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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 (e.g., eutectic alloys) with most metals in conjunction with being a
component in low-melting alloys.
Gallium is a metallic element in Group IIIA of the periodic table. It Since the 1970s gallium metal has attracted a lot of interests. Galli-
was discovered in 1875 by a French chemist Paul-mile Lecoq de um combined with elements of group 15 displayed semiconducting
Boisbaudran (Moskalyk, 2003). This soft and silvery-blue metal has properties (Chou et al., 2008; Gupta et al., 2007), such as gallium arse-
an atomic weight of 69.723, a hardness of 1.5 mohs, and a specic nide (GaAs) and gallium nitride (GaN). They are valuable compounds
gravity (i.e., density) of 5.904 and 6.905 g/cm 3 for the solid and liquid, employed in advanced semiconductors for microwave transceivers,
respectively. A solid piece of gallium will liquefy when being placed in DVD's, laser diodes in compact discs and other electronic applications
one's hand. It exhibits an unusually large liquid range due to its low (Font et al., 2007). The supply and demand of gallium-bearing products
melting point of 302.98 K and high boiling point of 2676 K. Solid gal- have gradually increased during the past decade. Hence, it is important
lium has an orthorhombic crystal structure and displays a conchoidal to nd out an effective method of extraction of gallium.
fracture similar to glass. Gallium can exist in the form of six isotopes Gallium is a very widespread trace element. Its content in the litho-
of which only two, 69Ga (60.4%) and 71Ga (39.6%), are stable. Gallium sphere is about 10 ppm. Gallium is a cryptomorphic element whose aver-
can form many substances such as bromides, chlorides, hydrides, age clarkes (geochemical density indicators) in the lithosphere are
iodides, nitrides, oxides, selenides, sulphides and tellurides. Gallium relatively high. Due to the practical inability to form its own minerals in
has the oxidation states of +1 and + 3 valences. Although the ele- natural conditions, it is considered quite rare (Poledniok, 2008). Given
ment is stable with water it reacts vigorously with halogens even at the geochemical afnity between Al and Ga, the latter occurs mainly con-
low temperatures. The element rapidly dissolves in either aquaregia centrated in bauxites and hosted by diaspore, various aluminosilicates
or concentrated sodium hydroxide in an aqueous medium. It also re- (such as clays), apatite, nepheline and frequently alunite. Ga also has a
acts with strong oxidants. The element is suited to readily form alloys 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
Corresponding author at: School of Metallurgy and Resource, Anhui University of
al., 2007). It is therefore not economical to mine any minerals for merely
Technology, Maanshan, PR China. Tel.: + 86 138 5550 5238. recovering gallium. Generally, gallium is recovered as by-product mainly
E-mail address: zhaozhuo1018@163.com (Z. Zhao). 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 for Al. Generally, this precipitate contains 0.10.2% of gallium. Inevita-
rstly proposed by Aluminum Company of America (Alcoa) (Frary bly, impurities such as SiO2 and Fe2O3 still remain in the precipitate.
and Oakmont, 1952). In 1957, a gallium recovery process, known as For aluminum and gallium separation by introducing lime milk,
lime method, was developed and applied to produce 2 tons of galli- major reactions are as follows:
um by Shandong alumina renery (China). Actually, the lime method
was developed based on Sintering Process which was employed by NaAlGaOOHHCO3 s H2 O NaHCO3 AlGaOH3 s 1
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 2NaHCO3 CaOH2 Na2 CO3 CaCO3 s 2H2 O 2
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 2GaOH3 s Na2 CO3 CaOH2 2NaGaOH4 CaCO3 s 3
precipitate. This precipitate is then dissolved by using lime milk for Dawsonite is decomposed to Al(OH)3, Ga(OH)3 and CaCO3, of which
separating gallium from aluminum. Finally gallium is recovered Ga(OH)3 dissolves in Na2CO3 solution, while almost all of Al(OH)3 still
from the NaGa(OH)4NaAl(OH)4 solution by a second carbonation remains in precipitate. However, with the increase of lime milk dosage,
precipitation and the gallium concentrate is re-dissolved with NaOH the Na2CO3 in solution will be causticized in Eq. (4):
solution for gallium electrowinning after purication. Fig. 1 shows
the typical owsheet of the lime method. Na2 CO3 CaOH2 2NaOH CaCO3 4
After normal precipitation, the sodium aluminate solution (known
as spent liquor containing 0.030.05 g/l Ga) is subjected to the 1st Both Al(OH)3 and Ga(OH)3 will dissolve into the formed NaOH solu-
total carbonation precipitation to precipitate gallium, resulting in a tion, resulting in poor separation of aluminum and gallium, as shown in
gallium-enriched residue. This procedure should be carried out at Eq. (5):
low temperature (~80 C), until that the NaHCO3 concentration in
AlGaOH3 NaOH NaAlGaOH4  5
the liquor reaches about 60 g/l. The precipitation ratio of gallium
can reach up to 90%, but gallium cannot be completely precipitated In order to ensure a complete AlGa separation with minimal gallium
due to the high solubility of gallium in Na2CO3\NaHCO3 solution. loss, lime milk should be added in two steps. For the rst step, the objec-
The solution should be cooled gradually with continuous agitation tive is to causticize Na2CO3 singly, making gallium and aluminum dis-
during precipitation to reduce the gallium loss. solved. The operation conditions of this process include: lime dosage
The precipitate obtained by 1st total carbonation precipitation with CaO/CO2 =1/1 (molar ratio), liquid solid ratio 3, temperature
mainly consists of Al(OH)3 and dawsonite (Na2OAl2O32CO2nH2O). 9095 C, and treatment time 1 h. As a result, about 3040% of aluminum
Gallium is present in the dawsonite due to isomorphic substitution and 85% of gallium dissolve into solution. The purpose of the second step
Z. Zhao et al. / Hydrometallurgy 125126 (2012) 115124 117

is to precipitate most of aluminum as 3CaOAl2O36H2O. Simultaneously Bayer liquor


gallium remains in solution because gallium concentration is lower than
CO2 selective carbonation Al(OH)3
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 liquor
increase of gallium loss.
After the AlGa separation the obtained gallium-bearing solution CO2 total carbonation
is then treated by the 2nd total carbonation precipitation, to make
residue
further enrichment of gallium, which is benecial to subsequent elec-
trolysis process. In this step, the gallium precipitation ratio is more than
NaAl(OH)4 solution dissolution
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 solution
as lead and zinc, ensuring a high-quality electrolyte. After purication,
the solution contains 210 g/l of gallium. Optimum conditions for elec- purification
trolysis process include: electric current density 400600 A/m2, tempera-
ture 6070 C and Na2O concentration 140160 g/l. The materials for purified solution
cathode and anode are stainless steel and nickel, respectively. During
electrolysis, gallium deposits on the cathode, accompanied by hydrogen electrolysis
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- gallium
cation with hydrochloric acid at higher temperature to leach out other
impurities, gallium with 99.99% of purity can be produced. Fig. 2. Flowsheet of carbonation method.
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 concentration. It has been discovered that in strong basic solution alumi-
aluminum and gallium with Ca(OH)2. As a result, the aluminum in the num hydroxide precipitates at a pH value of 10.6 while gallium hydroxide
circulated liquor was nally transformed to 3CaOAl2O36H2O. Generally, at 9.49.7 (Xu and Xu, 2002). When CO2 is blown slowly through Bayer
the Al2O3/Ga mass ratio in the cycled liquor is about 450, therefore 7 tons liquor, it will cause a gradual decrease of the solution pH due to the reac-
of 3CaOAl2O36H2O will be generated when 1 kg gallium is produced tion between CO2 and NaOH (Eqs. (6) and (7)). When the solution pH
(calculated based on gallium recovery 50%). The treatment for the large drops to 10.6 aluminum hydroxide begins to precipitate out according
quantities of 3CaOAl2O36H2O residues is one of the key problems for to Eq. (8). The NaOH generated by Eq. (8) is continuously neutralized
lime method. Furthermore, during the rst step of total carbonation the by CO2 keeping the solution pH stable at about 10.6. Consequently, alumi-
composition of circulating liquor is considerably changed to contain num hydroxide deposits little by little while leaving gallium un-
about 60 g/l of NaHCO3. This spoiled solution cannot be reintroduced precipitated.
into the production cycle without further treatment, which interferes
with the normal sequence of the operations during the production of CO2 2NaOH Na2 CO3 H2 O 6
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 CO2 Na2 CO3 H2 O 2NaHCO3 7
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
NaAlOH4 AlOH3 NaOH 8
produce CO2 for carbonation precipitation procedure. To summarize, the
lime method was originally developed for Sintering Process, which was After primary AlGa separation, the solution is treated by total
employed by Shandong alumina renery at that time. However, Sintering carbonation precipitation to transform all the gallium into an alumi-
Process for alumina production has almost been phased out due to its num hydroxide richer in gallium. The enriched material is selectively
high energy consumption. Therefore, lime method has also been phased dissolved in appropriate amounts of sodium aluminate solution (k,
out in practice nowadays. Since the 1990s Shandong alumina renery i.e. the molar ratio between Na2Ok and Al2O3 in solution, 2.53.0).
has changed its gallium recovery process to ion exchange which is In this step, the volumes of sodium aluminate solution are carefully
much more efcient. controlled to dissolve gallium singly while leaving most of aluminum
undissolved in the solid. A purication procedure is used to remove the
2.1.2. Carbonation method impurities such as organics and heavy metals. An electrolytic technique is
The rst substance used for AlGa separation to extract gallium applied to the resulting solution of sodium gallate and sodium aluminate
from Bayer liquor is CO2, which was discovered and patented in to produce pure gallium (Font et al., 2007; Moskalyk, 2003).
1947 by Pechiney Compagnie of France (Beja, 1947). However, the This method is an environment-friendly process. Compared with
patent only proposed to prepare a mixture of alumina and gallium lime method, the process is shortened by introducing one total car-
oxide, a further treatment for pure gallium production was not men- bonation precipitation. The liquor from the total carbonation precipi-
tioned. Based on the patent, carbonation method for metallic gallium tation step can be recycled to partially replace CO2 in the slow
recovery was developed and subsequently employed by many alumi- carbonation precipitation. The key issues of optimization of gallium
na reneries. recovery and alumina production have basically been solved. The
Fig. 2 illustrates a typical carbonation method. Upon treating the sodi- main problem of this method is the proper treatment of large quanti-
um aluminate solution containing gallium with CO2 slowly (i.e. selective ties of aluminum hydroxide with poor quality generated by the slow
carbonation precipitation) in the presence of aluminum hydroxide carbonation precipitation. According to calculation, producing 1 kg
seeds, about 90% aluminum hydroxide rst precipitates out; meanwhile gallium generates about 1.5 tons of aluminum hydroxide with poor
gallium remains unchanged resulting in increasing the liquor's gallium 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- at the cathode. The anode can be made of nickel, which is particularly
itation steps, the process is labor intensive. This method had been advantageous because of its low oxygen-evolved overvoltage.
widely used in 1970s by many alumina reneries worldwide, such Vanadium, chromium and iron contained in electrolyte are quite
as Pechiney Compagnie (France), Ajka Timfoldgyar Alumina Co. Ltd. harmful for the electrolysis. After 4 or 5 h duration of the electrolysis,
(Hungary) and Guizhou alumina renery (China). However, with all these elements deposit at the cathode. Furthermore, the increase
the continuous development of the technologies these alumina ren- of the vanadium concentration leads to a remarkable decrease of
eries have changed their gallium recovery method to more effective the hydrogen overvoltage. Purication is needed before the electroly-
methods. 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
2.2. Electrochemical methods 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
2.2.1. Mercury cathode electrolysis cathodic potential of 1.92.2 V, a current density of 45 A/m2, a tempera-
Mercury cathode electrolysis was discovered by Bereteque (1955). ture of 4550 C, and a duration of 1824 h.
It employs liquid mercury as the cathode thereby allowing the possi- The second step is extracting the gallium in the mercury with a
ble precipitation of gallium during the electrolysis process. A typical content of 0.31% by using a caustic alkali solution, for instance, the
process known as Alusuisse process is shown in Fig. 3. caustic soda solution. The extraction is favored by a temperature in-
Theoretically, gallium cannot deposit on cathode when gallium- crease. At room temperature the attack is very slow. In industrial
containing aqueous solution is electrolyzed because gallium belongs to practice, this step is carried out at a temperature of higher than
more electronegativity metal than hydrogen with a standard electrode 100 C with a strong stirring. If the gallium content in the mercury
potential of 0.521 V. Fortunately, the hydrogen overvoltage at mercury is very low, the little amount of sodium which has deposited at the
is very high, and additionally the deposition potential of gallium can be cathode may be sufcient to dissolve the gallium after having reacted
reduced by the formation of amalgam between mercury and deposited with the water. It is advantageous to extract the gallium in a vessel
gallium. Consequently, gallium ions can discharge at mercury cathode made from stainless steel. The catalysis by stainless steel takes place
to generate metallic gallium, even if the gallium concentration is low in at the wall of the vessel and the stainless steel is not corroded. Ac-
Bayer liquor. cordingly, the stainless steel tank is adopted for the extraction in
Generally, this approach consists mainly of a sequence of three practice. At the end a sodium gallate (NaGa(OH)4) solution con-
procedures. The rst step is electrolyzing the sodium aluminate solu- taining 20 g/l of gallium is obtained. The separated mercury is reused
tion with a cathode formed by stirred liquid mercury and an anode for electrolysis, but it needs to be puried regularly to remove iron
made from a metal which is insoluble under the conditions of the and other accumulated impurities.
electrolysis. As a result the gallium is deposited in the metallic state The third procedure is electrolyzing the alkali gallate solution to recov-
at the cathode. er metallic gallium in the free state according to the known process which
A low circulation of the mercury of the cathode will not make the has been used in the above-mentioned lime or carbonation method. The
process effective. It needs a rather strong stirring, which acts chiey electrolyte after electrolysis can be reused to extract gallium from mercu-
on the surface of the mercury but without rupturing the continuity ry, but it needs purication when the impurities accumulate to a certain
of the surface. In other words, it must be avoided to pulverize the level to apparently affect the electrolysis, or alternatively it can be sent
mercury with a formation of droplets and to create a gyratory motion back to the alumina production system.
causing an interruption in continuity at the surface of the cathode. If Compared with the fractional precipitation methods, this method has
the stirring is not sufciently strong, the objectives of the process less inuence on normal alumina production. However, it is inconvenient
are not reached. The variation of the number of revolutions of the stir- and expensive because of the necessity of employing considerable
rer from the single to the double or inversely may cause a variation of amount of mercury due to the low solubility of gallium in mercury. It
the yield from one to ten or inversely. Without the stirring, the gallium has been discovered that gallium has a solubility of 1.3% in mercury at
deposit is insignicant. In Alusuisse process, an electrolytic cell with a the normal temperatures (Miyake, 1969). When 2000 tons of ores con-
rotary mercury cathode is adopted to guarantee moderate stirring. taining 0.002% of gallium is treated in a day, it is calculated that 640 m2
This apparatus can also signicantly reduce the mercury consumption of mercury cathode surface is required in the case of the rst electrolysis.

spent liquor
liquor new mercury
filtration mercury cathode electrolysis

gallium amalgam pure mercury


solution vanadium
residue NaOH
decomposition mercury purification
return to alumina solution
production process NaGa(OH)4 solution

Na2S/H2S purification

filtration sulfide residue

purified NaGa(OH) 4 solution

secondary electrolysis

gallium

Fig. 3. Flowsheet of mercury cathode electrolysis method.


Z. Zhao et al. / Hydrometallurgy 125126 (2012) 115124 119

Thus, a rather large amount of mercury must be kept in circulation to with aluminum has two disadvantageous features prohibitive to the
isolate relatively very small quantities of gallium or to react such practical application of the method: (a) the reaction proceeds at an ex-
small quantities of gallium with sodium. Particularly, there are many tremely low rate, and (b) the aluminum consumption rate is tremendous-
disadvantages including the long duration of the electrolysis, the dif- ly high, running into 10 times or more of the theoretically required
culty in precipitation and agitation, the inevitable co-precipitation of quantity (due to the competitive process of hydrogen liberation which
impurities, the additional generation of sodium amalgam, and the goes on simultaneously with the gallium reduction). Moreover, violent
circulatory pumping of large quantities of caustic soda and sodium- evolution of hydrogen causes the formation of ne gallium particles
and-gallium-containing mercury. The fatal drawback of this method which can re-dissolve into the solution despite the presence of aluminum.
is the use of high toxicity of mercury, and it has been prohibited for An improved process for gallium cementation from the Bayer li-
use in most countries. Alusuisse has once shut down 2/3 of its gallium quor with metallic aluminum in the form of turnings or coarse lings
extraction facilities. Sumitomo Chemical cancelled the contract with was reported (Westwood et al., 1977). The caustic mother liquor
Alusuisse for the joint venture for a gallium recovery line in 1978 (L, from the precipitation of alumina is processed in an autoclave at an
2002). So far only in the Czech Republic (Ziar Aluminum Works), elevated temperature ranging from 60 to 450 C and under a pressure
Germany and Hungary (MAL Hungarian Aluminum Inc.) this technique of 2100 atmospheres in the presence of an oxygen-containing atmo-
is still active in production (Moskalyk, 2003). sphere. As a result the cementation of gallium was accelerated. However,
this process cannot evade the natural drawbacks caused by the usage of
2.2.2. Cementation metallic aluminum.
The development of the cementation method has gone through sever- In industrial application, an alloy of aluminum and gallium, called
al stages. Initially, in order to cope with the problem of a low current ef- aluminum gallama,is used as a cementing agent to realize the cemen-
ciency of mercury cathode electrolysis, the sodium amalgam obtained by tation of gallium from the Bayer liquor. This idea was proposed by
electrolysis in a sodium chloride solution using mercury as a cathode Shalavina et al. (1976) and thereafter was adopted by many alumina
(Yamada et al., 1982) was used to cement gallium from the Bayer liquor refeneries for gallium recovery. This process is more effective than the
instead of using mercury electrolysis to form gallium amalgam. The previously described techniques. The cementation procedure is car-
other two subsequent steps, i.e. the extraction of gallium from mercury ried out by a use of a liquid galliumaluminum alloy, which is easier
and the second electrolysis to produce metallic gallium, remained to agitate, thereby eliminating concentration limitations and mini-
unchanged. This is the well-known VAW/INGAL process, which was orig- mizing electrode passivation. The effect of the agitation intensity of
inally applied in Vereingte Aluminum-Werke Aktiengesellschaft (VAW) the gallama and the liquor on the gallium recovery ratio was studied
and INGAL Corporation in Germany. The cementation of gallium with so- at a stirring speed from 0 to 760 rpm, with the liquor containing
dium amalgam is favored by the high gallium concentration in the Bayer 0.25 g/l of gallium and 150 g/l of sodium oxide, at a temperature of
liquor, high sodium amalgam concentration, long contact time and fewer 60 C. It was found that as the speed of the stirrer went up from 0 to
impurities (Varadharaj and Rao, 1986). Compared with mercury cathode 760 rpm , the degree of cementation rose from 16% to 99.5%. Higher
electrolysis, cementation with sodium amalgam is more efcient, and it agitation speeds boosted the cathode and anode processes due to the
does not need external current but deposit gallium based on the natural enhanced diffusion of ions toward the active surface of the aluminum
electrode potential difference between metals. However, it has inevitably gallama. Thus, the cementation process must be preferably affected
the same serious drawbacks as the mercury electrolysis method, such with the liquor and the gallama being intensively stirred.
as the usage and re-processing of high toxicity and large quantities of Temperature has a favorable effect on the gallium reduction rate. At a
mercury, and the probability of contamination of the sodium aluminate higher temperature, the rate of diffusion increases so that the diffusion
liquors with mercury. component of the absorption layer diminished, providing easier access
Dotzer (1965) patented a method for the cementation of gallium for gallium ions to the interface. However, a higher liquor temperature
in the Bayer liquor by an addition of nely distributed active alumi- reduces the overvoltage which prevents the hydrogen evolution, there-
num in place of sodium amalgam. The cementation of gallium from by promoting the competitive cementation process. But in the tempera-
the aluminate liquor has thermodynamic advantages because of the ture range of Bayer liquor used for gallium extraction from 30 C to 70 C,
more electronegative character of aluminum as compared to gallium, the former factor was found to be more important than the latter one.
according to the reaction Eq. (9): Consequently, cementation must preferably be effected at an elevated
temperature.
NaGaOH4 Al NaAlOH4 Ga 9 Electrochemical and structural studies of aluminum gallamas with
different aluminum levels (from 0.2 to 6.0% by weight) indicated that
As a comparison based on the standard reduction potentials of
the effectiveness of the cementation to a large extent depended on
2.35 V for Al(OH)4/Al and 1.22 V for Ga(OH)4/Ga, there is a
the aluminum content of the gallama. Aluminum gallamas were
theoretical potential difference of 1.15 V, which is approximately the
found to be a non-uniphase system. Aluminum is partially dissolved
same as attained compared to Na+/Na, when using sodium amalgam
in the alloy, but the major part of it is present in a solid form with
in accordance with the above-mentioned method. In this case, the use
gallium-plated on the surface. Therefore, in case of a low concentra-
of mercury as an intermediate medium can be avoided.
tion of gallium ions in the catholyte and a large excess of aluminum,
During cementation, the following undesirable side reactions may
the aluminium in the gallama is not fully utilized and the share of
take place:
free aluminum taking no part in the gallium ion discharge is high.
Al NaOH 3H2 O NaAlOH4 1:5H2 10 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
Ga NaOH 3H2 O NaGaOH4 1:5H2 11
aluminate liquor. During industrial production the gallamas used for
The re-dissolution of the precipitated gallium can be prevented by cementation contain from 0.2% to 1.0% aluminum by weight because
supplying sufcient aluminum in excess to the gallate. As a result, the the Bayer liquor generally accumulates 0.150.5 g/l of gallium.
reaction as expressed in Eq. (10) is adversely promoted leading to an Compared with previously mentioned cementing agents, i.e. sodium
undesired extra consumption of aluminum. This may also prohibit amalgam and aluminum, aluminum gallama have the advantages of:
gallium from cementation duo to the masking of aluminum surface (a) the solubility of gallium in aluminum gallama is innite, (b) the pro-
by hydrogen evolution. Therefore, the process of gallium cementation 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- hydroxyl ions are liberated as shown in the following reaction (Sato
tial of hydrogen on the alloy is higher than that on metallic aluminum. and Oishi, 1986; Sato and Sato, 1991):
Therefore, this is the most wide-spread cementation method which has 
been applied in many alumina reneries. Abisheva and Zagorodnyaya MeOH4 3HRorg MeR3;org OH 3H2 O 12
(2002) reported that gallium production in Kazakhstan, e.g. Pavlodar Alu-
where HRorg represents Kelex 100. After extraction, the metal cation
mina Plant, is mainly from Bayer caustic solutions containing relatively
replaces hydrogen ion in the organic phase. Simultaneously, sodium
high gallium concentrations from 0.2 g/l to 0.5 g/l gallium. The cementa-
in the Bayer liquor is also extracted into the solvent:
tion process is based on the adoption of aluminum gallama. The impuri-
ties in the aluminate solutions, such as soda, are crystallized and 
Na OH HRorg NaRorg H2 O 13
removed from the solutions prior to cementation. The feedstock con-
taining sodium aluminate solution from 0.26% gallium is stirred at In a typical test, a solvent consists of 8.5% of Kelex 100, in combination
760 rpm at a temperature of around 60 C with the liquid aluminum- with 10.0% of n-decanol and 81.5% of kerosene as a modier and diluent,
gallium alloy to increase the degree of cementation resulting in a recovery respectively. When this organic phase is contacted with a Bayer liquor
of Ga up to 99.5%. containing 270 mg/l of gallium, about 80% of the gallium can be extracted
The cementation method permits extracting gallium directly from the after about 3 h at 28 C. Meanwhile about 3.0% of aluminum and 0.6% of
sodium aluminate liquor of high- and low-gallium concentration from sodium in the liquor are co-extracted. The production of a high purity gal-
0.1 g/l to 1.0 g/l. It has many positive features including an increased lium strip solution is promoted by selectively stripping sodium and alu-
product purity of the gallium and a relatively high gallium recovery of minum before gallium. Several acid stripping systems were investigated,
5080%, effective gallium extraction, and improved economy of eco- and the best condition for co-extraction of aluminum and sodium is at
friendly gallium production. The main disadvantage of this method is its 6 M HCl leaving only gallium in the organic phase. This is because, unlike
strict requirement for the extremely high purity of the solution, especially Al, Ga can be found in large chloro-complex species (e.g. RH2+GaCl4) if
for very low vanadium concentration. The cementation speed of vanadi- the HCl concentration is higher than 2 M, which may be trapped by
um ions is higher than gallium ions, leading to the rapid decomposition Kelex 100 inside the organic phase. On the contrary, aluminum is gener-
of galliumaluminum alloy and the remarkable decrease of gallium re- ally incapable of forming higher chloro-complexes. Subsequently, gallium
covery. It has been proved by industrial practices that the V2O5 concentra- can be stripped with 2 M HCl. This treatment avoids gallium loss into the
tion in the solution should be kept lower than 0.22 g/l. The purity of the primary strip solution, and gives the lowest impurity levels in the second-
used alloy also has an inuence on the cementation efciency. For in- ary strip solution.
stance, if the iron content in the alloy is high, it will cause a decrease of According to the conclusions drawn from thermodynamic and kinetic
the gallium recovery and a increase of the residue quantity. Another analyses by several researchers who have studied the extraction proce-
drawback is the stock of a large quantity of metallic gallium, which is dure (Pesic and Zhou, 1988; Puvvada, 1999; Sato and Oishi, 1986), the
quite valuable, in the process. 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
2.3. Solvent extraction expressed by a three-step mechanism (Zhou and Pesic, 1989):

k1
The earliest applications of gallium solvent extraction were in a Na MeOH4 NaMeOH3 OH 14
chloride system and it has long been recognized that gallium is read- k1

ily extracted from strongly acidic chloride solutions (Mihaylov and


k2
Distin, 1992). Swift (1924) showed that gallium can be loaded selec- NaMeOH3 HRorg Na MeROH2;org H2 O 15
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 MeROH2;org 2HRorg MeR3;org 2H2 O 16
operations during the recovery of germanium and gallium from the
ue dust (Powell, 1954; Powell et al., 1951). The solvent extraction Here the forward and reverse rate constants of the transformation of
for gallium recovery from Bayer liquor was rst introduced in 1967 the gallate ions are expressed with k1 and k 1, respectively, whereas k2
(Bhat and Sundararajan, 1967), where Bayer liquor was treated by the is the rate constant of the rst chelation step of the extraction process.
fractional precipitation similar to the above-mentioned lime method The third reaction expressing the completion of chelation is considered
for a preliminary separation of gallium from aluminum. The precipitate kinetically fast enough to reach the equilibrium.
containing about 0.6% Ga2O3 was dissolved in hydrochloric acid having At higher concentration of the reagent in the organic phase, and
3 M free acid. From this solution gallium was extracted with 20% TBP considering the NaMe(OH)3+ extractable species in a steady state,
(tributyl phosphate) and then recovered by water stripping, and a the rate of Ga extraction can be inuenced by the factors in the fol-
total gallium recovery of 90% was obtained. In this process gallium sol- lowing equation (Zhou and Pesic, 1989):
vent extraction still takes place in the chloride system, and it is adopted
for a concentration purpose rather than a direct extraction of gallium d K 0 k1 k2 cNa cMeOH4  cHQ
MeQ 3  17
from Bayer liquor. It has the same drawback as the lime method, for in- dt k1 cOH
stance, the destruction of the alumina liquor. A process for recovering
gallium from Bayer liquor by means of direct liquid/liquid extraction is where K' represents the total equilibrium constant of reactions (14)
known from a French Patent (Heigorsky and Leveque, 1976; Helgorsky and (15). This equation indicates a less obvious effect of NaOH con-
and Leveque, 1974). In this process Kelex 100, 8-hydroxyquinoline centration because the Na + and OH ions have opposite effects. Nev-
(oxin, or oxime), substituted with a long alkyl chain (e.g. 7-(4- ertheless, the experiments have shown that the NaOH concentration
ethyl-1-methyloctyl), was investigated and patented for gallium extrac- signicantly enhances the extraction rate (Sato and Oishi, 1986).
tion. Kelex 100 has been proven as the most suitable and generally This may be interpreted in terms of structural transformations of
accepted commercially available extractant exclusively suitable for galli- the hydrated ions (Kekesi, 2007). The main ions Na +, OH , and the
um recovery from Bayer liquor, compared to other extractants such as hydroxo-complex A1(OH)4 and Ga(OH)4 species are present in var-
acetylacetone (Breteque and Beerli, 1975). ious hydrated forms. The characteristic formulas are: [Na4H2O] +,
During the contact of Kelex 100 with Bayer liquor, gallium or alu- [OH4H2O] and [A1(OH)4H 2O] (Zambo, 1986). A special feature
minum is extracted through a cation exchange mechanism in which of the aluminate complex is that two molecules of water are stronger
Z. Zhao et al. / Hydrometallurgy 125126 (2012) 115124 121

bound to the ionic structure. Transferring aluminum from the aqueous well as its recovery. It may be attributed to the masking of Kelex 100
to the organic phase may be hindered by the relatively large hydrate by the hydrolyzed cation of octylamine (NH3+). Additions of petroleum
sphere and possible association of ions in the aqueous solution. As the sulphonate up to 0.5 vol.% of organic phase has increased the rate of
strongly hydrated hydroxo-complex aluminate ion can hardly lose its gallium extraction by reducing the equilibrium time to 45 min along
voluminous hydration sphere, it is not preferred to be bound by the with a gallium recovery of 80%. The addition of Versatic 10 acid was
chelating functional group of the extractant. However, increasing the found to be benecial both for the kinetics and recovery. At 2.5 vol.%
NaOH concentration may promote the dehydration of the aluminate Versatic 10, a gallium recovery of 98% was obtained in 15 min. Minor
species, thereby enhancing the extracting reaction. The hydration of deviations in the rst order kinetic plots were observed for octylamine
the hydroxo-gallate species is similar but observed less extensive and petroleum sulphonate additions, however, in the case of Versatic 10
compared to aluminum. the rst order kinetics were obeyed, indicating that the mass transfer
It has been suggested that the slow rate of extraction was attributed mechanism is directly related to the interfacial area and to the
to the slow interfacial formation of intermediate activated species such interfacial chemistry in the presence of surfactants. Studies conducted
as Na+Ga(OH)3OH- (Eq. (14)) at below 1 M total sodium, or Na22+ by Borges and Masson (1994) on the solvent extraction of gallium from
Ga(OH)3 at high sodium levels, where gallium extraction is extremely a weak Brazilian Bayer process liquor containing 110 mg/l Ga, 1625 g/l
slow. Sato and Oishi (1986) have also presumed that the rate limiting Al2O3, and 108120 g/l of Na2O using 10.0% Kelex 100 (5.0% Versatic 10,
step lies in the organic and aqueous solution interface and can be 8.0% n-decanol and 77.0% kerosene) showed a gallium recovery of 90%
expressed as the rst order rate equation given in Eq. (18): in 2 min. Through the incorporation of surfactants, such as Versatic acid,
into the organic phase forming microemulsion the problem associated
Gaaq;i with the slow kinetics of gallium extraction can be solved. However, the
ln kobs  t min 18
Gaaq;t use of organic acids in contact with highly alkaline Bayer solutions ex-
poses the problems of increased aqueous solubility and substantial organ-
where [Ga]aq, i is the initial concentration of gallium in the aqueous ic losses which, in turn, would lead to changes in the composition of the
phase, [Ga]aq, t is the concentration of gallium at time t (min), kobs is mixture during continuous operation.
the observed rate constant. Attempts to nd a reagent which loads gallium from Bayer solu-
As demonstrated by Pesic and Zhou (1988) using synthetic and tion both more rapidly and with better selectivity than Kelex 100
real Bayer solutions, recovery rates also depend strongly on the have been unsuccessful. The extraction of gallium with various
choice of diluent and modier. Kerosene is the conventional diluent, bidentate ligands such as -diketones, 4-benzoylpyrazol-5-ones,
but other possible diluents such as Kermac 470B, Aromatic 150, N-benzoylhydroxylamines and 8-quinolinols, as well as some analo-
Escaid 200 and cyclohexane have shown to improve the extraction ki- gous thio-derivatives in the pH region of 112 in the presence of tar-
netics in synthetic solutions (Pesic and Zhou, 1988; Zhou and Pesic, trate has been investigated (Uhlemann et al., 1981). The results
1989). Kerosene has been used successfully in tests with industrial showed that for the extraction of gallium from highly alkaline solutions,
solutions (Borges and Masson, 1994). Ketones were superior to alco- only 7-alkyl-8-quinolinols are suitable. Bauer and Pescher-Cluzeau have
hols or TBP as modiers. However, without decanol, problems with a focused on changing the substituent position of the alkyl group on the
third phase formation persisted during the acid stripping. Pesic and 8-quinoline structure and various synthesized 5-substituted-8 hydro-
Zhou (1989) also studied the effect of ultrasound on the kinetics of xyquinolines to study the kinetics of gallium extraction from 3.5 M
gallium extraction using Kelex 100 and reported 15 times improve- NaOH solutions. They reported that the rate of the phase transfer
ment both in synthetic and real solutions. The increase was ascribed was the rst order with respect to gallium and extractant concentra-
to the production of a large interfacial area and an increased circula- tions, and found to be slower than that of Kelex 100 (Bauer and
tion within the droplets. However, the nal recoveries using ultra- Pescher-Cluzeau, 1987). The reason was attributed to the less inter-
sound were found to be not more than 50% for real liquors. facial concentration of the synthesized extractants compared to that
Another method for increasing the reaction rate is based on delib- of Kelex 100.
erate creation of a water-in-oil microemulsion in the organic phase Fig. 4 shows a typical owsheet for the solvent extraction method
(Dantas et al., 2002; Mihaylov and Distin, 1992; Puvvada, 1999; patented by Patcha and Puvvada (2008). After multistage countercur-
Puvvada et al., 1996). Fourre and Bauer (1983) have shown that a rent extraction, sodium aluminate solution returns to alumina pro-
microemulsion was produced by the addition of a long chain alcohol duction process, while the gallium loaded organic phase is washed
such as butanol and the sodium salt of a long chain carboxylic acid and stripped for further processing. The unloaded organic phase can
such as octanoate to the organic phase containing Kelex 100. These be reused after washing to remove the residual acid. Afterwards the
additives, acting as surfactants, are surface active compounds which stripped gallium-containing liquor is subjected to stage-two extrac-
consist of two functional parts, namely, a hydrophilic part, which is tion by TBP or Aliquat 336 (tri capryl methyl-ammonium chloride).
the water soluble polar part, and the lipophilic part, which is the oil This stage of extraction is employed to reduce the consumption of
soluble non-polar part of the molecule. When a surfactant is added acid and alkali, and to make further purication. After stage two strip-
to a mixture of oil and water, a thin lm of the surfactant molecules ping gallium-enriched solution is obtained. Finally, the solution is
is adsorbed at the oilwater interface causing an emulsion, with the electrolyzed to produce gallium, preceded by precipitation, ltration
lipophilic part submerged in oil and the hydrophilic part in water. and purication with alkali.
Factors contributing to increased recovery rates may include a de- Solvent extraction is an efcient approach for gallium recovery
crease in the interfacial tension or interfacial energy of the interface from Bayer liquor. It has the advantages of a simple owsheet and a
caused by adsorbed surfactants. Loading rates up to 20 times faster high gallium recovery ratio. In addition, it does not destruct the com-
than obtained by conventional means were reported. Microemulsion position of the circulating solution, thus has no inuence on alumina
formation and an enhanced recovery from Bayer solution have also production in the primary circuit. However, the application of solvent
been demonstrated using Kelex 100, dodecanol and Versatic 911 in extraction in large scale industrial practice for gallium recovery has
kerosene (Bauer and Cote, 1988). not been reported. This is probably due to the slow extraction kinet-
Puvvada et al. (1996), Puvvada (1999), Patcha and Puvvada (2008) ics, the expensive and the large consumption of extractant caused
have compared the effect of different surfactants, and their dosages by degradation and dissolution during prolonged use with the high
on the kinetics and recovery of gallium from Bayer liquor in Kelex basic medium, and the possibility of the contamination of the circu-
100-isodecanolkerosene system. The addition of octylamine to the lating liquor by dissolved extractant thereby affecting the normal
organic phase was found to reduce the rate of gallium extraction as production process (e.g. precipitation).
122 Z. Zhao et al. / Hydrometallurgy 125126 (2012) 115124

2.4. Ion exchange It has been proven by practice that the current ion exchange
method is now accepted as the most effective method for the gallium
The relatively low concentration of gallium in Bayer liquor suggests recovery from Bayer liquor, and has been applied in most alumina
that an ion exchange process would be superior to other methods in reneries for industrial production (e.g. Henan branch of Chalco.).
terms of energy consumption and reagent losses. The application of ion Based on the original process proposed by Kataoka et al. (1984),
exchange for gallium separation was initially reported in a chloride sys- new resins having the basic structure of one _NOH group and anoth-
tem just like solvent extraction. In the process proposed by Nagumo and er active group have been developed for industrial application (Feng
Murakoshi (1964) for purifying crude aluminum hydroxide obtained by and Li, 2006), for example, Duolite ES-346 and DHG586.
alkali decomposition and simultaneously recovering gallium, a solution Riveros (1990) investigated the extraction of gallium from Bayer
obtained by re-dissolving aluminum hydroxide with hydrochloric acid solutions using the commercial amidoxime resin Duolite ES-346,
was subjected to anion exchange with resin to separate gallium from with the structure of RC (_NOH)NH2, where R represents the
aluminum. The obtained extract was treated with further purication resin matrix. Results show that Duolite ES-346 exhibited good extrac-
to prepare gallium concentrate. By using Amberlite IRA-400, a quaterna- tive properties for gallium from Bayer liquor in terms of the loading
ry ammonium type of anionic exchange resin, almost 100% of the galli- capacity, kinetics and selectivity. The maximum loading of about
um in the solution was extracted. The rst process for a direct gallium 5 g Ga/l of wet settled resin was obtained, which is about 8 times higher
extraction from highly alkaline Bayer liquor employing ion exchange than the maximum loading of 600 mg Ga/l obtained with 10% Kelex
was patented by Kataoka et al. (1984). They discovered that some 100, 5% Versatic 911 and 10% isodecanol in hydrocarbon solvent such
chelating resins having a combination of one _NOH group and another as Varsol. However, the resin was found to be unstable in a strong
active group, such as \NH2, \OH, \SH or _NH, exhibit extracting acid media, and this may ascribe to the degradation of the amidoxime
properties for gallium. By using vinylamidoxime polymer, which was groups (Sahni and Reedijk, 1984; Vernon and Zin, 1981) to hydroxamic
synthetized by the reaction of polyacrylonitrile ber, hydroxylamine hy- acid (Eq. (19)), which cannot extract gallium from Bayer liquor but is
drochloride and aqueous sodium hydroxide solution, as resin to contact known to extract copper (Vernon and Kyfn, 1977).
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
RCNOHNH2 H H2 ORCONHOH NH4 19
reach 96% while that of aluminum was only 0.1%. Comparisons among
vinylamidoxime polymer resins, Duolite A-161 (a strongly basic ion Tests of the cyclic use indicated that the resin is sufciently stable in
exchange resin), Sumichelate Q-10 (a dithiocarbamic acid type chelate dilute sulphuric acid solutions to permit a long-term operation. But the
resin), and 10% Kelex 100 (with 10% n-decanol80% kerosene) showed long-term performance of the resin and the reagent consumption need
that, under the above-mentioned conditions, Kelex 100/n-decanol/ to be determined by industrial application. Another problem is the co-
kerosene can extract approximately 25% of gallium and 2% of aluminum, extraction of vanadium (Bautista, 2003). It was found that vanadium
while the other two resins loaded only about 1% gallium. Although the was extracted to a considerable extent by Duolite ES-346, and was not
developed resin exhibited higher gallium extraction rate and selectivity readily eluted from the resin, and this fact suggested that vanadium
for gallium over aluminum than Kelex 100 system, it did not attract would build up in the resin upon recirculation and reduce the loading
enough attention at that time due to the fragility of the amide-oxime of gallium. Simultaneously, this build-up of vanadium would give rise
groupings and the degradation of the resin during a cyclic use. During to a serious operational problem. Possible ways were proposed to
that period, research works still mainly focused on improving the extrac- solve these problems, such as shortening the contact time and scrub-
tion kinetics related to Kelex 100 system, but began to gradually intro- bing with concentrated sodium hydroxide. But all these trials would
duce the application of ion exchange resins. Several researchers (Cote cause the decrease of gallium recovery and other side effects.
and Bauer, 1986; Lamerant, 1992; Yotsuyanagi and Nishiyama, 1986) in- Fig. 5 shows a typical owsheet applied in Henan branch of Chalco
vestigated the gallium extraction with Kelex 100-impregnated resins for gallium production using the ion exchange method. Ion exchange
(e.g. Amberlite XAD-7 and Amberlite XAD-2), and reported that gallium has now been generally acknowledged as the best method for recov-
was loaded more rapidly by Kelex 100/octanol/kerosene-impregnated ery of gallium from Bayer liquor because of its advantages such as the
resin than in the equivalent liquid system, but an addition of Versatic compact process, high recovery rate, easy operation, and non-effect on
911 to promote a microemulsion to the Kelex 100/octanol/kerosene alumina process. It is employed by almost all the new gallium production
gave the highest reaction rates. With impregnated resins, the rate- lines for recovering gallium from Bayer liquor. Unfortunately, the co-
determining step was considered to be the diffusion of metal ions into extraction of vanadium and the degradation of the amidoxime groups
the resin pores. are still the major issues during industrial operations. Consequently,

Bayer liquor
return to alumina
stage one extraction aqueous phase production process
orginic phase water NaOH

washing stage two stripping neutralization and precipitation

HCl stage one stripping stage two extraction filtration NaOH

washing water alkali dissolution and purification

electrolysis
washing water aqueous phase
gallium
washing agents
preparation

Fig. 4. Flowsheet of extraction method.


Z. Zhao et al. / Hydrometallurgy 125126 (2012) 115124 123

further investigations are needed to solve these problems. Since vanadi- circuit for further aluminum recovery. This hinders its application
um is a relatively valuable metal, the recovery of vanadium prior to galli- for industrial production.
um would be a good idea for the future research, thus to solve the The electrochemical method is based on the amalgamation of gallium,
problem of vanadium co-extraction during gallium recovery from the and it does not spoil the aluminate solution. However, the high potential
Bayer liquor. 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
3. Conclusions mercury, and special safety precautions have to be taken.
Solvent extraction of gallium from Bayer liquor have been investi-
Bayer liquor is the largest resource for gallium production. Based gated with considerable efforts worldwide, focusing mainly on Kelex
on the literature information, the four major extraction methods 100 due to its good extraction ability for gallium in strong basic solu-
have been summarized and discussed: fractional precipitation, elec- tions. The slow extraction rate, the use of various expensive organic
trochemical deposition, solvent extraction and ion exchange. agents, the sensitivity to many process parameters have made the
In the fractional precipitation method, the controlled carbonation solvent extraction practically less attractive and prevented its wide-
in stages and lime milk addition are used as a conventional approach spread industrial use.
for gallium enrichment. One major problem is the spoiled solution Ion exchange has been accepted as the most efcient method and is
after gallium precipitation which cannot be integrated in the Bayer 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 Heigorsky, J., Leveque, A., 1976. Process for liquid/liquid extraction of gallium, US Patent.
Helgorsky, J., Leveque, A., 1974. Procd de rcupration du gallium de solutions trs
compact process circuit, fast reaction kinetics and high recovery rate, ex- basiques par extraction liquide/liquide, French Patent.
cellent selectivity for extracting gallium over aluminum. Duolite ES-346 Kataoka, Y., Matsuda, M., Yoshitake, H., Hirose, Y., 1984. Method for recovery of gallium,
and DHG586 are generally used as industrial resins. The major unsolved US Patent.
Kekesi, T., 2007. Gallium extraction from synthetic Bayer liquors using Kelex 100-
problems are the co-extraction of vanadium and the degradation of the kerosene, the effect of loading and stripping conditions on selectivity. Hydrometal-
amidoxime, and more research and development are needed. lurgy 88 (14), 170179.
Given the current trends for the gallium demand in electronics in- Lamerant, J.M., 1992. Process for extracting and purifying gallium from Bayer liquors,
US Patent.
dustry, it is expected that research in the gallium recovery from Bayer Lee, H.S., Nam, C.W., 1998. A study on the extraction of gallium from gallium arsenide
liquor will continue to grow. Since solvent extraction and ion exchange scrap. Hydrometallurgy 49 (12), 125133.
have been proven as highly effective methods in the gallium recovery L, L., 2002. The recovery of gallium from alumina renery. Light Met. 5, 1517.
Lu, X., Wang, L., Wang, X., Niu, X., 2008. Research progress in gallium recovery technology.
rate, attentions should be paid to the increase of extraction kinetics of
Nonferrous Met. 60, 105108.
Kelex 100 system, and nding solutions to the co-extraction of vanadium Mihaylov, I., Distin, P.A., 1992. Gallium solvent extraction in hydrometallurgy: an overview.
and the degradation of the amidoxime groups during ion exchange. Hydrometallurgy 28 (1), 1327.
Miyake, S., 1969. Method for directly electrochemically extracting gallium from circu-
lating aluminate solution in the Bayer process by eliminating impurities, US Patent.
Acknowledgements Moskalyk, R.R., 2003. Gallium: the backbone of the electronics industry. Miner. Eng. 16
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