Hydrometallurgy 105 (2010) 115–119

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Hydrometallurgy
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / h yd r o m e t

Recovery of high grade phosphoric acid from wet process acid by solvent extraction
with aliphatic alcohols
M.I. Amin a,⁎, M.M. Ali a, H.M. Kamal a, A.M. Youssef b, M.A. Akl b
a
Nuclear Materials Authority, Cairo, Egypt
b
Chemistry Department, Faculty of Science, Mansoura University, Mansoura, Egypt

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

Article history: High grade phosphoric acid was obtained using liquid–liquid extraction with aliphatic alcohols to separate
Received 15 April 2010 metal and fluoride ion impurities in the aqueous phase. The influence of alcohol chain length, alcohol
Received in revised form 22 August 2010 concentration, organic/aqueous phase ratio, temperature, shaking time and phosphoric acid concentration
Accepted 22 August 2010
on P2O5 extraction was studied. Scrubbing with acid and stripping with water were also investigated. n-
Available online 27 August 2010
Octanol proved to be the most efficient and selective alcohol. The temperature had a slight positive effect and
Keywords:
the extraction was enhanced by increasing P2O5 and with the increase of organic/aqueous phase ratio. The
High grade phosphoric acid optimum organic/aqueous phase ratio for stripping was determined to be 2.0. For 9.2 M H3PO4, 98% of
Solvent extraction fluoride ion was removed whereas almost complete removal of iron, manganese, copper, cadmium and zinc
Aliphatic alcohols was attained.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction solvent mixture was determined (Hannachi, et al., 2007). The

Wet process phosphoric acid (WPA) contains many impurities
beside solids and organic matters (Shlewit and Khorfan, 2002). In
particular, the reduction of fluoride content during the manufacture of
WPA to a very low concentration has been studied (Hanna et al.,
1998) and there has been a wide interest over the last few years to
develop a process for the purification of commercial WPA using
solvent extraction. Many solvents were tried but aliphatic alcohols
have the advantages of being efficient, cheap, easy to use, separate
quickly and do not pollute the food grade acid produced. N-heptanol
has been used to extract P2O5 from WPA (Khorfan et al., 2001), and it
was possible to remove 97% of the metals and 82% of the fluoride. The
factors affecting the extraction of H3PO4 by n-heptanol included
temperature, mixing time and the concentration of n-heptanol which
had a positive effect; so the solvent was used without dilution. The
extraction of uranium and heavy metals was negligible, while the
extraction of fluorine and iron was relatively small. The solvent
extraction of phosphoric acid from various aqueous solutions has also
been investigated using tributyl-phosphate (TBP) (Moussa, 2007) and
methyl isobutyl ketone (MIBK). Purification of WPA with mixtures of
MIBK and TBP gave the greatest recovery of P2O5 with 55% MIBK-45%
TBP and a phase diagram of the ternary system H3PO4-water-optimal
⁎ Corresponding author. Tel.: + 2 0105273009.
E-mail address: mostafa_nma@yahoo.com (M.I. Amin).
purification of commercial H3PO4 from metallic impurities was
studied using 2.55 M TBP in kerosene (Abu-Raia, 2006) and about
90% P2O5 in 9.2 M H3PO4 could be extracted in three stages at room
temperature. However, the purification of WPA with MIBK was
systematically studied (Feki et al., 2002) with regard to the
distribution of the major impurities (Ca2+, Mg2+, Al3+, Fe3+, SO2−
4 ,
and F−) between the conjugated phases at 40 °C. The purity of H3PO4
was computed by counter current multistage extraction using the
McCabe-Thiele method. The aim of the present work is to compare
and contrast butanol, hexanol and octanol in kerosene as extractants
for H3PO4 to determine the role of the different parameters
contributing to the extraction process. A major aim was the
specification of phosphoric acid, before and after solvent extraction
to achieve a high grade product, and the determination of the
McCabe-Thiele extraction diagram.
2. Experimental
2.1. Materials and measurements
Normal butanol, hexanol and octanol (BDH) with 99% purity were
used. Commercial WPA with the following components
(P2O5 = 44.0%, Fe = 2.6%, Cu = 0.0012%, Cd = 0.001%, F = 0.7%) was
supplied from Abu-Zaabal Co., Cairo, Egypt. Abu Tartur bentonite was
used. All chemicals and reagents were of A.R. grade and used without
further purification. Fe, Cd and Cu were determined by GBC 932-AAS.
The fluoride content was determined by ion selective electrode, a
Genway, model 3330 pH meter equipped with Orion model 94-09 BN
fluoride electrode. P2O5 was determined spectrophotometrically. The

0304-386X/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2010.08.007
116 M.I. Amin et al. / Hydrometallurgy 105 (2010) 115–119

concentration of P2O5 in the solvent was calculated from the material

balance. The yield was calculated from the equation:

½P 2 O5 feed acid –½P 2 O5 raffinate

YieldðY %Þ = × 100
½P 2 O5 feed acid

The distribution ratio (D) was calculated from the total concen-
tration of P2O5 in the organic and aqueous phases.

2.2. Analytical procedures

2.2.1. Acid pre-treatment
Crude phosphoric acid (9.2 M) was mixed with bentonite
(11.67 g/L) for 30 min and the acid was left to settle down.
Polyacrylamide (0.5 mg/L) as a flocculating agent was added to
enhance the settlement of the suspended materials.
2.2.2. Production of partially purified phosphoric acid
Pre-treated phosphoric acid was partially purified (El-Asmy
et al., 2008) before applying a solvent extraction technique to
decrease the concentration of fluoride and iron by precipitation
using 5.9 g/L SiO2 + 10.5 g/L Na2CO3 followed by addition of 26.7 g/L
K2SO4.
2.2.3. Extraction of P2O5
The extraction of P2O5 was carried out from different concentra-
tions of WPA. The different parameters investigated were: solvent
concentration, temperature, shaking time and organic/aqueous phase
ratio. Different volumes of organic and aqueous phases were
equilibrated for 10 min under vigorous shaking in a thermostatted
water bath. After phase separation, the concentration of P2O5 in the
aqueous phase before and after extraction was determined. Also, the
′
extraction percent (Eextn %) were calculated
100D
ðE′Extn: % Þ =
D + V aq = V org
Shaking time is an important factor in reaching equilibrium in
liquid-liquid extraction processes. In this work, the effect of shaking
time was investigated between 1 and 30 min under the following
conditions: (H3PO4 = 9.20 M, O/A = 1:1, 1:3 and 1:5 for butanol,
hexanol and octanol respectively, T = 25 °C). It was found that there
was little difference in extraction after shaking for 5 min indicating a
rapid diffusion controlled process. Therefore, for all tests shaking was
conducted for 10 min unless otherwise stated.
2.2.4. Scrubbing and stripping process
The organic extract was preferably scrubbed (washed) with pure
aqueous phosphoric acid before stripping with water at 25 °C. In this
step, a large portion of undesirable impurities could be removed from
the organic extract if present. The factors affecting washing and
stripping efficiency were studied keeping the shaking time constant at
5 min. The distribution coefficient and stripping efficiency were
calculated.
Fig. 1. Effect of the number of carbon on E′extn. % of P2O5 (O/A = 4; 9.2 M H3PO4; pure
alcohols used without dilution; room temperature).
and its increase retards P2O5 extraction — possibly due to decreasing
water solubility in the alcohols.
3.1.2. Effect of phosphoric acid concentration
The effect of partially purified phosphoric acid concentration on
′
Eextn % was investigated within the concentration range 3.99–
9.20 M. The results in Fig. 2 reveal that Eextn ′ % continuously
increases with the increase of the acid concentration to reach 65,
56 and 35% for butanol, hexanol and octanol, respectively, from
9.2 M H3PO4. In the extracted species, the protons of the acid may
form a hydrogen bond with the oxygen atom of the alcohol.
Solvation of H3PO4 by the alcohol may also be enhanced by
dissolved water in the organic phase that can hydrogen bond to
both the acid and the alcohol molecules.
Moussa (2007) has studied the effect of phosphoric acid
concentration on the extraction efficiency of P2O5 using TBP as the
organic solvent and obtained similar trends and data.
3.1.3. Effect of alcohol concentration
The effect of solvent concentration on the P2O5 extraction from
partially purified phosphoric acid (9.20 M) was achieved within the
alcohol concentration range (0.63–6.31 M) at room temperature
′
using kerosene as a diluent. The results in Fig. 3 show that the Eextn %
of the P 2 O 5 increases linearly with the increase of alcohol
concentration.
When the distribution coefficient was calculated and log D was
plotted versus log [alcohol], Fig. 4 shows straight lines were obtained
with slopes of 1.287, 1.462 and 1.645 for butanol, hexanol and octanol,
respectively, indicating about 1.5 mol of alcohol associated with acid
in the organic phase.
3.1.4. Effect of organic to aqueous phase ratio
The effect of changing O/A. phase ratio between 1.0 and 6.0 on E ′extn %
of P2O5 from 9.20 M phosphoric acid was investigated using the different
alcohols. The obtained results in Fig. 5 indicate that E′extn % of P2O5
increases significantly by increasing the O/A phase ratio but with butanol,
little further extraction was obtained using O/A ratios more than 2.

3. Results and discussion

3.1. Liquid-liquid extraction of P2O5 from wet process phosphoric acid

3.1.1. Effect of carbon chain length of the alcohol

The effect of the alcohol carbon chain length on Eextn ′ % was
investigated using 9.2 M phosphoric acid and butanol, hexanol and
octanol without dilution (O/A = 4) while other extraction conditions
were the same. The results in Fig. 1 show Eextn′ % decreased with the
increase of the chain length of the solvent. The chain length may be Fig. 2. Effect of phosphoric acid concentration on E′extn. % of P2O5 (O/A = 1; room
considered as a barrier for the transfer of P2O5 from the aqueous phase temperature; pure alcohols).
 M.I. Amin et al. / Hydrometallurgy 105 (2010) 115–119
Fig. 3. Effect of alcohol concentration in kerosene on E′extn. % of P2O5.
Fig. 4. log D as a function of the log alcohols concentration (O/A = 1 butanol; O/A = 3
hexanol; O/A = 5 octanol).
3.1.5. Effect of temperature
The extraction of P2O5 from the partially purified phosphoric acid
was investigated at different temperatures between 278 and 333 K.
The O/A phase ratios were 1:1, 3:1 and 5:1 for butanol, hexanol and
octanol respectively. The results in Fig. 6 indicate that E′extn % of P2O5
increased from 63 to 68% for butanol, 58 to 64% for hexanol and 64 to
70% for octanol.
The results are also plotted in Fig. 7 in the form of ln D versus 1000/
T K which fit a straight line equation with slope values of −0.3817,
−0.4277 and −0.4803 for butanol, hexanol and octanol respectively.
The relation between the equilibrium constant K and the temperature
is given by Van't Hoff equation (Khorfan et al., 2001):
2
d ln K = dT = ΔH = R:T
which by integration becomes ln K = ln D = (-um constant K.
The calculated enthalpy changes (ΔH) for butanol, hexanol and
octanol are 3.1, 3.5 and 3.9 kJ/mol, respectively. The positive values of
ΔH reflect the positive effect of extraction temperature which seems
to depend on the chain length of the alcohol extractant.
Fig. 5. Effect of organic to aqueous phase ratio on E′extn. % of P2O5.
117
Fig. 6. Effect of temperature on E′extn. % of P2O5 (O/A = 1 butanol; O/A = 3 hexanol;
O/A = 5 octanol).
3.2. McCabe-Thiele diagrams for phosphoric acid extraction
McCabe Thiele diagrams were established to optimize P2O5
extraction from 9.20 M partially purified phosphoric acid using pure
butanol (10.86 M), hexanol (7.88 M) and octanol (6.31 M) respec-
tively, as shown in Fig. 8. They were used to calculate that 3 counter
current stages achieved about 86, 93 and 87% extraction at 25 °C using
butanol, hexanol and octanol respectively.
3.3. Scrubbing process
The organic extract may still have impurities. Scrubbing of the
organic extract is conventionally carried out using an aqueous
solution of pure phosphoric acid. Because the scrubbing process is
an important step towards getting high grade product, the effect of
the concentration of pure phosphoric acid used for washing was
studied at 25 °C in the range of 2.08 to 5.46 M for butanol, 3.24 to
8.92 M for hexanol and 2.18 to 7.98 M for octanol. The aim was to
determine the equilibrium acid concentration that does not transfer
acid between the phases when the concentration of loaded acid in the
organic phases to start with was 25 wt.% as P2O5.
When using a ratio of loaded organic phase to washing acid of 1.0,
the results revealed that by increasing the acid wash concentration,
the P2O5 transferring from the organic phase to the wash phase
decreased to zero at 4.26, 5.91 and 7.61 M acid wash concentration for
butanol, hexanol and octanol, respectively.
3.4. Stripping process
The re-extraction of P2O5 from the loaded organic solvent
containing 25 wt.% P2O5 was investigated using distilled water at an
O/A ratio of 1.0 to obtain dilute phosphoric acid. The concentrations of
the stripped acids were 16, 20 and 23 wt.% for butanol, hexanol and
octanol respectively. High purity concentrated phosphoric (62 wt.%)
Fig. 7. ln D as a function of 1000/T.
118 M.I. Amin et al. / Hydrometallurgy 105 (2010) 115–119

Fig. 8. McCabe-Thiele diagram for the extraction of P2O5 using (a) butanol; (b) hexanol; (c) octanol.

was thereafter obtained by evaporation. Evidently, Estr ′ % increased

with the increase of the chain length of the solvent, a trend opposite to
the extraction process (Fig. 1) which is not surprising.
The effect of increasing the A/O phase ratio from 0.25 to 4.00 on the
P2O5 stripping from butanol, hexanol and octanol at room tempera-
ture is shown in Fig. 9. Clearly, increasing the A/O ratio, improves the
P2O5 stripping efficiency which reaches a maximum at an A/O
ratio = 2.0. A further increase in A/O ratio was associated with only
a very slight increase of P2O5 stripping.

3.5. Removal of impurities from phosphoric acid

Phosphoric acids are graded according to their physical properties

and the concentration of some metallic and non-metallic impurities Fig. 9. Effect of aqueous to organic phase ratio on E′Str.. % of P2O5.
 M.I. Amin et al. / Hydrometallurgy 105 (2010) 115–119 119

Table 1 Table 2
Physical properties and impurity content of the different grades of phosphoric acid. Chemical composition of different types of phosphoric acid.

Constituent Phosphoric acid grades Type of phosphoric Element, ppm

acid
TGA FGA PGA AGA Fe F- Cu Cd Zn Mn

H3PO4% w/w 85.0% 85.0% 85.0% 86.0% Crude WPA 40560.0 11230.0 18.6 15.0 620.0 1860.0
P2O5% w/w 61.6% 61.6 61.6% 62.0 Partially purified WPA 10140.0 499.2 18.6 15.0 620.0 1860.0
Density at 25 °C 1.6 1.6 1.6 1.7 Finally produced WPA 525.0 100.0 N.D 0.05 25.8 2.3
using butanol
Concentration ppm Finally produced WPA 80.0 20.0 N.D N.D 1.0 N.D
Fe 20.0 20.0 20.0 15.0 using hexanol
F− 100.0 10.0 10.0 10.0 Finally produced WPA 10.0 10.0 N.D N.D N.D N.D
NO−3 20.0 5.0 5.0 5.0 using octanol
SO−4 200.0 100.0 50.0 20.0
N.D. not detected.
Cu 20.0 10.0 5.0 5.0
Pb 10.0 5.00 1.0 3.0

concentrations of 4.26, 5.91 and 7.61 M for butanol, hexanol and

contained. Four grades are reported in literature. These grades are
arranged according to their quality as: technical grade acid TGA b food
grade acid FGA b pharmaceutical grade acid PGA b analytical grade
acid AGA. Table 1 lists the physical properties and impurities content
of these four grades which reveal little difference in the physical
properties, but pronounced differences in the impurities content
expressed in ppm.
The impurities determined in this investigation for crude acid,
partially purified acid and finally produced acid are shown in Table 2
which indicates that the finally produced acids are by far more
superior compared with any of the grades reported in literature.
Although the finally produced acids obtained in this investigation are
more or less of the same grade, the acid obtained by extraction with
octanol contains the least impurities. Table 2 reveals also that the
efficiencies of the alcohols used could be arranged as: n-octanol N n-
hexanol N n-butanol referring thus to the function of the chain length.
4. Conclusions
Purification of wet process phosphoric acid was carried out by
solvent extraction using n-butanol, n-hexanol and n-octanol. Acid was
extracted from impure 9.2 M H3PO4 at 25 °C with an aqueous/organic
phase ratio equal 1:1, 1:3 and 1:5 for butanol, hexanol and octanol,
respectively. McCabe Thiele diagrams indicate 86%, 94% and 87% acid
extraction in 3 stages using butanol, hexanol and octanol, respectively.
Scrubbing of the loaded organic extract containing 25 wt.% P2O5 was
made by shaking the loaded organic solvent with pure phosphoric acid
octanol, respectively. Stripping of the acid from the organic phase with
distilled water at room temperature was best achieved with an aqueous/
organic phase ratio of 2. The stripping efficiencies of the alcohols follow
the order: octanol N hexanol N butanol. The finally produced WPA was
found to be highly pure compared with all the acid grades reported in
literature. The concentrations of iron and fluoride ion were determined
for octanol extracted WPA to be 10 and 10 ppm respectively. The
concentrations of Cu, Cd, Mn and Zn were too low to be determined.
References
Abu-Raia, A., 2006. Purification of commercial phosphoric acid using organic solvents,
M.Sc Thesis, Faculty of Science, Tanta University, 112–119.
El-Asmy, A.A., Serag, H.M., Mahdy, M.A., Amin, M.I., 2008. Purification of phosphoric
acid by minimizing iron, copper, cadmium and fluoride. Sep. Purif. Technol. 61,
287–292.
Feki, M., Stambouli, M., Pareau, D., Ayedi, H.F., 2002. Study of the multicomponent
system wet process phosphoric acid–methyl isobutyl ketone at 40 °C phase
equilibria and extraction performances. Chem. Eng. 88, 71–78.
Hanna, A.A., Sibak, A.H., Ali, A.F., 1998. Reduction of fluorine content in crude wet-
process phosphoric acid. Journal of Engineering and Applied Science 45, 633–642.
Hannachi, A., Habaili, D., Chtara, C., Ratel, A., 2007. Purification of wet process
phosphoric acid by solvent extraction with TBP and MIBK mixtures. Sep. Purif.
Technol. 55, 212–217.
Khorfan, S., Shino, O., Wahoud, A., 2001. Extraction of H3PO4 from wet phosphoric acid
by nC4–nC7 alcohols. Periodica Polytechnica Chemical Engineering 45, 139–145.
Moussa, A.I., 2007. Extraction of phosphoric acid from various aqueous solutions using
tributyl phosphate. Chem. Eng. 51, 39–44.
Shlewit, H., Khorfan, S., 2002. Purification of phosphoric acid by solvent extraction with
TBP/kerosene. Solvent Extr. Res. Dev., Jpn. 9, 59–63.