Separation and Purification Technology 309 (2023) 123048

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Separation and Purification Technology

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One-step wet-process phosphoric acid by-product CaSO4 and

its purification
Keneng Fang a, Li Xu a, Min Yang a, Qianlin Chen a, b, *
a
School of Chemistry and Chemical Engineering, Guizhou University, Guiyang 550025, Guizhou, PR China
b
Collaborative Innovation Center of Guizhou Province for Efficient Utilization of Phosphorus and Fluorine Resources, Guizhou University, Guiyang 550025, Guizhou, PR
China

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

Keywords: In this study, phosphate ore powder was used as raw material, and anhydrous calcium sulphate (CaSO4) with
Wet-process phosphoric acid P2O5 and F− contents of only 0.01% and 0.03% was prepared by one-step acidification at atmospheric pressure
One-step acidification through regulating the sulphuric acid concentration and reaction conditions. Experimentally received: when the
CaSO4
sulfuric acid concentration is 35 vol%, the liquid–solid ratio is 3.5 mL/g and the reaction time is 2 h, the made
Purification
calcium sulfate is CaSO4, and its P2O5 and F− content is just 0.03% and 0.05%. On the other hand, H3PO4
extraction rate of the corresponding filtrate can reach to 72.35%, and the F− content in H3PO4 remains only
0.02%. After including 3 wt% of OA in this reaction, the elimination of SiO2 impurities reached 89.62%, leading
to the final purity of CaSO4 of 96.65%. We also investigated the mechanism for the removal of impurities such as
P, F, and Si during the system and explained the mechanism for the formation of CaSO4. This study not only
improves the yield of H3PO4 but also the availability of phosphogypsum by producing CaSO4. This can be
considered as a reference pathway to enhance the benefits of wet- process phosphoric acid.

1. Introduction molecules. Therefore, CaSO4 can be regarded as a practical green ma­

Phosphoric acid is a significant chemical raw material, which is
extensively employed in a variety of industries, including fertilizer,
metallurgy, food, medicine, and other fields. The primary method for
producing phosphoric acid is a wet process [1–3]. The sulphuric acid
method is one of the most popular wet process, as reflected in equation
(1). The sulphuric acid method produces 4.5–5 t of phosphogypsum (PG)
for each 1 t of phosphoric acid produced [4]. Phosphogypsum can be
classified into dihydrate phosphogypsum (CaSO4⋅2H2O), hemihydrate
phosphogypsum (CaSO4⋅0.5H2O), and anhydrous phosphogypsum
(CaSO4) based on its water content. The phosphogypsum produced as a
by-product of the conventional wet phosphoric acid process is typically
CaSO4⋅2H2O, and until then there were few methods to obtain CaSO4
from phosphate ore in just one step [5].
Ca5F(PO4)3 + 5H2SO4 + 5nH2O → 3H3PO4 + 5CaSO4⋅nH2O + HF↑
Compared to CaSO4⋅2H2O, CaSO4⋅0.5H2O, CaSO4 has several ad­
vantages, such as a huge certain surface area, improved thermal sta­
bility, superior chemical resistance, and a high affinity for organic
terial for further applications [6–9]. For instance, it can replace CaCO3
as a filler in polymers, along with being employed in several applica­
tions, such as rubber, paper, ceramics, medical carriers, and energy
storage materials [10–15]. At present, CaSO4 is normally prepared from
CaSO4⋅2H2O or CaSO4⋅0.5H2O, and it is rarely received from phosphate
ore in one step. The preparation procedures are mainly high-
temperature calcination, hydrothermal method, and solvent heat pro­
cedure. But such techniques require high temperature or pressure,
restricted preparation states, higher cost, and low yield, which makes it
complex to receive large-scale industrial utilization [16,17]. In addition,
there is no clear explanation for the formation process of CaSO4.
Therefore, the search and evaluation of the formation procedure of
CaSO4 with low energy consumption and impurities (or no impurities)
are one of the major breakthrough concepts for the resource utilization
of PG.
(1) The formation of phosphogypsum impurities from wet phosphoric
acid by-products is complicated and varied. But the number and type of
impurities in phosphogypsum rely on the nature and formation of the
phosphate ore. Mainly, there are water-soluble phosphorus compounds
(H3PO4, Ca(H2PO4)2⋅2H2O, CaHPO4⋅2H2O, and so on.), water-soluble

* Corresponding author at: School of Chemistry and Chemical Engineering, Guizhou University, Guiyang 550025, Guizhou, PR China.
E-mail address: cql1018@163.com (Q. Chen).

https://doi.org/10.1016/j.seppur.2022.123048
Received 30 October 2022; Received in revised form 16 December 2022; Accepted 26 December 2022
Available online 29 December 2022
1383-5866/© 2022 Elsevier B.V. All rights reserved.
K. Fang et al.
Fig. 1. Experimental flow diagram.
fluorine compounds (NaF, Na3AlF6, Na2SiF6, Na3FeF6, etc.), insoluble
phosphorus, fluorine (mainly calcium phosphate and calcium fluoride),
eutectic phosphorus (CaHPO4⋅2H2O), insoluble solid SiO2, residual
acids, trace heavy metals (e.g. zinc, copper, chromium, cadmium, etc.),
and organic matter [18–22].
PG has global production of around 258 million tons/year, in which
China hold around 75 + million tons/year of production [23,24]. Only a
small fraction of this PG is reused or recycled, while the rest is disposed
of by landfilling, stockpiling, and disposal [25]. And, the impurity ions
including P and F from the stockpiled PG soaked by rainwater will then
run off and create more pollution in the soil and groundwater [26].
Moreover, the presence of impurities in PG, such as eutectic phosphorus,
F− , and SiO2 can seriously affect the performance of PG-based materials.
Thus, purification and decontamination of PG are the keys to deter­
mining its resource utilization.
Numerous academics have explored how to remove contaminants
from PG, and popular techniques include water washing, acid dissolu­
tion, and calcination [27–29]. For instance, Cai et al. considered a 2%
oxalic acid solution to decrease the P2O5 in raw PG from 1.03% to 0.18%
and utilised the PG after removing the impurity for construction mate­
rials (the condition for PG to be considered for construction materials is
that the P2O5 content is lower than 0.2%) [30]. Cao et al. decreased F− in
raw phosphogypsum by high-temperature calcination at 800 ◦ C, from
0.99% to 0.18%, while the impact on P2O5 content at this temperature
was not significant [31]. It is evident from this research that the elimi­
nation of intercrystalline impurities can only be received by decreasing
the structure of the crystal or by creating it to experience a crystal
structure transformation. Although high-temperature calcination can
significantly decrease the F− content of PG, it had no clear impact on the
P2O5 content of PG under these circumstances. As reflected from the
above literature, the P2O5 and F− content in the conventional industrial
by-product PG are much more than the maximum approved content in
construction materials (0.2%). Also, the simultaneous removal of P2O5
and F− impurities are hard to get if only one technique is used. In this
thesis, a one-step acidification technique was considered to create CaSO4
from phosphate ore powder by regulating the sulphuric acid concen­
tration, while greatly decreasing the P2O5 and F− contents of CaSO4.
For the acid-insoluble SiO2, neither the acidolysis solution method
nor the calcination method has any considerable impact on the removal,
2
Separation and Purification Technology 309 (2023) 123048
therefore it must be considered with regard to its modification to ensure
easy separation and removal. There are various common surface modi­
fiers, but the quality of the phosphoric acid requires to be considered
and modifiers without additional impurities (relative to the reaction
system) need to be identified. Fatty acids, including hydrocarbons, are
easily removed by thermal decomposition, and such modifiers are nor­
mally oleic acid (OA) and stearic acid (SA). OA has a faster dissolution
rate and better dispersion in sulphuric acid–water reaction systems as it
is a liquid at room temperature [32]. Also, OA is a fatty acid that can be
utilised as a surfactant to help in lowering the reaction system’s viscosity
and the powder’s dispersion, which will make it easier for the calcium
sulphate to crystallise throughout the reaction. Thus, OA was considered
as an additive in this experiment, but no relevant application of OA in
wet phosphoric acid processes has been reported before [33,34].
In this research, sulphuric acid one-step acidification was considered
to acidify phosphate ore at room temperature and pressure, and the
impacts of sulphuric acid concentration and liquid–solid ratio on the
leaching of phosphorus and fluorine from phosphate ore and the crys­
talline form of its by-product calcium sulphate were examined. In
addition, the impact of oleic acid addition on SiO2 impurities in CaSO4
and its removal mechanism was investigated, and the process and
mechanism of CaSO4 formation were related. The effect of different
reaction conditions on the F− content, organic carbon content, and
extraction rate in H3PO4 was investigated. Compared to the by-
production of CaSO4⋅2H2O, this method increases the yield of wet
phosphoric acid, resulting into a purer CaSO4 by-product. This not only
improves the availability of PG as a by-product but also offers a refer­
ence for the industrial production of CaSO4.
2. Experimental section
2.1. Experimental materials and reagents
The phosphate ore considered in the experiments came from Wejin
County, Guizhou, China. The phosphate ore was cleaned, crushed,
ground, and then sieved through a 100 mesh to create phosphate ore
powder. Fig. 2 demonstrates the XRD test results of the phosphate ore
powder. The major mineral phases of the ore are quartz (SiO2), dolomite
(CaMg(CO3)2), and fluorapatite (Ca5(PO4)3F). All chemical reagents
K. Fang et al. Separation and Purification Technology 309 (2023) 123048

* *
* *
* * ** *

Fig. 2. (a) XRD pattern and (b) particle size distribution map of phosphate ore.

used in the experiments were analytically pure. The water used in the 2.3. Analysis and characterization
experimental work was deionised water (resistivity 18.25 MΩ) unless
otherwise noted. 2.3.1. Analytical testing of acidolysis solution and phosphoric acid samples
Considering the quinolone phosphomolybdate weight method, the
determination of P2O5 content was done according to GB/T1871.1-
2.2. Acid leaching and phosphoric acid extraction experiments of
1995, and the H3PO4 extraction rate was computed. Total organic car­
phosphate ore
bon was obtained by German-Jena-miltiN/C 3100 for determining the
total organic carbon in the acidolysis solution received under several
1. Phosphate ore powder acid leaching experiment: In a 250 mL three-
preparation conditions. The ion-selective electrode method was used.
necked flask, phosphate ore powder, water, and sulphuric acid were
The acidolysis solution and H3PO4 received from the above reverse
mixed into a slurry at a liquid–solid ratio of 3 mL/g and the reaction
extraction were tested based on the JC/T2073-2011 method for total
was stirred at a constant temperature of 60 ◦ C in a constant tem­
fluorine determination to get the F− content in the acidolysis solution
perature reactor with uniform stirring. At the end of the reaction, the
and phosphoric acid samples. Three parallel experiments were carried
filtrate is obtained by filtration (i.e. acidolysis solution). The solid
out on the contents of P2O5 and F− , and the data in the text are the
phase calcium sulphate samples were washed with deionised water
average of the results of them.
until the washings were neutral and then dried in Petri dishes at
60 ◦ C for 24 h (The experimental flow is shown in Fig. 1).
2.3.2. Analytical and characterization tests of calcium sulfate
2. Experiment to extract H3PO4: H3PO4 was removed from the filtrate
According to GB/T5484-2012 “Chemical analysis method of gyp­
of step 1 by considering a mixture of tributyl phosphate (TBP) and n-
sum”, the water crystallization concentration of calcium sulphate sam­
butanol in a volume ratio of 3:1 as an extraction phase, where the
ples was determined. The data for the water of crystallisation content in
volume ratio of the filtrate to extraction phase was 1:4. Following the
this experiment are the average of the results of three parallel experi­
completion of extraction, the organic phase, including H3PO4 and the
ments. The P2O5 content of the product calcium sulphate was deter­
remaining aqueous phase, were received. The P2O5 content Y1 in an
mined by GB/T1871.1-1995 using the quinolone phosphomolybdate
aqueous phase and the P2O5 content Y2 in the filtrate were obtained
weight method. The F− the content of solid samples were deternibed
based on the quinolone phosphomolybdate weight method of GB/
based on JC/T2073-2011. The YDZ-R automatic blue light whiteness
T1871.1-1995. The H3PO4 extraction rate was computed based on
metre was used to measure the blue light whiteness of calcium sulphate
the following equation.(The units of Y1 and Y2 are wt%).
samples.
X = [(Y2-Y1)/Y2] × 100%.
The morphology of the samples was detected by considering scan­
The organic phase obtained in the extraction experiment was back-
ning electron microscopy (SEM, Germany-Zeiss-ZEISS sigma500, pre­
extracted from ultra-pure water (organic phase: aqueous phase =
pared with EDS, EHT = 5.00 kV). By using X-ray diffraction (XRD,
8:1) to receive a phosphoric acid sample after the extraction. The F−
RIKEN-SmartLab 9 KW, Japan) at a scan rate of 10 ◦ /min and a 2θ of
content of the phosphoric acid sample was determined based on the
5–85◦ , the phase of the samples was determined. The functional group
total fluorine determination method in JC/T2073-2011.
structure of the products was examined (FT-IR, Nicolet is5) through
3. Preparation experiments with the addition of oleic acid: After the
Fourier infrared spectroscopy. The microstructure of CaSO4 was exam­
screening of single-factor experiments, the acid concentration was
ined by transmission electron microscopy (TEM, FEI Talos f200s, with
35 vol%, the liquid–solid ratio was 3.5 mL/g, and the reaction time
SAED) and its elemental mapping was obtained. The formation of
was 2 h. An appropriate amount of oleic acid was added to the re­
phosphate ore and CaSO4 was received through X-ray fluorescence
action after the slurry was adusted. The solid phase product was
spectroscopy (XRF, Zetium/EDX-LE).
extracted from the organic phase after the completion of reaction to
remove the SiO2 impurities that had been altered by OA, followed by
cleaning the calcium sulphate with ultrapure water and drying to get
pure CaSO4. While the impurities in the organic phase were cleaned
with ethanol, filtered, and dried in preparation for further testing
and analysis.

Table 1
Chemical composition of phosphate ore.
Constituent CaO P2O5 F SiO2 Fe2O3 Al2O3 MgO MnO other

Content(wt%) 57.02 24.17 2.05 3.95 1.38 0.93 9.58 0.08 0.84

3
K. Fang et al. Separation and Purification Technology 309 (2023) 123048

Fig. 3. (a) Bluish whiteness and water of crystal content of calcium sulphate prepared under different reaction conditions; (b) XRD of calcium sulphate prepared
under different reaction conditions; (c) FT-IR of calcium sulphate prepared under different reaction conditions; (d) P2O5 and F− content of calcium sulphate prepared
under different reaction conditions (The reaction conditions for 1, 2, 3, 4 and 5 are reflected in Fig. 3(d), with φ showing the sulphuric acid concentration).

3. Results and discussion

Table 2
Chemical composition of calcium sulphate made under several conditions.
3.1. Analysis of the phase composition of phosphate ore
Constituent/wt% CaO SO3 P2O5 SiO2 Fe2O3 Al2O3 other

The findings of the XRD tests performed on the phosphate ore are 3 wt%OA 41.70 57.65 0.02 0.41 0.08 0.04 0.10
shown in Fig. 2(a). The main phase composition of the phosphate ore 35 vol% 41.84 56.78 0.03 1.03 0.10 0.11 0.11
25 vol% 41.66 55.47 0.76 1.42 0.18 0.15 0.36
received from the XRD data analysis is fluorapatite, dolomite, and a
small amount of quartz. Fig. 2(b) showed that the particle diameter of
D90 is 111.12 µm. In addition, the chemical composition of the phos­ optimal for 2 h. With an increase in OA addition, the contents of P2O5
phate ore was obtained through XRF testing and the results are shown in and F− in CaSO4 gradually reduced and then stabilized, and the inclu­
Table 1. This indicates that the phosphate ore used was of low to me­ sion of 3 wt% OA was the best. The relevant experimental results are
dium grade. reflected in Figs. S1–S9, as supporting information.
Fig. 3(a) represents that the water content of the prepared calcium
3.2. Effect of different reaction conditions on calcium sulfate products sulphate was 12.48 % with 25 vol% sulphuric acid concentration,
indicating that the product calcium sulphate includes water of crystal­
3.2.1. Effect of different reaction conditions on impurities and their lization. The water crystallization content of the calcium sulphate
crystalline forms in calcium sulfate samples made under the rest of the conditions was less than 0.5%,
In order to obtain the optimal preparation conditions of CaSO4, the therefore the calcium sulphate prepared at this time could be initially
reaction sulphuric acid concentration (25 vol%–65 vol%), liquid–solid judged to be CaSO4. Moreover, it can be determined from Fig. 3(a) that
ratio (2.5–5 mL/g), reaction time (5–360 min), and OA addition (1–10 the whiteness value improved to some extent from 54.8% to 60.7% after
wt%) were optimized and screened through the single-factor experi­ the optimization of experimental conditions. This is due to an increase in
mental techniques for obtaining an optimal preparation condition of sulphuric acid concentration or liquid–solid ratio that caused further
CaSO4. The experimental outcomes under optimal conditions for every carbonization of organic matter during the reaction. It should also be
single factor are reflected in Fig. 3. It was discovered experimentally that highlighted that the whiteness of CaSO4 made when 3 wt% OA included
the calcium sulphate’s P2O5 and F− contents fell with increasing con­ was significantly improved and its whiteness value reached to 75.0%.
centration and remain fluctuating, with the lowest sulphuric acid con­ The trace amounts of non-ferrous transition metals (Fe, Mn, Cr, etc.)
centration being 35 vol%. The P2O5 and F− the content of CaSO4 initially create a significant influence on the whiteness of gypsum along with
drop as the liquid–solid ratio increases before stabilising and reaching an organic carbon content. XRF tests were then carried out on CaSO4 made
inflection point at 3.5 mL/g. by including 3 wt% OA, and the outcomes are reflected in Table 2, where
The content of P2O5 and F− in CaSO4 slowly reduced and then sta­ the Fe2O3 content was determined to be 0.08%. The addition of 3 wt%
bilized with the prolongation of the reaction time, and the reaction was OA, on one side, can create the SiO2 impurities and carbonized organic

4
K. Fang et al.
Fig. 4. SEM images of (a) CaSO4⋅2H2O prepared at a sulfuric acid concentration of 25 vol% and (b) CaSO4 prepared by adding 3 wt% OA and its particle size
distribution map.
matter easy to detach and eliminate through surface modification (refer
to Section 3.4 for the removal mechanism), resulting into decrease of the
CaSO4 impurity content. While OA− can chelate with metal ions and
decrease the metal ion content in CaSO4, eventually making CaSO4
whiteness higher. Also, the purity of CaSO4 made by including 3 wt% OA
was computed as 96.64%, in accordance with the GB/T 5483-2008.
To further illustrate the presence of structural changes in the calcium
sulphate crystals grown under several conditions, XRD and FT-IR tests
were performed on the pertinent samples and the results are reflected in
Fig. 3 (b) and (c). It can be found that the XRD pattern of the prepared
sample matches the PDF standard card pattern of CaSO4⋅2H2O
(PDF#33-0311) when the acidity is 25 vol%, and combined with the FT-
IR test analysis. It is clear that the calcium sulphate prepared at this
point is primarily CaSO4⋅2H2O [35]. Also, when the acid concentration
improved to 35 vol% the XRD pattern of its samples was equal to the PDF
standard card pattern of CaSO4 (PDF#70-9090). No characteristic ab­
sorption peaks of water molecules were also identified in the IR spec­
trum, which was aligned with the water of crystallization and XRD test
results. This reflects that all the calcium sulphate prepared under this
circumstances was CaSO4. Furthermore, at an acid concentration of 35
vol%, a liquid–solid ratio of 3.5:1 mL/g and a reaction time of 2 h, the
actual yield of CaSO4 was calculated by conservation of matter of cal­
cium atoms to be 95.99%.
As demonstrated in Fig. 3(d), the high quantity of P2O5 and F− in the
CaSO4⋅2H2O synthesised at a 25 vol% concentration is mostly due to the
ease with which the CaSO4⋅2H2O produced at this concentration can
eutectic with CaHPO4⋅2H2O. Second, the larger particle size of
CaSO4⋅2H2O leads to relatively poor mobility, which prevents the
generated HF and SiF4 gas from escaping in a timely manner. They will
react with impurities in the liquid phase to form fluorosilicates and other
substances, leading to the high P2O5 and F− concentrations in
CaSO4⋅2H2O.
The solid product is CaSO4 when the sulphuric acid concentration is
increased to 35 vol%, resulting in the destruction of the conditions for
eutectic phosphorus formation. A rise in sulphuric acid concentration
increases the amount of H+ in the system which inhibits the ionisation of
H3PO4. This decreases the amount of HPO2− 2−
4 and FPO4 in the system
(PO3−4 reacts with the fluoride in the system to create FPO 2−
4 ), leading to
limited conditions to form eutectic phosphorus, therefore, the mass
fraction of P2O5 in the CaSO4 received at this point is decreased [36].
When the settings were optimized, it was discovered that the peak po­
sition of CaSO4 was considered to be consistent with the CaSO4 standard
card, and the peak intensity steadily increased, suggesting that the de­
gree of crystallization gradually improved. When its degree of crystal­
lization is better, the fewer defects on its surface or inside, the less it
includes impurity ions including P, F, and so on.
5
Separation and Purification Technology 309 (2023) 123048
The reduction in F− content is mainly due to the fact that when the
acid concentration increases, the high concentration of sulphuric acid in
contact with the phosphate ore releases a large amount of heat. This can
result into a brief high temperature at the beginning of the reaction. The
reaction of the fluoride in the system with the acid readily also produces
SiF4 and HF gases, which are highly likely to escape driven by the CO2,
water vapour and early high temperatures generated by the reaction
[37].
The SiF4 and HF gases escaping from the actual production can be
collected in NaOH solution and after collection and purification can be
used in other applications. Secondly, the rise of sulphuric acid concen­
tration not only encourages the dissolution of partially insoluble fluorine
but also persuades the transformation of calcium sulphate crystalline
shape. This results into reduction of particle size, which enhances the
fluidity of the reaction slurry and makes it easier for the generated HF
and SiF4 gas to escape. Along with the above-mentioned functions of
eliminating impurities and complexing metal ions, adding 3 wt% OA
increases the dispersion of the reaction system, enhances the crystal­
lisation of calcium sulphate, and supports the leaching of P and F ions
including in the reaction system.
Fig. 3(d) reflects that after a sulphuric acid concentration of 35 vol%,
with or without OA; the P2O5 and F− in the prepared anhydrous calcium
sulphate are effective less the limits for other application materials, like
the application to construction materials requiring lower than 0.2%
P2O5 in PG. As noted in the introduction, the P2O5 and F− contents of
traditional wet phosphoric acid by-product phosphogypsum is around
1%, but in contrast to the anhydrous calcium sulphate made using this
process, our impurity content is quite low, which is assumed to be
considered in more areas.
3.2.2. SEM of calcium sulfate prepared under different conditions
SEM images of calcium sulphate synthesised under various condi­
tions are shown in Fig. 4. As shown in Fig. 4, the calcium sulphate
sample generated at a 25 vol% concentration has a plate-like structure
with visible surface cracks and associated smaller particles. It can be
determined that there are some CaSO4 along with the XRD test analysis,
while the main product is CaSO4⋅2H2O.
The rectangular structure of CaSO4 produced by adding 3 wt% OA to
the reaction has a clean, flat surface, and rectangular structure. This is
primarily because, under these circumstances, a CaSO4 crystal nucleus is
created. It is also required to continuously absorb Ca2+ and SO2− 4 from
the system in order to maintain growth, thus, a large amount of SO2− 4 is
wrapped around the nucleus. This also creates a “protective film” that
prevents other impurity ions from entering or adsorbing the interior and
surface of CaSO4. Fig. 4(b) further reflects that the average particle
diameter of 1.32 µm is significantly less than that of CaSO4⋅2H2O. This is
K. Fang et al.
Fig. 5. (a) TEM image of, (b) HRTEM image, (c) elemental imaging image, (d) SAED image and (e) EDS spectrum of CaSO4.
Fig. 6. (a) FT-IR spectrum and (b) XRD pattern of collected impurities.
mainly due to an increase in acid concentration that leads not only to a
shift in the crystal structure of calcium sulphate, but also to a rise in
nucleation sites and rates. Moreover, excess sulphuric acid had an
inhibitory impact on its axial growth, leading to a smaller CaSO4 particle
diameter [38].
3.2.3. TEM analysis of CaSO4
The findings of TEM tests were performed on CaSO4 generated by
adding 3 wt% OA in the reaction as indicated in Fig. 5, in order to better
understand the microscopic morphology of CaSO4. As reflected in Fig. 5
(a), the prepared calcium sulphate crystals have a clear outline and
smooth surface with a good cubic structure and a particle diameter of
approximately 1 μm. The lattice stripe spacing of 0.345 nm can be
computed from the HRTEM image of CaSO4 in Fig. 5(b), corresponding
to the (0 2 0) crystal plane of CaSO4 by making a comparison of the XRD
standard card. The selected area diffraction (SAED) pattern of CaSO4 is
reflected in Fig. 5(d), and because the bright spots on the SAED pattern
have a circular distribution, the produced CaSO4 is polycrystalline.
Furthermore, in combination with elemental mapping and EDS spec­
troscopy, as shown in Fig. 5(c) and (e), it can be seen that the prepared
6
Separation and Purification Technology 309 (2023) 123048
CaSO4 has a low content of P2O5 and F− and the atomic fractions of Ca, S
and O are more consistent with the chemical formula of CaSO4. This also
demonstrates the comparatively high purity of the CaSO4 prepared in
the study.
3.3. Mechanism of SiO2 removal by oleic acid
The impurities that were created following the addition of OA were
collected and put through FT-IR tests, in order to further investigate the
form and mechanism of SiO2 impurity removal by OA. The test results
are shown in Fig. 6(a), where the antisymmetric stretching vibration
peak of Si-O-Si appears at 467 cm− 1. The symmetric and antisymmetric
stretching vibration peaks of Si-O appear at 794 cm− 1 and 1080 cm− 1. At
1740 cm− 1 is a peak of C–– O stretching vibration in oleic acid, and at
1625 cm− 1 and 1465 cm− 1 are the major characteristic peaks of asym­
metric and symmetric stretching vibration of C–– O in the oleic acid root.
At 3450 cm− 1 is the O–H stretching vibration absorption peak of the
carboxyl group. Moreover, at 2855 cm− 1, 2920 cm− 1, and 2965 cm− 1
are a telescopic vibrational absorption peaks of –(CH2)– [39].
More XRD tests were conducted on the impurities, and the findings
K. Fang et al. Separation and Purification Technology 309 (2023) 123048

are presented in Fig. 6(b). According to a comparison with the SiO2

standard card (PDF#85-1053), the primary phases are SiO2 and a
portion of CaSO4. Thus, it can be determined that OA has changed SiO2
through physical and chemical adsorption. This results in an easy sep­
aration and removal because of its hydrophobic nature after modifica­
tion [40,41]. In order to clearly illustrate the impact of eliminating SiO2
impurities, calcium sulphate manufactured under various conditions
was examined by XRF and the outcomes are shown in Table 2. According
to the experimental results, SiO2 was significantly removed from CaSO4
when 3 wt% of OA was added, leading to only 0.41 wt%. In particular,
the removal of SiO2 touched 89.62% and 71.13% relative to phosphate
ore and when the by-product was CaSO4⋅2H2O, respectively.

3.4. The formation process and mechanism of CaSO4

When phosphate ore powder comes into contact with an aqueous

solution of sulphuric acid, the reaction immediately produces amor­
phous calcium sulphate. The different reaction environment impacts the Fig. 7. XRD diagram of calcium sulphate prepared by 30 vol% sulphuric acid
activity of water molecules along with the crystal nucleation environ­ concentration.
ment. This results into structural rearrangement of the ions and water
molecules in the amorphous calcium sulphate, leading to the formation Where aw denotes the water activity, and by the same token we get:
of three distinct crystal structures of calcium sulphate, namely
CaSO4⋅2H2O, CaSO4⋅0.5H2O, and CaSO4 [42]. According to classical CaSO4⋅2H2O ↔ CaSO4 + 2H2O K4 = Ksp, DH/Ksp, AH = a2w (5)
nucleation theory, the smaller the molecule size, the lower the interfa­
From the above equation (4), we can determine that when K3 is more
cial energy and the higher the nucleation supersaturation, the easier it is
than a1.5w , the equilibrium moves towards the right to create
to reduce the activation energy required for crystal nucleation, which is
CaSO4⋅0.5H2O. When the acid concentration goes up to 30 vol%, the
also more conducive to crystal nucleation and growth [43].
equilibrium constant K3 is only linked with the temperature, therefore
At a sulphuric acid concentration of 25 vol%, it is mainly
the rise of sulphuric acid concentration at the similar reaction temper­
CaSO4⋅2H2O and CaSO4⋅0.5H2O that hold a nucleation advantage.
ature makes the water activity in the system reduce, causing the reaction
Although CaSO4⋅2H2O has a larger molecular volume CaSO4⋅2H2O
(4) to shift to the right, and finally, CaSO4⋅0.5H2O is received. This is
crystals predominate in the low supersaturation zone, whereas the high
consistent with the experiment’s results, which demonstrate that
supersaturation region is dominated by the low interfacial energy
CaSO4⋅0.5H2O is produced when the sulphuric acid concentration is
CaSO4⋅2H2O [44]. The thermodynamic condition of CaSO4⋅2H2O is
raised to 30 vol% as seen in Fig. 7.
quite stable because of the lower solubility of CaSO4⋅2H2O at room or
The calcium sulphate structure is altered from CaSO4⋅2H2O to
low temperature, which holds a relatively higher supersaturation during
CaSO4⋅0.5H2O, as reflected in Fig. 8. In contrast to the crystalline water
nucleation, therefore CaSO4⋅2H2O is highly likely to nucleate, crystal­
of CaSO4⋅2H2O which is placed between the bilayer structure, the
lize, and grow in this environment. Also, the concentration of sulphuric
crystalline water of CaSO4⋅0.5H2O is situated in the pore channel, its
acid is less, and its ability to divest water molecules is fragile (dehy­
structure is more compact and the spatial site resistance impact is more,
dration of concentrated sulphuric acid), therefore the water molecules
therefore the energy needed to remove the water molecules is more at
are subject to low resistance for easily entering into the internal amor­
this time, thus the acid concentration should be kept rising.
phous calcium sulphate and happen in various degrees of structural
After raising the sulphuric acid concentration to 35 vol%, the excess
rearrangement, thus the generation of CaSO4⋅2H2O.
sulphuric acid will cause a rise in the number of protons in the solution,
As the sulphuric acid concentration gradually increases to 30 vol%,
occupying the lone pair of electrons necessary for the formation of
high concentrations of sulphuric acid exist in the solution as molecules,
hydrogen bonds between water molecules and SO2− 4 in CaSO4⋅2H2O. It
carrying the “sulphonic acid groups”. The results into an increase in its
prevents water molecules from entering the interior of the crystal to
absorption of water molecules (i.e. dehydration of the high concentra­
build crystalline water. While the rise in concentration allows the con­
tion of sulphuric acid). Therefore, the greater the concentration of this
centration of Ca2+ and SO2− 4 in the system to become higher than the
group is, the stronger the absorption of water molecules is, so that the
supersaturation of CaSO4 that causes the precipitation of CaSO4 (AH)
number of water molecules entering the internal rearrangement reaction
crystal nuclei; therefore driving reactions (4) and (5) in the way of
of amorphous calcium sulphate is reduced due to the greater resistance.
positive reaction and eventually completing the conversion to CaSO4.
In addition, the decrease in pH affects the water activity in the system on
Furthermore, when the acid concentration was 35 vol% in this
the one hand and increases the solubility of CaSO4⋅2H2O (DH) on the
experiment (corresponding to 6.3 mol/L in the literature), CaSO4⋅2H2O
other. The increase of acid concentration in the system reduces the
and CaSO4⋅0.5H2O could not be stabilized in the system and their stable
activation energy required for the nucleation of CaSO4⋅0.5H2O (HH),
phase was only CaSO4 [45]. Thus, when the sulphuric acid concentra­
leading to the nucleation of CaSO4⋅0.5H2O and the precipitation of
tion gets to 35 vol%, the additional sulphuric acid makes it hard for
crystals. At this time, the reaction system is undergoing two reactions:
water molecules and other impurity ions from entering or absorbing to
dissolution of CaSO4⋅2H2O and crystallisation of CaSO4⋅0.5H2O. The
the inside or surface of CaSO4 crystals. The actual experimental out­
reaction equation for this process is shown below.
comes are reflected in Fig. 3(b), and the existence of CaSO4 as the only
CaSO4⋅2H2O ↔ Ca2+ + SO2−
4 + 2H2O K1 = Ksp, DH (2) reaction product at an acid concentration of 35 vol% supports the above.
In the present experimental system, the effect of OA on the formation
CaSO4⋅0.5H2O ↔ Ca 2+
+ SO2−
4 + 0.5H2O K2 = Ksp, HH (3) and growth of CaSO4 crystals was not evident in the TEM and other
Where Ksp denotes the dissolution equilibrium constant of the crys­ analyses due to the small amount of OA added and the fact that the
tal, when both are in equilibrium: reacting SiO2 and a small part of CaSO4 removed in the separation and
removal stage.
CaSO4⋅2H2O ↔ CaSO4⋅0.5H2O + 1.5H2O K3 = Ksp, DH/Ksp, HH = a1.5
w (4)

7
K. Fang et al. Separation and Purification Technology 309 (2023) 123048

Fig. 8. (a) shows the cell diagram of CaSO4⋅2H2O; (b) shows the cell diagram of CaSO4⋅0.5H2O; (c) shows the cell diagram of CaSO4.

Fig. 9. (a) P2O5 content and F− content in the acidolysis solution obtained at different sulfuric acid concentrations; (b) P2O5 content and F− content in the acidolysis
solution obtained at different reaction conditions; (c) Extraction rate of H3PO4 corresponding to different reaction conditions; (d) F− content in H3PO4 corresponding
to different reaction conditions. (The reaction conditions for 1, 2, 3, 4, and 5 are reflected in Fig. 9(d), with φ signifying the sulphuric acid concentration).

3.5. Effect of different reaction conditions on the content of P2O5 and F−
in the acidolysis solution and the extraction rate of H3PO4
In order to examine the impacts of CaSO4 and CaSO4⋅2H2O by the
one-step acidification technique on P2O5, F− content and H3PO4
extraction rates in the acidolysis solution in this research, the acidolysis
solution received under various reaction circumstances was obtained
through correlation analysis, and the outcomes are reflected in Fig. 9.
According to Fig. 9(a), the amount of P2O5 in the acidolysis solution
changes in an N-shaped pattern as the sulphuric acid concentration rises.
When the sulphuric acid concentration was 35 vol%, this decreased the
probability of eutectic phosphorus formation due to the solid product
being CaSO4, leading to a higher P2O5 content in the liquid phase [46].
The sulphuric acid concentration is more than 35 vol%, with the con­
centration of rising slurry viscosity also going up, which is not conducive
to the diffusion of P-containing ions. On the other hand, when 65 vol%
was extended, the reduction of solid phase particle size and the existence
of a large amount of SO2− 4 around CaSO4 nuclei made it difficult to
adsorb P-containing ions, therefore the P2O5 content in the acidolysis
solution was increased.
Moreover, it can be determined from Fig. 9(a) that its corresponding
F− content in the acidolysis solution first falls with increasing sulphuric
acid concentration before stabilizing and reaching a minimum value of
0.03% at 55 vol%. This reduction is due to the fact that the increase in
sulphuric acid concentration accelerates the phosphate ore decomposi­
tion, in order to increase the exothermic heat of the reaction, facilitate
the escape of the SiF4 and HF gases produced in the system, and improve
the separation efficiency of the fluorine.
The final sulphuric acid concentration of 35 vol% was chosen and
further developments in the experimental conditions were sustained,
and the test outcomes are reflected in Fig. 9(b), (c), and (d). From Fig. 9
(b), it can be determined that the P2O5 content in the acidolysis solution
tends to improve gradually as the reaction conditions are optimized, but
the inclusion of OA creates the P2O5 content to reduce by 0.4%, as it
consumes part of the sulphuric acid to be carbonized. On the other hand,
there was no significant impact on the F− content, which was main­
tained at 0.17%.
As demonstrated in Fig. 9(c), the rate of H3PO4 extraction greatly
increased when sulphuric acid concentration was increased from 25 vol
% to 35 vol%, but the impact of subsequent changes in experimental
conditions was negligible. The H3PO4 extraction received by including 3
wt% OA was 72.23%. Moreover, the F− the content of H3PO4 received

8
K. Fang et al.
Table 3
NOPC values in H3PO4 samples prepared under different conditions.
Reaction conditions 1 4 5 This work was supported by the Natural Science Research Project of
NOPC (mg/L) 2.45 2.50 7.25
by reverse extraction under the above conditions was computed, and the
outcomes are reflected in Fig. 9(d). The F− content in the H3PO4
received by including 3 wt% OA is only 0.02%, which is 81.82% less
than the F− content in H3PO4 when the by-product is CaSO4⋅2H2O,
which greatly enhances the separation efficiency of fluorine in H3PO4.
In order to examine the impact of changing conditions on the overall
organic carbon content in H3PO4, the H3PO4 samples made under
several conditions were tested for entire organic carbon, and the out­
comes are reflected in Table 2. As represented in Table 3, the NOPC
values of H3PO4 prepared corresponding to CaSO4⋅2H2O and CaSO4 by-
products were not significantly different, reflecting that the quality of
H3PO4 products was not seriously influenced while CaSO4 was prepared.
The inclusion of 3 wt% OA enhances the total organic carbon content in
the H3PO4 sample, as OA is a fatty acid. Although its total organic carbon
content improved, its value was much less than the urban wastewater
discharge standard (20 mg/L).
In summary, under optimum reaction condition (4), the P2O5 content
in the acidolysis solution increased by 46.93%, the H3PO4 extraction
rate increased by 44.30% and the F− content in H3PO4 decreased by
81.82% compared to the by-production of CaSO4⋅2H2O. Furthermore,
when 3 wt% oleic acid were added to the reaction, it did not seriously
affect the yield and extraction rate of H3PO4.
4. Conclusion
(1) The experimental outcomes reflected that at a sulphuric acid
concentration of 35 vol%, a liquid–solid ratio of 3.5 mL/g, and a
reaction time of 2 h, the calcium sulphate made was CaSO4 and
compared with the by-product CaSO4⋅2H2O; the P2O5 content
went up by 46.93% in the filtrate, the H3PO4 extraction rate
raised by 44.30% under the similar conditions and the F− content
in H3PO4 reduced by 81.82 %. Mainly, the P2O5 and F− contents
of the anhydrous calcium sulphate received at this time were only
0.03% and 0.05%, respectively.
(2) In this research, it was determined that when there is an excess of
sulphate, on the one hand, the higher concentration of sulphuric
acid shows its water absorption, averting water molecules from
accessing the interior of calcium sulphate crystals and supporting
the creation of CaSO4. The excess SO2− 4 in the system wraps
around the calcium sulphate nuclei, creating conditions for the
growth of CaSO4 crystals; secondly. It creates a “protective film”
that obstacles impurity ions including F and P from entering or
adsorbing to the interior or surface of CaSO4 crystals, causing in
CaSO4 with a lower P and F content.
(3) Under the optimum circumstances, after the addition of 3 wt%
OA to the reaction, the system’s SiO2 was easily disconnected and
eliminated due to the OA’s hydrophobic modification. In contrast
to the raw phosphate ore powder, the SiO2 removal rate under
this state reached 89.62%, and the final CaSO4 with a purity of
96.65% was produced.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
The data that has been used is confidential.
9
Separation and Purification Technology 309 (2023) 123048
Acknowledgments
the Education Department of Guizhou Province (No. QJJ[2022]001).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.seppur.2022.123048.
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