materials

Article
A Novel Process to Recover Gypsum from Phosphogypsum
Junhui Xiao 1,2,3,4, * , Tao Lu 2 , Yuanfa Zhuang 2 and Huang Jin 2

1 Sichuan Provincial Engineering Lab of Non-Metallic Mineral Powder Modification and High-Value
Utilization, Southwest University of Science and Technology, Mianyang 621010, China
2 Postdoctoral Research Station, Dongfang Boiler Group Co., Ltd., Chengdu 611731, China;
lut@dbc.com.cn (T.L.); zhuangyf@dbc.com (Y.Z.); jinh@dbc.com (H.J.)
3 Key Laboratory of Ministry of Education for Solid Waste Treatment and Resource Recycle,
Southwest University of Science and Technology, Mianyang 621010, China
4 Institute of Multipurpose Utilization of Mineral Resources, Chinese Academy of Geological Sciences,
Chengdu 610041, China
* Correspondence: xiaojunhui33@163.com; Tel.: +86-139-9019-0544

Abstract: In this study, we investigated a coarse phosphogypsum containing 49.63% SO3 , 41.41%
CaO, 10.68%, 4.47% SiO2 , 1.28% P2 O5 , 0.11% F, CaSO4 ·2H2 O purity of 80.65%, and whiteness of
27.68. Phosphogypsum contains calcium sulfate dehydrate as the main mineral, with small amounts
of brushite, quartz, muscovite, and zoisite. Harmful elements, such as silicon, phosphorus, and
fluorine, are mainly concentrated in the +0.15 mm and −0.025 mm fraction, which can be pre-selected
and removed by the grading method to further increase the CaSO4 ·2H2 O content. Gypsum was
recovered using a direct flotation method, which included one roughing, one scavenging, and two
cleaning operations, from −0.15 mm to +0.025 mm. The test results show that a gypsum concentrate
with a CaSO4 ·2H2 O purity of 98.94%, CaSO4 ·2H2 O recovery of 80.02%, and whiteness of 37.05
was achieved. The main mineral in the gypsum concentrate was gypsum, and limited amounts of
muscovite and zoisite entered the gypsum concentrate because of the mechanical entrainment of the
flotation process.





 Keywords: phosphogypsum; gypsum; classification; flotation
Citation: Xiao, J.; Lu, T.; Zhuang, Y.;
Jin, H. A Novel Process to Recover
Gypsum from Phosphogypsum.
Materials 2022, 15, 1944. https:// 1. Introduction
doi.org/10.3390/ma15051944
Phosphogypsum is mainly obtained from the phosphate fertilizer industry and is a
Academic Editor: Petrica Vizureanu solid waste residue produced by a wet preparation of phosphoric acid. The global cumula-
Received: 13 February 2022
tive emissions of phosphogypsum total approximately 6 billion tons, which is increasing
Accepted: 3 March 2022
at a rate of 150 million tons/year. It is projected that the total amount of phosphogypsum
Published: 5 March 2022
will double by 2025–2045 [1,2]. Phosphogypsum is an industrial by-product of gypsum
with a low utilization rate owing to its large discharge, complex impurity composition,
Publisher’s Note: MDPI stays neutral
and difficult treatment. The accumulation of large amounts of phosphogypsum can cause
with regard to jurisdictional claims in
environmental risks. Therefore, effective treatment and efficient utilization of phospho-
published maps and institutional affil-
gypsum are urgently needed. The main impurities in phosphogypsum are divided into
iations.
three categories: phosphorus, fluorine, and organic impurities. Phosphorus impurities in
phosphogypsum mainly consist of soluble phosphorus (H3 PO4 , H2 PO4− , and HPO4 2− ),
insoluble phosphorus (Ca3 (PO4 )2 ), and eutectic phosphorus (CaHPO4 ·2H2 O). The fluorine-
Copyright: © 2022 by the authors.
containing impurities in phosphogypsum mainly consist of soluble fluorine (NaF and KF)
Licensee MDPI, Basel, Switzerland. and insoluble fluorine (Na3 AlF6 , CaSiF6 , and CaF2 ). Organic impurities in phosphogypsum
This article is an open access article mainly consist of organic matter inherent in phosphate rock and organic additives added
distributed under the terms and in the production process [3–5]. The comprehensive utilization rate of phosphogypsum is
conditions of the Creative Commons low, owing to the various complex impurities and the difficult occurrence state. Presently,
Attribution (CC BY) license (https:// the main separation and purification methods for phosphogypsum are as follows.
creativecommons.org/licenses/by/ Phosphorus and fluorine in phosphogypsum are largely soluble in water. Owing to
4.0/). their solubility in water, they can be effectively removed by rinsing, filtering, leaching,

Materials 2022, 15, 1944. https://doi.org/10.3390/ma15051944 https://www.mdpi.com/journal/materials

Materials 2022, 15, 1944 2 of 15

and dehydration. However, the single water-washing process consumes a large amount of
water and a high amount of energy. The newly generated wastewater causes secondary
pollution, and the wastewater needs to be treated separately to meet the national discharge
standards before discharge, which significantly increases the treatment cost. Therefore,
this process has not been applied on a large scale. Moreover, it is necessary to realize
stepwise water recycling through technological improvements, reduce water consumption,
and recycle wastewater-soluble impurities, such as phosphorus and fluorine, in green and
low-cost ways [6–8].
Organic impurities can be removed by conventional flotation. This process includes
pouring phosphogypsum and water into flotation equipment in the right proportions and
using the natural floating of organic impurities to scrape off the impurities. This process
is suitable for treating phosphogypsum with a high organic content and can improve the
whiteness of phosphogypsum; however, this method has low efficiency and no significant
removal effect on soluble impurities. Due to the fact that the water used in the flotation
process can be recycled, it is often combined with the water-washing process. Presently, the
purification of phosphogypsum by adding a flotation agent has also been widely studied.
This treatment method involves the addition of alkaline-modified materials, such as quick
lime, into phosphogypsum; the alkaline-modified material reacts with the soluble phos-
phorus and soluble fluorine and converts the refractory inert materials to precipitates. This
method can homogenize phosphogypsum with high-quality fluctuations and low organic
matter content. Lime neutralization treatment is widely used in the production of cement
retarders because of its simple process, low investment, obvious effect, and low amount
of secondary pollution. However, this method can only temporarily solve the harmful
effects of soluble phosphorus and fluorine. Soluble phosphorus and fluorine precipitate
after a long time, and this method cannot remove the adverse effects of organic matter
on phosphogypsum. In the process of calcination at 800 ◦ C, the P2 O5 in phosphogypsum
is converted into stable inert phosphate, and a small amount of organophosphorus and
hydrogen fluoride can be removed by volatilization. Unlike other calcination processes,
flash sintering aims to transform soluble phosphorus and fluorine into inert substances
without water washing. The flash-burning method is usually combined with the lime neu-
tralization method to avoid the volatilization of fluoride, which pollutes the environment
and causes secondary pollution; however, this method has high energy consumption, large
initial investment, and its equipment is prone to corrosion [9–13].
In summary, extensive research on phosphogypsum pretreatment has been performed
by scientists and technicians. However, each method has some disadvantages, and there are
still some gaps in large-scale industrial applications. Thus, it is necessary to combine various
pretreatment methods to learn from each of them, which is an important research direction
in the future. In addition, the authors believe that flotation is a promising method. Organic
impurities surfaced by reverse flotation, CaSO4 ·2H2 O surfaced by forward flotation, and
then a small amount of lime phosphorus fixation and fluorine were added to the forward-
flotation-filtered concentrate, such that phosphogypsum could be completely purified at a
low cost. However, further experiments are required to verify this hypothesis.

2. Materials and Methods

2.1. Materials
The test samples used in this study were taken from phosphogypsum produced by
a phosphorus chemical enterprise in the Deyang Region, Sichuan Province, China. The
content of CaSO4 ·2H2 O in the phosphogypsum was 80.65%, and the whiteness was 27.68.
The water content of the phosphogypsum was less than 5%, and the particle size was less
than 1 mm. The main chemical compositions of the samples are shown in Table 1.
Materials 2022, 15, 1944 3 of 15

Table 1. Main chemical composition analysis of phosphogypsum (mass fraction, %).

SO3 CaO SiO2 P2 O5 Al2 O3 Fe2 O3 K2 O SrO MgO F TiO2 BaO Na2 O Y2 O3
49.62 41.41 5.47 1.28 0.63 0.31 0.20 0.12 0.12 0.11 0.10 0.07 0.05 0.01

The main chemical reagents used in this test were sulfuric acid, sodium silicate,
sodium hexametaphosphate, starch, carboxymethylcellulose, dodecylamine, mixed amine,
octadecylamine, dodecyltrimethylammonium chloride, and pine oil. All reagents were
of analytical grade and were obtained from a producing area in Tianjin Tianli Chemical
Reagent Co., Ltd., Tianjin, China.

2.2. Experiment
Flotation (roughing, scavenging) aimed at improving the recovery of gypsum concen-
trate was performed using an XFD-1.5 L hanging tank flotation machine (Jinlin Exploration
Machinery Plant, Changchun, China) operating at a spindle speed of 1650 r/min. A 500 g
mass of phosphogypsum was added to the 1.5 L flotation tank. Flotation (cleaning) aimed
at further increasing the purity and whiteness of the gypsum concentrate was performed
using an XFD-1.0 L hanging tank flotation machine (Jinlin Exploration Machinery Plant,
Changchun, China) operating at a spindle speed of 1,650 r/min. A 300 g mass of gypsum
concentrate was added to the 1.0 L flotation tank. Distilled water (1.0 L) was added, and
the pulp was stirred and mixed for 3 min, followed by adjustment to the required pH using
sulfuric acid. After 5 min of pulping, the depressant was added to the slurry and condi-
tioned for 3 min. The collectors were then added and agitated for 3 min. Before aeration,
frothers (pine oil) were added to improve the bubbles and stirred for an additional 3 min.
After 3 min of flotation, the froth (gypsum concentrate) and in-tank product (flotation
tailings) were separately filtered, the samples were filtered, dried at 40 ◦ C, weighed, and
the gypsum recovery was calculated according to Equation (1).

R = (Q1 × G1 )/(Q0 × G0 ), (1)

where R is the recovery of gypsum (%), Q1 is the weight of the flotation concentrate
(g), G1 is the calcium sulfate dehydrate of the flotation concentrate, Q0 is the weight of
phosphogypsum (g), and G0 is the calcium sulfate dehydrate of phosphogypsum (g).

2.3. Analyses
The whiteness of the gypsum concentrate samples was measured using a WSD-3C
whiteness instrument manufactured by Beijing Kangguang Optical Instrument Co., Ltd.
The equipment was preheated for 30 min before the test, and calibration was subsequently
performed using a standard colorimetric plate. After calibration, the samples were tested.
The purity of the calcium sulfate dihydrate in the phosphogypsum was determined by the
content of crystallized water in the gypsum. The mass fraction of calcium sulfate dihydrate
(G) in the sample was calculated using Equation (1). Gypsum recovery was calculated
using Equation (2):
G = 4.7885 × H, (2)
where G is the purity of calcium sulfate dihydrate (%), and 4.7785 is the coefficient of
calcium sulfate dehydrate content converted from crystal water content, which is equal to
the molecular weight of the calcium sulfate dihydrate divided by the molecular weight of
two water molecules. H represents the crystal water content (%).
The chemical compositions of the solid materials (including phosphogypsum, gyp-
sum concentrate, and flotation tailings) were analyzed using a Z–2000 atomic absorption
spectrophotometer (Hitachi Co., Ltd., Tokyo, Japan). The mineral phase compositions of
the aforementioned solid substances were examined using an XRD (X’ Pert Pro, Panaco,
The Netherlands). The microstructures of the solid products were investigated using scan-
ning electron microscopy (SEM, S440, Hirschmann Laborgerate GmbH & Co. KG, Eberstadt,
Materials 2022, 15, x FOR PEER REVIEW 4 of 15

Materials 2022, 15, 1944 electron microscopy (SEM, S440, Hirschmann Laborgerate GmbH & Co. KG, Eberstadt, 4 of 15
Germany) equipped with an energy-dispersive X-ray spectroscopy (EDS) detector
(UItra55, CarlzeissNTS GmbH, Hirschmann Laborgerate GmbH & Co. KG, Eberstadt,
Germany).
Germany) equipped with an energy-dispersive X-ray spectroscopy (EDS) detector (UItra55,
CarlzeissNTS GmbH, Hirschmann Laborgerate GmbH & Co. KG, Eberstadt, Germany).
3. Results
3. Results
3.1. Process Mineralogical Analysis of Phosphogypsum
3.1. Process Mineralogical Analysis of Phosphogypsum
Figure 1a shows the X-ray diffraction (XRD) patterns of the samples. Phosphogyp-
Figure 1a
sum mainly shows calcium
contains the X-raysulfate
diffraction (XRD)(CaSO
dehydrate patterns4·2H of2O),
the along
samples.
withPhosphogypsum
small amounts
mainly contains calcium sulfate dehydrate (CaSO · 2H
of CaPO3(OH)·2H2O, SiO2, Kal2SiO10(OH), and Ca2Al3[SiO12]OH. This indicates
4 2 O), along with small amounts of
that the
CaPO (OH) · 2H 2 O, SiO2 , Kal2 SiO 10 (OH), and Ca 2 Al 3 [SiO 12 ]OH.
crystalline phase of phosphogypsum is mainly gypsum, and the main mineral impurities
3 This indicates that the
crystalline
are brushitephaseand of phosphogypsum
silicaluminate is mainly
minerals, which gypsum,
need toand the main mineral
be removed impurities
in the subsequent
are brushite and silicaluminate minerals, which need to be removed
purification. The results in Table 2 and Figure 2b show that, compared with the content of in the subsequent
purification.
SiO The results in Table 2 and Figure 2b show that, compared with the content
2, F, and P2O5 in different fractions, those in the +0.15 mm fraction were 12.89%, 0.41%,
of SiO
and 2 , F, respectively,
5.08%, and P2 O5 in whereas
different those
fractions,
in thethose
−0.025inmm the fraction
+0.15 mm fraction
were 13.17%,were 12.89%,
0.35%, and
0.41%, and 5.08%, respectively, whereas those in the − 0.025 mm fraction
1.56%, respectively. This further indicates that the impurity elements, i.e., silicon, fluorine, were 13.17%,
0.35%,
and and 1.56%,are
phosphorus, respectively. This further
mainly concentrated in indicates
the +0.15 that mmthe andimpurity
−0.025 mmelements, i.e.,
fractions.
silicon, fluorine, and phosphorus, are mainly concentrated in the +0.15 mm and −0.025 mm
Therefore, in this study, the +0.15 mm and −0.025 mm products with two particle sizes
fractions. Therefore, in this study, the +0.15 mm and −0.025 mm products with two particle
were pre-selected by a classification method, and gypsum was further recovered from the
sizes were pre-selected by a classification method, and gypsum was further recovered from
−0.15 and +0.025 mm raw materials by flotation.
the −0.15 and +0.025 mm raw materials by flotation.

60,000
(a) 1-CaSO4·2H2O 500,000
1 (b) 1-CaPO3(OH)·2H2O 2-CaSO4·2H2O 3-SiO2
50,000
2-CaPO3(OH)·2H2O 450,000
1
3-SiO2 400,000
2 1 2 1
2 3 32 −0.025～0 mm
40,000 2 4-KAl2SiAlO10(OH)2
Intensity (a.u.)

350,000 −0.038～+0.025 mm
5-Ca2AlO3[Si3O12]OH
Intensity (a.u.)

−0.045～+0.038 mm

30,000
300,000 −0.074～+0.045 mm

250,000 −0.1～+0.074 mm
20,000 200,000
150,000
10,000 11 1
−0.15～+0.1 mm
2 100,000
23 5
4 +0.15 mm
0 50,000

0 10 20 30 40 50 60 70 80 90 0
0 10 20 30 40 50 60 70 80 90
2θ (deg.)
2θ (deg.)

Figure
Figure 1.
1. XRD
XRD patterns
patterns of
of the
the phosphogypsum
phosphogypsum (a)
(a) and
and the
the different
different grain-sized products (b).

98 100
(a) Table 2. Grain-sized analysis of phosphogypsum
Dodecylamine (mass fraction, %).
95 (b)
97
Octadecylamine
Mixed amine
Fraction (mm) Yield SO3 CaOchloride SiO2
Dodecyltrimethylammonium
P90
2 O5 Al2 O3 Fe2 O3 K2 O MgO F
96 85
+0.15 7.60 41.17 38.35 12.89 5.08
80
1.00 0.57 0.34 0.10 0.41
−95
0.15~+0.1 11.21 51.89 43.23 2.93 1.15 0.28 0.21 0.08 0.02 0.004
Recovey (%)
Purity (%)

75
−0.1~0.074 19.01 51.76 44.24 2.25 1.01 0.25 0.18 0.06 0.06 0.005
94 70
−0.074~0.045 14.23 52.08 44.09 2.15 1.03 0.19 0.26 0.05 0.02 0.006
−0.045~+0.038 17.35 51.86 43.93 2.34 65
1.03 0.26 0.28 0.05 0.02 0.005
93
−0.038~+0.025 10.26 51.09 43.39 3.24 60
1.16 0.40 0.35 0.08 0.03 0.003
−920.025~0 20.34 44.81 37.28 13.17 1.56
55 1.36 0.87 0.39
Dodecylamine 0.12 0.35
Totals 100.00 49.55 42.10 5.46 1.47
50 0.54 Octadecylamine
0.39 0.15 0.06 0.11
91 Mixed amine
45
Dodecyltrimethylammonium chloride
90 40
50 100 150 200 250 300 350 400 450 500 550 50 100 150 200 250 300 350 400 450 500 550
Dosage ( g/t ) Dosage ( g/t )
 −0.15～+0.1 mm
2 100,000
23 5
4 +0.15 mm
0 50,000

0 10 20 30 40 50 60 70 80 90 0
0 10 20 30 40 50 60 70 80 90
2θ (deg.)
Materials 2022, 15, 1944 2θ (deg.) 5 of 15

Figure 1. XRD patterns of the phosphogypsum (a) and the different grain-sized products (b).

98 100
(a) Dodecylamine
95 (b)
97
Octadecylamine
Mixed amine 90

96
Dodecyltrimethylammonium chloride 85

80
95

Recovey (%)
Purity (%)

75

94 70

65
93
60

92 55 Dodecylamine
50 Octadecylamine
91 Mixed amine
45
Materials 2022, 15, x FOR PEER REVIEW Dodecyltrimethylammonium chloride5 of 15
90 40
50 100 150 200 250 300 350 400 450 500 550 50 100 150 200 250 300 350 400 450 500 550
Dosage ( g/t ) Dosage ( g/t )
37.5
Dodecylamine
37.0 (c) Octadecylamine
36.5 Mixed amine
36.0 Dodecyltrimethylammonium chloride
35.5
35.0
Whiteness

34.5
34.0
33.5
33.0
32.5
32.0
31.5
31.0
50 100 150 200 250 300 350 400 450 500 550

Dosage ( g/t )

2. Effects
Figure 2. Effects of
ofdosages
dosagesofofdodecylamine,
dodecylamine,octadecylamine, mixed
octadecylamine, mixedamine, and
amine, dodecyltrimethy-
and dodecyltrime-
thylammonium chloride
lammonium chloride onon gypsum
gypsum purification:(a)
purification: (a)gypsum
gypsumpurity,
purity,(b)
(b) gypsum
gypsum recovery, and (c)
(c)
gypsum whiteness.

3.2. Effects
Table of Flotation
2. Grain-sized Flowsheet
analysis Parameters on (mass
of phosphogypsum Gypsum Purification
fraction, %).
3.2.1. Collectors Dosages
Fraction (mm) Yield SO3 CaO SiO2 P2O5 Al2O3 Fe2O3 K2O MgO F
A study on the surface properties of gypsum showed that the gypsum surface was
+0.15 7.60 41.17 38.35 12.89 5.08 1.00 0.57 0.34 0.10 0.41
charged, and the cationic collector was easily adsorbed onto its surface. Amine flota-
−0.15~+0.1 11.21 51.89 43.23 2.93 1.15 0.28 0.21
tion agents such as dodecylamine and quaternary ammonium salt are common cationic 0.08 0.02 0.004
−0.1~0.074
collectors that are19.01 51.76
widely used44.24 2.25 mineral
in numerous 1.01 0.25 0.18 [14–17].
separations 0.06 The 0.06effects
0.005of
−0.074~0.045 14.23 52.08 44.09 2.15 1.03 0.19 0.26
dodecylamine, octadecylamine, mixed amine, and dodecyltrimethylammonium chloride 0.05 0.02 0.006
−0.045~+0.038
on the separation17.35 51.86 43.93
and purification 2.34 were
of gypsum 1.03 investigated
0.26 0.28under0.05 0.02 0.005
the following test
−0.038~+0.025
conditions: 10.26concentration
flotation 51.09 43.39of 25%, 3.24 flotation
1.16 pulp
0.40 pH0.35 0.08 sulfuric
= 2.5 using 0.03 acid,
0.003a
pine−0.025~0
dosage of 4020.34 44.81
g/t; the 37.28
results 13.17 in1.56
are shown Figure1.36
2a–c). 0.87 0.39same
Using the 0.12
amount 0.35of
collector, the
Totals order of collecting abilities
100.00 49.55 42.10 5.46 of gypsum
1.47 was found
0.54 to
0.39be: mixed
0.15 amine >
0.06 0.11dode-
cylamine > dodecyltrimethylammonium chloride > octadecylamine. With an increase in the
dosage
3.2. of MA,
Effects the purity
of Flotation of CaSO
Flowsheet 4 ·2H2 O in
Parameters on the concentrate
Gypsum decreased gradually, and the
Purification
recovery of gypsum
3.2.1. Collectors Dosagesincreased gradually. When the dosage of mixed amine reached 200 g/t
and continued to increase, the purity of CaSO4 ·2H2 O and whiteness of the concentrate
A study
decreased on the surface
significantly, mainly properties
owing to of thegypsum
increaseshowed that the
in the dosage gypsum
of the surface
reagents, was
resulting
charged, and the cationic collector was easily adsorbed onto its surface. Amine
in an increased floatation of the concentrate and the easy inclusion of other impurities. flotation
agents suchthe
Regarding as dodecylamine
cost of the mixingandofquaternary
reagents, ammonium
a mixed aminesaltdosage
are common
of 200cationic collec-
g/t is suitable
tors that are widely used ofin CaSO
numerous mineral separations [14–17]. The effects of dodec-
for flotation. The purity 4 ·2H2 O in the concentrate was 95.89%, the recovery of
ylamine, octadecylamine, mixed amine,
CaSO4 ·2H2 O was 79.93%, and the whiteness and dodecyltrimethylammonium
was 35.63. chloride on the
separation and purification of gypsum were investigated under the following test condi-
tions: flotation concentration of 25%, flotation pulp pH = 2.5 using sulfuric acid, a pine
dosage of 40 g/t; the results are shown in Figure 2a–c). Using the same amount of collector,
the order of collecting abilities of gypsum was found to be: mixed amine > dodecylamine
> dodecyltrimethylammonium chloride > octadecylamine. With an increase in the dosage
of MA, the purity of CaSO4·2H2O in the concentrate decreased gradually, and the recovery
Materials 2022, 15, x FOR PEER REVIEW 6 of 15
Materials 2022, 15, 1944 6 of 15

3.2.2. Depressants Dosages

3.2.2. Depressants Dosages
Sodium silicate,
Sodium silicate,sodium
sodium hexametaphosphate,
hexametaphosphate, starch,
starch, and carboxymethylcellulose
and carboxymethylcellulose were
were as
used used as flotation
flotation agentsagents for gangue
for gangue minerals minerals
[18–20], [18–20],
and theand the effects
effects of different
of different dosagesdos- on
ages on gypsum
gypsum flotationflotation were investigated
were investigated under the under the following
following test conditions:
test conditions: flotationflotation
concen-
concentration
tration of 25%, of 25%, flotation
flotation pulp pHpulp = 2.5pH = 2.5sulfuric
using using sulfuric
acid, mixed acid,amine
mixeddosage
amineof dosage
200 g/t, of
200 g/t, and pine dosage of 40 g/t. The results in Figure 3a–c
and pine dosage of 40 g/t. The results in Figure 3a–c show that sodium silicate, sodium show that sodium silicate,
sodium hexametaphosphate,
hexametaphosphate, and carboxymethylcellulose
and carboxymethylcellulose influence gangue influence gangue
minerals. minerals.
However, the
However,
addition of the addition
ST can reduceofthe STpurity
can reduce
of CaSO the·2HpurityO, of CaSO
the recovery4·2H2O, the recovery rate of
rate of CaSO · 2H O, and
4 2 4 2
CaSO
the 4·2H2O, and the whiteness of the concentrate, which further indicates that the inhib-
whiteness of the concentrate, which further indicates that the inhibitory effect of the
itoryinhibitors
four effect of the four inhibitors
on gangue mineralsonis gangue minerals
as follows: sodium is silicate
as follows: sodium silicate > car-
> carboxymethylcellulose
boxymethylcellulose > sodium hexametaphosphate
> sodium hexametaphosphate > starch. Sodium silicate can be selectively > starch. Sodium silicate can be selec-
adsorbed onto
tively adsorbed onto the surface of gangue minerals, this
the surface of gangue minerals, this results in an increase in the hydrophilicity ofresults in an increase ingangue
the hy-
drophilicity
minerals andofchanges
gangue to minerals and changes
the surface electrical toproperties
the surfaceof electrical
gangue properties
minerals. of gangue
Thus, the
minerals.
gangue Thus, the
minerals andgangue
gypsumminerals
surfacesand gypsum surfaces
are negative, increasing arethenegative, increasing
electrostatic repulsionthe
electrostatic
between gypsumrepulsion between
and gangue gypsumreducing
minerals, and gangue minerals, reducing
the agglomeration the agglomera-
of mineral particles,
tion improving
and of mineral particles, and improving
the dispersion the dispersion
of the flotation of the flotation
system [21–23]. An increasesystem in [21–23].
the dosage An
increase in the dosage of sodium silicate improved the quality
of sodium silicate improved the quality of the concentrate; however, when the dosage of the concentrate; how-
ever,
of whensilicate
sodium the dosage of sodium
exceeded silicate
400 g/t, exceeded
the purity 400 g/t,
of CaSO the
4 ·2H 2 Opurity
and the of CaSO
whiteness4·2H2O of and
the
the whiteness
concentrate of the concentrate
decreased, decreased,ofand
and the recovery CaSO the4 ·recovery of CaSO4to
2H2 O increased ·2H a 2O increased
certain extent.to
a certain extent.
Therefore, a sodiumTherefore,
silicateadosage
sodiumofsilicate
400 g/tdosage
is ideal, ofand
400 the
g/t is ideal,ofand
purity CaSO the4 ·purity
2H2 O in of
CaSO
the 4·2H2O in the
concentrate concentrate
increased increased
to 96.38%, to 96.38%,increased
the whiteness the whiteness
to 36.63,increased
and thetorecovery36.63, andof
CaSO 4 · 2H
the recovery 2 O increased
of CaSO 4 to
·2H 281.51%.
O increased to 81.51%.

100 90
(a) Sodium silicate (b)
99 87
Sodium hexametaphosphate
98 Starch 84
97 Carboxymethylcellulose
81
96
Recovey (%)

78
Purity (%)

95

94 75

93 72
92
69 Sodium silicate
91
66
Sodium hexametaphosphate
90 Starch
89 63 Carboxymethylcellulose
88 60
0 200 400 600 800 0 200 400 600 800

Dosage ( g/t ) Dosage ( g/t )

39
Sodium silicate
(c) Sodium hexametaphosphate
38
Starch
Carboxymethylcellulose
37

36
Whiteness

35

34

33

32

31
0 200 400 600 800

Dosage ( g/t )

Figure 3. Effects
Figure Effectsof
ofthe
thedosages
dosagesofofsodium silicate,
sodium sodium
silicate, hexametaphosphate,
sodium starch,
hexametaphosphate, andand
starch, carbox-
car-
ymethylcellulose on gypsum purification: (a) gypsum purity, (b) gypsum recovery, and (c) gypsum
boxymethylcellulose on gypsum purification: (a) gypsum purity, (b) gypsum recovery, and (c) gyp-
whiteness.
sum whiteness.
Materials 2022, 15, x FOR PEER REVIEW 7 of 15
Materials 2022, 15, 1944 7 of 15

3.2.3. pH Value of Pulp

3.2.3. pH Value of Pulp
Different flotation pH values of the pulp tests were conducted under the following
Different
conditions: flotation
flotation pH values of
concentration of 25%,
the pulp tests
mixed weredosage
amine conducted
of 200under the following
g/t, sodium silicate
dosage of 400 g/t, and pine dosage of 40 g/t; the results are shown in Figure 4a–c.silicate
conditions: flotation concentration of 25%, mixed amine dosage of 200 g/t, sodium When
dosage
the pH ofof the
400pulp
g/t, and
is lowpine
(pHdosage of 40the
= 1.5–2.0), g/t; the results
separation ofare shownand
gypsum in Figure
quartz 4a–c. When
is different,
the pH of the pulp is low (pH = 1.5–2.0), the separation of gypsum and quartz is different,
and the separation effect of gypsum and quartz is better. When the pH of the pulp is
and the separation effect of gypsum and quartz is better. When the pH of the pulp is higher
higher (pH > 2.0), the difference in separation between gypsum and quartz becomes small,
(pH > 2.0), the difference in separation between gypsum and quartz becomes small, and
and the separation effect of gypsum and quartz is poor. This is because the isoelectric
the separation effect of gypsum and quartz is poor. This is because the isoelectric point of
point of gypsum is pH = 1–2, and that of quartz is pH = 2.3–3.0. When the pH of the slurry
gypsum is pH = 1–2, and that of quartz is pH = 2.3–3.0. When the pH of the slurry was
was higher than 2.3, both the gypsum and the quartz minerals were negatively charged
higher than 2.3, both the gypsum and the quartz minerals were negatively charged on the
on the surface, which could be adsorbed by the cationic collector and showed good float-
surface, which could be adsorbed by the cationic collector and showed good floatability;
ability; thus, they could not be separated. When the pulp pH is ≤2, the gypsum mineral
thus, they could not be separated. When the pulp pH is ≤2, the gypsum mineral surface
surface with a negative charge can exhibit cationic collector electrostatic adsorption,
with a negative charge can exhibit cationic collector electrostatic adsorption, whereas a
whereas a quartz surface with positive charge or no charge cannot exhibit cationic collec-
quartz surface with positive charge or no charge cannot exhibit cationic collector adsorption,
tor adsorption, to achieve gypsum and quartz separation. A gypsum surface potential of
to achieve gypsum and quartz separation. A gypsum surface potential of PZC = 2.3 is
PZC = 2.3 ischarged
negatively negatively
overcharged
a wide pHoverrange,
a wide pHa range,
and cationic and a cationic
collector can collector
easily becan easily
adsorbed
be adsorbed
onto the gypsum onto surface.
the gypsum surface. The
The molecular molecular
layer layer ofcrystal
of the gypsum the gypsum crystal
water and the water
Ca–O
and the Ca–O bond are weak and easy to dissociate from these
bond are weak and easy to dissociate from these positions when broken, which alsopositions when broken,
leads
which alsohydrophilic
to natural leads to natural hydrophilic
gypsum. gypsum.
It is also easy to It is also the
achieve easy to achieveofthe
separation separation
hydrophobic
of hydrophobic
organic matter andorganic matter
other and other
impurities fromimpurities from phosphogypsum
phosphogypsum and gypsum and gypsuma
by adding
by adding a foaming agent [24–28]. After comprehensive consideration,
foaming agent [24–28]. After comprehensive consideration, the purity, whiteness, the purity, white-
and
ness, andofrecovery
recovery CaSO4 ·2H of 2CaSO 4·2H2O in the concentrate were 96.38%, 36.63, and 84.08%, re-
O in the concentrate were 96.38%, 36.63, and 84.08%, respectively, at
spectively,
pH = 2.0. at pH = 2.0.
98 90
(a) gypsum purity (b) gypsum recovery
88
97
86
96
84
Recovery (%)

95
82
Purity (%)

94 80

78
93
76
92
74
91
72

90 70
1.0 1.5 2.0 2.5 3.0 3.5 1.0 1.5 2.0 2.5 3.0 3.5
pH pH
37.0
(c) gypsum whitness
36.5

36.0

35.5
Whitness

35.0

34.5

34.0

33.5

33.0
1.0 1.5 2.0 2.5 3.0 3.5
pH

Figure
Figure 4.
4. Effects
Effectsofofflotation
flotationpH
pHvalue
valueonon
gypsum purification:
gypsum (a) (a)
purification: gypsum purity,
gypsum (b) (b)
purity, gypsum re-
gypsum
covery, and (c) gypsum whiteness.
recovery, and (c) gypsum whiteness.
Materials 2022,
Materials 2022, 15,
15, 1944
x FOR PEER REVIEW 8 8of
of 15
15

3.2.4.
3.2.4. Flotation
Flotation Concentration
Concentration
The
The effects of
effects ofdifferent
differentdosages
dosagesonon gypsum
gypsum flotation
flotationwere
wereinvestigated
investigated under the fol-
under the
lowing conditions: pH = 2.0 (H SO ), mixed amine dosage of 200
following conditions: pH = 2.0 (H2 SO4 ), mixed amine dosage of 200 g/t, sodium silicate
2 4 g/t, sodium silicate dos-
age of 400
dosage g/t,g/t,
of 400 andand pine dosage
pine dosage of of
4040g/t; thethe
g/t; results
resultsare areshown
shownininFigure Figure 5a–c.
5a–c. Flotation
Flotation
concentration
concentration is an important process parameter parameter that that influences
influences the the beneficiation
beneficiation index,
index,
mainlyinfluences
which mainly influencesthe thepulp
pulp filling
filling capacity,
capacity, the the concentration
concentration of reagents
of reagents in theinpulp,
the
pulp,
and theand the flotation
flotation time.time. Generally,
Generally, a proper
a proper increase
increase in the
in the concentration
concentration of the
of the float-
floating
ing material
material can can
reducereduce the probability
the probability of particles
of particles (especially
(especially coarse
coarse particles)
particles) falling
falling off
off the
the bubble,
bubble, thusthus improving
improving thethe recovery
recovery of of useful
useful mineralsfrom
minerals fromcoarse
coarseparticles.
particles. A high
concentration
concentration of of the
thematerial
materialplays
playsan animportant
importantrole roleininweakening
weakening thethe influence
influence of of den-
density
and and
sity particle sizesize
particle on onthethe
velocity
velocityof ofthethe upper
upper floating
floatingend end[29–34].
[29–34].However,
However, owing
owing to
fine particle
the fine particlesize sizeofofthethephosphogypsum
phosphogypsum material,
material, thethe
CaSOCaSO
4·2H 4 ·22H 2 O content
O content in theincon-
the
concentrate
centrate decreased
decreased significantly;
significantly; the the whiteness
whiteness of theof concentrate
the concentrate alsoalso decreased
decreased when when
the
the concentration exceeded 30%, and the recovery
concentration exceeded 30%, and the recovery of the CaSO44·2H2O of the CaSO · 2H O increased slightly.
2 increased slightly.
Therefore,
Therefore, 30%30% isisthe
theideal
idealselection
selectionofofflotation
flotationconcentration,
concentration,and and the thepurity
purityandandrecovery
recov-
of CaSO
ery 4 ·2H
of CaSO 2 O in
4·2H 2Othe concentrate
in the concentrate areare96.18%
96.18%andand 84.16%, respectively,
84.16%, respectively, andandthe the
whiteness
white-
of theofconcentrate
ness the concentrate is 36.28.
is 36.28.
98 100
(a) gypsum purity 98 (b) gypsum recovery
97 96
94
96 92
90
Recovery (%)

95
88
Purity (%)

86
94
84
82
93
80

92 78
76
91 74
72
90 70
20 25 30 35 40 45 20 25 30 35 40 45
Concentration ( mass fraction, % ) Concentration ( mass fraction, % )
38
(c) gypsum whitness
37

36

35
Whitness

34

33

32

31

30
20 25 30 35 40 45
Concentration ( mass fraction, % )

Figure 5. Effects of flotation concentration on gypsum purification: (a)

(a) gypsum
gypsum purity,
purity, (b) gypsum
recovery, and (c) gypsum whiteness.
recovery, and (c) gypsum whiteness.

3.2.5. Time
3.2.5. Time of
of Flotation
Flotation Scavenging
Scavenging
To further
To further improve
improve the
the comprehensive recovery rate
comprehensive recovery rate of
of gypsum
gypsum from from phosphogyp-
phosphogyp-
sum, scavenging tests were performed to determine suitable times
sum, scavenging tests were performed to determine suitable times for the recoveryfor the recovery of
of gyp-
gypsum. The test conditions for the roughing flotation were a flotation concentration
sum. The test conditions for the roughing flotation were a flotation concentration of 30%, of
30%,= pH
pH 2.0 =
(H2.0 (H SO4 ), mixed
2SO4),2 mixed amineamine
dosagedosage
of 400ofg/t,
400sodium
g/t, sodium
silicatesilicate dosage
dosage of g/t,
of 400 400 and
g/t,
and pine dosage of 20 g/t. The test conditions for scavenging I were MA dosage
pine dosage of 20 g/t. The test conditions for scavenging I were MA dosage of 200 g/t, pine of 200 g/t,
 Mass Fraction (%) Whiteness
roducts Yield Purity Recovery
Individual Cumulative
Individual Cumulative Individual Cumulative Individual Cumulative
C1 62.54
Materials 2022, 15, 194462.54 96.45 96.45 74.72 74.72 36.28 36.28 9 of 15
C2 7.55 70.09 96.25 96.43 9.00 83.72 33.16 35.94
C3 0.76 70.85 92.16 96.38 0.87 84.59 29.63 35.88
T1 1.18 72.03 76.34
pine dosage of 96.05
20 g/t, and the1.12 85.71of scavenging
test conditions 7.35 II were MA
35.41dosage of 100 g/t
T2 27.97 100 41.23 80.72 14.29 100.00 8.15 27.78
and pine dosage of 10 g/t. The technological process is illustrated in Figure 6, and the
Totals 100.00 80.72 are listed in Table 3. 100.00
results 27.78

Phosphogypsum

Grading

−0.15～+0.025 mm −0.025～0 mm −0.15～0 mm Tailings (T2)

Roughing ScavengingⅠ ScavengingⅡ Tailings (T1)

Concentrate (C1) Concentrate (C2) Concentrate (C3)

Figure 6. Scavenging test flowsheet of the recovery of gypsum from phosphogypsum.

Figure 6. Scavenging test flowsheet of the recovery of gypsum from phosphogypsum.

An increase
Tablein
3. the time of scavenging
Scavenging test results ofcan
theimprove thegypsum
recovery of recovery rate
from of gypsum; how-
phosphogypsum.
ever, after two scavenging operations, the whiteness of the gypsum concentrate decreased
significantly, and, after twoMass
cleaning operations,
Fraction (%) the whiteness reduced to 29.63%. Owing
Whiteness
Products to the increase
Yield in scavenging times, the consumption of flotation
Purity Recoveryreagents increased cor-
respondingly. In the case of the flotation process with one roughing and oneIndividual scavenging Cumulative
Individual Cumulative Individual Cumulative Individual Cumulative
step, a gypsum concentrate with a CaSO4·2H2O purity of 96.43%, a whiteness of 35.94, and
C1
a62.54
CaSO4·2H2O62.54
recovery of 96.45
83.72% can be96.45obtained. 74.72 74.72 36.28 36.28
C2 7.55 70.09 96.25 96.43 9.00 83.72 33.16 35.94
C3 3.2.6.
0.76 Time of70.85
Flotation Cleaning
92.16 96.38 0.87 84.59 29.63 35.88
T1 1.18 Gypsum concentrate76.34
72.03 4·2H2O purity1.12
with a CaSO96.05 of 96.43%, whiteness
85.71 of 35.94,
7.35 and 35.41
T2
CaSO
27.97
4·2H2O recovery of 83.72% was obtained from the effects of flotation scavenging, us-
100 41.23 80.72 14.29 100.00 8.15 27.78
ing the flotation process of one roughing and one scavenging step. The technological pro-
Totals 100.00 80.72 100.00 27.78
cess of flotation cleaning shown in Figure 7 was used to further purify the gypsum con-
centrate; the test conditions of the roughing flotation were a flotation concentration of
30%, pH = 2.0 (H2An SO4increase
), a mixed amine
in the dosage
time 400 g/t, acan
of scavenging sodium
improve silicate dosage ofrate
the recovery 400ofg/t,
gypsum; how-
and a pine dosage of 40
ever, after g/t;scavenging
two the test conditions
operations,of scavenging
the whiteness were an gypsum
of the MA of dosage 200 decreased
concentrate
g/t and pine significantly,
dosage of 20 g/t.and,The results
after in Table 4operations,
two cleaning indicate that theawhiteness
two-stagereduced
concentration
to 29.63%. Owing
process can improve the purity,
to the increase whiteness,
in scavenging and the
times, recovery of the gypsum
consumption concentrate.
of flotation reagentsThe
increased corre-
purity of the CaSO ·2H O, the recovery of the CaSO ·2H O, and the whiteness were
spondingly. In the case of the flotation process with one roughing and one scavenging step,
4 2 4 2

98.94%, 79.87%, and 37.05,

a gypsum respectively.
concentrate with a CaSO4 ·2H2 O purity of 96.43%, a whiteness of 35.94, and a
CaSO4 ·2H2 O recovery of 83.72% can be obtained.

3.2.6. Time of Flotation Cleaning

Gypsum concentrate with a CaSO4 ·2H2 O purity of 96.43%, whiteness of 35.94, and
CaSO4 ·2H2 O recovery of 83.72% was obtained from the effects of flotation scavenging,
using the flotation process of one roughing and one scavenging step. The technological
process of flotation cleaning shown in Figure 7 was used to further purify the gypsum
concentrate; the test conditions of the roughing flotation were a flotation concentration
of 30%, pH = 2.0 (H2 SO4 ), a mixed amine dosage 400 g/t, a sodium silicate dosage of
400 g/t, and a pine dosage of 40 g/t; the test conditions of scavenging were an MA of
dosage 200 g/t and pine dosage of 20 g/t. The results in Table 4 indicate that a two-stage
concentration process can improve the purity, whiteness, and recovery of the gypsum
concentrate. The purity of the CaSO4 ·2H2 O, the recovery of the CaSO4 ·2H2 O, and the
whiteness were 98.94%, 79.87%, and 37.05, respectively.
Materials 2022,15,
Materials2022, 15,1944
x FOR PEER REVIEW 10 of
10 of 15
15

Phosphogypsum

Grading

−0.15～+ 0.025 mm + 0.15 mm −0.025～0 mm Tailings (T2)

Scavenging Tailings (T1)

Roughing

CleaningⅠ CleaningⅡ Cleaning Ⅲ Concentrate (C)

Middlings (M1) Middlings (M2) Middlings (M3)

Figure7.
Figure 7. Cleaning
Cleaning test
test flowsheet
flowsheetof
ofthe
therecovery
recoveryof
ofgypsum
gypsumfrom
fromphosphogypsum.
phosphogypsum.

Table4.4.Cleaning
Table Cleaningtest
testresults
resultsof
ofrecovering
recoveringgypsum
gypsumfrom
fromphosphogypsum.
phosphogypsum.

Mass Fraction(%)
Mass Fraction (%) Whiteness
Whiteness
Products Yield
Yield
Purity
Purity
Recovery
Recovery
Products Individual Cumulative
Individual Cumulative Individual Cumulative Individual Cumulative Individual Cumulative
Individual Cumulative Individual Cumulative Individual Cumulative
C 64.56 64.56 98.98 98.98 79.11 79.11 37.07 37.07
C 64.56 64.56 98.98 98.98 79.11 79.11 37.07 37.07
M3 0.19 64.75 95.88 98.97 0.22 79.33 35.75 37.07
M
M32 0.19
0.46 64.75
65.21 95.88
94.65 98.97
98.94 0.22
0.54 79.33
79.87 35.75
35.26 37.07
37.05
M
M21 0.46
0.96 65.21
66.17 94.65
93.12 98.94
98.86 0.54
1.11 79.87
80.98 35.26
32.37 37.05
36.98
MT11 5.87
0.96 72.04
66.17 65.25
93.12 91.31
98.86 4.74
1.11 85.72
80.98 6.66
32.37 34.52
36.98
TT12 27.96
5.87 100.00
72.04 41.24
65.25 80.77
91.31 14.28
4.74 100.00
85.72 8.67
6.66 27.72
34.52
Totals
T2 100.00
27.96 100.00 80.77
41.24 80.77 100.00
14.28 100.00 27.72
8.67 27.72
Totals 100.00 80.77 100.00 27.72
3.2.7. The Entire Flowsheet Test of Recovering Gypsum from Phosphogypsum
The technological process of recovering gypsum from phosphogypsum was obtained
3.2.7. The Entire Flowsheet Test of Recovering Gypsum from Phosphogypsum
using a single flotation process test, a scavenging test, and a cleaning test. To obtain the
The index
product technological process
of the entire of recovering
process, the processgypsum
shownfrom phosphogypsum
in Figure 8 was adoptedwastoobtained
perform
using a single flotation process test, a scavenging test, and a cleaning test.
the entire flowsheet test. The results in Tables 5 and 6 show that gypsum concentrates To obtain the
product index4·2H
with a CaSO of the entire process, the process shown in Figure 8 was adopted to perform
2O purity of 98.94%, a CaSO4·2H2O recovery of 80.02%, and a whiteness
the entire flowsheet test.
of 37.05 were obtained. The The results
contentinofTables
silicon,5 and 6 show that
phosphorus, gypsumand
fluorine, concentrates with a
other impurities
CaSO ·2H2 O purity
in the4gypsum of 98.94%,
concentrate CaSO4 ·2Hlow;
wasarelatively 2 O recovery
therefore, ofthe
80.02%, and gypsum
obtained a whiteness of 37.05
concentrate
were
could be used as a high-quality raw material for the preparation of α-hemihydrateinhigh-
obtained. The content of silicon, phosphorus, fluorine, and other impurities the
gypsum concentrate was relatively low; therefore,
strength gypsum or β-hemihydrate building gypsum. the obtained gypsum concentrate could
be used as a high-quality raw material for the preparation of α-hemihydrate high-strength
gypsum or β-hemihydrate building gypsum.
Materials 2022,15,
Materials2022, 15,1944
x FOR PEER REVIEW 11 of
11 of 15
15

Phosphogypsum

Grading

+0.15 mm −0.1～+0.025 mm −0.025 mm

3 min × H2SO4 pH=3

3 min × NaSiO3 400 g/t
3 min × Mixed amine 400 g/t
3 min × Pine oil 40 g/t

Roughing

3 min × H2SO4 pH=3

3 min × NaSiO3 400 g/t
3 min ×Mixed amine 400 g/t
3 min × Pine oil 40 g/t
Scavenging

CleaningⅠ

CleaningⅡ

Gypsum concentrates Tailings

Figure8.8.The
Figure Therecovery
recoveryof
ofgypsum
gypsumfrom
fromphosphogypsum
phosphogypsumusing
usinggrading
gradingand
andflotation.
flotation.

Table5.5.Entire
Table Entireflowsheet
flowsheettest
testresults
resultsofofthe
therecovery
recoveryofofgypsum
gypsumfrom
fromphosphogypsum.
phosphogypsum.

MassMass
Fraction (%)(%)
Fraction
Products
Products Whiteness
Whiteness
YieldYield Purity
Purity Recovery
Recovery
Gypsum
Gypsum concentrates 65.27 65.27 98.92
98.92 80.02
80.02 37.12
37.12
concentrates
Tailings 34.73 46.43 19.98 9.96
Tailings 34.73 46.43 19.98 9.96
Totals 100.00 80.69 100.00 27.69
Totals 100.00 80.69 100.00 27.69

Table6.6.Main
Table Mainchemical
chemicalcomposition
compositionanalysis
analysisofofgypsum
gypsumconcentrates
concentrates(mass
(massfraction,
fraction,%).
%).

SO33
SO CaO
CaO SiO
SiO22 P22O55
P Al2 O
Al 2O33 FeFe
2 O23O3 K2K
O2O SrO MgO
SrO MgO FF TiO22
TiO BaO
BaO Na22O
Na O YY22O
O33
52.52
52.52 44.88
44.88 0.32
0.32 0.05
0.05 0.05
0.05 0.02
0.02 0.05
0.05 0.01
0.01 0.06
0.06 0.01
0.01 0.02
0.02 0.01
0.01 0.01
0.01 0.01
0.01

4. Discussion
4. Discussion
Figures99and
Figures and10
10show
showthatthat gypsum
gypsum minerals
minerals and
and gangue
gangue minerals
minerals in
in untreated
untreated phos-
phos-
phogypsum adhere to each other, and fine mineral particles are attached to the surface
phogypsum adhere to each other, and fine mineral particles are attached to the surface of the of
the gypsum crystals. The main mineral in the gypsum concentrate
gypsum crystals. The main mineral in the gypsum concentrate was gypsum (CaSO4 ·2H2 O);was gypsum
(CaSO4·2H
however, the2O); however, the brushite (CaPO3(OH)·2H2O) mineral phase and quartz (SiO2)
brushite (CaPO3 (OH)·2H2 O) mineral phase and quartz (SiO2 ) were not found.
were not found. Meanwhile,
Meanwhile, tiny amounts tiny amounts
of muscovite of muscovite
(KAl2 SiO (KAl2SiO10(OH)) and zoisite
10 (OH)) and zoisite (Ca2 Al3 [SiO12 ]OH)
(Ca 2Al3[SiO12]OH) entered the gypsum concentrate owing to mechanical entrainment of
entered the gypsum concentrate owing to mechanical entrainment of the flotation process.
the flotation process. Figure 11a–d shows further that the phosphogypsum, after grading
Materials 2022, 15, 1944 12 of 15
Materials 2022, 15, x FOR PEER REVIEW 12 of 15
Materials 2022, 15, x FOR PEER REVIEW 12 of 15

Figure 11a–d shows further that the phosphogypsum, after grading and flotation of the
and
andflotation
flotation ofofthe
thegypsum
gypsumconcentrate,
concentrate, dispersed
dispersed and
and had
hadaasmooth
smooth crystal
crystalsurface,
surface,
gypsum concentrate, dispersed and had a smooth crystal surface, which indicates that the
which indicates
which indicates that that the phosphogypsum
the phosphogypsum through classification
through classification of pre-treatment
of pre-treatment using
using
phosphogypsum through classification of pre-treatment using direct flotation can effec-
direct
directflotation
tively flotation
remove can
caneffectively
effectively
impurities remove
in the remove impurities
impuritiesin
phosphogypsum inthe
thephosphogypsum
phosphogypsum
concentrate, concentrate,
concentrate,
thus significantly thus
improvingthus
significantly
the improving
product quality
significantly the
of thethe
improving product
gypsum
product quality of
concentrate. the gypsum concentrate.
quality of the gypsum concentrate.

35,000 1-CaSO4·2H2O
35,000 1-CaSO4·2H2O
30,000 2-KAl2SiAlO10(OH)2
30,000 2-KAl2SiAlO10(OH)2
1 3-Ca2AlO3[Si3O12]OH
25,000 1 3-Ca2AlO3[Si3O12]OH
25,000
Intensity (a.u.)
Intensity (a.u.)

20,000
20,000

15,000
15,000

10,000
10,000

5,000 1 11 11
5,000 1
32
0 32
0
−5,000
−5,000 0 10 20 30 40 50 60 70 80 90
0 10 20 30 40 50 60 70 80 90
2θ (deg.)
2θ (deg.)
Figure
Figure 9. XRDpatterns
9. XRD patterns of
of gypsum
gypsum concentrates.
concentrates.
Figure 9. XRD patterns of gypsum concentrates.

Figure 10. Photographs of characterization analysis of purification process of phosphogypsum.

Figure10.
Figure 10.Photographs
Photographsof
ofcharacterization
characterizationanalysis
analysisofofpurification
purificationprocess
processofofphosphogypsum.
phosphogypsum.
Materials
Materials 2022,
2022, 15,
15, x1944
FOR PEER REVIEW 1313ofof15
15

11,000
(b)
(a) 10,000 O
9,000

8,000
P1
Si
7,000

Intensity (cps)
6,000

5,000

4,000

3,000 Ca
S
2,000
Al K Ca
1,000 C Mg
0

−1,000
0 2 4 6 8 10
Binding energy (Kev)
11,000
(d)
(c) 10,000
O
9,000

8,000 P2
7,000
Intensity (cps)

6,000 S

5,000
4,000
Ca
3,000

2,000

1,000

−1,000
0 2 4 6 8 10
Binding energy (Kev)

Figure
Figure 11.
11. SEM-EDS
SEM-EDSanalysis
analysis of
of (a,b)
(a,b) phosphogypsum,
phosphogypsum, and
and (c,d)
(c,d) gypsum
gypsum concentrates.
concentrates.

5. Conclusions
5. Conclusions
The following are the
The the main
mainconclusions
conclusionsbasedbasedon onthe theresults
results obtained
obtained in in
this study
this studyon
thethe
on recovery
recovery of gypsum
of gypsum from phosphogypsum:
from phosphogypsum:
(1)
(1) Phosphogypsum
Phosphogypsumcontained contained80.65% 80.65%CaSO
CaSO44·2H·2H2O 2 Oandandwhiteness
whitenessof of27.68.
27.68. TheThe mainmain
mineral is CaSO ·2H O with small amounts of brushite,
mineral is CaSO4 ·2H2 O with small amounts brushite, quartz, muscovite, and
4 2 quartz, muscovite, andzoisite
zois-
ite
in in phosphogypsum.Harmful
phosphogypsum. Harmfulelements,
elements,such
such as as silicon,
silicon, phosphorus, and and fluorine,
fluorine,
are
aremainly
mainlyconcentrated
concentratedin inthe
the +0.15
+0.15mmmmand and −0.025
−0.025mm mmfraction;
fraction;these
thesecan canbe bepre-
pre-
selected
selectedand andremoved
removed by by the
the grading
grading method
method to increase the the CaSO
CaSO44·2H·2H22O O content
content
and
andreduce
reducethe theprocessing
processingcost. cost.
(2)
(2) A novel direct flotation process,consisting
A novel direct flotation process, consistingof ofoneoneroughing,
roughing,one onescavenging,
scavenging, and and twotwo
cleaning
cleaningoperations,
operations, were were employed
employed to recover gypsum gypsum from fromthe the− −0.15
0.15 to ++ 0.025
0.025 mm mm
fractionmaterials.
fraction materials.The Theaddition
additionof ofNaSiO
NaSiO33enhanced
enhancedthe theremoval
removalofofgangue
gangueminerals.
minerals.
Furthermore, the addition
Furthermore, additionof ofaamixed
mixed amine
amine enhanced
enhanced thethe
capture
captureof CaSO
of CaSO4 ·2H42·2H
O. The
2O.
test results
The show that
test results show gypsum with a CaSO
that gypsum with 4 · 2H
a 2 O content
CaSO 4 ·2H 2of
O 98.94%,
content CaSO
of · 2H
98.94%,
4 2O
recovery
CaSO 4·2H2ofO 80.02%,
recoveryand whiteness
of 80.02%, andof 37.05 wasofobtained
whiteness 37.05 wasunder the following
obtained under the con- fol-
ditions:conditions:
lowing flotation roughing concentration
flotation roughing of 30%, pH
concentration = 2.0pH
of 30%, (H=2 SO ), mixed
2.04 (H amine
2SO4), mixed
dosage of 400 g/t, pine dosage of 40 g/t, flotation scavenging
amine dosage of 400 g/t, pine dosage of 40 g/t, flotation scavenging of mixed amine of mixed amine dosage
of 200 g/t,
dosage of 200sodium silicate
g/t, sodium dosage
silicate of 400ofg/t,
dosage 400and g/t, pine
and pinedosage of 20ofg/t.
dosage Gypsum
20 g/t. Gyp-
concentrate
sum concentrate could be used
could as a as
be used high-quality
a high-qualityraw raw material to prepare
material α-hemihydrate
to prepare α-hemihy-
high-strength
drate high-strengthgypsum or β-hemihydrate-building
gypsum or β-hemihydrate-building gypsum.gypsum.
Materials 2022, 15, 1944 14 of 15

(3) The results of XRD and SEM-EDS demonstrated that the main mineral in the gypsum
concentrate was gypsum; however, brushite mineral phase and quartz were not found.
Meanwhile, a tiny amount of muscovite and zoisite entered the gypsum concentrate
owing to the mechanical entrainment of the flotation process.

Author Contributions: This is a joint work of the four authors; each author was in charge of their
expertise and capability: J.X. of Writing, review, editing, and conceptualization; T.L. of software; Y.Z.
of validation and data curation; and H.J. of methodology. All authors have read and agreed to the
published version of the manuscript.
Funding: This study was funded by the Sichuan Science and Technology Program (Grant Nos.
22ZDYF1399, 2021YJ0057, 2021YFG0268) and the Research Fund Program of the Key Laboratory of
the Guangdong Provincial Key Laboratory of Radioactive and Rare Resource Utilization (Grant Nos.
2018B030322009).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest. The authors alone are responsible
for the content and writing of the article.

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