Separation and Purification Technology 341 (2024) 126855

Contents lists available at ScienceDirect

Separation and Purification Technology

journal homepage: www.elsevier.com/locate/seppur

Simultaneous removal of Al3+, Mg2+ and F- from wet-process phosphoric

acid achieved by a co-precipitation strategy
Binbin He a, b, c, Ying Fu c, Yun Zu a, b, *, Yunxiang Nie a, b, Yi Mei a, b, *
a
Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, PR China
b
Yunnan Provincial Key Laboratory of Energy Saving in Phosphorus Chemical Engineering and New Phosphorus Materials, Kunming 650500, PR China
c
National Engineering and Technology Research Center for Development & Utilization of Phosphate Resources, Kunming 650600, PR China

A R T I C L E I N F O A B S T R A C T

Editor: Luo Guangsheng Fluorine (F) is a high-value resource that has been overlooked in the production of wet-process phosphoric acid
(WPA) due to its high susceptibility to complexation with metal cationic impurities, hindering F efficient re­
Keywords: covery and subsequent phosphoric acid purification. In this paper, a co-precipitation strategy is proposed for
Wet-process phosphoric acid recovering F from the WPA. Varieties of combinations between metal cation (Na+, Mg2+ and Al3+) and F- with
Fluorine recovery
different molar ratios in aqueous and phosphoric acid systems are designed to explore the co-precipitated
Co-precipitation strategy
regulation. Results show that the simultaneously removal efficiencies of Al3+, Mg2+ and F- can be higher than
NaxMgyAlzFw precipitation
90 % in the form of NaAlMgF6 and Na3AlF6 precipitations as the n(Na+): n(Al3+): n(Mg2+): n(F-) = 5: 1.5: 1: 6 in
pure systems. DFT calculations further confirm that the NaMgAlF6 precipitation is the most stable structure
identified by using XRD Rietveld refinement. Based on this fact, extra Na+ and F- are added into the industrial
WPA, so that the Na+, Al3+, Mg2+ and F- are co-precipitated in the form of NaAlMgF6, and the ultimate removal
efficiencies can exceed 90 % under the optimal conditions. Besides, low-cost cycling recovery of Na+ and F- are
also investigated. These findings are promising for the efficient utilization of F resources from phosphate rock
and other ores, which is of great economic and environmental significance.

1. Introduction
Fluorine (F) is very important for human health and also a key
element in the chemical industry [1]. The global output of F-containing
chemicals is approximately 8 million tonnes annually. One of common
naturally-occurring F resources is fluorspar, a mineral ore comprised of
fluorite (CaF2) [2]. However, the global reserve of fluorspar is only 320
million tonnes in 2019. With the vigorous development of F-containing
products in recent years, such as electrolytes and separator membranes
for lithium-ion batteries [3,4], the F-containing ores are in short supply.
In fact, about 90 wt% of F resources in nature are associated with
phosphate rocks which usually contain 3 ~ 4 wt% F. However, more
than 90 % phosphate rocks are currently used to produce the so-called
wet-process phosphoric acid (WPA), while only 40 wt% F has been
converted into fluorosilicic acid (H2SiF6) for F recovery. The unrecov­
ered F (about 1.8 million tonnes of F in China) in the WPA remains and
enters into the downstream chemical products, and subsequently enters
into the soil, water and air, resulting in a great damage to natural
environment and human health.
The WPA is a widely chemical raw material for the production of
various high-value phosphorus chemical products, such as fertilizers,
feed additives and battery cathode material (LiFePO4), etc. [5–8]. The
production of WPA is directly related to world’s consumption of phos­
phate that dramatically exceeds 20 million tons in China [9]. At present,
the sulfuric acid route has been used to leach phosphate rock for pro­
ducing the WPA, with calcium sulfate dihydrate (phosphogypsum,
CaSO4⋅2H2O) as a by-product [10,11]. Although the bulk gypsum cake
can be filtered and separated, there are still many impurities in the WPA,
such as anionic impurities (e.g., sulfate and fluorine, etc.), cationic im­
purities (e.g., Al3+, Fe3+, Ca2+ and Mg2+, etc.) as well as organic impu­
rities [12]. Overall, the F- present in the WPA (as HF and H2SiF6) can
form various complexes with metal impurities (i.e., Na+, K+, Ca2+ and
Al3+, etc.), which have a significant impact on the concentration of WPA,
subsequent precipitation, and water-soluble phosphorus degradation in
the product. In our previous work, a competitive complexation behavior
between fluorine species and metal cations has been disclosed [13]. The
result has found that it was significant to achieve the removal of Al3+
and Mg2+ cations while removing F. This is because the removal of Al3+

* Corresponding authors.
E-mail addresses: zuyun1990@126.com (Y. Zu), meiyi412@126.com (Y. Mei).

https://doi.org/10.1016/j.seppur.2024.126855
Received 29 January 2024; Received in revised form 16 February 2024; Accepted 18 February 2024
Available online 23 February 2024
1383-5866/© 2024 Elsevier B.V. All rights reserved.
B. He et al.
and Mg2+ cations can increase the subsequent concentration efficiency
and mitigate the degradation of the water-soluble phosphorus, thus
facilitating the production of high-quality phosphorus chemicals.
Multiple methods, including air stripping, vacuum filtration, solvent
extraction, and precipitation have been developed for the industrial
removal or recovery of F from the WPA [14–18]. Solvent extraction can
produce high-purity phosphoric acid. However, this process is compli­
cated, expensive and wastes a large amount of acid. Air stripping and
vacuum filtration are the most widely used processes for recovering F
from WPA in China and some South-East Asian countries. However, the
F yield from these processes is generally less than 40 %. By comparison,
the precipitation method can be regarded as an economic way of
recovering F from WPA because of their low-cost and ease of operation.
Despite research on the development of suitable precipitants, the
industrialisation of precipitation method for recovering F from WPA has
been hindered by low F recovery efficiency and high P2O5 loss caused by
adsorption and inclusion of phosphoric acid into the precipitates,
resulting in secondary pollution and solid wastes. Furthermore, the
resulting F-containing precipitates usually have low purity, hindering
their direct use in further processes.
In this work, a co-precipitation strategy of metal cations (Al3+ and
Mg ) and F- is proposed, controlling a certain molar ratio between
2+
them, to achieve the simultaneous removal of F-, Mg2+ and Al3+,
depending on the previous study of the chemical forms of F- in the WPA.
This study finds that the formation of NaxMgyAlzFw precipitations in
industrial WPA can preferentially remove metal impurities according to
the relevant theoretical results obtained. Ultimately, above 90 % F
removal efficiency can be achieved. This strategy has been successfully
applied in the phosphoric acid purification process.
2. Experimental
2.1. Chemicals
Potassium sulfate (K2SO4, 99.0 wt%), anhydrous sodium sulfate
(Na2SO4, 99.0 wt%), phosphoric acid (H3PO4, 85.0 wt%), hydrofluoric
acid (HF, 40.0 wt%), hexafluorosilicic acid (H2SiF6, 40.0 wt%), mag­
nesium nitrate hexahydrate [Mg(NO3)2⋅6H2O, 99.0 wt%] and aluminum
nitrate nonahydrate [Al(NO3)3⋅9H2O, 99.0 wt%] were purchased from
Aladdin Chemical Reagent Ltd.. The industrial WPA was provided from
Yunnan Phosphate Co., Ltd., China. Deionized water with a resistivity of
18 MΩ cm was used throughout the experiments.
2.2. Experimental system
MgyFw-H2O system: 2.56 g of Mg(NO3)2⋅6H2O was respectively
added into 1.90, 2.85, 3.80, 4.75 and 5.70 g of HF solution (40.0 wt%).
Subsequently, the above solution was fixed to 100 mL by deionized
water and stirred for 10 min at room temperature.
MgyFw-H3PO4 system: 2.56 g of Mg(NO3)2⋅6H2O and 9.35 g H3PO4
(85.0 wt%) were respectively added into 1.90, 2.85, 3.80, 4.75 and 5.70
g of HF solution (40.0 wt%). Subsequently, the above solution was fixed
to 100 mL by deionized water and stirred for 10 min at room
temperature.
NaxMgyFw-H2O system: 2.56 g of Mg(NO3)2⋅6H2O and 14.20 g
Na2SO4 were respectively added into 1.90, 2.85, 3.80, 4.75, 5.70, 6.65,
7.60 and 8.55 g of HF solution (40.0 wt%). Subsequently, the above
solution was fixed to 100 mL by deionized water and stirred for 10 min
at room temperature.
NaxMgyFw-H3PO4 system: 2.56 g of Mg(NO3)2⋅6H2O, 14.20 g
Na2SO4 and 9.35 g H3PO4 (85.0 wt%) were respectively added into 1.90,
2.85, 3.80, 4.75, 5.70, 6.65, 7.60 and 8.55 g of HF solution (40.0 wt%).
Subsequently, the above solution was fixed to 100 mL by deionized
water and stirred for 10 min at room temperature.
AlyFw-H2O system: 3.75 g of Al(NO3)3⋅9H2O was respectively added
into 0.48, 0.95, 1.43, 1.90, 2.85, 3.80, 4.75 and 5.70 g of HF solution
2
Separation and Purification Technology 341 (2024) 126855
(40.0 wt%). Subsequently, the above solution was fixed to 100 mL by
deionized water and stirred for 10 min at room temperature.
AlyFw-H3PO4 system: 3.75 g of Al(NO3)3⋅9H2O and 9.35 g H3PO4
(85.0 wt%) were added into 2.85, 4.75, 5.70, 6.65, 7.60 and 8.55 g of HF
solution (40.0 wt%). Subsequently, the above solution was fixed to 100
mL by deionized water and stirred for 10 min at room temperature.
NaxAlyFw-H2O system: 3.75 g of Al(NO3)3⋅9H2O and 4.26 g Na2SO4
were added into 2.85, 3.33, 3.80, 4.28 and 4.75 g of HF solution (40.0 wt
%). Subsequently, the above solution was fixed to 100 mL by deionized
water and stirred for 10 min at room temperature.
NaxAlyFw-H3PO4 system: 3.75 g of Al(NO3)3⋅9H2O, 4.26 g Na2SO4
and 9.35 g H3PO4 (85.0 wt%) were added into 4.75 g of HF solution
(40.0 wt%). Subsequently, the above solution was fixed to 100 mL by
deionized water and stirred for 10 min at room temperature.
NaxMgzAlyFw-H2O system: 3.75 g, 5.64 g of Al(NO3)3⋅9H2O and
0.71 g, 1.42 g, 2.13 g, 2.85 g, 3.55 g, 4.26 g, 4.97 Na2SO4 were added
into 0.48, 0.95, 1.43, 1.90, 2.38, 2.85, 3.33 g of HF solution (40.0 wt%).
Subsequently, the above solution was fixed to 100 mL by deionized
water and stirred for 10 min at room temperature.
NaxMgzAlyFw-H3PO4 system: 3.75 g, 5.64 g of Al(NO3)3⋅9H2O, 9.35
g H3PO4 (85.0 wt%) and 0.71 g, 1.42 g, 2.13 g, 2.85 g, 3.55 g, 4.26 g,
4.97 Na2SO4 were added into 0.48, 0.95, 1.43, 1.90, 2.38, 2.85, 3.33 g of
HF solution (40.0 wt%). Subsequently, the above solution was fixed to
100 mL by deionized water and stirred for 10 min at room temperature.
WPA system: Based on the chemical forms of F- in the WPA, for
fluosilicic acid, 40 wt% sodium sulfate was fully mixed at room tem­
perature for 10 min, filtered and separated, and the filter cake was fully
washed with pH = 7. After drying, the product was sodium fluosilicic
acid. For other residual F-, the filtrate was added with 40 wt% HF and 40
wt% sodium sulfate, and reacted in a constant temperature with water
bath at 40 ◦ C for 12 min. The mixture was filtered and separated, and the
precipitation was rinsed with deionized water to pH = 7, dried and
characterized.
At 100 ◦ C, the HF and Na2SO4 were decomposed and precipitated by
adding 60 wt% sulfuric acid. Under the condition of negative pressure,
the HF volatilized and was absorbed by water to form 40 wt% HF so­
lution. Then, the 60 wt% calcium hydroxide was slowly added to the
remaining solution until the pH value was 3.8, filtration separation, the
obtained filtrate was Na2SO4 solution, and the filter cake was used as the
raw material of aluminum and magnesium chemical products.
2.3. Characterizations
The contents of metal cations were performed on an inductively
coupled plasma atomic emission spectrometer (ICP-AES, Thermo Fisher
Scientifific, iCAP 7000, USA), calculated by using a standard curve
based on respective known ion concentration. The phosphate ion con­
centration in the solution was measured by ion chromatography (IC,
Metrohm IC-883). The F- concentration was determined by the standard
method using an ion-selective electrode. Under neutral conditions, the
electrode potential of the solution was measured directly using a satu­
rated glycury electrode as a reference electrode. The pH was measured
by Swiss Bandon T905 potentiometric titrator, with a composite pH
glass electrode and a double-pore diaphragm (3 mol/L KCl). The buffer
solution pH = 6.86 (mixed phosphate) and 4.00 (potassium hydrogen
phthalate) were used for calibration at 25 ◦ C. After the calibration, the
electrodes were put into the solution to be tested and recorded by con­
trolling 905 titrando software.
In addition, the content of H2SiF6 in the industrial WPA was
measured by potassium nitrate. The resulting proportion of fluosilicate
was about 0.48 ~ 0.49 wt% (0.26 mol/L) using the equation (1), which
was basically consistent with the calculated results of chemical com­
positions. Take a typical case, excess potassium glutamate (ca. 2.80 g)
was added into the industrial WPA (ca. 102.10 g) to form the potassium
fluosilicate solid–liquid slurry and then was filtered and separated. The
filter cake was potassium fluosilicate (cf. Figures S1 and S2), fully
B. He et al. Separation and Purification Technology 341 (2024) 126855

Table 1 on a D/MAXRB instrument (Rigaku, Japan) equipped with Cu-Kα radi­

Precipitation situations and removal efficiencies of Mg2+ and F- for the MgyFw ation (λ = 0.154 nm, 40 kV, 30 mA). Data were collected with a
and NaxMgyFw in aqueous and phosphoric acid systems. diffraction angle (2θ) ranged from 5 to 90◦ . The phases were determined
Molar ratio Mg2+ removal F- removal Phenomenon by comparison with the registered patterns of the JCPDS reference data
efficiency (%) efficiency (%) files. Rietveld refinement of the data was done to define the numbers of
Mg2+: F- = 1: (4, 6, 8, 0 0 No ionic occupation in different locations of samples using the GSAS soft­
10, 12) precipitation ware package.
Na+: Mg2+: F- = 10: 1: 0 0 No The surfaces of the samples were imaged by SEM using a FEI Quanta
(4, 6, 8, 10, 12, 14, 16 precipitation
650 microscope (FEI Company, Hillsboro, OR) equipped with a tungsten
18)
filament operated at an accelerating voltage of 15 kV.

2.4. Removal tests of metal cation or fluorine

Table 2
Precipitation situations and removal efficiencies of Al3+ and F- for the AlyFw and
NaxAlyFw in aqueous solutions.
The removal efficiency of metal cation or F- was calculated by
equation (2):
Molar ratio Al3+ removal F- removal Phenomenon
efficiency (%) efficiency (%) Ci − Cf
RemovalefficiencyofmetalcationorF − (%) = × 100% (2)
3+ -
Al : F = 1: (1, 2, 3, 0 0 No Ci
4, 6, 8, 10, 12) precipitation
Al3+: F- = 1: 14 10.50 21.80 Precipitation where Ci and Cf were the initial and final concentrations of metal cation
Al3+: F- = 1: 16 11.70 25.90 Precipitation (or F-) in the WPA, respectively.
Al3+: F- = 1: 18 13.50 29.50 Precipitation
Na+: Al3+: F- = 3: 1: 6 100.00 87.72 Precipitation
Na+: Al3+: F- = 3: 1: 7 100.00 86.70 Precipitation 3. Results and discussion
Na+: Al3+: F- = 3: 1: 8 100.00 86.45 Precipitation
Na+: Al3+: F- = 3: 1: 9 100.00 86.19 Precipitation 3.1. Precipitation and removal efficiency of metal cation and F- in pure
Na+: Al3+: F- = 3: 1: 100.00 89.51 Precipitation system
10

3.1.1. MgyFw and NaxMgyFw in aqueous and phosphoric acid systems

washed with deionied water and dried at 80 ◦ C. The mass of fluosilicate
was calculated according to the potassium fluosilicate.
2K+ +H2 SiF6 = K2 SiF6 ↓+2H+
X-ray diffraction (XRD) was used to characterize the properties of
precipitates. Powder X-ray diffraction (XRD) patterns were conducted
Table 1 displays the precipitation situations and removal efficiencies
of Mg2+ and F- for the MgyFw and NaxMgyFw in aqueous and phosphoric
acid systems. It can be seen that no MgyFw and NaxMgyFw precipitations
(1) can be found as the molar ratio of n(Mg2+): n(F-) = 1: 4 ~ 12 and n(Na+):
n(Mg2+): n(F-) = 10: 1: 4 ~ 18, indicating that the Na+, Mg2+ and F-
cannot form precipitation in both aqueous solutions and pure phos­
phoric acid under an any molar ratio conditions, which is consistent

Fig. 1. (a) XRD pattern, (b) SEM and (c) EDX element mapping images of the AlyFw precipitation in aqueous solution.

3
B. He et al. Separation and Purification Technology 341 (2024) 126855

Fig. 2. (a) XRD pattern of the NaxAlyFw precipitation in aqueous solution; (b) SEM and (c) EDX element mapping images of the NaxAlyFw precipitation in aqueous
solution as the n(Na+): n(Al3+): n(F-) = 3: 1: 10.

with the results reported by James R. Lehr in the literature [19]. The
ultimate removal efficiencies of Mg2+ and F- are also close to zero. Table 3
Precipitation situations and removal efficiencies of Al3+ and F- for the AlyFw and
Combined with the previous relevant study [20], this phenomenon
NaxAlyFw in phosphoric acid solution.
might be mainly due to the weak complexation ability of Mg2+ with F-
and the inability to form precipitation in aqueous and phosphoric acid Molar ratio Al3+ removal F- removal Phenomenon
efficiency (%) efficiency (%)
solutions.
Al3+: F- = 1: (6, 0 0 No
10, 12) precipitation
3.1.2. AlyFw and NaxAlyFw in aqueous and phosphoric acid systems
Al3+: F- = 1: 14 2.7 2.2 Precipitation
According to the calculation of HSC chemical 6.0 software, the ΔGo Al3+: F- = 1: 16 8.9 7.8 Precipitation
< 0 means that the AlF3⋅3H2O precipitations can be formed theoreti­ Al3+: F- = 1: 18 15.7 14.4 Precipitation
cally. Based on this fact, the precipitation phenomena are shown in Na+: Al3+: F- = 3: 100 94.6 Precipitation
Table 2 when the Al3+ and F- are added into the aqueous solution with 1: 10

sufficient stirring at 25 ◦ C. As can be seen from Table 2, the pre­

cipitations cannot be formed in the aqueous solution as the molar ratio
of n(Al3+): n(F-) = 1: (1, 2, 3, 4, 6, 8, 10, 12). Once the molar ratio of n
(F-): n(Al3+) exceeds 14, a small amount of precipitation slowly appears,
but the removal efficiencies of Al3+ and F- are less than 30 % even if the n
(F-): n(Al3+) is up to 18. The corresponding XRD pattern and SEM images
of the precipitation are shown in Fig. 1. It can be seen from the XRD
pattern (Fig. 1a) that the precipitation is defined as the AlF3⋅3H2O
(PDF#43–0436) [13]. As can be seen from Fig. 1b, the precipitation
presents oval spherical and the rest is flocculent, indicating poor pre­
cipitation crystallization in the aqueous solution. In the EDX mapping
images (Fig. 1c), only two elements of Al and F can be observed and are
uniformly distributed in the precipitation. According to the relevant
study [21], it is known that a certain amount of AlF3⋅3H2O precipitation
can be formed only in the presence of sufficient amount of HF in the
solution.
On the basis of the above results, if the Na+ cations are added into the
aqueous solution (Table 2), a new precipitation can be observed as the
molar ratio of n(Na+): n(Al3+): n(F) = 3: 1: (6, 7, 8, 9, 10). The XRD
pattern in Fig. 2a shows that the main phase of the precipitation sample
is the monoclinic structure of Na3AlF6 (PDF#25–0772) [22], with a
space group of P21/n and a density of 2.97 g/cm3. The synthesized
precipitation is a single phase with no additional peaks. This phenom­
enon indicates that the presence of Na+ cation can promote the disso­
ciation of Al-F complexes and is benefit for the formation of Na3AlF6
precipitation. Additionally, it can be seen that the position and intensity
of the characteristic diffraction peaks associated with the Na3AlF6 are
basically unchanged when the n(F-) changes from 6 to 10 with a constant
n(Na+): n(Al3+) = 3: 1, indicating that the main phase of formed pre­
cipitation is single and no new crystalline phase is generated even if
continually increasing the F- content as the Al3+ content is certain. As
the n(Na+): n(Al3+): n(F) = 3: 1: 10, it can be seen that the removal
efficiencies of Al3+ and F- can reach approximately 100 % and 90 %
respectively (Table 2), indicating that the NaxAlyFw precipitation can
simultaneously effective remove the Al3+ and F-. However, it can be
clearly seen in Fig. 2b and 2c that the Na3AlF6 precipitation is fine-
grained and bonded together, forming flocs. This will lead to the diffi­
culties in the subsequent filtering and separation.
According to the formation conditions of NaxAlyFw precipitation in
aqueous solution, the Al3+ and F- are added into pure phosphoric acid

4
B. He et al. Separation and Purification Technology 341 (2024) 126855

Fig. 3. (a) XRD pattern, (b) SEM and (c) EDX element mapping images of the AlyFw precipitation in phosphoric acid.

Fig. 4. XRD (a), SEM (b) and (c) EDX element mapping images of NaxAlyFw precipitation in phosphoric acid.

(24 % P2O5) at room temperature to analysis the precipitation situations
and removal efficiencies of Al3+ and F-. As shown in Table 3, the AlyFw
precipitation is poorly defluorinated in phosphoric acid and the removal
efficiency of F- is only about 14.4 % at the molar ratio of n(Al3+): n(F-) =
1: 18, which is lower than that in the aqueous solution, mainly due to the
phosphoric acid inhibited the dissociation of F- in hydrofluoric acid. The
XRD pattern and SEM images of AlyFw precipitation are shown in Fig. 3.
It can be seen that the characteristic diffraction peaks assigned to the
AlF3⋅3H2O precipitation with no other phases are observed in phos­
phoric acid (Fig. 3a). Besides, the particles of precipitation are ellip­
soidal and the particle size distribution is not uniform (Fig. 3b). A small
amount of phosphorus is entrapped in the precipitation (Fig. 3c). This is
mainly because the precipitation particles formed are small and difficult
to be washed out completely by phosphoric acid.

5
 B. He et al. Separation and Purification Technology 341 (2024) 126855

Table 4 the density, viscosity and secondary precipitation of phosphoric acid

Precipitation situations and removal efficiencies of Al3+, Mg2+ and F- for the increased. Such phosphoric acid entered into the phosphate fertilizer
NaxAlyMgzFw in aqueous solution. will not only reduce the content of water-soluble phosphorus in the
Molar ratio Al3+ removal Mg2+ removal F- removal Phenomenon fertilizer, but also make the physical properties of fertilizer products
efficiency, % efficiency, % efficiency, % become worse, caking sex rise, etc. [24,25]. Thus, the ability to achieve
Na+: Al3+: 0 0 0 No deep defluorination and Al3+ while removing Mg2+ is significant.
Mg2+: F- precipitation In this section, the precipitation situations and removal efficiencies
= 1: 1: 1: of metal cation and F- are firstly studied by adding different proportions
1
of Na+, Al3+, Mg2+ and F- into the aqueous solution system. The result is
Na+: Al3+: 0 0 0 No
Mg2+: F- precipitation shown in Table 4. It can be seen that when the contents of both F- and
= 2: 1: 1: Na+ are too low, no precipitation is formed, mainly due to the first
2 formation of Al-F complexes [13]. As the contents of F- and Na+ rise, the
Na+: Al3+: 0 0 0 No removal efficiencies of Al3+ and Mg2+ increase. When the molar ratio of
Mg2+: F- precipitation
= 3: 1: 1:
n(Na+): n(Al3+): n(Mg2+): n(F-) = 5: 1.5: 1: 6, the removal efficiencies of
3 Al3+, Mg2+ and F- are higher than 90 %. It can be seen from the XRD
Na+: Al3+: 48.9 44.5 38.4 Precipitation pattern (Fig. 5a), that the resulting precipitation is defined as the
Mg2+: F- mixture of NaAlMgF6 (PDF#25–0841) and Na3AlF6, compared to the
= 4: 1: 1:
single Na3AlF6 precipitation formed in the aqueous solution. The Mg2+
4
Na+: Al3+: 65.4 55.4 58.1 Precipitation is precipitated and removed in the form of NaAlMgF6. At this situation,
Mg2+: F- the simultaneous removal of F-, Al3+ and Mg2+ can be achieved. Ac­
= 5: 1: 1: cording to the calculation of HSC Chemical 6.0 software, the formation
5 of NaAlMgF6 precipitation is spontaneous due to the ΔGo < 0. The
Na+: Al3+: 99.4 83.8 88.7 Precipitation
precipitation morphology is spherical particle-like and bonded to each
Mg2+: F-
= 6: 1: 1: other (Fig. 5b). It is further demonstrated from the EDX mapping images
6 (Fig. 5c) that the precipitation is mainly composed of Al, Mg and F
Na+: Al3+: 98.1 83.4 88.2 Precipitation elements.
Mg2+: F-
When the Na+, Al3+, Mg2+ and F- are simultaneously added into the
= 7: 1: 1:
6 pure phosphoric acid (24 % P2O5), so that the molar ratio is up to the n
Na+: Al3+: 99.6 80.1 82.6 Precipitation (Na+): n(Al3+): n(Mg2+): n(F-) = 5: 1.5: 1: 6. The precipitation situations
Mg2+: F- and removal efficiencies of metal cation and F- are shown in Table 5. It
= 5: 1: 1: can be seen that the removal efficiencies of F-, Al3+ and Mg2+ in the
6
phosphoric acid solution is basically the same as that in aqueous solu­
Na+: Al3+: 99.5 96.7 84.5 Precipitation
Mg2+: F- tion, exceeding 90 %. The precipitation is also the mixture of NaAlMgF6
= 5: 1: 1: and Na3AlF6 (Fig. 6a). Meanwhile, the SEM image shows that the pre­
7 cipitation is incompletely developed crystallographically, and small
Na+: Al3+: 96.98 93.68 95.17 Precipitation
particles adhere to the surface of large particles, but the particle diam­
Mg2+: F-
= 5: 1.5:
eter becomes obviously larger compared with the aqueous system
1: 6 (Fig. 6b), mainly due to the fact that the phosphoric acid inhibits the
Na+: Al3+: 96.94 93.55 85.23 Precipitation dissociation of F- in hydrofluoric acid, slowing down the production rate
Mg2+: F- of precipitated nuclei and promoting the growth of crystals. Meanwhile,
= 6: 1.5:
the EDX mapping images in Fig. 6c show that a very small amount of
1: 7
phosphorus is entrapped in the precipitation.

Once the Na+ cations are added into the above precipitation, the
removal efficiencies of F- and Al3+ can respectively reach nearly 94.6 %
and 100 % as the molar ratio of n(Na+): n(Al3+): n(F) = 3: 1: 10. It can be
seen from the XRD pattern (Fig. 4a) that the formed precipitation is also
defined as the Na3AlF6, which is consistent with the aqueous solution. It
can be seen from the SEM images (Fig. 4b), that the particle size dis­
tribution of precipitation is not uniform, with fewer large particles and
more fine-grained grades and sticking together, which is also basically
consistent with the aqueous solution. EDX mapping images show that
the majority of the precipitation is F- and Al3+, interspersed with a small
amount of phosphorus (Fig. 4c). This is also because the Na3AlF6 pre­
cipitation is too fine and bonded together and the phosphorus is difficult
to wash out.
3.1.3. NaxAlyMgzFw in aqueous and phosphoric acid systems
From the previous sections of this paper, it is known that the Nax
AlyFw precipitation is effective in removing F- and Al3+ from aqueous
and pure phosphoric acid solution, but the industrial WPA is made from
phosphate ore. Except for the elemental phosphorus, there are other
elements such as fluorine, aluminum and magnesium, which enter into
the WPA [23]. Among them, the presence of magnesium will affect the
crystallization and filtration strength of calcium sulfate, and it will also
significantly reduce the H+ concentration in phosphoric acid, leading to
3.2. Structure identification of precipitations
3.2.1. AlF3⋅3H2O precipitation
Rietveld refinement plot is performed using the XRD experimental
data in Fig. 1, where the XRD refinement plots of precipitation for the n
(Al3+): n(F) = 1: 18 is shown in Fig. 7. The AlF3⋅3H2O (PDF#43–0436) is
chosen as the initial model for Rietveld refinement using the TOPAS
program. For the refinement, the voigt function with a blue dashed line
is used. A better peak match is obtained by the refinement, including
refinement of the peak profile, atomic positions, lattice and background
parameters, instrumentation factors, and occupation parameters, and
the important factors are shown in Table S1. On the other hand, Table S2
also shows the symmetry, space group, atomic coordinates, and occu­
pancy of the prepared samples.
3.2.2. Na3AlF6 precipitation
Rietveld refinement is performed using the XRD experimental data in
Fig. 2, where the XRD refinement plot of precipitation for n(Na+): n
(Al3+): n(F) = 3: 1: 10 is shown in Fig. 8. The Na3AlF6 (PDF#25–0772) is
chosen as the initial model and Rietveld refinement is performed using
the TOPAS program. For the refinement, the voigt function with a blue
dashed line is used. A better peak match is obtained by the refinement,
including refinement of the peak profile, atomic positions, lattice and

6
­
B. He et al. Separation and Purification Technology 341 (2024) 126855

Fig. 5. (a) XRD pattern, (b) SEM and (c) EDX element mapping images of NaxAlyMgzFw precipitation in aqueous solution.

with the generalized gradient approximation (GGA) of the Perdew-

Table 5
Burke-Emzerhof (PBE) generalization function [27]. The binding en­
Precipitation situations and removal efficiencies of Al3+, Mg2+ and F- for the
ergies of three precipitates are calculated using DFT with the following
NaxAlyMgzFw in phosphoric acid solution.
equation:
Molar ratio Al3+ removal Mg2+ removal F- removal Phenomenon
efficiency (%) efficiency (%) efficiency (%) Ef = Evacancy + EF2*(1/2) − Etotal (3)
Na+: Al3+: 96.57 93.42 95.01 Precipitation
Mg2+: F- = where Evacancy and Etotal are the energies with/without F-atom va­
5: 1.5: 1: 6 cancies, respectively, and EF2*(1/2) is the energy of a single 1/2F2 (g). By
calculation, the integral crystal orbital Hamiltonian (bond energy) of
AlF3⋅3H2O, Na3AlF6 and NaMgAlF6 precipitates are shown in Fig. 10. It
background parameters, instrumentation factors, and occupation pa­
can be seen that the larger the bond energy, the better the stability, thus
rameters, and the important factors are shown in Table S3. Meanwhile,
the stability of precipitates is ordered as follows: NaMgAlF6 > Na3AlF6
Table S4 shows the symmetry, space group, atomic coordinates, and
> AlF3⋅3H2O. It can be seen that the NaMgAlF6 performs the best
occupancy of the prepared samples. The results show that the atomic
stability.
occupancy of the precipitated crystals does not change significantly and
an accurate crystal structure is obtained under the conditions of constant
3.4. Removal of metal cation and F- with NaxMgyAlzFw precipitation in
Al3+ and F- molarity, and increasing the amount of Na+ cations.
WPA
3.2.3. NaMgAlF6 precipitation
To achieve the removal of Mg2+ and Al3+ and the F recovery in WPA,
Rietveld refinement is performed using the XRD experimental data in
it can be seen that the NaMgAlF6 is the most stable precipitation struc­
Fig. 5, and the result is shown in Fig. 9. It can be seen that there is a small
ture, combined with the stability research in Section 3.2. Thus, this
amount of Na3AlF6 when the Al3+ molar concentration in the solution
section adopts the NaMgAlF6 precipitation to remove F- from WPA. As
exceeds that of Mg2+, except for the NaMgAlF6. Hence, the main pre­
can be seen from the molar concentration of Na+, Mg2+, Al3+ and F- in
cipitation NaMgAlF6 (PDF#25–0841) is chosen as the initial model for
liquid phase WPA in Table 6, the molar number of Al3+ is less than that
Rietveld refinement using the TOPAS program. For the refinement, the
of Mg2+, and F- (except fluorosilicic acid), indicating that it can only
voigt function with a blue dashed line is used. A better peak match is
forms the NaMgAlF6 precipitation, according to the reaction conditions
obtained by the refinement, including refinement of the peak profile,
of pure phosphoric acid system, thus achieving the deep removal of
atomic positions, lattice and background parameters, instrumentation
metal cation and fluorine.
factors, and occupation parameters, and the important factors are shown
Under the reaction condition at 40 ◦ C for 12 min, when 4.5 g HF (40
in Table S5. In addition, Table S6 also shows the symmetry, space group,
wt%) and 4.0 g Na2SO4 (40 wt%) are added to 100 g WPA, the removal
atomic coordinates, and occupancy of the prepared samples.
efficiencies of F-, Al3+ and Mg2+ are 95.9 %, 99.1 % and 65.1 %,
respectively (Table 7). The solubility data of NaMgAlF6 precipitation in
3.3. DFT calculations WPA in Supporting Material.
To realize the recycling and reusage of F- in precipitation and reduce
First-principle DFT calculations are performed using the Vienna Ab the removal cost, the NaAlMgF6 is converted into HF and Na2SO4 for
initio Simulation Package (VASP) and the Projection Augmented Wave reusage. Among them, the first step is to decompose the precipitation by
(PAW) method [26]. The exchange generalization function is treated adding 60 wt% sulfuric acid, subsequently water absorption to form the

7
B. He et al.
Fig. 6. (a) XRD pattern, (b) SEM and (c) EDX element mapping images of NaxAlyMgzFw precipitation in phosphoric acid solution.
Fig. 7. XRD refinement of AlF3⋅3H2O precipitation in aqueous solution.
HF solution (40 wt%), and the recovery efficiency up to 95.6 %. The
remaining solution is Na2SO4 mixed solution containing impurities such
as Al3+ and Mg2+, which is precipitated and purified by calcium hy­
droxide solution with mass fraction of 60 %. The recovery efficiency of
Na2SO4 can reach about 98.4 %.
4. Conclusions
In this paper, a co-precipitation strategy is proposed for recovering F
from the WPA. Varieties of combinations between metal cation (Na+,
Mg2+ and Al3+) and F- with different molar ratios in aqueous and
phosphoric acid systems are designed to explore the co-precipitated
regulation. The results show that the simultaneously removal effi­
ciencies of Al3+, Mg2+ and F- can be higher than 90 % in the form of
NaAlMgF6 and Na3AlF6 precipitations as the n(Na+): n(Al3+): n(Mg2+):
n(F-) = 5: 1.5: 1: 6 in pure systems. XRD Rietveld refinement is employed
to identify the geometric structure of NaMgAlF6 precipitation. DFT
8
Separation and Purification Technology 341 (2024) 126855
calculations further confirm its stability, being the most, compared with
the AlF⋅3H2O and Na3AlF6 precipitations. On basis of this fact, extra Na+
and F- are added into the industrial WPA, so that the Na+, Al3+, Mg2+
and F- are co-precipitated in the form of NaAlMgF6, and the ultimate
removal efficiencies can exceed 90 % under the optimal conditions.
Besides, the Na+ and F- in the form of HF and Na2SO4 are low-cost
cycling recovered. The recovery efficiencies can reach about 95.6 and
98.4 %, respectively.
CRediT authorship contribution statement
Binbin He: Writing – original draft, Visualization, Validation,
Methodology, Investigation, Formal analysis, Data curation. Ying Fu:
Validation, Investigation, Formal analysis, Data curation. Yun Zu:
Writing – review & editing, Supervision, Resources, Methodology,
Funding acquisition, Formal analysis, Conceptualization. Yunxiang
Nie: Investigation, Formal analysis, Data curation. Yi Mei: Writing –
B. He et al. Separation and Purification Technology 341 (2024) 126855

Fig. 8. XRD refinement of Na3AlF6 precipitation in aqueous solution.

Fig. 9. XRD refinement of NaMgAlF6 precipitation in aqueous solution.

Fig. 10. Bond energy of AlF3⋅3H2O (a), Na3AlF6 (b) and NaMgAlF6 (c) precipitation as a function of -ICOHP.

review & editing, Supervision, Resources, Project administration, Declaration of competing interest
Methodology, Funding acquisition, Formal analysis, Conceptualization.
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence

9
B. He et al. Separation and Purification Technology 341 (2024) 126855

Table 6 [6] S. Kounbach, M.B. Embarek, L. Mahi, R. Boulif, R. Beniazza, R. Benhida,

Mole fractions of Na+, Mg2+, Al3+ and F- in liquid phase WPA. Simultaneous determination of H2SiF6, HF and total fluoride in fluorosilicic acid
recovered from wet phosphoric acid production by potentiometric titration,
Component Al3+ Mg2+ FTotal FH2 SiF6 Na+ Microchem. J. 175 (2022) 107152.
[7] Y. Zuo, Q. Chen, C. Li, C. Kang, X. Lei, Removal of fluorine from wet-process
mol/L 2.0 3.2 6.4 2.0 0.48 phosphoric acid using a solvent extraction technique with tributyl phosphate and
silicon oil, ACS Omega 4 (2019) 11593–11601.
[8] L. Xing, F. Yang, X. Zhong, Y. Liu, H. Lu, Z. Guo, G. Lv, J. Yang, A. Yuan, J. Pan,
Ultra-microporous cotton fiber-derived activated carbon by a facile one-step
Table 7 chemical activation strategy for efficient CO2 adsorption, Sep. Purif. Technol. 324
Chemical analysis of liquid phase WPA before and after purification. (2023) 124470.
[9] J. Deng, Z. Ma, Q. Qin, W. Liu, B. Wang, A residue reutilization strategy on
Component Concentration fluorine-containing water purification, J. Clean. Prod. 371 (2022) 133613.
[10] L. Wang, C. Wang, Y. Yu, X. Huang, Z. Long, Y. Hou, D. Cui, Recovery of fluorine
Before purification After purification
from bastnasite as synthetic cryolite by-product, J. Hazard. Mater. 209 (2012)
P2O5, wt.% 24.53 24.11 77–83.
Fe2O3, wt.% 0.84 0.82 [11] Z. Wang, D. Li, N.S. Gruda, Z. Duan, X. Li, Fertilizer application rate and nutrient
Al2O3, wt.% 1.09 0.002 use efficiency in Chinese greenhouse vegetable production, Resour. Conserv. Recy.
MgO, wt.% 1.26 0.40 203 (2024) 107431.
FTotal , wt.% 1.21 0.10 [12] Y. Lee, C. Chang, Y. Lin, Y. Lin, Effect of fermented lemon peel as a functional feed
additive on growth, non-specific immune responses, and Vibrio alginolyticus
FH2 SiF6 , wt.% 0.37 0.06
resistance in whiteleg shrimp, Litopenaeus vannamei, Aquacult. Rep. 34 (2024)
Removal efficiency of F-, % 91.7
101918.
[13] B. He, Y. Zhu, Y. Zu, Y. Nie, Y. Mei, Designing an efficient fluorine recovery
strategy for wet-process phosphoric acid purification by disclosing competitive
the work reported in this paper. complexation behavior between fluorine species and metal cations, Sep. Purif.
Technol. 320 (2023) 124219.
[14] K. Sanaa, G. Bouchaib, G. Fabrice, V. Christophe, S. Youssef, Purification of
Data availability industrial wet phosphoric acid solution by sulfide precipitation in batch and
continuous modes: Performance analysis, kinetic modeling, and precipitate
The data that has been used is confidential. characterization, J. Clean. Prod. 380 (2022) 135072.
[15] D.F. Lisbona, K.M. Steel, Recovery of fluoride values from spent pot-lining:
Precipitation of an aluminium hydroxyfluoride hydrate product, Sep. Purif.
Acknowledgments Technol. 61 (2008) 182–192.
[16] X. Liu, L. Huang, Z. Liu, D. Zhang, K. Gao, M. Li, A novel, clean, closed-loop process
for directional recovery of rare earth elements, fluorine, and phosphorus from
This work was financially supported by the National Natural Science mixed rare earth concentrate, J. Clean. Prod. 321 (2021) 128784.
Foundation of China (Grant No. 22068019), Applied Basic Research [17] B. Long, S. Chen, Z. Li, Y. Ding, Solubility of ammonium fluoride in aqueous
Program of Yunnan Province, China (Grant Nos., 202101BE070001- sodium fluoride solutions of various concentrations from dilute to saturated at
298.15 K for fluorine recovery from wet-process phosphoric acid, J. Mol. Liq. 299
031, 202301AT070445). (2020) 112247.
[18] R.K. Will, The benefits of isolating & utilizing F from phosphate operations, Proc.
Eng. 138 (2016) 267–272.
Appendix A. Supplementary material [19] J.R. Lehr, A.W. Frazier, J.P. Smith, Phosphoric acid impurities, precipitated
impurities in wet-process phosphoric acid, J. Agric. Food Chem. 14 (1966) 27–33.
Supplementary data to this article can be found online at https://doi. [20] M. Rashad, U. Sabu, G. Logesh, C. Srishilan, M. Lodhe, A. Joy,
M. Balasubramanian, Mullite phase evolution in clay with hydrated or anhydrous
org/10.1016/j.seppur.2024.126855. AlF3, J. Eur. Ceram. Soc. 40 (2020) 5974–5983.
[21] M. Rashad, M. Balasubramanian, Characteristics of porous mullite developed from
clay and AlF3⋅3H2O, J. Eur. Ceram Soc. 38 (2018) 3673.
References [22] J. Li, H. Guo, H. Zhang, T. Li, Y. Gong, First-principles molecular dynamics
simulation of the ionic structure and electronic properties of Na3AlF6 molten salt,
[1] B. He, Y. Zhu, Y. Zu, Y. Nie, Y. Mei, Efficient and cost-effective fluorine recovery Chem. Phys. Lett. 718 (2019) 63–68.
from liquid-phase wet-process phosphoric acid via two-step precipitation method, [23] A. Kruger, W.W. Focke, Z. Kwela, Effect of ionic impurities on the crystallization of
Sep. Purif. Technol. 325 (2023) 124687. gypsum in Wet-process phosphoric acid, Ind. Eng. Chem. Res. 40 (2001) 1364.
[2] Y. Ren, P. Ning, G. Qu, N. Ren, F. Wu, Y. Yang, X. Chen, Z. Wang, Y. Hu, Nano [24] H. Li, W. Ge, J. Zhang, Control foaming performance of phosphate rocks used for
biomass material functionalized by β-CD@Ce(NO)3 as a high performance wet-process of phosphoric acid production by phosphoric acid, Hydrometall. 195
adsorbent to removal of F from wastewater, Chemosphere 311 (2023) 136859. (2020) 105364.
[3] C. Yu, S. Huang, H. Xu, J. Yan, K. Rong, M. Sun, Optimal charging of lithium-ion [25] S. Kabiri, I.B. Andelkovic, R.C. Silva, Engineered phosphate fertilizers with dual-
batteries based on lithium precipitation suppression, J. Energy Storage 82 (2024) release properties, Ind. Eng. Chem. Res. 59 (2020) 5512–5524.
110580. [26] W. Zhang, X. Cui, M. Lu, X. Zhao, A conjugate frequency modulation FRM method:
[4] F. Yang, W. Li, X. Zhong, W. Tu, J. Cheng, L. Chen, J. Lu, A. Y, J. Pan, The alkaline Applications in polyphase DFT filter bank, Digit. Signal Process. 145 (2024)
sites integrated into biomass-carbon reinforce selective adsorption of acetic acid: In 104349.
situ implanting MgO during activation operation, Sep. Purif. Technol. 297 (2022) [27] A. Tanaka, A. Saito, T. Murata, A. Nakata, T. Miyazaki, Large-scale DFT
121415. calculations of multi-component glass systems (SiO2)0.70(Al2O3)0.13(XO)0.17 (X
[5] B. Peng, Z. Ma, Y. Zhu, L. Tang, Release and recovery of F and iodine in the = Mg, Ca, Sr, Ba): Accuracy of classical force fields, J. Non-Cryst. Solids 625 (2024)
production and concentration of wet-process phosphoric acid from phosphate rock, 122714.
Miner. Eng. 188 (2022) 107843.

10