Journal of Environmental Chemical Engineering 10 (2022) 108076

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Journal of Environmental Chemical Engineering

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Separation of calcium chloride from waste acidic raffinate in HCl wet

process for phosphoric acid manufacture: Simulated and
experimental study
Li Lv a, Hang Liao a, Tao Zhang a, Shengwei Tang a, Weizao Liu b, *
a
School of Chemical Engineering, Sichuan University, Chengdu 610065, China
b
College of Materials Science and Engineering, Chongqing University, Chongqing 400044, China

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

Editor: Teik Thye Lim Phosphoric acid manufacture by HCl wet process is a phosphogypsum-free route, which is promising for
replacing traditional H2SO4 wet process. However, large amount of CaCl2-containing acidic raffinate was dis­
Keywords: charged after solvent extraction of H3PO4. In this study, pure CaCl2⋅2H2O was recovered from the raffinate. The
Calcium chloride ionic forms and residual amount changes with the pH rise in the raffinate was first simulated by Visual MINTEQ
Phosphoric acid
software, and found the precipitation for the components was in the following sequential order of
Calcium hydrophosphate
Si>F>P>Al>Cr>Pb≈Mg. Based on the calculation, one-step and multi-steps neutralization processes were
Neutralization
Raffinate designed for separation of impurities. Feed grade calcium hydrophosphate can be separated from the raffinate by
multi-steps neutralization. A well-crystallized CaCl2⋅2H2O assaying 98.9 wt% was obtained after evaporative
crystallization of the fluorine-depleted solution. Combined with our previous studies on the phosphate ore
digestion and H3PO4 solvent extraction, a complete HCl wet process for H3PO4 manufacture was established.

1. Introduction process is considered as an alternative to replace H2SO4 wet process. In

Phosphoric acid (H3PO4) is an important chemical intermediate,
whose derivates are widely used in fertilizer, food, medicine, feed and
electronic etching industries [1–3]. Currently, thermal process and wet
process are the main methods for H3PO4 manufacture [4,5]. In the
thermal process, phosphate ore is first reduced by carbon to generate
phosphorus gas (1400–1600 ◦ C), followed by oxidizing to phosphorus
pentoxide and then absorbing by water [6]. Although high quality
H3PO4 can be produced by thermal process, high energy consumption
and high-grade phosphate ore feedstock are required, limiting its wide
industrial applications. Whereas, in the wet process, strong acid such as
sulfuric acid, hydrochloric acid, nitric acid is used to leach phosphate
ore and generate H3PO4 [7–10]. Among them, H2SO4 wet process is the
current commercial method due to the fact that this method is relatively
easy for separation H3PO4 from the leachate [11]. However, large
amount of valueless phosphogypsum would be generated (4.5–5 tons of
phosphogypsum for producing one ton phosphoric acid), occupying
precious land and polluting surrounding environment [12,13]. It was
reported that the annual output of phosphogypsum worldwide is esti­
mated to be approximately 160 million tons [14]. Therefore, HCl wet
the HCl wet process, phosphate ore is first decomposed by HCl to yield
soluble calcium chloride and phosphoric acid as described in reaction
(1) [15–18]. After removal of impurities, phosphoric acid in the leachate
is separated by solvent extraction and a raffinate rich in CaCl2 is
generated [19–23]. However, most of studies focused on the phosphate
ore digestion and phosphoric acid solvent extraction processes, ignoring
the treatment of the raffinate.
Ca5(PO4)3F+10HCl=3 H3PO4+5CaCl2+HF (1)
In our previous study, the parameters optimization and kinetics of
leaching process were investigated [16]. It was found that almost all of
the phosphorus can be dissolved in 0.488 mol/L HCl solution at 40 ◦ C
within 10 min. Thereafter, Fe3+ was removed from the leachate by
solvent extraction with 12.5 vol% of tributyl phosphate (TBP) and 87.5
vol% kerosene; Fe3+ was completely removed after a three-stages
countercurrent extraction [22]. The Fe3+ depleted solution was then
subjected to a four-stages countercurrent extraction with 80 vol% TBP
and 20 vol% kerosene, and 83% H3PO4 can be separated, leaving a
raffinate containing around 25–30 wt% CaCl2 and 2.5–3 wt% P2O5 as

* Corresponding author.
E-mail address: liuwz@cqu.edu.cn (W. Liu).

https://doi.org/10.1016/j.jece.2022.108076
Received 23 February 2022; Received in revised form 8 June 2022; Accepted 9 June 2022
Available online 13 June 2022
2213-3437/© 2022 Elsevier Ltd. All rights reserved.
L. Lv et al. Journal of Environmental Chemical Engineering 10 (2022) 108076

Table 1
Chemical compositions of the phosphate ore, leachate and raffinate.
Ca P Si F Al Fe K Na Mg Pb Cr

Phosphate ore (wt%) 26.9 12.6 9.95 1.85 0.91 0.77 0.38 0.21 0.11 < 0.01 < 0.01
Leachate (mg/L) 102700 77330 2145 4495 1755 3512 855 780 665 26 14.5
Raffinate (mg/L) 109400 12970 1275 4070 2028 ND 805 560 558 13.7 5.9

ND: not detected

well as some intractable ions such as fluorine, chromium, lead [23]. It
was estimated that 7–8 tons of raffinate would be generated for
manufacturing one ton phosphoric acid by the above process [23].
Therefore, the raffinate should be treated properly for the large-scale
industrial application of phosphoric acid manufacture by HCl wet
process.
For the treatment of CaCl2-containing waste water, several methods
were explored. Wang et al. [24] used waste H2SO4 or Na2SO4 to pre­
cipitate the calcium as gypsum. The gypsum can be used as construction
materials, but the impurities-containing waste acid did not be disposed.
Guo et al. [25] converted CaCl2 into CaCO3 and NH4Cl by adding
ammonia water and ammonium carbonate. The impurities can be
precipitated with CaCO3 and relative pure NH4Cl can be obtained after
evaporative crystallization. However, this method suffered from poor
economy and hardly industrial popularization.
Since the complicated compositions of the raffinate (containing
various poisonous components such as heave metal ions and fluorine), it
should be treated properly to avoid its negative effects on the sur­
rounding environments. In this study, calcium chloride was recovered
from the above raffinate by neutralization with hydrated lime. Firstly,
the ionic forms and residual amount changes with the pH rise in the
raffinate was calculated by Visual MINTEQ software to judge the
precipitated sequential order of each component in thermodynamic.
After that, the batch experiments by two routes i.e. one-step neutrali­
zation and multi-steps neutralization were compared to recover phos­
phorus in the raffinate. Parameter optimization and preliminary
material balance of the two routes were conducted. The precipitated
residues were characterized by X-ray diffraction, scanning electron mi­
croscope and thermal analysis. The results obtained in this study com­
bined with our previous study provided a theoretical and experimental
foundation for phosphoric acid manufacture by HCl wet process.
2. Experimental
2.1. Materials
Phosphate ore used in this study was provided from Huidong County,
Sichuan Province, China and its chemical composition is shown in
Table 1. The mineral phases analysis was reported in our previous study,
and the main phases were fluorapatite (Ca5(PO4)3F) and quartz (SiO2)

Fig. 1. Effects of pH value on the forms and distribution of various ions (calculated by Visual MINTEQ software; a: fluorine, b: aluminum, c: phosphorus, d: silicon).

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L. Lv et al. Journal of Environmental Chemical Engineering 10 (2022) 108076

[16]. All chemical reagents used for the experiments and analysis, such
as Ca(OH)2, poly aluminium chloride, TBP and kerosene were of
analytical grade.

2.2. Experimental procedure

The phosphate ore was leached with 0.488 mol/L HCl at 40 ◦ C for 10
min to obtain a leachate with chemical compositions also shown in
Table 1. The leachate was then subjected to solvent extraction by TBP
and kerosene with the optimal conditions obtained in our previous study
for removal of Fe3+ and separation of H3PO4 [22,23]. The chemical
compositions of resulted raffinate are presented in Table 1. As seen, it
contained considerable amount of calcium and phosphorus as well as
more than 4000 mg/L intractable fluorine ion. It should be mentioned
that the raffinate exhibited slight acidic (c[H+]=0.93 mol/L).
The ionic forms and residual amount changes with the pH rise in the
raffinate was calculated by Visual MINTEQ software [26], which was
based on the thermodynamic parameters such as equilibrium constant Fig. 2. Effects of pH value on the residual amounts of various impurities
and Gibbs free energy to calculate the interactions of chemical sub­ (calculated by Visual MINTEQ software).
stances and their formation as well as distribution. According to the
chemical compositions of the raffinate (Table 1), the ion species and 3. Results and discussion
concentrations were input into the software, and the simulated tem­
perature was selected as 25 ◦ C. 3.1. Ionic forms and residual amount changes
The obtained raffinate was subjected to neutralization for removal of
impurities. In detail, different amounts of hydrated lime (0–12 g) was Fig. 1 depicts the ionic forms changes with the pH rise. As seen, the
added into 200 mL raffinate at required temperature and the mixture main form of fluorine and aluminum in the original raffinate was AlF3-x x
was stirred with a rate of 180 r/min for 60 min. After that, the slurry was (x = 1–3). The complex stability constant for its ionization are 6.1, 11.5
filtrated to obtained precipitated mother liquid and residue. The con­ and 15, respectively. Therefore, the stable form of AlF3-x
x is related to the
centrations of various ions in the mother liquid was measured and the mole ratio of F- to Al3+ (F/Al). At low F/Al, AlF2+ and F- are the main
corresponding removal efficiencies can be calculated by comparing their ions, while AlF2+and AlF3 become the stable forms at large F/Al [27].
concentration before and after neutralization. The residues were rinsed With the pH value rise, AlF3-x
x was ionized stepwise and the resulted F
-
sufficiently and dried at 100 ◦ C for 12 h before characterizations. combined with Ca2+ to form insoluble CaF2. Trace CaF2 was then dis­
The remained fluorine in the neutralized raffinate was further solved in the solution and ionized to CaF+ (Reaction 2–3). While, the
removed by flocculation with poly aluminium chloride (PAC) and ionized Al3+ was reacted with OH- to form Al(OH)3 precipitation and
polyacrylamide (PAM) as flocculant. In detail, 0.1 wt% PAM and 0–3 g/L soluble Al(OH)-4 due to the lower solubility of Al(OH)3 (0.015 g/L) than
PAC were added into 20 mL neutralized raffinate. The feedstocks were AlF3 (5.59 g/L) (Reaction 4–5) [28].
fully mixed at a water bath with a temperature of 25 ◦ C and stirring rate
of 300 r/min. After mixed sufficiently, the stirring rate was turned down AlF+
2 → AlF
2+
+ F- → Al3+ + 2 F- (2)
to 10 r/min and kept for 60 min. Then, the slurry was filtrated to obtain -
F + Ca 2+
→ CaF2 (s) → CaF2 (aq) → CaF + F + -
(3)
a fluorine-depleted solution. The fluorine content in the solution was
measured to determine its removal efficiency. Al 3+ -
+ 3OH → Al(OH)3 (s) (4)
After removal of fluorine, the solution was then evaporated and
crystallized to obtained calcium chlorine powder. The evaporation Al(OH)3 (s) + OH- → Al(OH)-4 (5)
experiment was carried out in an oil bath. In detail, 100 mL fluorine- For the phosphorus, the initial form was H3PO4 due to its low ioni­
depleted solution was poured into a round-bottom flask and placed in zation equilibrium constant. With the increase of pH value, its ionization
an oil bath with temperature of 110 ◦ C and stirring rate of 180 r/min. was promoted owing to the consumption of H+. The ionized H2PO-4
After completely dried, the crystallized CaCl2 was collected and ground further combined with Ca2+ to form Ca(H2PO4)2. Owing to high solu­
before characterizations. bility of Ca(H2PO4)2 (18 g/L), it would ionize to CaH2PO+ 4 (Reaction
6–7). Thus, CaH2PO+ 4 was the dominated form in the pH value range of
1–6. As the pH value continued to increase, H2PO-4 further ionized
2.3. Analysis and characterization stepwise to HPO2- 3- 2+
4 and PO4 , which reacted with Ca to form insoluble
CaHPO4 (0.043 g/L) and Ca3PO4 (0.02 g/L). Since the formation of
The concentrations of P, Mg, Al, Si, Pb and Cr in the solution were HPO2- 3-
4 prior to PO4 , the main precipitation of phosphorus was CaHPO4.
measured by inductively coupled plasma optical emission spectrometer The trace phosphorus in the solution existed as CaPO-4 (Reaction 8–9).
(ICP-OES, Spectro ARCOS, Germany), while F was measured by fluorine-
ion selective electrode (DX219-F Fluoride, Mettler Toledo, US). X-ray H3PO4 → H2PO-4 + H+ (6)
fluorescence was conducted for the total analysis of solid samples with a
2 H2PO-4 + Ca 2+
→ Ca(H2PO4)2 → CaH2PO+ + H2PO-4 (7)
Rh Kα radiation source (XRF-1800, Shimadzu, Japan). X-ray diffraction 4

patterns (XRD) were carried out by a Rigaku X-ray diffractometer (D/ H2PO-4 → H+ + HPO2- + 3-
4 → H + PO4 (8)
Max2500pc) with a Cu Kα radiation source (40 kV, 150 mA). Data points
were acquired by step scanning from 10◦ to 80◦ with a rate of 12◦ /min. PO3-
4 + Ca 2+
→ CaPO-4 (9)
Surface morphologies of the samples were obtained by scanning electron For the silicon, the initial forms were H4SiO4 and SiF2-
With the 6.
microscope (SEM, Zeiss Gemini). Thermal analysis of the samples was increase of pH value, SiF2-
6 disappeared with the solo form of H4SiO4 in
carried out on a simultaneous thermogravimetry-differential scanning the pH value range of 2–7. As the pH value continued to increase, H3SiO-4
calorimetry (TG-DSC, Mettler Toledo, 1100LF, Switzerland).

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L. Lv et al. Journal of Environmental Chemical Engineering 10 (2022) 108076

Table 2 of temperature on the removal efficiency of impurities (pH=10, 60 min).

Precipitated reactions at different pH intervals. The reaction temperature had little impact on the removal of impurities.
pH intervals Reaction The removal efficiencies for Mg and Cr decreased at high temperature
owing to the higher solubilities of their hydroxides. Therefore, this
0–2 SiF2-
6 + 2 H3O →SiO2↓+ 6HF
+

0–2 H4SiO4→SiO2↓+ 2 H2O process can be operated at room temperature.

0–5 2 F-+ Ca2+→CaF2↓ Fig. 4 shows the XRD patterns of precipitated residue and its roasted
1–5 HPO2- 2+
4 +Ca →CaHPO4↓ products at 200 ◦ C and 1000 ◦ C, respectively. The precipitated residue
1–5 3CaHPO4 + 4OH-+ 2Ca2+→Ca5(PO4)3OH↓+ 3 H2O exhibited an amorphous state with some weak peaks corresponding to
2–5 Al3++3OH-→Al(OH)3↓
4–7 Cr3++3OH-→Cr(OH)3↓
CaF2 and Ca5(PO4)3OH. After roasting at 200 ◦ C for 12 h, the peaks of
8–10 Pb2++2OH-→Pb(OH)2↓ CaF2 and Ca5(PO4)3OH became obvious, and they transformed to
8–10 Mg2++2OH-→Mg(OH)2↓ Ca5(PO4)3F after roasting at 1000 ◦ C. The peaks of CaHPO4 were not
found, which was due to the conversion to more stable Ca5(PO4)3OH at
high pH with reaction equation shown in Table 2. No peaks related to Al,
was the dominated form.
Si, Cr, Pb and Mg were observed due to the low concentration in the
Fig. 2 shows the residual amount changes of various elements in the
original raffinate and presented as amorphous forms in the precipitated
solution with the pH value variation. As seen, the amounts of each
residue.
component in raffinate decreased with the increase of pH value. The
Fig. 5 shows the SEM images of the precipitated residue and the
precipitation of each component was in the following sequential order of
roasted samples at 200 ◦ C and 1000 ◦ C. As seen, the precipitated residue
Si > F> P > Al> Cr> Pb≈ Mg. At pH= 10, almost all of the impurities
was irregular and amorphous with a loose and porous surface, indicative
were precipitated from the raffinate with residual amount less than 1%.
of good adsorption capacity. After roasting at 200 ◦ C, it became compact
Based on the above ionic forms of each element, the precipitated re­
with less porous structure. After roasting at 1000 ◦ C, some hexagonal
actions were summarized in the Table 2. The main precipitations for
fluorapatite crystal structure can be found, indicating that the reaction
each elements were SiO2, CaF2, CaHPO4/Ca5(PO4)3OH, Al(OH)3, Cr
between Ca5(PO4)3(OH) and CaF2 occurred at high temperature. the
(OH)3, Pb(OH)2, Mg(OH)2, respectively. Further increase of pH value
would lead to the dissolution of aluminum as form of Al(OH)-4. There­
fore, the final pH value should be controlled within 10 in the subsequent
experiments.

3.2. One-step neutralization

Based on the above thermodynamic calculation, pH value has great

impact on the removal efficiency of impurities and almost all of the
impurities can be removed when the pH value of raffinate is adjusted to
10. Therefore, different amounts of hydrated lime were added into the
raffinate to see the effects of pH value on the removal efficiency of im­
purities (25 ◦ C, 60 min), and the results are displayed in Fig. 3a. As seen,
with the increase of pH value, the precipitation of each component was
in the following sequential order of Al > F > P > Si > Cr > Mg > Pb,
which was slightly different from the results obtained by thermody­
namic calculation. More than 90% of Al, F and P can be removed when
pH value reached around 2, which was lower than that obtained by
thermodynamic calculation. This may be due to the formation of Al
(OH)3 and Ca5(PO4)3OH colloids, which would adsorb and co-
Fig. 4. XRD patterns of (a) precipitated residue; (b) precipitated residue after
precipitate other components [29]. As predicted, almost all of the im­
roasting at 200 ◦ C; (c) precipitated residue after roasting at 1000 ◦ C.
purities can be removed at pH value around10. Fig. 3b shows the effects

Fig. 3. Effect of (a)pH value and (b) reaction temperature on the removal efficiency.

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L. Lv et al. Journal of Environmental Chemical Engineering 10 (2022) 108076

Fig. 5. SEM images of (a) precipitated residue; (b) precipitated residue after roasting at 200 ◦ C; (c) precipitated residue after roasting at 1000 ◦ C.

results were in agree with the XRD.

Fig. 6 displays the thermogravimetry analysis of the precipitated
residue. The thermal decomposition of precipitated residue can be
divided into three stages [30,31]. The first stage was the release of
adsorbed water in the temperature range of 25–110 ◦ C. The second stage
was the release of bound water corresponding to the temperature range
of 110–160 ◦ C. The last stage was the decomposition of Ca5(PO4)3(OH),
CaF2 and various hydroxides in the temperature range of 600–1000 ◦ C.
The main reaction in the last stage were shown in Reaction 10–12.

Ca5(PO4)3(OH)+CaF2→2Ca5(PO4)3F+H2O+CaO (10)

2 Me(OH)3→Me2O3+3 H2O (Me=Al or Cr) (11)

2 M(OH)2→MO+H2O (M=Mg or Pb) (12)

3.3. Multi-steps neutralization

Fig. 6. TG/DTG curves of precipitated residue.
Although one-step neutralization can remove almost all of the

Fig. 7. Relationship between pH value and removal efficiency of various ions.

Table 3
Ion concentrations in the raffinate and precipitated mother liquid obtained at different steps.
Concentration (mg/L) P F Mg Al Si Pb Cr

Raffinate 15350.0 4070.0 557.9 2028.0 1275.0 13.7 5.9

First step 11036.0 500.6 562.1 48.7 230.2 14.5 6.3
Second step 2008.6 428.5 583.8 0.5 8.0 14.8 6.2
Last step 3.50 37.00 5.50 0.50 1.45 0.05 0.00

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L. Lv et al. Journal of Environmental Chemical Engineering 10 (2022) 108076

Fig. 8. XRD patterns of (a) precipitated residue from first step; (b) precipitated
residue from first step and roasted at 1000 ℃; (c) precipitated residue from
second step; (d) precipitated residue from second step and roasted at 1000 ℃.
Fig. 9. Effects of the PAC dosage on the pH value and removal efficiency
impurities, considerable amount of phosphorus was co-precipitated with of fluorine.
the residue, resulting in the waste of phosphorus resource. It was noted
from Fig. 3a that aluminum and fluorine was precipitated prior to
phosphorus, whereas silicon, chromium, magnesium and lead after­
wards. Therefore, multi-steps neutralization was designed to recover
phosphorus. Fig. 7a shows the detailed relationship between pH value
(below 1.0) and removal efficiency of various ions. As seen, at pH= 0.48,
more than 90% of aluminum and 60% of fluorine were precipitated with
approximately 10% phosphorus loss. When pH was higher than 0.76, the
precipitation of aluminum and fluorine plateaued with removal effi­
ciencies of 98% and 88%, respectively. In this case, the loss of phos­
phorus was around 28%. The loss of phosphorus increased rapidly
thereafter. Therefore, the optimal pH value for the first step precipita­
tion was determined as 0.76. Table 3 shows the ion concentrations in the
precipitated mother liquid. It was interesting to find that 82% of silicon
can also be removed, which may be due to the adsorption of Al(OH)3 and
Ca5(PO4)3(OH) colloids. The precipitated mother liquid obtained at
pH= 0.76 was then subjected to the second step precipitation. Fig. 7b
shows the detailed relationship between pH value (0.76–2.15) and
removal efficiency of various ions. With the increase of pH value, the
Fig. 10. XRD pattern of the CaCl2 product.
removal efficiency of phosphorus increased rapidly and then became
stable, whilst that of other ions such as fluorine, chromium increased
In this study, the fluorine in the final mother liquid was removed by
slowly at first and then became fast. At pH= 1.14, the removal efficiency
flocculation with poly aluminium chloride (PAC) and polyacrylamide
of phosphorus reached 82% with 14.4% fluorine and 1.4% chromium
(PAM) as flocculant. Fig. 9 shows the effects of PAC dosage on the pH
co-precipitated. Higher pH value led to more fluorine and chromium co-
value and fluorine removal efficiency. As seen, addition of 1.5 g/L PAC
precipitation, thus the optimal pH value was selected as 1.14. The ion
can efficiently remove fluorine from 37 mg/L to less than 10 mg/L,
concentrations in the second step precipitated mother liquid were also
which meet the integrated wastewater discharge standard in China. The
presented in Table 3. It was found that almost all of the residual
trace fluorine would enter the final CaCl2 product after evaporative
aluminum and silicon in the first step precipitated mother liquid were
crystallization of the fluorine removed solution. Thus, the optimal PAC
co-precipitated as impurities in the obtained phosphorus product. Fig. 8
dosage was selected as 3 g/L, at which almost all of the fluorine can be
displays the XRD patterns of the precipitated residues obtained in the
removed.
first and second steps neutralization and their roasted samples at
1000 ◦ C. As seen, the precipitated residues obtained in the first step was
amorphous, and the peaks corresponding to Ca5(PO3)3F and Al2O3⋅SiO2 3.4. Evaporative crystallization of the fluorine-depleted solution
can be found after roasting at 1000 ◦ C. The results were in agreement
with the high removal efficiency of aluminum, silicon and fluorine. In After removal of impurities, a solution containing 35.5 wt% CaCl2
the second step precipitated residue, solo CaHPO4 peaks were observed was obtained, which was further subjected to evaporative crystallization
and decomposed to CaP2O6 after roasting. No peaks related to aluminum for preparing CaCl2 product. Generally, the solution was concentrated to
and silicon were found, indicative of low contents. XRF result of CaHPO4 around 45 wt% CaCl2, followed by spray drying and granulation. For the
product showed its composition meet the feed grade requirement (GB simplification, the solution was directly dried in an oil bath (110 ◦ C).
22549–2008). The second step precipitated mother liquid were Fig. 10 shows the XRD pattern of the CaCl2 product. A well-crystallized
continued to neutralize by adjusting pH value to 10, and the composi­ CaCl20.2 H2O was obtained. Fig. 11 displays the photograph and SEM
tions of resulted mother liquid are shown in Table 3. Almost all of the image of the CaCl2 product. The product appeared as white powder
impurities can be removed except fluorine, which would enter the final composed by spherical particles with diameter around 1.5 µm. The
CaCl2 product. Therefore, a deeply removal of fluorine should be product assaying 98.9 wt% CaCl2⋅2 H2O met the secondary standard for
conducted. industrial grade calcium chloride product.

6
L. Lv et al.
Fig. 11. Photograph and SEM image of the CaCl2 product.
Fig. 12. Material balances of one step and multi-steps neutralization processes.
3.5. Preliminary material balance
According to above experimental results, preliminary material bal­
ance for one step and multi-steps neutralization processes was con­
ducted, and the results are illustrated in Fig. 12. For the one step route,
78 kg hydrated lime was required to precipitate the impurities for one
ton of raffinate. While, 43 kg hydrated lime was used in the multi-steps
route, which was approximately 45% less than that of one step route,
indicative of higher utilization ratio. Besides, 32 kg CaHPO4 can be
recovered in the multi-steps route, which can generate revenues and was
essential for favorable economic viability in the process.
4. Conclusions
In this study, the separation of calcium chloride from HCl wet pro­
cess phosphoric acid raffinate was carried out by simulated calculation
and experimental study. The impurities in the raffinate was first
precipitated and removed by lime neutralization. The ionic forms and
precipitated rule of various impurities was simulated by Visual MINTEQ
software, and found the precipitation for the components was in the
following sequential order of Si > F> P > Al> Cr> Pb≈ Mg. Thereafter,
one step and multi-steps neutralization routes were compared. It was
found that all impurities can be removed by either process, but one step
neutralization produced more precipitated residue with approximately
double dosage of hydrated lime added. Besides, feed grade calcium
hydrophosphate can be separated from the raffinate by multi-steps
7
Journal of Environmental Chemical Engineering 10 (2022) 108076
neutralization. A well-crystallized CaCl2⋅2H2O assaying 98.9 wt% was
obtained after evaporative crystallization of the fluorine depleted solu­
tion. Combined with our previous studies on the phosphate ore digestion
and phosphoric acid solvent extraction, a complete route for phosphoric
acid manufacture by HCl wet process was established.
CRediT authorship contribution statement
Li Lv: Methodology, Investigation, Visualization, Conceptualization,
Writing – original draft. Hang Liao: Conceptualization, Project admin­
istration, Writing – review & editing. Tao Zhang: Investigation.
Shengwei Tang: Project administration, Supervision, Writing – review
& editing, Investigation. Weizao Liu: Funding acquisition, Resources,
Project administration, Supervision, Writing – review & editing.
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.
Acknowledgements
The authors are grateful for the financial support of the National Key
Projects for Fundamental Research and Development of China
(2018YFC1900201) and National Natural Science Foundation of China
L. Lv et al.
(No. 52104322).
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