Solvent Extraction Research and Development, Japan, Vol.

24, No 1, 23 – 35 (2017)

Purification of Wet Process Phosphoric Acid by Solvent Extraction using Cyclohexanol

Xing LI, Jun LI,* JianHong LUO,* Yang JIN and Da ZOU
Department of Chemical Engineering, Sichuan University Chengdu, Sichuan 610065, P. R. China
(Received July 16, 2015; Accepted September 30, 2015)

Solvent extraction using organic solvents is an important technology for the purification of wet process
phosphoric acid (WPA). In this study, the purification process of WPA, using a new type of solvent
extraction system, cyclohexanol diluted in kerosene, was investigated. The equilibrium phase diagram of
the system H3PO4  H2O  solvent mixtures at 313.2K was obtained. The effects of extraction time,
phosphoric acid concentration, cyclohexanol concentration, temperature, phase ratio on extraction
efficiency were studied. The extracted species was shown to be 2H3PO4 · 2C6H12O. The extraction process
of H3PO4 is exothermic and the enthalpy change, ᇞH, was obtained. Via a cross-current three-stage
extraction, the solvent mixtures have a high efficiency for phosphoric acid purification from the actual
industrial WPA with an H3PO4 extraction yield of 90.2% at room temperature. The study is capable of
enriching theoretical foundation and technical guidance for the phosphoric acid purification process.

1. Introduction
Phosphoric acid is an important mineral acid and commonly manufactured by two routes, thermal
and wet process. Wet process phosphoric acid (WPA) is a more economical and environmental-friendly
method of phosphoric acid production [1-3]. However, WPA contains various undesirable impurities and
must be purified during the downstream production. Many techniques have been investigated to purify
WPA such as crystallization, ion precipitation, solvent extraction and ion exchange. Improving
experimental results have led to growing acceptance of solvent extraction as an efficient, practical and
economical method which is now the most widely-used technique applied in the industrial production
process at present [4-6].
In the solvent extraction method, extensive research has been conducted to find a suitable extractant
which is efficient, of low toxicity with good flowability and selectivity to H3PO4. Many organic solvents
have been investigated, e.g. esters [7-8], ethers [9], ketones [10] and alcohols [11]. Aliphatic alcohols, such
as butanol, hexanol and octanol, have been studied as extractants diluted in kerosene for purification of
WPA. The experimental results show that alcohol-kerosene mixtures have the advantages of favorable
efficiency and selectivity to H3PO4 and are cheap, easy to use and they separate quickly without
emulsification and three phase formation [12]. Compared with these above-mentioned alcohol extractants,
cyclohexanol has good immiscibility with the aqueous solution and physicochemical stability due to its ring
structure. Cyclohexanol has been used for leaching and extraction. The experimental results indicate
favorable extraction efficiency of metallic ions in the ore leaching and good selectivity to iron in
liquid-liquid systems [13-14]. Kerosene is used as the diluent in an appropriate proportion to strengthen the
flowability and decrease the viscosity of the two-phase mixtures. On the other hand, kerosene will lower
the extraction ability in the solvent mixtures to some extent [15-16]. The cyclohexanol-kerosene mixture is

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an extraction system which has not yet been studied for WPA purification.
The aim of this work was to study the solvent extraction of H3PO4 from industrial WPA with
cyclohexanol diluted in kerosene. In this study, the equilibrium phase diagram of the system H3PO4  H2O
 solvent mixtures at 313.2K was investigated. The effects of several parameters such as extraction time,
phosphoric acid concentration, cyclohexanol concentration, temperature and phase ratio on the extraction
were investigated. The extracted species and the value of the enthalpy change of the extraction reaction
were determined. A cross-current three-stage extraction as well as scrubbing and stripping of the loaded
organic phase was applied to obtain purified diluted phosphoric acid from industrial WPA.

2. Experimental
2.1 Materials
Cyclohexanol was obtained from Jinshan Chemical Reagent Co. (Sichuan, China). Pure H3PO4 (≥
85%) was obtained from Kelong Chemical Reagent Co. (Sichuan, China). The reagents were both
analytically pure and used without further pretreated. Kerosene was provided by Zhongcui Chemical Co.
(Sichuan, China). Before use, the kerosene was washed with concentrated sulfuric acid then neutralized
with 5% Na2CO3 solution and washed with water until the pH was neutral and finally distilled at
458.2-528.2 K. The industrial raw WPA was supplied by Furui Chemical Plant (Yunnan, China), which was
obtained by decomposing phosphate ore using sulfuric acid. The composition of the industrial WPA is
shown in Table 1.

Table 1. Composition of the industrial WPA supplied by Furui Chemical Plant.

Composition H3PO4 SO42- F- Fe3+ Al3+ Mg2+ Zn2+ Cr3+

wt % 64.51 3.7350 0.3406 0.3550 0.6279 0.8596 0.0410 0.0058

2.2 Procedure
The equilibrium studies were carried out at T= 313.2 K in a water thermostat (± 0.1 K). Known
amounts of diluted pure phosphoric acid and solvent mixtures were mixed and shaken for 2 h and then left
to settle for 2 h to completely separate the two liquid phases. After separating thoroughly, the organic phase
and the aqueous phase were weighed and taken for analysis.
The extraction temperature was controlled and maintained in a water thermostat (± 0.1 K). Known
amounts of wet process phosphoric acid were diluted with deionized water to prepare the aqueous phase
while cyclohexanol was mixed with kerosene in an appropriate proportion to prepare the organic phase.
The prepared phosphoric acid and solvent mixtures were then mixed and stirred for a certain time. After
standing for a sufficient time, the mixtures completely separated into two equilibrated phases. The organic
phase and the raffinate aqueous phase were weighed and taken for analysis. The volume of the liquid
phases was also determined (± 0.1 mL).
The concentration of H3PO4 in the aqueous solution was identified by the phosphorus molybdic acid
quinoline weight method [17]. The water content in the organic phase was determined by the Karl-Fisher
potentiometric titration method using a compact potentiometric titrator (Metrohm 916 Ti-Touch,
Switzerland) [11]. Measurement of Fe3+ concentration in the aqueous solution was performed using a
UV-Visible spectrophotometer (Mapada UV-1100, China) at a wavelength of 510 nm [17]. The fluoride

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composition in the aqueous phase was determined by an ion meter (Radiometer PHM240, France) using a
fluoride selective electrode (ISE25F) with a saturated calomel electrode as the reference electrode. The
concentration of SO42- in the aqueous solution was identified using a UV-Visible spectrophotometer at a
wavelength of 440 nm [17]. Measurement of the concentration of other metallic ions (Al3+, Mg2+, Zn2+,
Cr3+) in the aqueous solution was performed with an ICP-AES (Thermo elemental iris advantage, USA).
FT-IR spectra (Nicolet 7100, USA) was used for the analysis of organic phase. The concentration of H3PO4
and other components in the organic phase were obtained from material balances. Deionized water was
used throughout the experiments.
The distribution coefficient (D) is calculated as

[c]( o )
D (1),
[c]( a )

where [c ]( o ) and [c ]( a ) are the molar concentrations of the component in the organic and aqueous phases

at equilibrium, respectively.
The separation factor (β) is calculated as
DH 3 PO4
β= (2),
Di

where DH 3 PO4 and Di are the distribution coefficients of H3PO4 and the impurity, respectively.

The extraction yield (E %) of H3PO4 is calculated as

Mass of H3PO4 in the organic phase
E%  100% (3)
Mass of H3PO4 in the initial solution

3. Results and Discussion

3.1 Equilibrium studies of the extraction system H3PO4  H2O  solvent mixtures
In this extraction system, it is necessary to establish the phase diagram of the system H3PO4  H2O 
solvent mixtures to reveal the distribution of H3PO4 between the aqueous and solvent phase. The solvent
mixture consists of 75% cyclohexanol and 25% kerosene. The composition of the conjugated phases is
obtained from material balances. All the percentages in this section represent the mass fractions (wt %).
The equilibrium phase diagram of the system H3PO4  H2O  solvent mixtures at 313.2 K is shown in
Figure 1. The conjugated phases are connected with tie-lines for each mixture. The plait-point marked in
the phase diagram is established according to the Hand method [18]. The composition data of the initial
mixtures and equilibrium phases at 313.2 K are given in Table 2. As the results show, the pseudo-ternary
system has two completely miscible liquid pairs which are water + H3PO4 and solvent mixtures + H3PO4. It
also has one partially miscible liquid pair, water + solvent mixtures. The plait-point of the system
demonstrates favorable capability of the solvent mixtures for purifying WPA due to the ability of the
organic phase to load high H3PO4 concentrations which is over 60%. The results also show that the solvent
mixtures have low solubility in the aqueous solution. In addition, the solubility of water in the solvent
mixtures increases slowly from 11.23% to 14.18% as the mass fraction of H3PO4 increases from 4.15% to
45.79% in the organic phase. The phase equilibrium study of the system indicates the solvent mixtures can
be considered as favorable candidates for the purification of WPA.

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Figure 1. Equilibrium phase diagram of the extraction system H3PO4  H2O  solvent mixtures (75%
cyclohexanol +25% kerosene) at 313.2K.

Table 2. Equilibrium data of the extraction system H3PO4 (1)  H2O (2)  solvent mixtures (75%
cyclohexanol +25% kerosene) (3) at 313.2K. a

Initial mixtures Aqueous phase Organic phase

w1 w2 w3 w1 w2 w3 w1 w2 w3
51.15 15.39 33.46 75.35 20.73 3.92 45.79 14.18 40.03
43.06 17.86 39.08 65.44 30.65 3.91 36.61 13.28 50.11
36.15 20.74 43.11 57.64 38.49 3.87 27.92 12.39 59.69
30.93 23.32 45.75 48.32 47.72 3.96 24.08 11.91 64.01
26.52 25.17 48.31 43.45 52.57 3.98 18.91 11.67 69.42
20.76 28.47 50.77 36.60 59.54 3.86 13.10 11.58 75.32
13.85 31.92 54.23 27.34 68.75 3.91 7.40 11.37 81.23
7.20 35.13 57.67 14.88 81.13 3.99 4.15 11.31 84.54
38.76 61.24 96.05 3.95 11.23 88.77
a
w is the mass fraction (%) ; blanks: does not exist or not detected.

3.2 Effect of extraction time

The effect of extraction time, ranging from 3min to 30min, on the extraction efficiency was
investigated (Figure 2). The distribution coefficients of H3PO4 increased rapidly from 0.14 to 0.23 in the
time range of 3-10 min and then it remained almost constant. The results indicate that it only took 10 min to
attain extraction equilibrium. The separation factors of Fe3+ and SO42- stop increasing when the extraction
time was over 15min. The extraction time of 15 min was used in the further experiments to ensure that
extraction equilibrium was achieved. In addition, excessive extraction time will lead to poor yields of
phosphoric acid, poor selectivity and longer phase separation times [19].

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Figure 2. Effect of extraction time on the distribution coefficient of H3PO4 and the separation factor for
Fe3+ and SO42-; [Cyclohexanol] = 1.90 mol/L, [H3PO4] = 5.07 mol/L, O/A = 4, T = 313.2K: (■) DH 3 PO 4 ; (ᇞ)
β for Fe3+; (○) β for SO42-.

3.3 The extracted complex

It is useful to know the stoichiometry of the extracted complex, which can be determined from the
extraction equilibrium studies. Assuming that phosphoric acid transfers into the organic phase in a neutral
form and exists in the organic phase as a complex of the form pH3PO4 · qC6H12O [20]. The extraction of
H3PO4 from the phosphoric acid solution by cyclohexanol can be described as

p (H3PO4 )( a )  q(C6H12O)( o )  p(H3PO4 )  q(C6 H12O)( o ) (4),

where the subscripts a and o stand for the aqueous and organic phases, respectively. p and q are the
stoichiometric coefficients of H3PO4 and cyclohexanol in the reaction above, respectively.
The equilibrium constant (Keq) of the extraction reaction in Eq. (4) is

[ pH3PO 4  qC6 H12O]( o )

Keq = (5)
[H3PO4]( a ) p  [C6H12O]( o ) q

The distribution coefficient of H3PO4 can be calculated as

[H 3PO4 ]( o ) p[ pH3PO 4  qC6 H12O]( o )

D  (6)
[H3PO 4 ]( a ) [H 3PO4 ]( a )

An indirect approximation method based on slope analysis was used to verify the stoichiometry of the
extracted species. Inserting Eq. (6) into Eq. (5) and then taking the logarithm of both sides of the resulting
equation leads to the expression

log D  log pK eq  ( p  1) log [H3PO 4 ]( a )  q log [C6 H12O]( o ) (7)

Inserting Eq. (6) into Eq. (7) gives

log [H 3PO 4 ]( o )  log pK eq  p log [H3PO 4 ]( a )  q log [C6 H12O]( o ) (8)

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After determining the values of p and q in the extraction reaction in Eq. (4), the extracted species can then
be determined.

3.3.1 Effect of H3PO4 concentration

The effect of H3PO4 concentration in the range of 1.63-6.94 mol/L on the extraction was studied.
The concentration of cyclohexanol in the initial organic phase remained 1.90 mol/L and the temperature
was maintained constant at 313.2K. The equilibrium distribution results for pure H3PO4 and the industrial
WPA used in this work (Table 1) were compared. Plots of log [H3PO4](o) versus log [H3PO4](a) are shown in
Figure 3. Using regression analysis, the following relations can be established from the obtained data:
The pure H3PO4 cyclohexanol system:

log [H3PO4 ]( o )  1.58  1.96 log [H3PO4 ]( a ) , R = 0.999 (9)

The industrial WPA cyclohexanol system:

log [H3PO4 ]( o )  1.66  2.01 log [H3PO4 ]( a ) , R = 0.998 (10),

where R is the correlation coefficient.

The H3PO4 concentration in the organic phase increased as the H3PO4 concentration in the aqueous
phase increased. For the same condition, the [H3PO4](o) of pure H3PO4 was higher than that of the industrial
WPA. This is mainly because the co-extraction of some impurities reduces the extraction efficiency of the
solvent mixtures. The slopes of the two lines are 1.96 and 2.01, respectively. According to the slopes of the
two lines, p in Eq. (4) equals 2 approximately.

Figure 3. Equilibrium isotherms for the analytical concentrations of the organic phase [H3PO4](o) and the
aqueous phase [H3PO4](a) for the extraction; [C6H12O] = 1.90 mol/L, O/A = 4, T = 313.2K: (□) pure H3PO4;
(■) industrial WPA.

3.3.2 Effect of cyclohexanol concentration

The effect of cyclohexanol concentration on the extraction was studied. The cyclohexanol
concentration was varied in the range of 1.64-1.90 mol/L. The concentration of H3PO4 in the initial aqueous

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phase remained at 2.85 mol/L and the temperature was maintained constant at 313.2K. As Figure 4 shows,
the distribution coefficients increased with an increase in the cyclohexanol concentration. It is preferable to
have a high extractant concentration for better extraction efficiency. Using regression analysis, the
following relation was established from the obtained data:

log D  1.15  1.90 log [C6 H12O] , R = 0.998 (11)

According to Eq. (11), the slope of the plot of log D versus log [C6H12O] is 1.90, which would give the
number of molecules of [C6H12O] engaged in the reaction (Eq. (4)). Therefore q in Eq. (4) approximately
equals 2.

Figure 4. Effect of cyclohexanol concentration on the distribution coefficient of H3PO4; [H3PO4] = 2.85
mol/L, O/A = 4, T = 313.2K.

3.3.3 IR absorption spectrum of the extracted complex

According to 3.3.1-3.3.2, the extraction mechanism of H3PO4 extraction with cyclohexanol can be
represented as follows:

2(H3PO4 )( a )  2(C6H12O)(o)  2(H3PO4 )  2(C6H12O)(o) (12)

The possible extracted complex of H3PO4–C6H12O is 2H3PO4 · 2C6H12O.

The IR spectrum of the extracted complex H3PO4–C6H12O (B) is shown in Figure 5, compared with
that of cyclohexanol (A) before extraction. The –OH bond stretching vibration at 3345 cm-1 in
cyclohexanol is shifted to a higher frequency at 3382 cm-1 and the peak is seen to be widened. This is
because of certain amounts of –OH bonds introduced with H3PO4 and H2O after complexation. In addition,
a peak is observed at 1642 cm-1, which is also ascribed to the stretching vibration of the –OH group. The
peak at 1069 cm-1 may be assigned to the stretching vibration of the C–O bond in cyclohexanol. In the
extracted complex, due to hydrogen bond formation, the electron cloud is distributed more averagely and 
the C–O bond stretching vibration frequency is lowered to 1067 cm-1.

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Figure 5. IR spectrum of cyclohexanol (A) and the H3PO4-cyclohexanol complex (B).

3.4 Effect of temperature

The effect of temperature in the range of 293.2K-338.2K on the extraction was investigated. The
concentration of H3PO4 in the initial aqueous phase and the concentration of cyclohexanol in the initial
organic phase remained as 5.07 mol/L and 1.90 mol/L, respectively.
Plots of log D versus 1/T are shown in Figure 6. Using regression analysis, the following relations
can be established from the obtained data:
H3PO4, in the range of 293.2K-308.2K:

log D  0.72  0.03  [1/ T 103 ] , R = 0.999 (13)

H3PO4, in the range of 308.2K-338.2K:

log D  1.03  0.12  [1/ T 103 ] , R = 0.997 (14)

Fe3+, in the range of 293.2K-338.2K:

log D  0.27  0.42  [1/ T 103 ] , R = 0.997 (15)

SO42-, in the range of 293.2K-338.2K:

log D  0.29  0.31 [1/ T 103 ] , R = 0.998 (16)

According to the Van’t Hoff equation [21]

Δ log D ΔH
 (17),
Δ(1 / T ) 2.303R
the distribution coefficients of H3PO4 decrease with an increase in temperature. In the range of
293.2K-308.2K, the value of the enthalpy change ᇞH of H3PO4 extraction is -0.590 kJ/mol and the value of
ᇞH is -2.434 kJ/mol when the temperature is over 308.2K, which is calculated from the slope of the linear
relation. This result indicates that the extraction reaction of H3PO4 is exothermic and the thermal effect will
increase at a certain temperatures. The volatilization of the solvent also increases at higher temperature.

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Increasing temperature has an adverse effect on the extraction efficiency, which is in agreement with the
previous study [10]. On the other hand, the distribution coefficients of Fe3+ and SO42- increase with higher
temperature. According to Eq. (15) and Eq. (16), the value of the enthalpy change for the extraction of Fe3+,
ᇞH, is 8.072 kJ/mol and that of SO42- the ᇞH is 5.876 kJ/mol, which indicates that the co-extraction
reaction of these two impurities is endothermic and the effect of temperature on the SO42- extraction is
smaller than that for Fe3+. Higher temperature has a negative effect on the H3PO4 extraction selectivity. The
selected optimal extraction temperature is 298.2K. The results show that the extraction system can perform
well at room temperature with low energy consumption and good selectivity so that it has good prospects
for industrial application.

Figure 6. Effect of temperature on distribution coefficients of H3PO4, Fe3+ and SO42-; [Cyclohexanol] =
1.90 mol/L, [H3PO4] = 5.07 mol/L, O/A = 4: (■) H3PO4; (ᇞ) Fe3+; (○) SO42-.

3.5 Effect of phase ratio

The effect of phase ratio (O/A) ranging from 1.0 to 5.0 on the extraction was studied. The
concentration of H3PO4 in the initial aqueous phase and the concentrations of cyclohexanol in the initial
organic phase remained as 5.07 mol/L and 1.90 mol/L, respectively. The temperature was maintained
constant at 298.2K.
Figure 7 shows that the extraction yields of H3PO4 increase from 51.0% to 80.2% as the phase ratio
is raised from 1.0 to 5.0. The result indicates that a higher extraction yield is obtained with a higher phase
ratio. This is because when the phosphate content in the aqueous phase is constant, increasing the phase
ratio can lead to higher extraction equilibrium values, thereby increasing the extraction yield. In addition, a
higher phase ratio gives better selectivity over impurities but higher viscosity of the two-phase mixtures
and more solvent consumption [7].

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Figure 7. Effect of phase ratio O/A on extraction yield of H3PO4 and separation factor for Fe3+ and SO42-
impurities: [Cyclohexanol] = 1.90 mol/L, [H3PO4] = 5.07 mol/L, T = 298.2K: (■) E %; (ᇞ) β for Fe3+; (○) β
for SO42-.

3.6 Cross-current multi-stage extraction of H3PO4

In order to predict the number of the theoretical stages required for the extraction process, a diagram
for the extraction by cyclohexanol diluted in kerosene was constructed at 298.2K [22]. Using regression
analysis, the following relations of the distribution of H3PO4 in the organic and aqueous phases were
established from the obtained equilibrium data:
Y  0.003 X 2  0.109 X + 0.661 , R = 0.996 (18)
where Y and X are the mass fraction of H3PO4 in the organic and aqueous phases, respectively.
From Figure 8, it can be calculated that the cumulative extraction yield of H3PO4 is 54.6%, 78.4%,
90.7% and 97.9%, respectively for each stage. The multi-stage extraction of H3PO4 from the industrial
WPA (Table 1) was conducted with the H3PO4 concentration in the initial aqueous phase and the
cyclohexanol concentration in the initial organic phase kept at 5.07 mol/L and 1.90 mol/L, respectively. The
temperature was maintained constant at 298.2K and the phase ratio, O/A, was 3. The calculated and
experimental values of the mass fraction of H3PO4 for each stage are compared in Table 3. The
experimental values correspond well with the calculated ones. The cumulative extraction yield of H3PO4 is
56.1%, 79.2%, 90.2% and 97.6%, respectively for each stage. Considering the H3PO4 yield and the
consumption of solvent, three-stage cross-current extraction is chosen as the optimal operation condition,
which can obtain a high extraction yield. On the other hand, kerosene used as the diluent in the solvent
mixtures can strengthen the flowability and decrease the viscosity of the two-phase mixtures but will lower
the extraction ability at the same time. Thus a balance between the extraction efficiency and the operating
conditions in the industrial application must be achieved. It can be concluded that cyclohexanol diluted in
kerosene is a good extractant for H3PO4 from industrial WPA.

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Figure 8. Diagram for the H3PO4 extraction by cyclohexanol and kerosene mixtures: [Cyclohexanol] = 1.90
mol/L, [H3PO4] = 5.07 mol/L, O/A = 4, T = 298.2K.

Table 3. Comparison between the calculated and experimental value of the H3PO4 concentration
of each stage (X for aqueous phase, Y for organic phase).

X, Y
X1 Y1 X2 Y2 X3 Y3 X4 Y4
(wt%)
Calculated 29.32 6.28 13.94 2.73 5.98 1.41 1.37 0.80
Experimental 28.32 6.49 13.42 2.82 6.32 1.34 1.55 0.75

3.7 Scrubbing and stripping

The organic phase loaded with H3PO4 after extraction still contains impurities including equilibrium
concentrations of some trace metallic impurities (Fe3+, Mg2+, Al3+, et.) and the co-extracted fluoride and
sulfate ions. Scrubbing of the organic phase using deionized water at a 10:1 O/A phase ratio is thus
conducted to remove these undesirable impurities. After scrubbing, the stripping of H3PO4 from the
scrubbed loaded organic phase can be conducted at a 4:1 O/A phase ratio through three stages cross-current
re-extraction using deionized water. The composition of the processed WPA is shown in Table 4. The
scrubbing and stripping operation was carried out at a constant temperature of 313.2K.
As Table 4 shows, scrubbing of the organic phase using deionized water is able to remove the
impurities efficiently after extraction. The loss of H3PO4 in the scrubbing process is less than 0.5% from the
loaded organic phase. By the above purifying process of extraction, scrubbing and stripping, the metallic
impurities are successfully removed to less than 5ppm in the purified diluted PA without any other
purifying technology.
Ion precipitation of sulfate using calcium carbonate or barium carbonate is generally conducted
before or after extraction to remove the sulfate ions further. The fluoride ions remaining in the purified
diluted PA after re-extraction can be efficiently removed in the concentration operation to produce PA of
food and analytical grade [23].

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 Table 4. Composition of different types of phosphoric acid.

H3PO4 F- SO42- Fe3+ Al3+ Mg2+ Zn2+ Cr3+

Composition
(wt %) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
Extracted
4.81 20.4 114.2 16.2 6.1 5.5 N.D N.D
organic phase
Scrubbed
4.49 15.1 74.7 5.1 1.1 1.3 N.D N.D
organic phase
Stripped
15.76 8.2 23.4 3.0 1.2 1.8 N.D N.D
phosphoric acid

4. Conclusion
In this work, purification of wet process phosphoric acid by solvent extraction with using
cyclohexanol diluted in kerosene has been studied. The equilibrium phase diagram of the system H3PO4 
H2O solvent mixtures (75% cyclohexanol + 25% kerosene) at 313.2K was obtained. The results show that
it takes 10 min to attain extraction equilibrium. Cyclohexanol concentration and phosphoric acid
concentration both have a positive effect on H3PO4 extraction. Therefore, the WPA can be pre-concentrated
to an appropriate degree to increase the purifying efficiency. The extracted species is demonstrated to be
2H3PO4 · 2C6H12O. The H3PO4 extraction process is exothermic with an enthalpy change, ᇞH, of -0.590
kJ/mol in the temperature range of 293.2K-308.2K and ᇞH is -2.434 kJ/mol when the temperature is over
308.2K. The solvent mixture have a high efficiency for phosphoric acid purification from industrial WPA
with an H3PO4 extraction yield of 90.2% via a cross-current three-stage extraction. Although still
experimental，the solvent mixture has the potential for the extraction system to be mixed with other
solvents that may lead to better immiscibility with the aqueous solution. Based on the low power
consumption and recycling of solvent, environment pollution is expected to be less than for other
techniques for WPA purification. The new process has good prospects for industrial application.

Acknowledgement

Project supported by the National Natural Science Foundation of China (No. 21306116) and the
Technology Commission Foundation of Sichuan Province of China (No. 2014JY0079).

References

1) A.A. El-Asmy, H.M. Serag, M.A. Mahdy, M.I. Amin, Sep. Purif. Technol., 61, 287-293 (2008).
2) N. Boulkroune, A.H. Meniai, Energ. Procedia, 18, 1189-1198 (2012).
3) L. Monser, M.B. Amor, M. Ksibi, Chem. Eng. Process, 38, 267-271 (1999).
4) M. Takahara, Production of phosphoric acid of high purity, US Patent, 3,917,805 (1975).
5) R. Kijkowska, D. Pawlowska-Kozinska, Z. Kowalski, M. Jodko, Z. Wzorek, Sep. Purif. Technol., 28,
197-205 (2002).
6) M.B. Elleuch, M.B. Amor, G. Pourcelly, Sep. Purif. Technol., 51, 285-290 (2006).
7) M.Y. Huang, B.H. Zhong, J. Li, J. Chem. Eng. Data, 53, 2029-2032 (2008).
8) H. Ahmed, H. Diamonta, C. Chaker, R. Abdelhamid, Sep. Purif. Technol., 55, 212-216 (2007).

- 34 -
9) B. Ahlem, M. Abdeslam-Hassen, B. L. Mossaab, Chem. Eng. Technol., 24, 1273-1280 (2001).
10) M. Feki, M. Stambouli, D. Pareau, H.F. Ayedi, Chem. Eng. J., 88, 71-80 (2002).
11) C.W. Ye, J. Li, J. Chem. Technol. Biot., 88, 1715-1720 (2013).
12) M.I. Amin, M.M. Ali, H.M. Kamal, A.M. Youssef, M.A. Akl, Hydrometallurgy, 105, 115-119 (2010).
13) N.M. Dacia, E.M. Hoxhaa, G. Vujičić, Fuel, 64, 520-522(1985).
14) R.K. Mishra, P.C. Rout, K. Sarangi, K.C. Nathsarma, Hydrometallurgy, 108, 93-99(2011).
15) Y. Jin, J. Li, J.H. Luo, D.S. Zheng, L. Liu, J. Chem. Eng. Data, 55, 3196-3199 (2010).
16) R. Sanghani, Procedia Eng., 83, 225-232 (2014).
17) Y. Zhang, G. Lin, Z. Li, Analysis for Ammonium Phosphate Production, first ed., Chengdu University
of Science and Technology Press, Chengdu (1991).
18) L.A. Robbins, R.W. Cusack, Liquid–liquid extraction operations and equipment, R.H. Perry, D.W.
Green, J.O. Maloney (Eds.), Perry’s Chemical Engineers Handbook, seventh ed., Mac Graw-Hill, New
York (1997).
19) H.H. Nejad, M. Kazemeini, Procedia Eng., 42, 1302-1312 (2012).
20) R. Dhouib-Sahnoun, M. Feki, H.F. Ayedi, J. Chem. Eng. Data, 47, 861-866 (2002).
21) U.K. Deiters, Fluid Phase Equilib., 336, 22-27 (2012).
22) Y. Jin, Y.J. Ma, Y.L. Weng, X.H. Jia, J. Li, J. Ind. Eng. Chem., 20, 3446-3452 (2014)
23) L.S. Wang, Z.Q. Long, X.W. Huang, Y. Yu, D.L. Cui, G.C. Zhang, Hydrometallurgy, 101, 41-47
(2010).

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