Removal of Ferric Ions from Aluminum Solutions
by Solvent Extraction, Part II: Kinetics Study
Xiaoxue Sun , Yuzhu Sun, and Jianguo Yu
School of Resources and Environmental Engineering, National Engineering Research Center for Integrated Utilization of Salt
Lake Resource, East China University of Science and Technology, Shanghai 200237, People’s Republic of China;
yzsun@ecust.edu.cn (for correspondence)
Published online 00 Month 2018 in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/ep.12867
Extraction and stripping kinetics of removal of ferric iron
from aluminum sulfate solutions using a synergic extractant
consisting of di-(2-ethylhexyl) phosphoric acid (P204) and
tertiary amine (N235) were reported, in order to explore the
basic data for the recovery of aluminum resources from coal
spoil.
The kinetics of extraction was studied in a highly stirred
tank using a focused beam reflectance measurement (FBRM)
and a Nikon microscope to monitor the contact between
aqueous phase and organic phase. The data were analyzed
in terms of a first-order reversible reaction model. The effects
of the stirring rate, FBRM data, and temperature on the
extraction rate showed that the reaction might be kinetically
controlled for extraction and be controlled by a mixed
diffusion-chemical reaction mechanism for stripping. The
extraction results were compared with those of the system
without N235. It was concluded that the presence of N235
decreases the extraction rate of ferric iron. VC 2018 American
Institute of Chemical Engineers Environ Prog, 00: 000–000, 2018
Keywords: ferric sulfate, extraction kinetics, stripping
kinetics
INTRODUCTION
Coal spoil (CS) is a by-product generated during mining,
washing, and processing of coal. CS is an economical source
of aluminum because of its high Al2O3 content (15–40 wt %)
[1]. Although many methods have been proposed for the
extraction of aluminum from CS, say hydrochloric acid route
[2] and nitric acid route [3], a sulfuric acid leaching route
[4–7] presents more promising prospects because today’s sul-
furic acid production is plentiful in China and sulfuric acid
could be recovered and reused for the whole process and
removal of ferric sulfate from aluminum sulfate by solvent
extraction is a key step in the process.
Removal of ferric iron (Fe31) from aluminum sulfate solu-
tions has been studied previously using a synergic extractant
consisting of di-(2-ethylhexyl) phosphoric acid (P204) and
tertiary amine (N235) [8], and the objective of this article is to
deal with extraction and stripping kinetics and to explain the
advantage of N235 addition from the perspective of kinetics.
The results of Fe31 extraction from aluminum sulfate solu-
tion by either N235 alone or P204 alone have been pub-
lished [9,10] and neither of them have higher extraction than
their mixed system.
C 2018 American Institute of Chemical Engineers
V ment, 200 mL each of the aqueous and organic solutions were
Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep
Various types of apparatus have been employed for
kinetic studies in solvent extraction [11], including the Lewis
cell [12], the constant interfacial cell with Laminar flow
[13,14], the rotating diffusion cell technique [15], the single
drop technique [16], and the highly stirred tank [17,18].
Although it is difficult to control the specific interfacial area,
the highly stirred tank is mainly used to derive information
on reaction orders [11] because the rates of extraction under
these experimental conditions are similar to those of techno-
logical or analytical extractions.
In this article, extraction and stripping kinetics were stud-
ied using a highly stirred tank, and the rate equations for
Fe31 extraction and stripping were correlated.
MATERIALS AND METHODS
Reagents and Equipment
Di-(2-ethylhexyl) phosphoric acid (P204, Shanghai Aoke
Industrial, China), tertiary amine (N235, Shanghai Rare-Earth
Chemical, China) and sulfonated kerosene (SK, Shanghai
Rare-Earth Chemical, China) were used without purification.
Al2(SO4)318H2O, Fe2(SO4)3, and H2SO4 (Analytical grade)
were purchased from Sinopharm Chemical Reagent.
Al2(SO4)318H2O was dissolved in deionized water. The solu-
tion was filtered through a G4 sand-core funnel (sand board
porosity of 4–7 lm) to eliminate residual solids, and then
recrystallized to obtain a highly pure starting material.
Focused beam reflectance measurement (FBRM) is an
effective online apparatus for tracking changes in scale, shape,
and number of droplets in real time, and is widely used in the
determination of the metastable zone width in crystallization.
In the current study FBRM (Lasentec S400A, Mettler Toledo)
was used to determine the reaction zone and kinetic regime
and this technique has not been utilized in extraction kinetics.
The outcome for the present study using FBRM is to measure
drop size distributions in stirred tank qualitatively, so that the
reaction zone and kinetic regime could be obtained. The oper-
ating parameters of FBRM were set as follows: measurement
speed 2 m s21, measurement duration 2 s, no time averaging
and no weighted chord length.
Procedures
The apparatus used for extraction and stripping kinetics
was a cylindrical reactor with a curved bottom (Figure 1), in
the center of which there was a sampling hole. In each experi-
Month 2018 1
preheated to a desired temperature. The starting aqueous solu- reaction model with respect to the metal cation was used in
tion was prepared with a mass ratio of Al31/Fe31 of 30.27, this article:
which was consistent with previous research results, by dis-
solving Al2(SO4)318H2O and Fe2(SO4)3 in deionized water, Fe31 31
(1)
ðaÞ
FeðoÞ
giving an initial pH of 1.5 to 2 and Fe31 concentration of
around 1.26 g L21. The organic solution of P204/N235 system
was prepared with a volume ratio of 3:3:4 for P204:N235:SK, where (a) refers to the aqueous phase and (o) the organic
while the P204 system with the volume ratio of 3:7 for phase. The rate expression is
P204:SK. The reaction began by adding the two phases to the
reactor and simultaneously starting the stirring motor and the Ci 2Ce Ci 2Ce
kf t5 ln (2)
stop-watch. Samples were collected by opening the valve on Ci Ct 2Ce
the sampling hole at predetermined time intervals. The sam- Ce Ci 2Ce
ples were centrifuged at 3000 rpm to remove any suspended kr t5 ln (3)
organic microdroplets from the aqueous phase. Fe31 concen- Ci Ct 2Ce
tration was determined by titration according to the national
standard GB/T 1574–1995 and experimental data were treated where kf and kr are the observed rate constants of the for-
following the method of Flett et al. [17]. Because all kinetic ward and backward reactions, respectively; Ci is the initial
experiments were carried out at low Fe concentration and concentration of Fe31 in the aqueous phase; Ce refers to the
high extractant concentration, which can be considered to be concentration of Fe31 in the aqueous phase at equilibrium,
at or near zero mass-transfer conditions, a first-order reversible and Ct indicates the concentration at time t. By plotting ðCi 2
Ce Þ=ðCi Þln ðCi 2Ce Þ=ðCt 2Ce Þ against time t for each kinetic
condition, a straight line is obtained, indicating that the
kinetic process can be treated as a first-order reversible
reaction.
The liquid–liquid contact under different revolving speeds
at 258C was detected by the FBRM probe situated near the
stirring impeller and samples were observed using a Nikon
biological microscope (Nikon E200, Nikon Corporation). All
samples were photographed within 20 s of collection so that
the authenticity of the droplets would not be distorted by
stratification.

RESULTS AND DISCUSSION

Figure 1. Experimental setup for kinetics. (1 thermostat, 2
mixer, 3 FBRM detector, and 4 computer). [Color figure can Extraction Kinetics Study
be viewed at wileyonlinelibrary.com] Reaction zone and regime: the criterion generally adopted
to identify the extraction regime is the dependence of the

Figure 2. Two-phase contact measured by FBRM at different stirring rates. P204/N235 system: (a) Chord count evolution; (b)
CLD evolution. P204 system: (c) Chord count evolution; (d) CLD evolution. Experimental conditions: 258C. [Color figure can be
viewed at wileyonlinelibrary.com]

2 Month 2018 Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep
Figure 3. Photographs taken by microscope at different stirring speeds. [Color figure can be viewed at wileyonlinelibrary.
com]

extraction rate on the stirring speed with a constant surface
area. Figure 2 shows the chord count evolution and the cor-
responding chord length distribution (CLD) measured by
FBRM under varied stirring speeds both for P204/N235 sys-
tem and for the only P204 system. A plateau occurred from
500 to 700 rpm (a) and CLD maintained the same in this area
(b) meaning that the surface area changed only slightly from
500 to 700 rpm, so it was taken to be constant using P204
and N235 as extraction agent. But for the only P204 system,
number of particles increased (c), while CLD decreased (d)
with rising stirring speed. Then no constant contacting area
of stirring speed could be observed in this system. The
photographs taken by the biological microscope are shown
in Figure 3 in P204/N235 system. It reveals that extensive
emulsification occurs at stirring speeds above 800 rpm,
which should be avoided in industrial operation.
The dependence of logkf in Eq. (2) on stirring speed is
shown in Figure 4. Experiments of using only P204 were
conducted as controlled groups and no plateau region could
be observed in this system from 250 to 800 rpm. It could be
concluded that diffusion effects were not eliminated even
when stirring speed increased to 800 rpm. However, in the
synergic system, plateau in the rate of Fe extraction in the
stirring speed range from 500 to 700 rpm indicated that the

Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep Month 2018 3
reaction might be kinetically controlled under these condi-
tions. To confirm this, another criterion was utilized to distin-
guish between a diffusion-controlled and a kinetic regime by
determining the apparent activation energy (Ea) from 15 to
858C at 650 rpm stirring speed.
Figure 5a,b were using 30% P204/30% N235 as extraction
agent, while (c) and (d) only 30% P204. Experimental param-
eters of the aqueous phase remained the same as Fe31 con-
centration of around 1.26 g L21 and pH of 1.5 to 2. Figure 5a
shows the effect of temperature on iron concentration in the
aqueous phase. The higher temperature enabled iron con-
centration to level off in a shorter time, but the Fe removal
was lower. As all these experiments were conducted at high
turbulent flow conditions in which intensive mixing was
used, this phenomenon could only be explained from the
viewpoint of thermodynamics, in that the reaction has a neg-
ative temperature dependence. This phenomenon is consis-
tent with what we have found before [8]. The apparent
activation energy (Ea) is calculated from the slope of a plot
of logkf against 1000/T, as shown in Figure 5b. The value of
Ea for temperatures from 15 to 358C was 218.94 kJ mol21
while that for temperatures from 45 to 858C is 220.65
kJ mol21. Negative temperature dependencies for rate coeffi-
cients indicates the presence of a potential well. A few com-
plex reactions have negative Ea and those reactions always

Figure 4. Dependence of logkf on stirring speed. Experi-

mental conditions: 258C, stirring speeds from 200 to Figure 6. Dependence of logkf on initial pH of aqueous
1000 rpm. phase.

Figure 5. Effect of temperature on Fe residual in aqueous phase, (a) 30% P204/30% N235, (c) 30% P204; Dependence of logkf
on temperature, (b) 30% P204/30% N235, (d) 30% P204. [Color figure can be viewed at wileyonlinelibrary.com]

4 Month 2018 Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep

Figure 7. Dependence of logkf on initial iron concentration
in aqueous phase.
Figure 8. Dependence of logkf on volume fraction of P2O4
in organic phase.
include an obviously exothermic and rapid equilibrium reac-
tion followed by a rate-controlling step. The specific reaction
rate theory [16] is therefore not applicable to the current
research. Figure 5c demonstrates dependence of Fe residual
in aqueous phase on time using 30% P204 as extractant. The
higher the temperature, the faster the extraction process and
the higher the Fe removal. The value of Ea could be calcu-
lated from Figure 5d as 34.14 kJ mol21, indicating that the
extraction process might be a mixed diffusion-chemical reac-
tion mechanism [16]. From Figure 5 one can conclude that
the addition of N235 into P204 decreases operating tempera-
ture, which means the extraction process can be conducted
at room temperature, at the same time, with shorter time to
achieve high Fe removal.
Effect of pH
Figure 6 presents the forward rate constant kf as a func-
tion of initial pH (0.3–1.5) in the aqueous phase. When 30%
P204/30% N235 were used as extraction agent, the slope of
the plot is 0.6187, indicating that the overall reaction order in
terms of pH is 0.6187. While the overall reaction order in
terms of pH is 0.1421 for only P204 system. Extraction
rate increased with increasing pH from 0.3 to 1.5 both for
P204/N235 system and for the only P204 system, and the
addition of N235 lowered extraction rate. It could be attrib-
uted to the formation of a large molecular association [8],
R’R’’POOH. . .NR3, which reduces effective collision fre-
quency with iron. The above assumption also applies to
Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep
Figure 9. Chord count evolution measured by FBRM at stir-
ring rates from 300 to 800 rpm. Experimental conditions:
258C.
Figure 10. Dependence of logkf on stirring speed. Experi-
mental conditions: 258C, stirring speeds from 250 to 800 rpm.
effects of iron concentration and extractant concentration on
Fe31 extraction rate.
Effect of Iron Concentration
The effect of initial iron concentration in the aqueous
phase was investigated as shown in Figure 7. The slope of
the plot is 0.8064, indicating that the overall reaction order in
terms of iron is 0.8064 in P204-N235 system, while it is
20.4259 in P204 system. A negative order also explains that
the increase of initial iron concentration would make the
extraction rate decrease.
Effect of Extractant Concentrations in the Organic Phase
The effect of extractant concentration on Fe extraction
was studied using a P204:N235 volume ratio of 1:1 and kf
was obtained as a function of initial volume fraction of P204
[P204]O from 10 to 40% (Figure 8). It was showed that the
overall reaction order is 0.1889 in terms of P204 concentra-
tion. When only P204 was used, the slope of the plot was
0.1863, indicating that the overall reaction order in terms of
iron was 0.1863. Fe extraction rate increased with rising
extractant concentration from 10 to 40%. The increase in ris-
ing extractant corresponds to more number of activated mol-
ecules per unit volume, which resulted in higher effective
collision frequency with iron. Moreover, the two lines in Fig-
ure 8 are almost parallel to each other, indicating that P204
plays the crucial role in extraction process.
Therefore the overall rate equation for P204-N235 system
can be written as:
Month 2018 5
Figure 11. Effect of temperature on iron concentration in organic phase at a stirring speed of 500 rpm. (a) Dependence of Fe
residual in organic phase on time. (b) Dependence of lnkf on temperature. [Color figure can be viewed at wileyonlineli-
brary.com]
Figure 12. Dependence of logkf on initial iron concentration
in organic phase and on sulfuric acid concentration in aque-
ous phase.
2d½Fe=dt5k  pH0:6187  ½Fe31 0:8064  ½P2 O4 0:1889
while, the overall rate equation for P2O4 system can be writ-
ten as:
2d½Fe=dt5k  pH0:1421  ½Fe31 20:4259  ½P2 O4 0:1863
Stripping Kinetics Study
The stripping kinetics study of P204-N235 extractant had
gone through the similar procedure as the extraction kinetics
process. The stripping kinetics study of only P204 extractant
could not be conducted because the reaction happened
instantaneously that the concentration detection was
imprecise.
Reaction zone and regime: first, chord count evolution
was measured by FBRM at stirring rates from 300 to 800 rpm
(Figure 9). A plateau occurred from 400 to 600 rpm and
500 rpm was chosen to conduct the subsequent research.
Figure 10 shows dependence of logkf on stirring speed from
250 to 800 rpm, however, no plateau could be found, which
might mean that the effect of diffusion was hard to eliminate.
Another criterion of temperature (Figure 11) proved this
explanation. The value of Ea was 42.63 kJ mol21. According
to the specific reaction rate theory [11,16], if Ea is larger than
42 kJ mol21, the process is controlled by chemical reaction.
If it is smaller than 20 kJ mol21, the process is controlled by
diffusion. The value in the middle is controlled by a mixed
6 Month 2018 Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep
diffusion-chemical reaction mechanism. About 42.63
kJ mol21 lies on the border of chemical reaction region, so
the effect of diffusion might not be eliminated thoroughly.
Dependence of logkf on initial iron concentration in
organic phase and on sulfuric acid concentration in aqueous
phase is shown in Figure 12. The initial iron concentration in
organic phase and logkf presents no good linear relationship,
while a good linear relationship between sulfuric acid con-
centration in aqueous phase and logkf indicates that the
overall reaction order in terms of sulfuric acid concentration
is 0.8611. Therefore, the overall rate equation for stripping
can be written as:
2d½Fe=dt5k½H2 SO4 0:8611 (6)
CONCLUSIONS
The kinetics of Fe extraction using P204-N235 extractant
and only P204 extractant, and kinetics of Fe stripping using
P204-N235 extractant, were studied in a highly stirred tank
utilizing FBRM technique to monitor the two-phase contact.
(4) The derived rate equations for Fe extraction using P204-N235
extractant and Fe stripping are as follows respectively:
2d½Fe=dt5k  pH0:6187  ½Fe31 0:8064  ½P2 O4 0:1889
(5) 2d½Fe=dt5k½H2 SO4 0:8611
The addition of N235 into P204 turned the extraction process
from a mixed diffusion-chemical reaction mechanism to a
chemical reaction mechanism. The experimental data
obtained in this article can serve as a reference to aluminum
recovery from CS.
NOMENCLATURE
Ce concentration of Fe31 in the aqueous phase at
equilibrium (g L21)
Ci initial concentration of Fe31 in the aqueous phase
(g L21)
Ct Fe31 concentration at time t (g L21)
Ea apparent activation energy (kJ mol21)
kf observed rate constant of the forward reaction
kr observed rate constant of the backward reaction
ACKNOWLEDGMENTS
This work was financially supported by the Natural Sci-
ence Foundation of China (NSFC, No. U1507105), National
Sci-Tech Support Plan (No. 2015BAB10B01), National Key R
& D Program (No. 2016YFC0401203).

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