Elimination of Cadmium from Wet Process Phosphoric Acid with Alamine 336

K. Nazari ∗ , A. Ghadiri
Ore Processing Center, Atomic Energy Organization of Iran (AEOI), Tehran, Iran

Abstract
Cadmium (Cd) is one of the toxic heavy metal in nature that could be found in phosphate
rocks and “Wet Process Phosphoric Acid” (WPA). In the experimental study, Cd was removed
from WPA by solvent extraction method, using amine extractants, preferably “Alamine 366” as
a tertiary amine extractant. In batch wise tests, extraction percent of Cd from WPA under
optimal conditions was identified 74±2.54% (confidence limit: 95%).
It is concluded that organic phase containing 1% (vol) Alamine 336 + 1.5% (vol) Iso-
dodecanol in B-65 kerosene has good stability and high efficiency in removal of Cd from
WPA. Average Cd extraction in the batch wise tests, after 20 recycling stages of organic phase
to solvent extraction circuit was identified 68.57%.

Keywords: WPA, cadmium, Alamine 336, solvent extraction, aromatic kerosene B-65.

Introduction
Cd is highly toxic metal to a wide variety of living organism including man, that could be
found in phosphate rocks in trace (<100 ppm). During the production of industrial phosphoric
acid, which is called “Wet Process Phosphoric Acid” (WPA), Cd directly enters to WPA. It is
notable that WPA is consumed in phosphate fertilizers, food and detergent industries and in
other industries. For this reason cadmium enters to environmental cycles. Since Cd is
extremely toxic and accumulated in human body, removal of this element from WPA is
essential.
Human exposure to Cd affects on pulmonary, kidneys, gut and liver and results in
common diseases, such as cancer of prostate, gastro-intestinal poisoning and bone damages
(Aylett,1973; Habashi, 1997). The normal content of Cd in agricultural fields lies between

∗
Corresponding author.
E-mail address: nazari@aeoi.org.ir
Phone: 021-8008616
Fax: 021-8008793

1
0.1-1 mg/kg (Habashi, 1997), and the maximum allowed concentration is 0.1 mg/m3 of air
(Aylett, 1973).
There are various treatment process, such as precipitation (Ennaassia et al., 2002),
ion exchange (Koopman et al., 1999), solvent extraction (Almela et al., 1998; Bierman et al.,
1985; Elyahyaoui and Bouhlassa, 2001; Frankenfeld et al., 1991; Koopman et al., 1999; Mellah
and Buaer, 1995; Plessen et al., 1984; Stenstrom and Aly, 1985) and membrane process
(Koopman and Witkamp, 2002; Urtiaga et al., 1999), which have been used to remove Cd from
WPA. Among the above methods, solvent extraction has good capability and high efficiency
for refining of WPA from Cd, before it is used in several industries.
The present work focuses on separation of Cd from WPA by solvent extraction method,
using amine extractants, preferably “Alamine 366” as a tertiary amine extractant, and the effect
of several parameters on Cd extraction are investigated and optimized in laboratory tests. With
applying McCabe-Thiele diagram, number of theoretical stage of extraction in different phase
ratios is determined. Finally stability and efficiency of organic phase in consequent recycling
of organic phase to extraction unit is investigated.

Experimental
Reagents
Alamine 336 (a mixture of Tri-n-octylamine and Tri-n-decylamine) (Stenstrom and Aly,
1985) from Henkel Ind., TBP, D2EHPA and TOPO from Fulka Ind. as extractants were used
without further purification. 1-2-4 Trimethylbenzene (Merck), aliphatic kerosene, A-55 and B-
65 kerosenes1 were implied as diluents. Table 1 shows the specification of A-55 and B-65
kerosene. Iso-dodecanol (C12H26O) from Merck was consumed in organic phase for preventing
third phase formation.

Table 1: Details of specification of kerosene

Density at 22 ºC
g Flash point Aromatic content % Kinematics viscosity at 19 ºC
Kerosene
( 3) (ºC) (vol) (cSt)
cm
A-55 0.871 55 82.5 0.839
B-65 0.838 71 82.5 0.933
Industrial phosphoric acid was purchased from Razi Petrochemical Plant of Iran. Some
analytical data for this acid are given in table 2. All the other chemicals used in this work were
of AR grade.

1
Produced by order of AEOI from Research Institute of Petroleum Industry of Iran

2
 Table 2: Analysis of components and elements in WPA
g g g g g g g
Constituent P2O5 (%) SO4 ( ) Cd ( ) U( ) As ( ) Fe ( ) Ca ( ) Cl ( )
L L L L L L L
Concentration 51 18.9 0.05 0.1185 <0.003 4.3 0.0023 5.325

Extraction and analytical procedure

For equal condition, mixing of extraction was performed in beaker (100 ml) with magnet-
stirrer, then two phases were decanted in separator funnel, after equilibrating, raffinate was
separated from loaded organic phase.
WPA contained fine solid particle (usually gypsum) and organics, with dark green-
brownish color. Before utilization, it was filtrated with weighting paper, 2 times, and then was
passed through a glass tube, containing 5% W/V active charcoal (+60 meshes).
Cd concentration in aqueous phase (before and after extraction) was analyzed using
Perkin-Elmer 5000 atomic absorption spectrophotometric unit. Cd concentration in organic
phase was calculated using mass balance method. The extraction percents of Cd (ECd) were
determined according to usual method (Habashi, 1993).

Results and Discussion

Determination of mixing time
For determination of equilibrium time of Cd distribution between two phases, the
experiments were carried out in different mixing times. In experiments, WPA 51% P2O5 was
contacted with organic phase containing 5% (vol) Alamine 336 + 4% (vol) Iso-dodecanol in B-
65 kerosene at O/A=1 (Organic/Aqueous) and T=30 ºC. Fig. 1 shows extraction percent of Cd
in different mixing times.
According to Fig. 1, most extraction percent of Cd was observed between 240-360
seconds, thus the average of these was selected as enough mixing time in next experiments (5
min).

Effect of WPA treatment with active charcoal and diluents selection

Fine suspension particles and organic materials in WPA result in decreasing of efficiency
of solvent extraction process. To study this effect, experiments using organic phases containing
different diluents were carried out under refined and non-refined WPA conditions with active
glassy charcoal. Treatment of WPA was performed with 5% W/V active charcoal (+60 mesh) in
tube. The results obtained (Fig. 2) show that treatment of WPA with active charcoal increases

3
extractability of Cd in WPA, due to decreasing organics, thus in next experiments, WPA is
refined with active charcoal (WPAAC). Analysis of Cd is shown that Cd values in WPA
100
90

Percent extraction of cadmium

80
70
60
50
40
30
20
10
0
0 50 100 150 200 250 300 350 400
Mixing time (s)

Fig. 1. Kinetics extraction of Cd (5% (vol) Alamine 336 + 4% (vol) Iso-dodecanol in B-65 kerosene,
WPA 51% P2O5, O/A=1, T=30 ºC)

decrease after treatment, due to adsorption of Cd with active charcoal. This phenomenon
can be considered as a potential of Cd removal from WPA in future works.
According to Fig. 2, nearly equal extraction percents of Cd were obtained with organic
phases containing different diluents. Using aliphatic kerosene in organic phase results in third
phase formation and poor phase separation (tow phases were emulsified), thus this kerosene
was passed over. Among the other diluents, 1-2-4 Trimethylbenzene and A-55 kerosene have
lower flash points than B-65 kerosene, also 1-2-4 Trimethylbenzene is high expensive than B-
65 kerosene for industrial solvent extraction processes, for this reason, B-65 kerosene was
selected as best diluents for refining of WPA from Cd.

Phosphoric acid without refining with active charcoal(ECd)%

Refining phosphoric acid with active charcoal(ECd)%

100
Percent extraction of cadmium

90
80
70
60
50
40
30
20
10
0
Aliphatic kerosene A-55 kerosene B-65 kerosene 1-2-4 trimethylbenzene
Diluent

Fig. 2. Effect of WPA treatment with active charcoal on Cd extraction (5% (vol) Alamine 336 +
4% (vol) Iso-dodecanol in different diluents, WPA 51% P2O5, O/A=1, mixing time=5 min, T=19.5 ºC)

Effect of extractant concentration

To analyze the influence of extractant concentration, several tests were carried out by
variation of Alamine 336 concentration in B-65 kerosene (without adding modifier). The

4
results obtained are shown in Fig. 3. According this figure, Cd extraction increases with
increasing extractant concentration till 1% (vol) Alamine 336, then decreases. This decrease
may be explained as being due to polymerization of Alamine 336, when high extractant
concentration is used (Ritcey and Ashbrook, 1984). This phenomenon can be investigated in
future.
100
90
Percent extraction of cadmium

80
70
60
50
40
30
20
10
0
0 2 4 6 8 10 12
Concentration of Alamine 336 in B-65 kerosene% (vol)

Fig. 3. Effect of extractant concentration on Cd extraction (WPAAC 51% P2O5, O/A=1,

mixing time=5 min, T=29 ºC)

When organic phase containing different concentrations of Alamine 336 were contacted
with WPAAC, an insoluble organic component was formed between WPA and organic solvent,
which is called “third phase”. This phase was very viscous with brown-reddish color. Several
experimental conditions, such as aqueous acidity, extracted metal, diluents and extractant
structure can affect the third phase (Xun et al., 2000). Different methods, such as raising
extraction temperature, using diluents with high aromatic contents and adding modifiers to
organic phase have been suggested for elimination of third phase in solvent extraction process.
Among of these methods, adding a modifier (like a long chain alcohol) to organic phase is
most common method for preventing of third phase in industrial solvent extraction process.
In this work, “Iso-dodecanol” was selected as modifier. Optimized Iso-dodecanol values
for different Alamine 336 concentration in B-65 kerosene were determined by titration. The
results are presented in Table 3.

Table 3: Optimized modifier values for different extractant concentrations

Alamine 336 in B-65 kerosene % (vol) 1 2 3 5 8 10 15
Corresponding Iso-dodecanol modifier in B-65 kerosene % (vol) 1.5 2.5 2.5 4 5 6 8

According to Fig. 3 and Table 3, organic phase containing 1%(vol) Alamine 336 + 1.5%
(vol) Iso-dodecanol in B-65 kerosene was considered as suitable organic phase in process.

5
 Effect of pre-equilibration of organic phase
Alamine 336 has base properties. In order to achieve extraction, initially it must be
converted to an appropriate amine salt in organic phase (Ritcey and Ashbrook, 1984); this
reaction is called “pre-equilibration”. Basically, pre-equilibration of organic phase takes place
according to Equation (1):
R 3 N (o) + HX (aq) ↔ R 3 NH + .X (o)
−
(1)

On contacting amine salt with an aqueous solution containing an anionic metal species
MX (m
m
- n) -
, anion exchange can be occurred as follows (Ritcey and Ashbrook, 1984):
− n) −
MX (m
m (aq)
+ (m − n)(R 3 N.HX) (o) ⇔ (R 3 NH + ) (m − n) .MX m− (o) + (m − n)X − (aq) (2)

To study this effect, analytical acid, such as hydrochloric, sulfuric, nitric and phosphoric
acids, corresponding to a concentration of 1 M acid, were contacted with organic phase
containing 1% (vol) Alamine 336 + 1.5% (vol) Iso-dodecanol in B-65 kerosene in O/A=1,
mixing time= 5 min and T=26 ºC. Fig. 4 shows extraction percent of Cd in different pre-
equilibration conditions.

100
90
Percent extraction of cadmium

80
70
60
50
40
30
20
10
0
Non per- 1M phosphoric 1 M nitric acid 1 M sulfuric acid 1 M hydrochloric
equilibration acid acid
Per-equilibration candition

Fig. 4. Effect of pre-equilibration of organic phase on Cd extraction (1% (vol) Alamine 336 +
1.5% (vol) Iso-dodecanol in B-65 kerosene, WPAAC 51% P2O5, O/A=1, mixing time=5 min, T=27 ºC)

According to Fig. 4, pre-equilibration with hydrochloric acid showed greatest increase in

extraction of Cd but one disadvantage of this, is entrance of Cl ions to WPA from per-
equilibrated organic phase then resulting to contamination of WPA. Based on influence of
pre-equilibrated organic phase with hydrochloric acid on Cd extraction and Eq. (2), extracted
anionic complex of Cd in WPA was predicted as an anionic chloride complex of Cd.

Effect of WPA concentration

A study of the effect of varying WPA concentration revealed (Fig. 5) that Cd extraction
increases with increasing of WPA concentration. Removal of Cd in high WPA concentration is

6
considered one advantage because of lowering consumed organic materials. For this reason, Cd
will be extracted from WPAAC 51% P2O5.

100
90
Percent extraction of cadmium 80
70
60
50
40
30
20
10
0
0 10 20 30 40 50 60
P2O5 %

Fig. 5. Effect of WPAAC concentration on Cd extraction (1% (vol) Alamine 336 + 1.5% (vol) Iso-
dodecanol in B-65 kerosene and per-equilibrated with 1 M HCl, O/A=1, mixing time=5 min, T=25 ºC)

Effect of extraction temperature

To investigate this effect, experiments were carried out in several temperatures. The results
obtained showed (Fig. 6) that the varying of temperature has no effect on Cd extraction. For
this reason, the process will be performed in ambient temperature. From this result can be
understood that the process is flexible in different environmental conditions and can be
considered one advantage in solvent extraction processes.

100
Percent extraction of cadmium

90
80
70
60
50
40
30
20
10
0
0 10 20 30 40 50 60 70 80
Temperature

Fig. 6. Effect of temperature on cadmium extraction (1% (vol) Alamine 336 + 1.5% (vol) Iso-dodecanol
in B-65 kerosene and per-equilibrated with 1 M HCl, WPAAC 51% P2O5, O/A=1, mixing time=5 min)

Extraction isotherm curve of cadmium

For plotting extraction isotherm curve of Cd from WPA, combination of “phase ratio
variations method” and “metal concentration variations method” were used simultaneously.
Increasing Cd concentration in WPA was performed by adding Cd chloride (CdCl2.H2O)
(Merck). The extraction experiments were carried out in optimized conditions (Fig. 7).

7
Increasing Cd concentration in organic phase results in saturation of organic phase. According
to Fig. 7, the maximum loading capacity of Cd using organic phase containing 1% (vol)
Alamine 336 + 1.5% (vol) Iso-dodecanol in B-65 kerosene was determined 1020 (mg/L).

1.2
Loading capasity
1 of organic phase
Cadmium concentration in
organic phase (g/L)

0.8

0.6

0.4

0.2

0
0 0.2 0.4 0.6 0.8 1
Cadmium concentration in aqueous phase (g/L)

Fig. 7. Extraction isotherm curve of cadmium (1% (vol) Alamine 336 + 1.5% (vol) iso-dodecanol in
B-65 kerosene, WPAAC 51% P2O5, mixing time=5 min T=18 ºC)

With applying McCabe-Thiele diagram, number of theoretical extraction stage for Cd

(CCd=50 mg/L), under optimized conditions in phase ratios (O/A): 0.5 and 1 were calculated 4
(Fig. 8) and 2 counter-current stages, respectively.

0.2
Cadmium concentration in organic

0.15
phase (g/L)

Isotherm curve
Operating line
0.1

0.05
Slope of operating
line: 2
0
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08
Cadmium concentration in aqueous phase (g/L)

Fig. 8. Number of theoretical extraction stage of cadmium using McCabe-Thiele diagram (O/A=0.5)

Efficiency of extractant in solvent extraction circuit

Due to aspects of economy and high cost of organic solvents, good stability of extractant
in solvent extraction cycles is an important parameter. Thereby preliminary tests were carried
out in order to identify the stability and efficiency of Alamine 336 in extraction of Cd from
WPA. According to this, a solvent extraction circuit as extraction-stripping cycle was designed.
The experiments in extraction unit were conducted in optimum conditions and O/A=1; and
then loaded organic phase was stripped at 3 cross-current stages, using tab water in O/A=1,

8
mixing time=3 min and ambient temperature. To study the stability and efficiency of Alamine
336, organic phase was repeatedly contacted with fresh WPA in 20 stages. Fig. 9 shows
extraction percent of Cd at 20 recycling stages of organic phase in batch wise tests. After 20
recycling of organic solvent to extraction unit, the average of Cd extraction in batch laboratory
tests was determined 68.57%; which is concluded Alamine 336 has good stability and
efficiency for removal of Cd from WPA.

100
90
Percent extraction of cadmium

80
70
60
50
40
30
20
10
0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Extraction cycle

Fig. 9. Extraction percent of cadmium in repeated extraction cycles (1% (vol) Alamine 336 +
1.5% (vol) Iso-dodecanol in B-65 kerosene, WPAAC 51% P2O5, O/A=1, mixing time=5 min, T=26 ºC)

Conclusions
1. According to batch tests, optimal experimental conditions for extraction of Cd from
WPA were determined as follows:
- Organic phase: 1% (vol) Alamine 336 + 1.5% (vol) Iso-dodecanol in B-65 kerosene
- Aqueous phase: WPAAC 51% P2O5
- Mixing time: 5 min
- Temperature: ambient temperature
2. In optimum conditions, the average of extraction percent of Cd from WPA, with 95%
confidence limit was identified 74±2.54%.
3. Among of diluents, B-65 kerosene was selected due to lower cost than others and high
efficiency in process.
4. Due to adsorption of Cd with active charcoal, Cd values in WPA decreased after
treatment of WPA with active charcoal. The results showed that the treatment of WPA with
active charcoal improves extractability of Cd, significantly.
5. The investigations showed that in spite of improving Cd extraction conditions by
per-equilibration of organic phase with 1 M HCl, this method is not suggested because of the
entrance of chloride ions to WPA from per-equilibrated organic phase.

9
 6. According to theory of tertiary amine extractants, anionic complex of Cd was predicted
as an anionic chloride complex of cadmium.
7. According to the experiments, extraction of Cd is independent to temperature variation.
8. With applying McCabe-Thiele diagram, number of theoretical extraction stage of Cd in
phase ratios (O/A): 0.5 and 1 were calculated 4 and 2 counter-current stages.
9. Organic solvent (1% (vol) Alamine 336 + 1.5% (vol) Iso-dodecanol in B-65 kerosene)
showed high stability and efficiency in extraction of cadmium. After 20 recycling stages of
organic solvent to extraction unit, the average of Cd extraction was calculated 68.57%.
10. Due to lower price of phosphate concentrate containing high concentration of
uranium and Cd, this process provides possibility for production of phosphoric acid from lower
cost sources.

Acknowledgments
The authors wish to tank the Ore Processing Centre and Jaber-Ibn-Hayan Research
Laboratory of AOEI, Razi Petrochemical Plant of Iran, Institute of Petroleum Industry of Iran,
and Analysis Laboratory of Ore Processing Centre.

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