysis, but it needs to be puried regularly to remove iron
and other accumulated impurities.
The third procedure is electrolyzing the alkali gallate solution to recov-
er metallic gallium in the free state according to the known process which
has been used in the above-mentioned lime or carbonation method. The
electrolyte after electrolysis can be reused to extract gallium from mercu-
ry, but it needs purication when the impurities accumulate to a certain
level to apparently affect the electrolysis, or alternatively it can be sent
back to the alumina production system.
Compared with the fractional precipitation methods, this method has
less inuence on normal alumina production. However, it is inconvenient
and expensive because of the necessity of employing considerable
amount of mercury due to the low solubility of gallium in mercury. It
has been discovered that gallium has a solubility of 1.3% in mercury at
the normal temperatures (Miyake, 1969). When 2000 tons of ores con-
taining 0.002% of gallium is treated in a day, it is calculated that 640 m2
of mercury cathode surface is required in the case of the rst electrolysis.
spent liquor
new mercury
mercury cathode electrolysis
gallium amalgam pure mercury
decomposition mercury purification
NaGa(OH)4 solution
purification
filtration sulfide residue
purified NaGa(OH) 4 solution
secondary electrolysis
gallium
 Z. Zhao et al. / Hydrometallurgy 125126 (2012) 115124
Thus, a rather large amount of mercury must be kept in circulation to
isolate relatively very small quantities of gallium or to react such
small quantities of gallium with sodium. Particularly, there are many
disadvantages including the long duration of the electrolysis, the dif-
culty in precipitation and agitation, the inevitable co-precipitation of
impurities, the additional generation of sodium amalgam, and the
circulatory pumping of large quantities of caustic soda and sodium-
and-gallium-containing mercury. The fatal drawback of this method
is the use of high toxicity of mercury, and it has been prohibited for
use in most countries. Alusuisse has once shut down 2/3 of its gallium
extraction facilities. Sumitomo Chemical cancelled the contract with
Alusuisse for the joint venture for a gallium recovery line in 1978 (L,
2002). So far only in the Czech Republic (Ziar Aluminum Works),
Germany and Hungary (MAL Hungarian Aluminum Inc.) this technique
is still active in production (Moskalyk, 2003).
2.2.2. Cementation
The development of the cementation method has gone through sever-
al stages. Initially, in order to cope with the problem of a low current ef-
ciency of mercury cathode electrolysis, the sodium amalgam obtained by
electrolysis in a sodium chloride solution using mercury as a cathode
(Yamada et al., 1982) was used to cement gallium from the Bayer liquor
instead of using mercury electrolysis to form gallium amalgam. The
other two subsequent steps, i.e. the extraction of gallium from mercury
and the second electrolysis to produce metallic gallium, remained
unchanged. This is the well-known VAW/INGAL process, which was orig-
inally applied in Vereingte Aluminum-Werke Aktiengesellschaft (VAW)
and INGAL Corporation in Germany. The cementation of gallium with so-
dium amalgam is favored by the high gallium concentration in the Bayer
liquor, high sodium amalgam concentration, long contact time and fewer
impurities (Varadharaj and Rao, 1986). Compared with mercury cathode
electrolysis, cementation with sodium amalgam is more efcient, and it
does not need external current but deposit gallium based on the natural
electrode potential difference between metals. However, it has inevitably
the same serious drawbacks as the mercury electrolysis method, such
as the usage and re-processing of high toxicity and large quantities of
mercury, and the probability of contamination of the sodium aluminate
liquors with mercury.
Dotzer (1965) patented a method for the cementation of gallium
in the Bayer liquor by an addition of nely distributed active alumi-
num in place of sodium amalgam. The cementation of gallium from
the aluminate liquor has thermodynamic advantages because of the
more electronegative character of aluminum as compared to gallium,
according to the reaction Eq. (9):
NaGaOH4 Al NaAlOH4 Ga 9 Electrochemical and structural studies of aluminum gallamas with
As a comparison based on the standard reduction potentials of
2.35 V for Al(OH)4/Al and 1.22 V for Ga(OH)4/Ga, there is a
theoretical potential difference of 1.15 V, which is approximately the
same as attained compared to Na+/Na, when using sodium amalgam
in accordance with the above-mentioned method. In this case, the use
of mercury as an intermediate medium can be avoided.
During cementation, the following undesirable side reactions may
take place:
Al NaOH 3H2 O NaAlOH4 1:5H2 10
Ga NaOH 3H2 O NaGaOH4 1:5H2 11
The re-dissolution of the precipitated gallium can be prevented by
supplying sufcient aluminum in excess to the gallate. As a result, the
reaction as expressed in Eq. (10) is adversely promoted leading to an
undesired extra consumption of aluminum. This may also prohibit
gallium from cementation duo to the masking of aluminum surface
by hydrogen evolution. Therefore, the process of gallium cementation
119
with aluminum has two disadvantageous features prohibitive to the
practical application of the method: (a) the reaction proceeds at an ex-
tremely low rate, and (b) the aluminum consumption rate is tremendous-
ly high, running into 10 times or more of the theoretically required
quantity (due to the competitive process of hydrogen liberation which
goes on simultaneously with the gallium reduction). Moreover, violent
evolution of hydrogen causes the formation of ne gallium particles
which can re-dissolve into the solution despite the presence of aluminum.
An improved process for gallium cementation from the Bayer li-
quor with metallic aluminum in the form of turnings or coarse lings
was reported (Westwood et al., 1977). The caustic mother liquor
from the precipitation of alumina is processed in an autoclave at an
elevated temperature ranging from 60 to 450 C and under a pressure
of 2100 atmospheres in the presence of an oxygen-containing atmo-
sphere. As a result the cementation of gallium was accelerated. However,
this process cannot evade the natural drawbacks caused by the usage of
metallic aluminum.
In industrial application, an alloy of aluminum and gallium, called
aluminum gallama,is used as a cementing agent to realize the cemen-
tation of gallium from the Bayer liquor. This idea was proposed by
Shalavina et al. (1976) and thereafter was adopted by many alumina
refeneries for gallium recovery. This process is more effective than the
previously described techniques. The cementation procedure is car-
ried out by a use of a liquid galliumaluminum alloy, which is easier
to agitate, thereby eliminating concentration limitations and mini-
mizing electrode passivation. The effect of the agitation intensity of
the gallama and the liquor on the gallium recovery ratio was studied
at a stirring speed from 0 to 760 rpm, with the liquor containing
0.25 g/l of gallium and 150 g/l of sodium oxide, at a temperature of
60 C. It was found that as the speed of the stirrer went up from 0 to
760 rpm , the degree of cementation rose from 16% to 99.5%. Higher
agitation speeds boosted the cathode and anode processes due to the
enhanced diffusion of ions toward the active surface of the aluminum
gallama. Thus, the cementation process must be preferably affected
with the liquor and the gallama being intensively stirred.
Temperature has a favorable effect on the gallium reduction rate. At a
higher temperature, the rate of diffusion increases so that the diffusion
component of the absorption layer diminished, providing easier access
for gallium ions to the interface. However, a higher liquor temperature
reduces the overvoltage which prevents the hydrogen evolution, there-
by promoting the competitive cementation process. But in the tempera-
ture range of Bayer liquor used for gallium extraction from 30 C to 70 C,
the former factor was found to be more important than the latter one.
Consequently, cementation must preferably be effected at an elevated
temperature.
different aluminum levels (from 0.2 to 6.0% by weight) indicated that
the effectiveness of the cementation to a large extent depended on
the aluminum content of the gallama. Aluminum gallamas were
found to be a non-uniphase system. Aluminum is partially dissolved
in the alloy, but the major part of it is present in a solid form with
gallium-plated on the surface. Therefore, in case of a low concentra-
tion of gallium ions in the catholyte and a large excess of aluminum,
the aluminium in the gallama is not fully utilized and the share of
free aluminum taking no part in the gallium ion discharge is high.
This aluminum is vigorously dissolved in an alkali liquor, liberating
plenty of hydrogen which screens the gallama surface, hampering galli-
um ion discharge. For this reason, the aluminum content in the gallama
is determined by the gallium concentration in the employed sodium
aluminate liquor. During industrial production the gallamas used for
cementation contain from 0.2% to 1.0% aluminum by weight because
the Bayer liquor generally accumulates 0.150.5 g/l of gallium.
Compared with previously mentioned cementing agents, i.e. sodium
amalgam and aluminum, aluminum gallama have the advantages of:
(a) the solubility of gallium in aluminum gallama is innite, (b) the pro-
cess is non-toxic with a low consumption of aluminum, (c) the deposited
120 Z. Zhao et al. / Hydrometallurgy 125126 (2012) 115124
gallium is stable if there is aluminum in the alloy and (d) the over poten-
tial of hydrogen on the alloy is higher than that on metallic aluminum.
Therefore, this is the most wide-spread cementation method which has
been applied in many alumina reneries. Abisheva and Zagorodnyaya
(2002) reported that gallium production in Kazakhstan, e.g. Pavlodar Alu-
mina Plant, is mainly from Bayer caustic solutions containing relatively
high gallium concentrations from 0.2 g/l to 0.5 g/l gallium. The cementa-
tion process is based on the adoption of aluminum gallama. The impuri-
ties in the aluminate solutions, such as soda, are crystallized and
removed from the solutions prior to cementation. The feedstock con-
taining sodium aluminate solution from 0.26% gallium is stirred at
760 rpm at a temperature of around 60 C with the liquid aluminum-
gallium alloy to increase the degree of cementation resulting in a recovery
of Ga up to 99.5%.
The cementation method permits extracting gallium directly from the
sodium aluminate liquor of high- and low-gallium concentration from
0.1 g/l to 1.0 g/l. It has many positive features including an increased
product purity of the gallium and a relatively high gallium recovery of
5080%, effective gallium extraction, and improved economy of eco-
friendly gallium production. The main disadvantage of this method is its
strict requirement for the extremely high purity of the solution, especially
for very low vanadium concentration. The cementation speed of vanadi-
um ions is higher than gallium ions, leading to the rapid decomposition
of galliumaluminum alloy and the remarkable decrease of gallium re-
covery. It has been proved by industrial practices that the V2O5 concentra-
tion in the solution should be kept lower than 0.22 g/l. The purity of the
used alloy also has an inuence on the cementation efciency. For in-
stance, if the iron content in the alloy is high, it will cause a decrease of
the gallium recovery and a increase of the residue quantity. Another
drawback is the stock of a large quantity of metallic gallium, which is
quite valuable, in the process.
2.3. Solvent extraction
The earliest applications of gallium solvent extraction were in a
chloride system and it has long been recognized that gallium is read-
ily extracted from strongly acidic chloride solutions (Mihaylov and
Distin, 1992). Swift (1924) showed that gallium can be loaded selec-
tively from 6 M HCl into diethyl ether over virtually any probably co-
existing elements, except germanium and iron (Fe(III)). In the 1940s
the solvent extraction of gallium was rstly introduced to commercial
operations during the recovery of germanium and gallium from the
ue dust (Powell, 1954; Powell et al., 1951). The solvent extraction
for gallium recovery from Bayer liquor was rst introduced in 1967
(Bhat and Sundararajan, 1967), where Bayer liquor was treated by the
fractional precipitation similar to the above-mentioned lime method
for a preliminary separation of gallium from aluminum. The precipitate
containing about 0.6% Ga2O3 was dissolved in hydrochloric acid having
3 M free acid. From this solution gallium was extracted with 20% TBP
(tributyl phosphate) and then recovered by water stripping, and a
total gallium recovery of 90% was obtained. In this process gallium sol-
vent extraction still takes place in the chloride system, and it is adopted
for a concentration purpose rather than a direct extraction of gallium
from Bayer liquor. It has the same drawback as the lime method, for in-
stance, the destruction of the alumina liquor. A process for recovering
gallium from Bayer liquor by means of direct liquid/liquid extraction is
known from a French Patent (Heigorsky and Leveque, 1976; Helgorsky
and Leveque, 1974). In this process Kelex 100, 8-hydroxyquinoline
(oxin, or oxime), substituted with a long alkyl chain (e.g. 7-(4-
ethyl-1-methyloctyl), was investigated and patented for gallium extrac-
tion. Kelex 100 has been proven as the most suitable and generally
accepted commercially available extractant exclusively suitable for galli-
um recovery from Bayer liquor, compared to other extractants such as
acetylacetone (Breteque and Beerli, 1975).
During the contact of Kelex 100 with Bayer liquor, gallium or alu-
minum is extracted through a cation exchange mechanism in which
hydroxyl ions are liberated as shown in the following reaction (Sato
and Oishi, 1986; Sato and Sato, 1991):

MeOH4 3HRorg MeR3;org OH 3H2 O 12
where HRorg represents Kelex 100. After extraction, the metal cation
replaces hydrogen ion in the organic phase. Simultaneously, sodium
in the Bayer liquor is also extracted into the solvent:

Na OH HRorg NaRorg H2 O 13
In a typical test, a solvent consists of 8.5% of Kelex 100, in combination
with 10.0% of n-decanol and 81.5% of kerosene as a modier and diluent,
respectively. When this organic phase is contacted with a Bayer liquor
containing 270 mg/l of gallium, about 80% of the gallium can be extracted
after about 3 h at 28 C. Meanwhile about 3.0% of aluminum and 0.6% of
sodium in the liquor are co-extracted. The production of a high purity gal-
lium strip solution is promoted by selectively stripping sodium and alu-
minum before gallium. Several acid stripping systems were investigated,
and the best condition for co-extraction of aluminum and sodium is at
6 M HCl leaving only gallium in the organic phase. This is because, unlike
Al, Ga can be found in large chloro-complex species (e.g. RH2+GaCl4) if
the HCl concentration is higher than 2 M, which may be trapped by
Kelex 100 inside the organic phase. On the contrary, aluminum is gener-
ally incapable of forming higher chloro-complexes. Subsequently, gallium
can be stripped with 2 M HCl. This treatment avoids gallium loss into the
primary strip solution, and gives the lowest impurity levels in the second-
ary strip solution.
According to the conclusions drawn from thermodynamic and kinetic
analyses by several researchers who have studied the extraction proce-
dure (Pesic and Zhou, 1988; Puvvada, 1999; Sato and Oishi, 1986), the
general extraction rate was reported to be very slow. The reaction rate
of metal extraction from the Me(OH)4 gallate or aluminate ions can be
expressed by a three-step mechanism (Zhou and Pesic, 1989):
k1
Na MeOH4 NaMeOH3 OH 14
k1
k2
NaMeOH3 HRorg Na MeROH2;org H2 O 15
MeROH2;org 2HRorg MeR3;org 2H2 O 16
Here the forward and reverse rate constants of the transformation of
the gallate ions are expressed with k1 and k 1, respectively, whereas k2
is the rate constant of the rst chelation step of the extraction process.
The third reaction expressing the completion of chelation is considered
kinetically fast enough to reach the equilibrium.
At higher concentration of the reagent in the organic phase, and
considering the NaMe(OH)3+ extractable species in a steady state,
the rate of Ga extraction can be inuenced by the factors in the fol-
lowing equation (Zhou and Pesic, 1989):
d K 0 k1 k2 cNa cMeOH4  cHQ
MeQ 3  17
dt k1 cOH
where K' represents the total equilibrium constant of reactions (14)
and (15). This equation indicates a less obvious effect of NaOH con-
centration because the Na + and OH ions have opposite effects. Nev-
ertheless, the experiments have shown that the NaOH concentration
signicantly enhances the extraction rate (Sato and Oishi, 1986).
This may be interpreted in terms of structural transformations of
the hydrated ions (Kekesi, 2007). The main ions Na +, OH , and the
hydroxo-complex A1(OH)4 and Ga(OH)4 species are present in var-
ious hydrated forms. The characteristic formulas are: [Na4H2O] +,
[OH4H2O] and [A1(OH)4H 2O] (Zambo, 1986). A special feature
of the aluminate complex is that two molecules of water are stronger
 Z. Zhao et al. / Hydrometallurgy 125126 (2012) 115124
bound to the ionic structure. Transferring aluminum from the aqueous
to the organic phase may be hindered by the relatively large hydrate
sphere and possible association of ions in the aqueous solution. As the
strongly hydrated hydroxo-complex aluminate ion can hardly lose its
voluminous hydration sphere, it is not preferred to be bound by the
chelating functional group of the extractant. However, increasing the
NaOH concentration may promote the dehydration of the aluminate
species, thereby enhancing the extracting reaction. The hydration of
the hydroxo-gallate species is similar but observed less extensive
compared to aluminum.
It has been suggested that the slow rate of extraction was attributed
to the slow interfacial formation of intermediate activated species such
as Na+Ga(OH)3OH- (Eq. (14)) at below 1 M total sodium, or Na22+
Ga(OH)3 at high sodium levels, where gallium extraction is extremely
slow. Sato and Oishi (1986) have also presumed that the rate limiting
step lies in the organic and aqueous solution interface and can be
expressed as the rst order rate equation given in Eq. (18):
Gaaq;i
ln kobs  t min 18
Gaaq;t
where [Ga]aq, i is the initial concentration of gallium in the aqueous
phase, [Ga]aq, t is the concentration of gallium at time t (min), kobs is
the observed rate constant.
As demonstrated by Pesic and Zhou (1988) using synthetic and
real Bayer solutions, recovery rates also depend strongly on the
choice of diluent and modier. Kerosene is the conventional diluent,
but other possible diluents such as Kermac 470B, Aromatic 150,
Escaid 200 and cyclohexane have shown to improve the extraction ki-
netics in synthetic solutions (Pesic and Zhou, 1988; Zhou and Pesic,
1989). Kerosene has been used successfully in tests with industrial
solutions (Borges and Masson, 1994). Ketones were superior to alco-
hols or TBP as modiers. However, without decanol, problems with a
third phase formation persisted during the acid stripping. Pesic and
Zhou (1989) also studied the effect of ultrasound on the kinetics of
gallium extraction using Kelex 100 and reported 15 times improve-
ment both in synthetic and real solutions. The increase was ascribed
to the production of a large interfacial area and an increased circula-
tion within the droplets. However, the nal recoveries using ultra-
sound were found to be not more than 50% for real liquors.
Another method for increasing the reaction rate is based on delib-
erate creation of a water-in-oil microemulsion in the organic phase
(Dantas et al., 2002; Mihaylov and Distin, 1992; Puvvada, 1999;
Puvvada et al., 1996). Fourre and Bauer (1983) have shown that a
microemulsion was produced by the addition of a long chain alcohol
such as butanol and the sodium salt of a long chain carboxylic acid
such as octanoate to the organic phase containing Kelex 100. These
additives, acting as surfactants, are surface active compounds which
consist of two functional parts, namely, a hydrophilic part, which is
the water soluble polar part, and the lipophilic part, which is the oil
soluble non-polar part of the molecule. When a surfactant is added
to a mixture of oil and water, a thin lm of the surfactant molecules
is adsorbed at the oilwater interface causing an emulsion, with the
lipophilic part submerged in oil and the hydrophilic part in water.
Factors contributing to increased recovery rates may include a de-
crease in the interfacial tension or interfacial energy of the interface
caused by adsorbed surfactants. Loading rates up to 20 times faster
than obtained by conventional means were reported. Microemulsion
formation and an enhanced recovery from Bayer solution have also
been demonstrated using Kelex 100, dodecanol and Versatic 911 in
kerosene (Bauer and Cote, 1988).
Puvvada et al. (1996), Puvvada (1999), Patcha and Puvvada (2008)
have compared the effect of different surfactants, and their dosages
on the kinetics and recovery of gallium from Bayer liquor in Kelex
100-isodecanolkerosene system. The addition of octylamine to the
organic phase was found to reduce the rate of gallium extraction as
121
well as its recovery. It may be attributed to the masking of Kelex 100
by the hydrolyzed cation of octylamine (NH3+). Additions of petroleum
sulphonate up to 0.5 vol.% of organic phase has increased the rate of
gallium extraction by reducing the equilibrium time to 45 min along
with a gallium recovery of 80%. The addition of Versatic 10 acid was
found to be benecial both for the kinetics and recovery. At 2.5 vol.%
Versatic 10, a gallium recovery of 98% was obtained in 15 min. Minor
deviations in the rst order kinetic plots were observed for octylamine
and petroleum sulphonate additions, however, in the case of Versatic 10
the rst order kinetics were obeyed, indicating that the mass transfer
mechanism is directly related to the interfacial area and to the
interfacial chemistry in the presence of surfactants. Studies conducted
by Borges and Masson (1994) on the solvent extraction of gallium from
a weak Brazilian Bayer process liquor containing 110 mg/l Ga, 1625 g/l
Al2O3, and 108120 g/l of Na2O using 10.0% Kelex 100 (5.0% Versatic 10,
8.0% n-decanol and 77.0% kerosene) showed a gallium recovery of 90%
in 2 min. Through the incorporation of surfactants, such as Versatic acid,
into the organic phase forming microemulsion the problem associated
with the slow kinetics of gallium extraction can be solved. However, the
use of organic acids in contact with highly alkaline Bayer solutions ex-
poses the problems of increased aqueous solubility and substantial organ-
ic losses which, in turn, would lead to changes in the composition of the
mixture during continuous operation.
Attempts to nd a reagent which loads gallium from Bayer solu-
tion both more rapidly and with better selectivity than Kelex 100
have been unsuccessful. The extraction of gallium with various
bidentate ligands such as -diketones, 4-benzoylpyrazol-5-ones,
N-benzoylhydroxylamines and 8-quinolinols, as well as some analo-
gous thio-derivatives in the pH region of 112 in the presence of tar-
trate has been investigated (Uhlemann et al., 1981). The results
showed that for the extraction of gallium from highly alkaline solutions,
only 7-alkyl-8-quinolinols are suitable. Bauer and Pescher-Cluzeau have
focused on changing the substituent position of the alkyl group on the
8-quinoline structure and various synthesized 5-substituted-8 hydro-
xyquinolines to study the kinetics of gallium extraction from 3.5 M
NaOH solutions. They reported that the rate of the phase transfer
was the rst order with respect to gallium and extractant concentra-
tions, and found to be slower than that of Kelex 100 (Bauer and
Pescher-Cluzeau, 1987). The reason was attributed to the less inter-
facial concentration of the synthesized extractants compared to that
of Kelex 100.
Fig. 4 shows a typical owsheet for the solvent extraction method
patented by Patcha and Puvvada (2008). After multistage countercur-
rent extraction, sodium aluminate solution returns to alumina pro-
duction process, while the gallium loaded organic phase is washed
and stripped for further processing. The unloaded organic phase can
be reused after washing to remove the residual acid. Afterwards the
stripped gallium-containing liquor is subjected to stage-two extrac-
tion by TBP or Aliquat 336 (tri capryl methyl-ammonium chloride).
This stage of extraction is employed to reduce the consumption of
acid and alkali, and to make further purication. After stage two strip-
ping gallium-enriched solution is obtained. Finally, the solution is
electrolyzed to produce gallium, preceded by precipitation, ltration
and purication with alkali.
Solvent extraction is an efcient approach for gallium recovery
from Bayer liquor. It has the advantages of a simple owsheet and a
high gallium recovery ratio. In addition, it does not destruct the com-
position of the circulating solution, thus has no inuence on alumina
production in the primary circuit. However, the application of solvent
extraction in large scale industrial practice for gallium recovery has
not been reported. This is probably due to the slow extraction kinet-
ics, the expensive and the large consumption of extractant caused
by degradation and dissolution during prolonged use with the high
basic medium, and the possibility of the contamination of the circu-
lating liquor by dissolved extractant thereby affecting the normal
production process (e.g. precipitation).
122 Z. Zhao et al. / Hydrometallurgy 125126 (2012) 115124
2.4. Ion exchange
The relatively low concentration of gallium in Bayer liquor suggests
that an ion exchange process would be superior to other methods in
terms of energy consumption and reagent losses. The application of ion
exchange for gallium separation was initially reported in a chloride sys-
tem just like solvent extraction. In the process proposed by Nagumo and
Murakoshi (1964) for purifying crude aluminum hydroxide obtained by
alkali decomposition and simultaneously recovering gallium, a solution
obtained by re-dissolving aluminum hydroxide with hydrochloric acid
was subjected to anion exchange with resin to separate gallium from
aluminum. The obtained extract was treated with further purication
to prepare gallium concentrate. By using Amberlite IRA-400, a quaterna-
ry ammonium type of anionic exchange resin, almost 100% of the galli-
um in the solution was extracted. The rst process for a direct gallium
extraction from highly alkaline Bayer liquor employing ion exchange
was patented by Kataoka et al. (1984). They discovered that some
chelating resins having a combination of one _NOH group and another
active group, such as \NH2, \OH, \SH or _NH, exhibit extracting
properties for gallium. By using vinylamidoxime polymer, which was
synthetized by the reaction of polyacrylonitrile ber, hydroxylamine hy-
drochloride and aqueous sodium hydroxide solution, as resin to contact
with Bayer liquor containing 189 mg/l of Ga, 80 g/l of Al2O3 and 80 g/l of
Na2O for 1 h at an ambient temperature, the gallium extraction ratio can
reach 96% while that of aluminum was only 0.1%. Comparisons among
vinylamidoxime polymer resins, Duolite A-161 (a strongly basic ion
exchange resin), Sumichelate Q-10 (a dithiocarbamic acid type chelate
resin), and 10% Kelex 100 (with 10% n-decanol80% kerosene) showed
that, under the above-mentioned conditions, Kelex 100/n-decanol/
kerosene can extract approximately 25% of gallium and 2% of aluminum,
while the other two resins loaded only about 1% gallium. Although the
developed resin exhibited higher gallium extraction rate and selectivity
for gallium over aluminum than Kelex 100 system, it did not attract
enough attention at that time due to the fragility of the amide-oxime
groupings and the degradation of the resin during a cyclic use. During
that period, research works still mainly focused on improving the extrac-
tion kinetics related to Kelex 100 system, but began to gradually intro-
duce the application of ion exchange resins. Several researchers (Cote
and Bauer, 1986; Lamerant, 1992; Yotsuyanagi and Nishiyama, 1986) in-
vestigated the gallium extraction with Kelex 100-impregnated resins
(e.g. Amberlite XAD-7 and Amberlite XAD-2), and reported that gallium
was loaded more rapidly by Kelex 100/octanol/kerosene-impregnated
resin than in the equivalent liquid system, but an addition of Versatic
911 to promote a microemulsion to the Kelex 100/octanol/kerosene
gave the highest reaction rates. With impregnated resins, the rate-
determining step was considered to be the diffusion of metal ions into
the resin pores.
Bayer liquor
stage one extraction aqueous phase
orginic phase water
washing stage two stripping
HCl stage one stripping stage two extraction
washing water
washing water aqueous phase
washing agents
preparation
Fig. 4. Flowsheet of extraction method.
It has been proven by practice that the current ion exchange
method is now accepted as the most effective method for the gallium
recovery from Bayer liquor, and has been applied in most alumina
reneries for industrial production (e.g. Henan branch of Chalco.).
Based on the original process proposed by Kataoka et al. (1984),
new resins having the basic structure of one _NOH group and anoth-
er active group have been developed for industrial application (Feng
and Li, 2006), for example, Duolite ES-346 and DHG586.
Riveros (1990) investigated the extraction of gallium from Bayer
solutions using the commercial amidoxime resin Duolite ES-346,
with the structure of RC (_NOH)NH2, where R represents the
resin matrix. Results show that Duolite ES-346 exhibited good extrac-
tive properties for gallium from Bayer liquor in terms of the loading
capacity, kinetics and selectivity. The maximum loading of about
5 g Ga/l of wet settled resin was obtained, which is about 8 times higher
than the maximum loading of 600 mg Ga/l obtained with 10% Kelex
100, 5% Versatic 911 and 10% isodecanol in hydrocarbon solvent such
as Varsol. However, the resin was found to be unstable in a strong
acid media, and this may ascribe to the degradation of the amidoxime
groups (Sahni and Reedijk, 1984; Vernon and Zin, 1981) to hydroxamic
acid (Eq. (19)), which cannot extract gallium from Bayer liquor but is
known to extract copper (Vernon and Kyfn, 1977).
RCNOHNH2 H H2 ORCONHOH NH4 19
Tests of the cyclic use indicated that the resin is sufciently stable in
dilute sulphuric acid solutions to permit a long-term operation. But the
long-term performance of the resin and the reagent consumption need
to be determined by industrial application. Another problem is the co-
extraction of vanadium (Bautista, 2003). It was found that vanadium
was extracted to a considerable extent by Duolite ES-346, and was not
readily eluted from the resin, and this fact suggested that vanadium
would build up in the resin upon recirculation and reduce the loading
of gallium. Simultaneously, this build-up of vanadium would give rise
to a serious operational problem. Possible ways were proposed to
solve these problems, such as shortening the contact time and scrub-
bing with concentrated sodium hydroxide. But all these trials would
cause the decrease of gallium recovery and other side effects.
Fig. 5 shows a typical owsheet applied in Henan branch of Chalco
for gallium production using the ion exchange method. Ion exchange
has now been generally acknowledged as the best method for recov-
ery of gallium from Bayer liquor because of its advantages such as the
compact process, high recovery rate, easy operation, and non-effect on
alumina process. It is employed by almost all the new gallium production
lines for recovering gallium from Bayer liquor. Unfortunately, the co-
extraction of vanadium and the degradation of the amidoxime groups
are still the major issues during industrial operations. Consequently,
return to alumina
production process
NaOH
neutralization and precipitation
filtration NaOH
alkali dissolution and purification
electrolysis
gallium
 Z. Zhao et al. / Hydrometallurgy 125126 (2012) 115124 123

further investigations are needed to solve these problems. Since vanadi-
um is a relatively valuable metal, the recovery of vanadium prior to galli-
um would be a good idea for the future research, thus to solve the
problem of vanadium co-extraction during gallium recovery from the
Bayer liquor.
3. Conclusions
Bayer liquor is the largest resource for gallium production. Based
on the literature information, the four major extraction methods
have been summarized and discussed: fractional precipitation, elec-
trochemical deposition, solvent extraction and ion exchange.
In the fractional precipitation method, the controlled carbonation
in stages and lime milk addition are used as a conventional approach
for gallium enrichment. One major problem is the spoiled solution
after gallium precipitation which cannot be integrated in the Bayer
circuit for further aluminum recovery. This hinders its application
for industrial production.
The electrochemical method is based on the amalgamation of gallium,
and it does not spoil the aluminate solution. However, the high potential
required for gallium deposition leads to co-deposition of impurities in the
solution such as vanadium. Because of the low solubility of gallium in
mercury, this method suffers from an excessive use of a large amount of
mercury, and special safety precautions have to be taken.
Solvent extraction of gallium from Bayer liquor have been investi-
gated with considerable efforts worldwide, focusing mainly on Kelex
100 due to its good extraction ability for gallium in strong basic solu-
tions. The slow extraction rate, the use of various expensive organic
agents, the sensitivity to many process parameters have made the
solvent extraction practically less attractive and prevented its wide-
spread industrial use.
Ion exchange has been accepted as the most efcient method and is
now widely applied to industrial practice by most alumina reneries for

spent liquor

press-filtration

float solution

adsorption

solution laoded resin

return to alumina washing refrigerator water

production process
neutralization refrigerator dilute sulfuric acid

desorption refrigerator desorbing agent

desorption solution resin

cool water
alkali neutralization washing

gallium slurry neutralization refrigerator dilute alkali

flocculant separation resin

wast liquor precipitate

dissolution alkali

galliium-bearing solution

H2O2 decomposition of flocculant

lime vanadium remove vanadiu-bearing residue

Na2S heavy metals remove heavy metals residue

purified solution

electrolysis

gallium

Fig. 5. Flowsheet of ion exchange method.

124 Z. Zhao et al. / Hydrometallurgy 125126 (2012) 115124
gallium recovery from Bayer liquor. It is more attractive because of its
compact process circuit, fast reaction kinetics and high recovery rate, ex-
cellent selectivity for extracting gallium over aluminum. Duolite ES-346
and DHG586 are generally used as industrial resins. The major unsolved
problems are the co-extraction of vanadium and the degradation of the
amidoxime, and more research and development are needed.
Given the current trends for the gallium demand in electronics in-
dustry, it is expected that research in the gallium recovery from Bayer
liquor will continue to grow. Since solvent extraction and ion exchange
have been proven as highly effective methods in the gallium recovery
rate, attentions should be paid to the increase of extraction kinetics of
Kelex 100 system, and nding solutions to the co-extraction of vanadium
and the degradation of the amidoxime groups during ion exchange.
Acknowledgements
This work was supported by the National Natural Science Founda-
tion of China (51104002).
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