Accepted Manuscript 

Thermodynamic analysis for the separation of tungsten and aluminium in alkaline medium using 
solvent extraction 
Chao Xiao, Li Zeng, Jianhua Wei, Liansheng Xiao, Guiqing Zhang 
PII: S0304-386X(17)30250-5 
DOI: doi: 10.1016/j.hydromet.2017.08.010 Reference: HYDROM 4632 
To appear in: Hydrometallurgy 
Received date: 29 March 2017 Revised date: 31 July 2017 Accepted date: 6 August 2017 
Please  cite  this  article  as:  Chao  Xiao,  Li  Zeng,  Jianhua  Wei,  Liansheng  Xiao,  Guiqing  Zhang  , 
Thermodynamic  analysis  for  the  separation of tungsten and aluminium in alkaline medium using 
solvent extraction, Hydrometallurgy (2017), doi: 10.1016/ j.hydromet.2017.08.010 
This  is  a  PDF  file  of  an  unedited  manuscript that has been accepted for publication. As a service 
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ACCEPTED MANUSCRIPT 
1 Thermodynamic analysis for the separation of tungsten and 
aluminium in alkaline medium using solvent extraction 
1,2 

Chao Xiao 
* 

, 
3,4 

Li Zeng 
* 

, 
3 

Jianhua Wei, 
3 

Liansheng Xiao, 
3 

Guiqing Zhang 
1. Faculty of Materials Science and Engineering, Guilin University of Technology, Guilin 541004, China 
2. Key Laboratory of Metals, Guilin 541004, 3. School of Metallurgy 4. CSIRO Mineral Resources WA, 6152, Australia. 
Abstract: The thermodynamic values of tungsten established, Guangxi Province for Clean Metallurgy and Comprehensive China. 
and Environment, Central South University, Changsha 410083, Flagship, Australian equilibrium and aluminium with the 
Minerals diagrams systems Research for of distribution W-H 
Centre, S 2 O C 7 and Conlon R of I 
China. Utilization P Street, T 

species Al-H 
2 O of Non-ferrous Waterford, Perth, 

at different pH 
equilibrium separately. The effects of the concentrations of U 
W, Al and Na 
2 

CO 
3 

in feed, at 298K were 

and the 
revealed solution decrease containing in that pH the the on pH tungsten the range 0.5 extractions mol/L to 
and 4.0-11.5 [W] 
aluminium of T 
W resulted and and 0.1 Al exist M in were mol/L the as A investigated. precipitation WO N 
[Al] 4 2 
T - Thermodynamic analysis results 
and 
Al ( OH ) - 4 
, respectively, in a 
in the pH range of 11.5-14.0. The 
of aluminium as Al(OH) 
3 

. The 
extractant with 
of quaternary ammonium D 
salt has stronger affinity with 
WO 4 2 
-

than that 
the precipitate controlling 99.2% factor achieved Key HCO- words: Al and β ( OH Al WO in 3 1.2%, at 
3 the by Tungsten; ) >9800. form - 4 pH direct . raffinate The respectively less C would This solvent 
solvent C Aluminium; than pH indicates result E extraction 11.5, higher extraction P after in T the 
causing that Thermodynamics; a than E 12-stage decrease in the of alkaline 11.5, tungsten efficient the 
counter-current the of emulsion medium. 
the extractions in separation Solvent raffinate alkaline in medium using the extractant with pH and the 
formation of Al(OH) 
3 

the solvent extraction process. By 

of tungsten and aluminium were 
extraction, resulting in a separation 
of tungsten and aluminium can be A 
extraction; Separation 
1. Introduction 
*Corresponding author at: Faculty of Materials Science and Engineering, Guilin University of Technology, Guilin 
541004, China or School of Metallurgy and Environment, Central South University, Changsha 410083, China. 
Email address: shawchao@qq.com (C.Xiao); yuanzhenxia_1104@aliyun.com (L.Zeng). 
 
ACCEPTED MANUSCRIPT 
)·4H Ammonium 
paratungstate (APT) with chemical formula of (NH 
4 

) 
10 

(H 
2 

W 
12 

O 
42 
2 

O is the 
main intermediate in the manufacture of tungsten metal and tungsten carbide. For the quality 
requirement of 0-grade APT product in Chinese National Standard GB/T 10116-2007, the content 
of aluminium is strictly limited to be less than 5 ppm (Anon, 2007). The traditional process for 
APT production is alkaline leaching (NaOH or Na 
2 

CO 
3 

) of tungsten concentrates followed by 

either ion exchange with strong base resin in alkaline media (pH ~9) or solvent extraction with 
organic tertiary amine extractant in tungsten concentrate is normally very of 0-grade APT even a certain 
amount leaching of silicon and arsenic in acid media (pH low, the final of Al 
2 

O 
3 is the concentrate APT added ~2-3). (Huang product into Since and the the could Zhang, leaching 
content still I 
1993). P meet system of T 
aluminium the With to requirement inhibit the in the the 
rapid 
growing demand for tungsten product and continuous exploitation of all the mineral resources of 
tungsten in the world, primary mineral supplies are becoming more and more insufficient to meet 
demands, resulting in increasing exploitation of secondary sources (Akcil et al., 2015; Kim et al., 
2015). Among secondary resources of tungsten, spent catalysts are regarded as the most important 
one for recycling tungsten due to not only their large amounts and metal values, but also 
environmental concerns if disposed off (Alsobaai et al., 2007; Amiri et al., 2011). However, the 
composition of the spent catalysts is very different from that of tungsten concentrates, especially 
in the aluminium content. The spent catalyst normally contains similar mass percentages of Al and 
WO 
3 

A 
N 
U 
S 
C 
R 
aluminium solutions from the of selectively significantly During aluminium purity alkaline around have 
more the is leach the suppressed 20% leach been past and than key tungsten C (Xie solutions tungsten. 
developed decade, 99% issue C et (Qin, was from E in al., some the of A P obtained, 2007; and 2002). 
spent spent APT mixed T reported. processes E Xu catalysts production catalysts Wang solution 
indicating D et M al., 2013). Therefore, from the spent for the separation Xiong et al. (2008) using ion 
exchange that the method of (NH 4 
) 
2 

CO 
3 after roasting and (2014) investigated the separation of tungsten and 
catalyst containing tungsten. 
of aluminium from studied the recovery of and a product of Na 2 
tungstate 
tungsten 
WO 
4 

with 
can be used for the separation 
and NH 
3 

·H 
2 

O was reported to 

aluminium from A 
tungstate solution by neutralisation. Although these the the processes leaching selective can of 
precipitation aluminium be used to treat was 
of 
the spent catalyst containing tungsten and aluminium, the obvious drawbacks include the release 
of large amounts of wastewater and the consumption of large amounts of chemical reagents, 
resulting in the high cost of treatment. Zhang et al. (2003; 2011; 2014a; 2014b; 2016) developed a 
novel process for tungsten hydrometallurgy based on direct solvent extraction (DSX) in alkaline 
medium. This new process has exhibited excellent adaptability for the treatment of leach solutions 
from not only high pressure leaching with Na 
2 

CO 
3 

for scheelites but also caustic soda leaching for 

 
ACCEPTED MANUSCRIPT 
wolframites. When proper operational conditions were controlled, the impurities of P, As, Si could 
almost be removed while sodium tungstate solution (Na 
2 

WO 
4 

) transformed to ammonium 
tungstate solution ((NH 
4 

) 
2 

WO 
4 

) in the DSX process. The raffinate could be returned to leaching 

step directly or after causticization with lime, resulting in the simplification of the flow sheet and 
large decrease in the release of wastewater and the consumption of reagents. This new process 
could also be used for the treatment of tungsten bearing spent catalysts (Zhao et al., 2014). 
However, in the extraction of tungsten from the caustic tungsten and aluminium, the precipitate of 
Al(OH) 
3 phase separation and leach solution of spent catalysts T 
containing 
formation of Al(OH) 
3 

even emulsion, which is very would harmful occur in to the continuous interface, I P 
resulting in slow 
operations. The 
release of 
HCO- 
3 tungsten species of 
To solve the problem, and W-H 
2 O, and the extractant, separately, precipitate species WO 4 
2 
-

. this relationship through when study thermodynamic between can aimed the be extractant, 
attributed at raffinate the establishment pH to quaternary the and pH U 
concentration decrease S 
of ammonium equilibrium C 
R in ratio the salt diagrams raffinate of due (N263), extracts 
of Al-H 
R 
4 

NHCO 
3 to to the 2 
O 
separation of tungsten and aluminium and process in the recovery of tungsten from spent 2. Na 
Thermodynamic The 2 CO 
3 thermodynamic -NaHCO 
Table 3 -H 

2 analysis 1 O Equilibrium are data listed and of P 

equilibrium in T discussion reactions Table E D 
1. 
therefore, catalysts. M 
analysis A the N successful to reactions in the and corresponding the provide theoretical guide for the 
application of the new DSX 
systems of Al-H 
2 

O, W-H 
2 

O and 
constants at 298 K. 
No. 1 
2 
WO WO A Equilibrium 4 2 4 - 2 C - + + 2 C H H E 
reaction 
Equilibrium constant 
 Reference (lgK) 
+ + = = HWO 4 - H 2 WO 4 
3.5 Baes and Mesmer, 1976 
8.1 Baes and Mesmer, 1976 
3 
7 WO 4 2 - + 8 H + = W 7 O 24 6 

- + 4 H 2 
O 65.19 Baes and Mesmer, 1976 
4 
7 WO 4 2 - + 9 H + = HW 7 O 24 5 
-+
4 H 2 
O 69.96 Cruywagen and Merwe, 1987 
5 
12 WO 4 2 - + 14 H + = HW 2 12 O 42 10 

-+
6 HO 2 
115.38 Cruywagen and Merwe, 1987 
 
ACCEPTED MANUSCRIPT 
2 6 
12 WO 4 - + 18 H + = HW 2 12 O 40 6 

-+
8 HO 2 
135.02 Rozantsev and Sazonova, 2005 
7 
H 2 
O = H + + OH - -14 Michalowski and Pietrzyk, 2006 
8 
Al 3 + + H 2 
O = AlOH 2 
+ + H + -4.97 Baes and Mesmer, 1976 
9 
Al 3 
+ + 2 H 2 O = Al ( OH ) + 2 + 2 H + -9.3 10 
Al 3 
+ + H 2 O = Al OH 3( ) 
+
H + -15 Baes Baes and and Mesmer, Mesmer, T 
1976 
1976 
11 
3 ( ) aq 
3 
Al 3 
+ + 4 H 2 O = Al ( OH ) - 4 

+ 4 H + R I P 
12 
2 Al 3 + + 2 H 2 O = Al 2 ( OH ) 4 2 
+ + 2 H + 13 3 Al 3 + + 4 H 2 O = Al 3 ( OH ) 5 4 
+ + 4 H + 14 
Al OH 3( ) 
= Al 3 
+ + OH - A -13.74 -31.2 -7.7 -23 N U 

S 
C Baes Baes Baes Baes and Mesmer, 1976 and Mesmer, 1976 
and and Mesmer, Mesmer, 1976 1976 
15 
( ) s 
3 
HCO 2 

M 
According to the was used instead of can be expressed as [ HWO 4 - ] = 
10 3.5 - 3 = CO 3 data from the activity follows: 
2 4 

- Table P + for H T the + 1, E thermodynamic calculation. D 

-10.33 Osseo-Asare, 1982 
analysis was conducted. The concentration The mathematical relationships of the species 
(1) 
[ WO - ][ E H + ] [ H 2 WO 4 8.1 C 
2 4 
2 [ W 7 O 24 6 - ] ] = 
= 10 10 65.19 A 

[ [ WO C WO 4 
2 - - ][ ][ 7 H H + ] + ] 8 
(2) 
(3) 
[ HW 7 O 24 5 - ] = 10 69.96 [ WO 4 

2 - ][ 7 H + ] 9 
(4) 
[ H 2 W 12 O 42 10 - ] = 
10 115.38 [ WO 4 
2 - ] 12 [ H + ] 14 

(5) 
[ H 2 W 12 O 40 6 - ] = 10 135.02 [ WO 4 
2 - ] 12 [ H + ] 18 

(6) 
 
ACCEPTED MANUSCRIPT 
14 [ OH - ][ H + ] = 
10 - (7) 
[ AlOH 2 + ] = 
10 - 4.97 [ Al 3 + ]/[ H + ] (8) 
[ Al ( OH ) + 2 
] = 
10 - 9.3 [ Al 3 + ]/[ H + ] 2 
(9) 
[ Al ( OH ) 3( aq 
) 

] = 10 - 15 [ Al 3 + ]/[ H + ] 
3 

[ Al ( OH ) - 4 
] = 
10 - 23 [ Al 3 + ]/[ H + ] 4 

I P 
T 
(10) 
(11) 
[ Al 2 ( OH ) 4 2 
+ ] = 10 - 7.7 [ Al 3 + ] 2 /[ H + ] 2 
[ Al 3 ( OH ) 5 4 
+ ] = 
10 - 13.74 [ Al 3 + ] 3 /[ H + ] 4 

(13) 
U 
S 
C 
R 
(12) 
(15) The [ [ [ = + W CO Al 12 [ WO ] 3 total 3 + × 2 - ][ = 10 ][ 4 2 OH [ - WO H 115.38 
concentrations ] + + - 10 ] 4 2 ] [ = 3 - WO 3.5 ] = 10 + [ 10 WO 4 [ 2 - - HWO 10.33 - ] 31.2 12 
4 2 [ [ - of H HCO ][ 4 - W H + ] ] + 14 + and 3 ] [ - + H + ] 1 T 10 Al 2 WO 8.1 in E 
[ 4 WO solutions ] D 135.02 + 7[ 4 2 - W ][ M 7 H O are + A 24 6 N 

(14) 
expressed 2 in Eqs. 16 and 17, respectively: T 
- ] + 7[ HW 7 O 24 5 - ] + 12[ H 2 W 12 O 42 10 - ] + 

12[ H 2 W 12 O 
40 6 
-

] P 
2 ] + 7 × 10 65.19 [ WO 4 2 - ][ 7 H + ] 8 + 7 × 
10 69.96 [ WO 4 

2 - ][ 7 H 
+

] 
9 
2 12 18 4 [ Al ] T 3 2 E 

×
10 [ WO - ] [ H + ] 2 3( ) (16) = [ Al + ] + [ = [ Al 3 + ] + 10 - 
4.97 [ AlOH Al 3 C 
+ ]/[ + H ] + + ] [ Al + 10 ( OH - 9.3 ) + ] + [ Al ( OH ) aq 
] + [ Al ( OH ) - 4 ] + 2[ Al 2 ( OH ) 4 2 3 + ] + 
3[ Al 3 ( OH 
) 5 4 
+

] 
+ 2 × 10 - 7.7 [ Al 3 A 
+ ] 2 C 
/[ H 
+ ] 2 + 3 × 10 - 
13.74 

[ [ Al Al 3 + + ]/[ ] 3 /[ H H + ] + 
2 ] + 4 10 - 15 [ Al 3 + ]/[ H + ] 3 + 
10 - 23 [ Al 3 + (17) ]/[ H 
+

] 
4 

Based on above 17 equations, the thermodynamic study with the systems of W-H 
2 

O and Al-H 
2 

O were conducted, respectively, to provide the theoretical guide for the separation of tungsten and 
aluminium using N263 as the extractant. 
Because tungsten is extracted by the quaternary ammonium salt with functional group of mixed HCO- 
3 

and 
CO 3 2 
-

in the DSX process, the reactions can be expressed as follows: 

( RN 4 ) 2 CO 3 + WO 4 2 - = ( RN 4 ) 2 WO 4 + CO 3 2 
- (18) 
 
2 R NHCO + WO - = ( R N ) WO + 2 HCO - (19) 
For the establishment of T-pH relationship with the Na 
2 

O system, assuming that the 

total concentration of extractant was 1 mol/L ([R 
4 

]=1.0 mol/L) and the feed 

solution contains A mol/L Na 
2 

-H 
2 NHCO 
3 

]+2[(R 
4 

N) 
2 

CO 
3 CO 
3 

and 0.5 mol/L Na 

2 

WO 
4 

with an A/O ratio of 1. If the tungsten is 

completely extracted, the raffinate should be the mixed solution of Na 
2 

and NaHCO 
3 

CO 
3 . The T is defined as the 
concentration ratio of R 
4 

NHCO 
3 

to the extractant, therefore, the 

concentrations of R 
4 

NHCO 
3 

and (R 
4 

N) 
2 

CO 
3 

are T mol/L and (0.5-0.5T) mol/L, respectively. According 

to the Eqs. 18 and 19, the concentrations of Na 
2 

in  raffinates  can  be  calculated 

to  be  (A+0.5-0.5T)  mol/L  and  T  mol/L, respectively. According to the Eq. 15, the pH of raffinates can be 
expressed by Eq. 20. 
10.33 10.33 3 
2 3 

CO 
3 

and NaHCO 
3 

pH = - lg[ H 
+

] = - lg( [HCO [ CO - ] × 10 - 
] - ) = - 
lg( A + × 
-

-
(20) 
2.1 Thermodynamic analysis of the Al-H 
2 

T 10 
0.5 0.5 
T 
) 
O system 
The concentration of main aluminium species as function of pH value in Al-H 
2 

O system with 
0.1 mol/L [Al] 
T 

at equilibrium is shown in Fig. 1. 

As can be seen, when the total aluminium concentration was 0.1 mol/L, the aluminium mainly 
exists in the form of Al(OH) 
3(s) 

precipitate in the pH range of 4.5-11.5. In the pH range of 3.5-5.0, 

the aluminium mainly exists as its cations such as 
AlOH 2 + 
and 
4 2 2 

Al 3 + 
, 
Al 3 ( OH ) 5 4 
+

, 
Al ( OH ) + 
. In the pH range of 11.5-14, the aluminium anion of 
Al ( OH ) - 4 
is the predominant 
species. 
-1 
Al(OH) 
3(s) 
l 
4 5 6 7 8 9 10 11 12 13 14 
Fig. 1 Concentration of the main aluminium species as function of pH value in the Al-H 
2 

O system ([Al] 
T 

=0.1 mol/L) 
-2 
-3 
-4 
-5 
-6 

ACCEPTED MANUSCRIPT 
2 4 3 4 4 2 4 3 

A 
C 
- 
1 

C 
g 
( 
c 
/ 
( 
m 
o 
l 
· 
L 
) 
E 
P 
T 
E 
D 
M 
) 
pH 

A 
N 
U 
CO 
3 

-NaHCO 
3 

S 
[Al] 
T Al3+ AlOH2+ Al(OH) 
2 
+ 
Al(OH) 
3(aq) Al(OH) 
4 
- 
Al 
2 
(OH) 
2 
4+ 
Al 
3 
(OH) 
4 
5+ 

C 
R 
I 
P 
T 
 
O 2.2 Thermodynamic analysis of the W-H 
2 

system 
The concentration of the main tungsten species as function of pH value in the W-H 
2 

O system 
with 0.5 mol/L [W] 
T 

at equilibrium is shown in Fig. 2. 

0 
-1 
-2 
-3 
10- 
H 
W 
O 
6- l 
2 
12 
40 -4 
-5 
-6 
4 6 8 10 12 14 

Fig. 2 Concentration of the main tungsten species as function of pH value in the W-H 
2 

O system ([W] 
T 

=0.5 mol/L) 
As can be seen, the tungsten mainly exists in the form of 
WO 4 2 
-

in the pH range of 8.0-14.0. 

In the pH range of 5.0-8.0, the tungsten mainly exists as its polymeric anions such as 
HW O - 
and 
10 2 12 42 W 7 O 24 
6 
-

. In the pH range of 3.5-5.0, the tungsten anion of 

HW 2 12 O 40 
6 
-

is the predominant 
species. 
2.3 Thermodynamic analysis of the Na 
2 

CO 
3 

-NaHCO 
3 

-H 
2 

O system 
The equilibrium pH as function of concentration ratio (T) between R 
4 

and the extractant 

with different Na 
2 

NHCO 
3 

CO 
3 

concentrations in the feed is shown in Fig. 3. 

ACCEPTED MANUSCRIPT 
A 
C 
- 
1 
g 
( 
c 
/ 
( 
m 
o 
l 
· 
L 
) 

C 
E 
P 
T 
E 
D 
M 
) 
pH 

A 
N 
U 
2- WO 
4 HWO 
4 
- 
H 
2 
WO 
4 W 
7 
O 
24 
6- 
HW 
7 
5- 
H 
2 
O 
 24 W 
12 
O 
42 

S 
C 
R 
I 
P 
T 
 
Al(OH)- 4 

Fig. 3 The pH as function of concentration ratio (T) between R 

4 

and the extractant at different 

Na 
2 

NHCO 
3 CO 
3 

concentrations in the feed 

It can be clearly seen that the raffinate pH decreased with the increase in the value of T. The 
increase in the Na 
2 

CO 
3 

concentration in the feed could allow the increase in the value of T to 
maintain the raffinate pH stable. For example, if the raffinate pH is controlled to be 11.5, when the 
concentration of Na 
2 

CO 
3 

in the feed increases from 0.5 to 1.0 and further to 2.0 mol/L, the values 
of T could increase from 0.065 to 0.10 and further to 0.15, correspondingly. 
For the leach solution containing 1.0 mol/L Na 
2 

CO 
3 

, 0.5 mol/L WO 

3 

and 0.1 mol/L Al, it can be 

inferred from Figs. 1 and 3 that the value of T has to be limited to less than 0.1 to maintain the 
raffinate pH higher than 11.5 in which the formation of Al(OH) 
3(s) 

could be avoided. For the 

extraction of tungsten from alkaline leach solutions containing high concentration of aluminium 
using the DSX process, practically, the Al(OH) 
3(s) 

formation during the process can be prevented 

by either regeneration of the stripped organic solution or neutralization of the 
HCO- 3 
in raffinate 
using NaOH. 
3. Separation of tungsten and aluminium in the DSX process of tungsten 
Generally speaking, it is economical to remove small amount of impurity from large amount of 
target metal. Although the small amount of aluminium could be precipitated at pH less than 11.5, 
the flocculent precipitate of Al(OH) 
3 

would result in difficult filtration and large tungsten loss due 

to the adsorption by Al(OH) 
3 

. More important, the solvent extraction of tungsten directly from 

alkaline solutions using N263 is the main process for the APT production. In the DSX process, not 
only the concentration of tungsten is enriched but also the species of tungsten is transformed from 

ACCEPTED MANUSCRIPT 

A 
C 
13 
(0.10,11.5) 
Al(OH) 
3(s) 
p 
12 
(0.15,11.5) 
11 
10 

C 
T 
9 
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 
(0.065,11.5) 

E 
P 
]=0.5mol·L-1 feed liquid [Na 
2 feed liquid [Na 
2 
CO 
3 
]=1.0mol·L-1 
feed liquid [Na 
2 
CO 
3 
]=2.0mol·L-1 

T 
E 
D 
CO 
3 

M 
H 
T 

A 
N 
U 
S 
C 
R 
I 
P 
 
WO sodium salt (Na 
2 

WO 
4 

) to ammonium salt ((NH 

4 
4 

). In addition, the raffinate can be returned 

to leaching step for recycling. It can be inferred from the thermodynamic analysis that the 
chemical property differences of tungsten and aluminium in aqueous solutions lie in the ionic 
potential and the solubility. In the pH range of 11.5-14.0, the differences in charge and radius of 
WO 4 2 
-

and 
Al ( OH ) - 4 
result in the different affinities of two species with the quaternary 
ammonium salt extractant and therefore, the separation of tungsten and aluminium can be 
achieved by multiple stage counter-current extraction at an equilibrium pH higher than 11.5. 
The chemical of Na 
2 

WO 
4 

, Na 
2 

CO 
3 

, Al 
2 

(SO 
4 

) 
3 

, NaAlO 
2 

and NaOH used for this study were of 

analytical grade. The organic solution consists of 50% (v/v) N263 and 25%(v/v) 2-octanol in 
sulfonated kerosene. Solvent extraction experiments were carried out by mechanically shaking the 
organic and aqueous phases in separatory funnels at room temperature for 5 min. Samples were 
collected and analyzed to determine the concentration of metals. The concentrations of WO 
3 

was 
determined by colorimetry using potassium thiocyanate. Aluminium was determined using 
inductively coupled plasma atomic emission spectrometry (ICP-AES). 
3.1 The effect of aluminium concentration in the feed 
It can be seen from Fig. 4 that with the increase in the aluminium concentration in the feed, the 
aluminium concentration in the loaded organic solution increased, but it was of interest that the 
extraction of aluminium decreased, indicating that the aluminium cannot be quantitatively 
extracted by the N263 extractant. It was also observed that the raffinate pH maintained stable at 
13.3 with fast and clear phase separation during the extraction. 
33 
Extraction of Al Al concentration in the Loaded organic phase 
30 

A 
C 
27 
24 
21 
18 
15 
0 2 4 6 8 10 12 14 16 
C 
Al 
in the feed/ g·L-1 
ACCEPTED MANUSCRIPT 
E 
x 
t 
r 
a 
c 
t 
i 
o 
n 
/ 

C 
E 
P 
T 
E 
D 
M 
) 
2 

A 
N 
U 
S 
C 
R 
I 
P 
3.0 
C 
2.5 
2.0 
1.5 
1.0 
0.5 
% 
0.0 

T 
- 
1 
i 
n 
t 
h 
e 
o 
r 
g 
a 
n 
i 
c 
p 
h 
a 
s 
e 
/ 
g 
· 
L 
A 
l 
 
Fig. 4 Effect of Al concentration in the feed on the DSX process of tungsten (Organic solution: 
50% N263 (100% 
CO 3 2 
-

form) +25% 2-octanol+25% sulfonated kerosene; pH 

Feed 

=13.1, A/O 
ratio=1.44/1; T=25 °C; t=5 min) 
3.2 The effect of tungsten concentration in the feed 
The effect of tungsten concentration in the range of 30-117 g/L WO 
3 

on the DSX process of 

tungsten is shown in Fig. 5. The single stage extraction test was conducted with a synthetic 
solution containing 1.676 g/L Al, 1.05 mol/L Na 
2 

CO 
3 

and a certain concentration of tungsten as a 

feed. The organic system consisted of 50% (v/v) N263 with the form of 100% 
CO 3 2 
-

and 25% 
(v/v) 2-octanol in sulfonated kerosene. It can be seen from Fig. 5 that the increase in the tungsten 
concentration in the feed resulted in the decrease in the extraction of aluminium, indicating that 
the extractant has larger affinity with 
WO 4 2 
-

than that with 

Al ( OH ) - 4 
. Therefore, the 
co-extracted aluminium species of 
Al ( OH ) - 4 
was replaced by the tungsten species of 
WO 4 2 
-

. 
The chemical reactions during the extraction can be expressed as follows. 
( RN 4 ) 2 CO 3 + WO 4 2 - = ( RN 4 ) 2 WO 4 + CO 3 2 
- (21) 
( R 4 N ) 2 CO 3 + 2 Al ( OH ) - 4 = 2 R 4 NAl ( OH ) 4 + 
CO 3 2 - (22) 
2 R 4 NAl ( OH ) 4 + WO 4 2 
- = ( R 4 N ) 2 WO 4 + 
2 Al ( OH ) - 4 
(23) 
90 
75 
60 
WO 
3 Al 
45 
E 
30 
15 
0 
20 40 60 80 100 120 

Fig. 5 Effect of tungsten concentration in the feed on the DSX process of tungsten (Organic 
solution: 50% N263 (100% 
CO 3 2 
-

form) +25% 2-octanol+25% sulfonated kerosene; pH 

Feed 

= 
12.25, A/O ratio=1.2/1; T=25 °C; t=5 min) 
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% 
WO 
3 

D 
concentraction in the feed/ g·L 

M 
A 
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-1 

S 
C 
R 
I 
P 
T 
 
3.3 The effect of T 
The effect of concentration ratio of R 
4 

NHCO 
3 

to the extractant on the DSX process of tungsten 

is shown in Fig. 6. It can be seen that the higher the T value is, the lower the raffinate pH is, which 
was consistent with the analysis in Fig. 3. When the equilibrium pH was in the range of 
11.46-12.31, the extraction of aluminium was in the range of 15.3%-11.1% with good phase 
separation, correspondingly. But when the equilibrium pH decreased to less than 11.46, the third 
phase was observed and the white precipitate of Al(OH) 
3(s) 

formed during the extraction, which 

was also consistent with the thermodynamic analysis in Fig. 1. Further decrease in equilibrium pH 
to 11.01-10.29 resulted in the precipitation of aluminium more than 90%, but still 3.88%-5.67% of 
aluminium was extracted. This indicated that the aluminium can be extracted as 
Al ( OH ) - 4 
and 
loaded on the organic solution. 
100 
The third phase Clear phase separation 80 
60 
Small amounts of precipitates 
40 E 
20 
0 
10.5 11.0 11.5 12.0 

Fig. 6 Effect of T on the DSX process of tungsten (Organic solution: 50% N263+25% 
2-octanol+25% sulfonated kerosene; pH 
Feed 

=1.05 
mol/L; A/O ratio=1.2/1; T=25 °C; t=5 min) 
3.4 Counter-current extraction test for the separation of tungsten and aluminium 
A test of 12-stage counter-current extraction was conducted using an organic system consisting 
of 50% (v/v) N263 with T of 0.1 and 25% 2-octanol in sulfonated kerosene and a synthetic 
solution containing 116.3 g/L WO 
3 

=12.25, C 
Al 

=1.676 g/L; C 
WO3 

=117 g/L; C 
Na2CO3 

, 107 g/L Na 

2 

CO 
3 

and 1.676 g/L Al with pH of 12.45. The test 

results showed that the extraction of WO 
3 

reached 99.2% while that of Al was only 1.2%, 

resulting in a very high separation factor β Al 
WO 
3 

of 9837. The pH of raffinate was 11.59. It was 

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1.8 
1.5 
1.2 % 
Large Extraction T Al concentration amounts of E of Al 
precipitates in D 
the raffinate 
0.9 
0.6 
C 

E 
P 
T 
Equilibrium pH 
0.3 
0.0 

T 
- 
1 
i 
n 
t 
h 
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r 
a 
f 
f 
i 
n 
a 
t 
e 
/ 
g 
· 
L 
A 
l 
 
also observed that the phase separation was fast and no third phase formed during the extraction, 
indicating that the DSX process of tungsten in alkaline medium can be used to preferentially 
extract tungsten rather than aluminium and the efficient separation of tungsten and aluminium can 
be achieved with no Al(OH) 
3 

formation during the process. 

3.5 Determination and identification of Al-Organic complex 
Infrared spectroscopy is a useful tool for identifying a known compound by comparison to 
published infrared data. In general, although it is not possible to determine the structure or 
composition of a metal quaternary ammonium salt complex by its infrared spectrum alone, the 
spectrum can provide several useful indicators. The Fourier transform infrared (FTIR) spectra of 
blank organic and two Al-organic complexes obtained under pH 12.25 and 10.21, respectively 
were compared in Fig. 7. 
When the infrared spectra of the complex 2 
# 

was compared with that of blank N263, it was 

found that the formation of new peak at 722.81 cm 
-1 

confirmed the association of bond of the 

metal ions (in the form of 
Al ( OH ) - 4 
) with the nitrogen atoms (Li et al., 2010). It was observed 
that no precipitates formation during the extraction of 2 
# 

sample, indicating the stable existence of 

Al-N263 complex 
R 4 NAl ( OH ) 4 
in the loaded organic solution. When the infrared spectra of 
the complex 3 
# 

was compared with that of blank N263, there was only slight distortion in the 
absorption frequency bond at 722.81 cm 
-1 

, indicating that the amount of 

Al ( OH ) - 4 
in the loaded 
organic solution was very small. The characteristic absorption peak of Al(OH) 
3 

was not detected, 

indicating that the precipitate of Al(OH) 
3 

formed during the extraction only existed in the interface 

of two phases, which resulted in the difficulty in phase separation. 

A 
C 
4000 3500 3000 2500 2000 1500 1000 500 

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3# 
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E 
3 2 
9 
5 
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2 
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5 
7 
. 
8 
8 
9 
2 
9 
2 
8 
. 
0 
9 
2 
9 
2 
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. 
2 

D 
4 
wave number/cm-1 
0 
2 
8 
5 
6 
. 
2 

M 
A 
N 
1 
6 
5 
0 
. 
7 
1 
6 
5 
1 
. 
0 
5 1 
6 
4 
4 
. 
6 
U 
5 
1 
4 
6 
0 
. 
4 
2 
4 
1 
3 
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2 
. 
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1 
3 
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7 
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1 
2 

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0 
1 
3 
7 
6 
. 
1 
C 
1 
0 
6 
0 
. 
5 
2 1 
0 
5 
9 
. 
8 
1 
0 
6 
1 
. 
7 
5 
8 
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1 
. 
8 
8 
8 
8 
5 
. 
3 
5 
8 
8 
3 
. 
7 

R 
9 
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2 
2 
. 
8 
1 
5 
6 
0 
4 
. 
8 
7 
2 
2 
. 
8 

I 
P 
T 
 
# Fig. 7 The infrared spectra of N263 alone and two Al-N263 complexes (1 
: Blank N263; 2 
# 

: [Al] 
Loaded 

=0.31 g/L, equilibrium pH=12.25; 3 

# 

: [Al] 
Loaded 

=0.085 g/L, equilibrium pH=10.21) 

4. Conclusions 
Based on the results obtained in this study, the following conclusions were made: 
(1) Thermodynamic analysis revealed that the tungsten and aluminium exist as 
WO 4 2 
-

and 
Al ( OH ) - 4 
in the pH range of 11.5-14, respectively. In the pH range of 5.0-11.5, the aluminium 
exists as precipitate of Al(OH) 
3 while salt extractant N263 with 
HCO- 3 
the tungsten as its anions. The use of quaternary T 
ammonium would 
result in the decrease in form during the DSX process of tungsten P 
in Na 
2 

CO 
3 

medium 
than 11.46. 
(2)The aluminium species of 
raffinate pH and 4 
the formation of Al(OH) R I 3 
precipitate at pH less 
good phase separation. The deteriorating Al ( OH ) - 
can be extracted species of Al(OH) 
3 

cannot be by extracted S N263 C 

to in form the stable complex with organic solution but 
(3) The counter-current high as extraction 9800, the indicating extraction phase of tungsten separation 
that at equilibrium the reached efficient 99.2% pH separation of while 11.59. that of N 
The tungsten of U 
aluminium separation and aluminium factor only 1.2% of using a 12-stage 
using the DSX process of tungsten Acknowledgment The authors are thankful to the in China alkaline D 
Scholarship medium. M 

A 
Council β Al WO 
3 

reached as 
can be achieved 
support. 
References: Akcil, petroleum Alsobaai, and nickel A., A.M., catalysts loading. Vegliò, Zakaria, Chemical and F., C Ferella, ash. 
R., C 
Waste Hameed, Engineering E F., Management, P Okudan, B.H., T Journal, E 2007. M.D., Vol. Gas Vol. Tuncuk, 45: oil 
132(1-3): 420-433. 
hydrocracking A., 2015. 77-83. 

(CSC201606375041) for financial 

A review of metal recovery from spent 
Amiri, F., Yaghmaei, A 
S., Mousavi, S.M., 2011. Bioleaching of tungsten-rich on NiW/USY spent hydrocracking catalyst: Effect catalyst of tungsten 
using 
Penicillium simplicissimum. Bioresource Technology, Vol. 102(2): 1567-1573. 
Anon, 2007. GB/T 10116-2007 Ammonium Paratungstate [S] 
Baes, C.F., Mesmer, R.E., 1976. The hydrolysis of cations. New York : John Wiley & Sons Inc, 1976. 
Chen, S.L., Zhang, G.Q., Xiao, L.S., Guan, W.J., 2014. Extraction of tungsten from simulated autoclave-soda 
leaching liquor of tungsten ore with quaternary ammonium salt of bicarbonate and carbonate. Chinese Journal of 
ACCEPTED MANUSCRIPT 
 
ACCEPTED MANUSCRIPT 
Nonferrous Metals, Vol. 24(12): 3155 (in Chinese). 
Cruywagen, J.J., Merwe, F.J., 1987. Tungsten (VI) equilibria: A potentiometric and calorimetric investigation. 
Journal of the Chemical Society, Dalton Transactions, Vol. 7: 1701-1705. 
Guan, W.J., Zhang, G.Q., 2011. Extraction of tungsten from simulated autoclave-soda leaching liquor of scheelite 
with quaternary ammonium salt. Chinese Journal of Nonferrous Metals, Vol. 21(7):1756-1762 (in Chinese). 
Huang, tungsten-bearing Vol. Kim, reduction Li, sodium Michalowski, 594-601. 
Osseo-Asare, 555-564. Qin, Tungsten Rozantsev, solutions Wang, Dissertation, Xie, Metal Xiong, X.B., 4: M.Q., Y.N., J.W., 
Materials 1-4 G., aluminate X.L., W.Z., Wang, Industry, of catalysts 2002. 2014. (in Chen, Lee, G.M., tungsten 2014. K., Xie, 
Chinese). T., Zhang, D.Q., & W.G., raw Industrial Study J., A 1982. Pietrzyk, solution. Sazonova, Vol. by Metallurgy M.Q., 
Xiong, (VI). materials pressure C Liang, Hwang, 17(6): on Solution Q.X., Chen, C Russian Chemical experience tungsten X.L., 
A., S., 40 O.I., Engineering, leaching. E I.S., on 1993. 2006. Zhou, (in J., Chen, chemistry the Journal P 2005. Lee, Chinese). 
Chen, recovery Journal quality A of The Q.S., T Z.Z., Journal J.Y., thermodynamic producing Thermodynamic of E Z.Z., Vol. of 
effect 2010. of 2007. Coordination of Han, process tungsten D Chinese 35(5): of leaching 2008. Industrial Relationship Study C., 
of tungstic M from 10-14 2015. adding Studies Universities, leaching liquor. study on A Chemistry, parameters spent acid 
recovering (in & Recovery N Engineering of between aluminium on Chinese). Journal using systems. catalyst. struvite U 
recovery Vol. Vol. waste of valuable of S electric of 31(8): tungsten Metallurgical 31(8): interconversions + ChangSha: Rare C 
oxide Chemistry, of water catalyst 1651 tungsten conductivity metals R Metals 552-558. during from system. I (in containing P 
Central Vol. from and Chinese). spent Transaction from T alka1ine-leaehing 28: of Talanta, Cemented waste and selective South 
alkaline 73-77. isopolyanions tungsten. ion W-Ni structure B, Vol. University, Carbides, 
catalytic 
leaching Vol. catalyst. 68(3): 
China 13: of of 
in 
solution of spent catalyst by ion exchange method. Metal Materials and Metallurgy Engineering, Vol. 36(1): 12 (in 
Chinese). 
Xu, A.Y., Ye, T., Zhao, S.H., 2013. Recovery of valuable metals from spent hydrogenation catalysts. .Conference 
paper in Applied Mechanics and Materials, 440: 97-103. 
Zhang, G.Q., Guan, W.J., Xiao, L.S., Zhang, Q.X., 2016. A novel process for tungsten hydrometallurgy based on 
direct solvent extraction in alkaline medium. Hydrometallurgy, Vol. 165: 233-237. 
 
ACCEPTED MANUSCRIPT 
Zhang, G.Q., Xiao, L.S., Guan, W.J., 2014. A method of recyclable extraction system in which tungsten can be 
extracted from alkaline coarse sodium without a process of extractant regeneration. China Patent, 103572075, 
2014. 
Zhang, G.Q., Zhang, Q.X., 2003. A new production technology for tungsten hydrometallurgy. Chinese Journal of 
Rare Metals, Vol. 27(2): 254 (in Chinese). 
Zhao, H., Zhang, G.Q., Han, C.M., 2014. Method for recovering tungsten, vanadium and titanium from SCR waste 
catalyst. China Patent, 104263946A. 2014. 

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Highlights 
1. Thermodynamic analysis on Al-H 
2 

O systems were 
conducted. 
2. The separation coefficient of 
3 

O, W-H 
2 

O and Na 
2 
β WO Al 

reached as high as 9800 using DSX. 

3. The Al-N263 complex was identified using FTIR. 

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-H 
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