Hydrometallurgy 189 (2019) 105109

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Separation and recovery of phosphorus from steelmaking slag via a selective T

leaching–chemical precipitation process
Chuan-Ming Dua,b, , Xu Gaob, Shigeru Uedab, Shin-Ya Kitamurab
⁎

a
School of Metallurgy, Northeastern University, Shenyang 110819, China
b
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577, Japan

ARTICLE INFO ABSTRACT

Keywords: Steelmaking slag, a significant by-product of steelmaking, contains a certain amount of phosphorus, which
Steelmaking slag makes it a potential phosphate source. To achieve its high value-added utilization, the P-concentrated C2S–C3P
C2S–C3P solid solution solid solution in slag is commonly separated. In this study, we adopted a selective leaching–chemical pre-
Phosphorus recovery cipitation process to recover P from steelmaking slag. The effects of the acid, pH, and valence of Fe in slag on the
Selective leaching
leaching characteristics of P were first investigated. Chemical precipitation was then adopted to extract P from
Chemical precipitation
the leachate. The characteristics of the final product were evaluated. The results indicate that the P-concentrated
solid solution was readily leached, whereas the Fe-rich magnesioferrite was resistant to dissolution in each acid
solution. In view of the utilization of the residue and reducing the production costs, hydrochloric acid was
considered the optimum leaching agent for dissolving the slag. The dissolution of steelmaking slag in the hy-
drochloric acid solution increased with a decrease in pH. In addition, 81.6% of the P in slag was dissolved at
pH 3, whereas the Fe leaching was negligible, exhibiting an improved selective leaching. Further, the P-removed
steelmaking slag can be reutilized in a steel plant to achieve waste-free steelmaking. In the following pre-
cipitation at pH 7, most of the P in the leachate was transformed into an insoluble calcium phosphate. This
process provides more than a 70% P recovery from steelmaking slag. The P2O5 content in the product obtained
reached 20.2 mass%, which can be applied as a fertilizer.

1. Introduction
Steelmaking slag, which is produced to remove the impurities of hot
metal through oxidation and the addition of lime, is a significant by-
product of the steelmaking process. The productivity of steelmaking
slag is approximately 0.11 tons per ton of molten steel (Nippon Slag
Association, 2018). Because the global output of steel has exceeded 1.5
billion tons (World Steel Association, 2018), the disposal and utilization
of such large amounts of steelmaking slag is an enormous challenge to
society and the environment. The major components in steelmaking
slag are CaO, SiO2, and FetO. Steelmaking slag also contains some va-
luable oxides such as P2O5 and MnO, which are considered potential
sources. However, steelmaking slag is normally applied as a concrete
material, or in road construction and landfills (Miki and Kaneko, 2015).
The intrinsic value of steelmaking slag has yet to be properly exploited.
With an increase in the environmental burden and depletion of natural
resources, the extraction of valuable elements from steelmaking slag
has drawn significant attention.
Phosphorus is an essential element for the growth of animals and
plants and is one of the significant strategic sources of fertilizer pro-
duction (Abelson, 1999). Although phosphate ores are the main raw
material for industrial phosphate, they are not evenly distributed
worldwide. For example, Japan has no natural phosphate ores
(Matsubae-Yokoyama et al., 2009). Because the high-grade phosphate
ore reserves are decreasing and the demand for fertilizer is strong, the
price of phosphate ore is continually increasing. To secure a sustainable
supply of P, it is critical to either recover P from waste wherever pos-
sible or develop alternative sources of P (Budhathoki et al. 2018). Al-
though P is vital for the chemical industry and agriculture, it is detri-
mental to steel products. Most of the P in hot metal needs to be removed
and concentrated in slag. P-bearing steelmaking slag is regarded a po-
tential P source owing to the extremely large amount produced
(Matsubae et al. 2016).
To increase the efficiency of P removal and reduce the consumption
of lime, hot metal dephosphorization is generally carried out using a
converter during the steelmaking process. During this process, the slag
is saturated with dicalcium silicate (2CaO∙SiO2) in a coexisting solid and
liquid state. The P2O5 generated from the oxidization of P in metal

⁎
Corresponding author at: 2-1-1 Katahira, Aoba-ku, Sendai, Miyagi 980-8577, Japan.
E-mail address: du.chuanming.d3@tohoku.ac.jp (C.-M. Du).

https://doi.org/10.1016/j.hydromet.2019.105109
Received 25 January 2019; Received in revised form 1 June 2019; Accepted 13 July 2019
Available online 15 July 2019
0304-386X/ © 2019 Elsevier B.V. All rights reserved.
C.-M. Du, et al.
reacts with the 2CaO∙SiO2, leading to the formation of a solid solution
of 2CaO∙SiO2–3CaO∙P2O5 (C2S–C3P) in the liquid phase (Suito et al.
1977). Ito et al. (1982) confirmed that the majority of P2O5 in steel-
making slag was enriched in a C2S–C3P solid solution, whereas the
other phases showed a lower P2O5 content. Thus, P recovery sub-
stantially depends on a separation of the solid solution from steel-
making slag. If shown to be practicable, a sustainable and waste-free
steelmaking process has the potential to be achieved. In addition to the
P recovery, the P-removed steelmaking slag, which contains higher
amounts of FetO and MnO, can be reutilized in a steel plant. Therefore,
the extraction of the C2S–C3P solid solution from steelmaking slag is of
significance in both the steelmaking and phosphate industries.
Many studies have been conducted to separate the solid solution
from steelmaking slag using the difference in physicochemical proper-
ties between different mineralogical phases. Kubo et al. (2010) adopted
magnetic separation to extract the nonmagnetic solid solution from the
Fe-rich matrix phase. Ono et al. (1980) and Li et al. (2016) attempted to
separate the solid solution, which had a lower density, through floa-
tation and centrifugalization, respectively. Miki and Kaneko (2015)
used CaO to absorb the Fe-rich liquid phase using the capillary phe-
nomenon to separate the solid solution. However, these methods are
costly in terms of energy and have a lower efficiency.
Because the C2S–C3P solid solution dissolves readily in water com-
pared to other mineralogical phases, Teratoko et al. (2012) proposed
the recovery of P from steelmaking slag through selective leaching of
the solid solution. Numata et al. (2014) confirmed this selective
leaching for the quenched steelmaking slag, whereas the extraction
efficiency of P was lower. Previously, our studies principally focused on
the selective leaching of P from steelmaking slag with a high P2O5
content (8 mass%), which is generated from the utilization of high-P
iron ores. The C2S–C3P solid solution in this slag contains a higher P2O5
content, resulting in lower water solubility (Teratoko et al. 2012). To
achieve an improved selective leaching, we should maximize the ex-
traction efficiency of the P-concentrated solid solution while mini-
mizing the leaching of other phases. Through a series of fundamental
studies, we determined that Na2O modification, a slow cooling of the
molten slag, and the use of citric acid as a leaching agent are ad-
vantageous to the selective leaching of P (Du et al. 2017a, b). For the P-
containing leachate, we proposed a novel method that makes the so-
luble P precipitate as calcium phosphate by adjusting the pH. It was
confirmed that most of the P is precipitated and recovered (Du et al.
2018a, b). These studies presented an efficient and energy-saving
method for the comprehensive utilization of the slag with a high P2O5
content, although the process is complex and expensive.
To achieve a high value-added utilization of normal steelmaking
slag (containing approximately 3 mass% P2O5), selective leaching and
chemical precipitation were applied to recover P from this slag. The
objective of this study is to reduce the production costs and realize an
improved selective leaching of P. Specifically, the effects of the acid,
pH, and valence of Fe on the leaching characteristics of P from furnace-
cooled steelmaking slag were first investigated. Precipitation using an
alkaline solution was then adopted to extract P from the leachate under
a nearly neutral condition. The characteristics of the final product and
its available P2O5 content were evaluated. Finally, we proposed a low-
cost process for P recovery and waste-free steelmaking.
2. Experimental method
2.1. Slag preparation
The slag preparation method used in this study is almost the same as
that described in previous papers (Du et al. 2017a, 2018c). Two types of
steelmaking slag containing Fe2O3 and FeO, respectively, were syn-
thesized using chemical reagents. The mixing ratios of the total Fe and
other oxides of each slag were virtually the same. The mixture of che-
mical reagents was first melted at 1823 K in a MgO crucible. The solid
2
Hydrometallurgy 189 (2019) 105109
Table 1
Actual composition of steelmaking slag with different valence of Fe (mass%).
CaO SiO2 Fe2O3 FeO P2O5 MgO MnO Al2O3
Slag A 31.19 19.86 27.79 0 3.29 10.24 4.58 3.05
Slag B 32.60 22.48 0 26.27 3.52 7.29 4.81 3.02
solution was then precipitated from the liquid slag during cooling. Fi-
nally, the sample was removed from the furnace at 1273 K. The atmo-
sphere while synthesizing the slag containing Fe2O3 and FeO was air
and Ar, respectively. Table 1 shows the actual composition of steel-
making slag with different valence of Fe, which was determined using
inductively coupled plasma-atomic emission spectroscopy (ICP-AES).
The mineral constituent of steelmaking slag and the average composi-
tion of the mineralogical phase were determined using X-ray diffraction
(XRD) analysis and electron probe micro analyzer (EPMA).
2.2. Selective leaching
The synthesized slag was crushed and ground with a particle size of
smaller than 53 μm. A total of 4 g of steelmaking slag was added to a
Teflon container with 400 mL of distilled water. The solution was mixed
using a rotary stirrer at 200 rpm for 2 h. All leaching experiments were
conducted at 298 K. To achieve the selective leaching of P from steel-
making slag, we need to control the pH of the solution at a constant
value. In the present study, hydrochloric acid (HCl, 1.5 mol/L), sulfuric
acid (H2SO4, 0.75 mol/L), nitric acid (HNO3, 1.5 mol/L), and citric acid
(H3C6H5O7, 0.75 mol/L) were selected as the leaching agents. Acid was
automatically pumped into the solution using a PC-controlled system
which connects with a pH meter. To study the effects of the acid and
valence of Fe in slag, the pH was maintained at 3. During leaching, the
solution was sampled and filtered through a 0.45 μm mixed cellulose
ester membrane filter. The concentration of each element released from
the slag into the leachate was determined using ICP-AES. After the re-
action, the slurry was filtered. The leachate was then used for the fol-
lowing P recovery, and the dried residue was weighed and analyzed
using XRD and EPMA.
2.3. Chemical precipitation
Following leaching in the hydrochloric acid solution at pH 3, the
leachates of slags A and B were used to extract P. The soluble P can be
precipitated by adjusting the pH to a higher value, although it is ne-
cessary to transform the metal-P precipitates into a plant-available
fertilizer by adding Ca2+ or NH4+ cations (Franz 2008). We selected a
saturated Ca(OH)2 solution as the source of Ca2+ ions and to adjust the
pH. When the pH of the leachate exceeded 7, a large amount of pre-
cipitate was formed. The cloudy leachate was first settled to allow a
solid–liquid separation. A concentrated precipitate was then collected
using centrifugal separation. After calcination at 773 K, a final phos-
phate product was obtained. The mineral composition of the product
was characterized using XRD, and the contents of each component were
determined using ICP-AES.
3. Results and discussion
3.1. Mineralogical composition of slag
The mineralogical phases in slag with different valence of Fe were
characterized using EPMA, as displayed in Fig. 1. Table 2 lists the
average compositions of the mineralogical phase in different slags.
Three major domains corresponding to three mineralogical phases were
identified in each slag. The white phase with high FetO, MgO, and MnO
contents was magnesioferrite. In addition to the large particles of
magnesioferrite, large amounts of fine particles are also present in the
C.-M. Du, et al. Hydrometallurgy 189 (2019) 105109

Fig. 2. Change in the concentrations of P and Fe in different acid solutions at

pH 3.

3.2. Leaching characteristic of steelmaking slag

Slag A was leached by various acid solutions at pH 3. Fig. 2 shows

the change in the concentrations of P and Fe with the leaching time for
different acid solutions. The leaching rate of the slag was high during
the initial stage, accounting for higher concentrations of P and Fe after
30 min. Their concentrations increased slightly after 60 min, indicating
that the leaching reaction approached equilibrium. The P concentration
in each acid solution exceeded 105 mg/L, which was considerably
higher than the Fe concentration. Citric acid exhibited a strong ability
to dissolve the slag. In the citric acid solution, the P concentration could
achieve a higher level within a short time, and the Fe concentration was
three-times higher than that in the other acid solutions. After 120 min,
Fig. 1. Micrographs of steelmaking slag with different valence of Fe. the P concentration in different acid solutions was almost the same
except for that in the sulfuric acid solution. The Fe concentration in the
Table 2 inorganic acid solutions was only approximately 8 mg/L.
Average compositions of the mineralogical phase in different slags (mass%). The extraction efficiency of element M (EM) from slag in different
acid solutions at pH 3 was calculated as follows:
CaO SiO2 FetO P2O5 MgO MnO Al2O3 Phase
CM V
Slag A 1 1.1 0.1 66.4 0.0 16.0 9.5 6.9 Magnesioferrite EM = × 100%
mM (1)
2 51.1 33.4 0.8 2.3 11.4 0.9 0.1 Merwinite (C3MS2)
3 59.4 27.0 1.2 9.0 2.1 1.2 0.1 Solid solution where CM is the M concentration after 120 min (mg/L), V is the leachate
(C2S–C3P)
volume (L) (considering the volumes of the sampled solution and the
Slag B 1 0.7 0.2 75.5 0.0 11.4 10.8 1.3 Magnesioferrite
2 50.5 32.0 3.6 3.0 9.2 1.6 0.1 Merwinite (C3MS2) added acid), and mM is the mass of M in 4 g of slag (mg). As displayed in
3 56.6 27.2 3.5 8.3 1.9 2.4 0.1 Solid solution Fig. 3, the dominating elements extracted during leaching were Ca, Si,
(C2S–C3P)

Fe2O3-containing slag. The other two phases, in which almost all of the
P2O5 was distributed, showed a similar color because of a low FetO
content. The greyish phase rich in P2O5 was the C2S–C3P solid solution.
The phase with a higher MgO content was considered merwinite whose
chemical formula is Ca3Mg(SiO4)2 (C3MS2). Owing to the slow cooling,
no glassy phase of the CaO–SiO2–FetO system was observed. Because
the P2O5 content in these slags was approximately 3 mass%, the P2O5
content in the solid solution was not high compared to that in slag with
a high P2O5 content (Shimauchi et al. 2009). For slag A, which con-
tained Fe2O3, the P2O5 content in the solid solution was 9.0 mass%. The
distribution ratio of P2O5 between the solid solution and merwinite was
higher than that in the FeO-containing slag, indicating a better en-
richment of P2O5 in the solid solution. For slag B, the FetO content in
the solid solution was higher than that in slag A. This is because Fe2+
ions have the same ionic valence as Ca2+ ions, and the radius is smaller
than that of Ca2+; thus, Fe2+ ions can replace Ca2+ ions and easily
Fig. 3. Effect of acid on the extraction efficiency of each element from slag at
enter the C2S–C3P solid solution (Du et al. 2018c).
pH 3.

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C.-M. Du, et al. Hydrometallurgy 189 (2019) 105109

and P, which were mainly distributed in the solid solution and mer-
winite. The extraction efficiency of Fe was negligible. These results
demonstrate that the P-concentrated solid solution was readily leached,
whereas the Fe-rich magnesioferrite was resistant to dissolution. Ap-
proximately 30% of the Mg was also dissolved, which was attributed to
a large dissolution of the merwinite. Overall, a selective leaching of P
from steelmaking slag was performed in each case. In the acidic solu-
tion, phosphate and silicate ions primarily existed in the form of
H2PO4− and H2SiO30 (Futatsuka et al. 2004). The major reactions
during leaching include the following:
2CaO SiO2 3CaO P2 O5 + 8H+ = 5Ca2 + + H2 SiO30 + 2H2 PO4 + H2 O
(2)

Ca3Mg(SiO4 )2 + 8H+ = 3Ca2 + + Mg2 + + 2H2 SiO30 + 2H2 O (3)

Ca2 + + C6 H5 O73 = Ca(C6 H5 O7 ) (4)

The mineralogical phases were leached in the citric acid solution
through two mechanisms (McDonald and Whittington 2008), namely,
direct displacement of the metal cations from the mineral structure by
H+ ions at a low pH and the formation of soluble organometallic com-
plexes by chelation. As described in Eq. (4), citrate ions (C6H5O73−)
function as a chelator of Ca2+, which favors a crystal lattice destruction
(Astuti et al. 2016). These actions lead to a higher extraction efficiency of
P and Fe from the slag. When sulfuric acid is used, the dissolved Ca2+
ions combine with sulfate ions to precipitate CaSO4. Thus, the extraction
efficiency of Ca is less than 40%. Because the CaSO4 precipitate wraps
the undissolved slag, it hinders a continuous leaching of the steelmaking
slag, resulting in the lowest P releasing capacity. Further, the residue
containing a CaSO4 precipitate is difficult to be reutilized in the steel-
making process because sulfur is a troublesome element during steel-
making. Nitric acid and hydrochloric acid are both monoacids. In these
inorganic acid solutions, the leaching of mineralogical phases principally
depends on H+ ions, and anions such as NO3− and Cl− ions have little
effect. Therefore, the leaching characteristics of each element in the ni-
tric and hydrochloric acid solutions were virtually the same. Approxi-
mately 81% of the P was extracted, whereas the leaching of Fe was in-
significant. Although the use of citric acid shows a slightly higher
dissolution ratio of P, the price of citric acid is far higher than that of
normal inorganic acids. Except for sulfuric acid, the price of hydrochloric
acid is lower. In view of reducing the production costs and the utilization
of the residue, hydrochloric acid was considered the most suitable
leaching agent for extracting P from steelmaking slag.
When hydrochloric acid was used as a leaching agent, the extraction
efficiencies of each element from slag A at different pH conditions are
as displayed in Fig. 4. The dissolution of the slag was promoted with a
decrease in the pH, resulting in higher extraction efficiencies of each
element. The extraction efficiencies of Ca, Si, and P were far higher than
those of other elements in each case. Fe could barely dissolve, and its
extraction efficiency was negligible. The leaching of P was insufficient
at pH 5. When the pH decreased to 3, almost a complete Ca extraction
was achieved; the extraction efficiencies of P and Si increased con-
siderably, reaching 81.6% and 73.7%, respectively. The P extraction
showed a slight improvement when the pH continued to decrease,
whereas the extraction efficiency of Fe almost doubled. Therefore, the
pH should be controlled at 3 to achieve an improved selective leaching
of P and reduce the acid consumption.
To evaluate the leaching characteristics of the mineralogical phases,
we first calculated the phase fractions in different slags using the phase
composition (listed in Table 2). The mass balance of each oxide and
phase fraction can be described as follows:
(%MO)slag = (%MO)i Xi
(5)
Xi = 1
(6)
where (%MO)slag is the MO content in slag, (%MO)i is the MO content in
Fig. 4. Extraction efficiency of each element in the hydrochloric acid solution
under various pH conditions.
Fig. 5. Phase fractions of slag A and the percentage of the dissolved slag under
various pH conditions.
phase i, and Xi is the phase fraction. The percentage of dissolved slag was
calculated on the basis of the extraction efficiency and slag composition.
In Fig. 5, we compared the percentages of the dissolved slag and residue
under various pH conditions with the phase fractions of slag A. The mass
fractions of the solid solution and merwinite were 29.6%–30.6%, re-
spectively. As discussed above, the solid solution and merwinite were
readily dissolved. The percentage of the dissolved slag was only 33.8% at
pH 5, which is less than the sum of the mass fractions of the solid solution
and merwinite. This indicates that the leaching of the solid solution was
insufficient, and that the residue contains a portion of the undissolved
solid solution. The percentage of the dissolved slag increased sig-
nificantly as the pH decreased. It was slightly lower than the sum of the
mass fractions of the solid solution and merwinite at pH 3, illustrating
that the majority of the slag was leached, with the exception of the Fe-
rich magnesioferrite. When the pH decreased from 3 to 2, the percentage
of the dissolved slag slightly increased.
Fig. 6 shows the extraction efficiencies of each element from slag
with different valence of Fe in the hydrochloric acid solution. Almost a
complete Ca extraction was achieved regardless of the valence of Fe in
the slag. The extraction efficiency of P from the FeO-containing slag
was only 67.3%, which is lower than that from the Fe2O3-containng
slag. However, the leaching of Fe, Mn, and Mg was considerably im-
proved when the Fe2O3 in the slag was transformed into FeO. The ex-
traction efficiency of Fe reached 6.1%. Selective leaching of P from
steelmaking slag worsened. In addition, a larger dissolution of Fe will
have a negative influence on the P recovery from the leachate because
the ferric phosphate is not suitable as a fertilizer. Therefore, for

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C.-M. Du, et al. Hydrometallurgy 189 (2019) 105109

Table 3
Residue compositions after leaching under various pH conditions (mass%).
Sample CaO SiO2 Fe2O3 P2O5 MgO MnO Al2O3

Slag A (Fe2O3) 31.19 19.86 27.79 3.29 10.24 4.58 3.05

Residue (HCl, pH = 2) 1.46 5.37 62.50 0.82 14.13 9.26 6.46
Residue (HCl, pH = 3) 1.04 6.33 61.73 0.84 14.45 9.27 6.34
Residue (HCl, pH = 4) 9.00 14.18 51.23 1.69 10.68 7.81 5.41
Residue (HCl, pH = 5) 14.50 18.21 43.83 2.25 9.65 6.80 4.75

Fig. 6. Extraction efficiency of each element from slag with different valence of
Fe.
practical steelmaking slag, which contains both FeO and Fe2O3, an
oxidization treatment is necessary to make the FeO in the slag trans-
form into Fe2O3. In general, steelmaking slag poured from a converter is
directly oxidized by blowing oxygen during the molten state.
Using the phase fractions of each slag, we calculated the mass fractions
of P and Fe distributed in each phase, and compared them with the ex-
traction efficiencies of P and Fe. As shown in Fig. 7, P was only distributed
in the solid solution and merwinite in each slag, whereas Fe was mostly
concentrated in the magnesioferrite. For the Fe2O3-containing slag, the
mass fraction of P distributed in the solid solution was approximately 80%.
The extraction efficiency of P was comparable to this value, illustrating
that most of the solid solution was leached, although some of the extracted
P was supplied from the merwinite. Because only a small portion of Fe2O3
was distributed in the solid solution and merwinite, the dissolution of Fe
was poor. For the FeO-containing slag, the extraction efficiency of P was
lower than the mass fraction of P distributed in the solid solution, showing
that the extraction efficiency of the solid solution was lower compared to
the Fe2O3-containing slag. The mass fraction of Fe distributed in the solid
solution and merwinite was approximately 8.4%, which was nearly equal
to the Fe extraction efficiency. This indicates that the extracted Fe was
supplied from the large leaching of the solid solution and merwinite, ra-
ther than the magnesioferrite.
3.3. Residue composition
Table 3. Compared to the original slag composition, the CaO, SiO2, and
P2O5 amounts in the remained slag decreased after selective leaching,
whereas the Fe2O3, MnO, and Al2O3 amounts increased. To achieve a
reutilization of the residue during the steelmaking process, the P2O5
content in the residue should be lowered as much as possible. When the
slag was leached at pH 5, the P2O5 content in the residue was still
higher, reaching 2.25 mass%. Because an improved selective leaching
of P was performed at a lower pH, the residue showed a lower P2O5
content and higher Fe2O3 content. The compositions of the residues
after leaching at pH 2 and 3 were almost the same. In these residues, the
P2O5 content decreased to 0.84 mass% and the Fe2O3 content exceeded
61 mass%. It is possible to utilize such materials as a steelmaking flux or
raw ironmaking material. Thus, the Fe2O3 and MnO remaining in the
residue is recovered, and the maximum value of the steelmaking slag is
exploited.
Fig. 8 shows a micrograph of the residue surface of the Fe2O3-con-
taining slag after leaching in the hydrochloric acid solution at pH 3. The
average compositions of the identified domains on the residue surface
are listed in Table 4. There were many holes on the surfaces of the large
particles. The residual slag mainly consisted of Fe, Mn, and Mg, which
was virtually identical to the magnesioferrite. In addition to the large
particles, smaller particles without holes were also observed. These
particles rich in Fe and Mg were also magnesioferrite. The P-containing
solid solution and merwinite were not detected on the residue surface.
This result demonstrates that the solid solution and merwinite were
readily leached compared to the magnesioferrite. Most of the P could be
extracted from the steelmaking slag.
Fig. 9 shows X-ray diffraction patterns of the Fe2O3-containing slag
and its residues after leaching at pH 3. Three crystalline phases were
observed in the original slag, which was consistent with the above
EPMA analysis. The peaks associated with the solid solution and mer-
winite were almost the same owing to their similar structures. After
leaching in the hydrochloric acid solution, the peaks associated with the
solid solution and merwinite weakened significantly, whereas the peaks
of the magnesioferrite intensified. This demonstrates that the majority

Following leaching in the hydrochloric acid solution, the average

composition of the residue was determined using ICP-AES, as listed in

Fig. 7. Mass fractions of P and Fe distributed in each phase, compared with Fig. 8. Micrograph of the residue surface of the Fe2O3-containing slag after
their extraction efficiencies. leaching.

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C.-M. Du, et al. Hydrometallurgy 189 (2019) 105109

Table 4
Average composition of each domain on the residue surface of slag A (mass%).
Point Ca Si P Fe Mn Mg Al

1 0.3 1.0 0.1 45.5 7.0 10.7 5.3

2 0.8 0.1 0.1 45.3 7.2 12.9 5.7

Fig. 9. X-ray diffraction patterns of the Fe2O3-containing slag and its residues.

of the solid solution and merwinite were extracted from the slag
through selective leaching, and the Fe-rich magnesioferrite remained.
When the slag was leached in the sulfuric acid solution, the amount of
the residue increased considerably. The main peaks in the residue were
associated with gypsum (CaSO4), which agrees with the above discus-
sion. The intensities of the peaks of magnesioferrite seemed weaker
because the amount of the precipitated gypsum was large. As men- Fig. 10. Change in the concentration of each element in the leachate with the
tioned above, the existence of gypsum will restrict the reuse of residue pH.
inside a steel plant.
Standard chemical potential of each substance and activity coefficient
3.4. Phosphorus extraction in the leachate at 298 K are used in the present work (Futatsuka et al. 2004). For the
leachate containing higher concentrations of Ca and P, various calcium
Fig. 10 shows the change in the compositions of the leachates of phosphates are able to precipitate depending on the pH and solution
slags A and B when the pH increased. The leachate of slag A mainly composition (Valsami-Jones 2001). It was reported that CaHPO4·2H2O
consisted of Ca, Si, and P ions, and had lower concentrations of Fe and (brushite, DCPD) is preferentially precipitated because of a fast nu-
Mn because of an improved selective leaching. As the pH of the leachate cleation and growth, although Ca5(PO4)3(OH) (hydroxyapatite, HAP)
increased, a chemical precipitation occurred, causing a decrease of the was the most thermodynamically stable calcium phosphate
concentration of each element. When the pH increased to 7, the P (Koutsoukos and Nancollas 1981; Lee et al. 2018). The reactions of
concentration decreased from 119.3 to 7.0 mg/L, exhibiting a sharp CaHPO4·2H2O in the solution and their Gibbs-free energy are expressed
decrease compared with the other elements. This illustrates that most of in Eqs. (8) and (9) (Futatsuka et al. 2004; Iglesia 2009). Using the
the phosphate ions in the leachate were precipitated, whereas the calculated equilibrium constant (K) and activity coefficients of ions (γ),
precipitation of silicate ions was not as significant. When the pH con- the relationship between Ca2+ and phosphate ions in the aqueous so-
tinued to increase, the concentrations of P, Fe, and Mn decreased to a lution can be determined, as described in Eqs. (10) and (11). The ac-
very low level, and the precipitation of silicate and Ca2+ ions began to tivity coefficient of the dissolved ion, i, was estimated using the De-
occur significantly. At pH 9, the P concentration was less than 1.0 mg/L, bye–Hückel theory, as expressed in Eq. (12) (Stokes and Robinson
and the Si concentration decreased to 85.1 mg/L. 1948).
The concentrations of Fe and Mn in the leachate of slag B were far
HPO24 + H+ = H2 PO4 G1° = 41005 J/mol (7)
higher than those in the leachate of slag A. The P concentration in the
leachate of slag B reached 101.8 mg/L, which is lower than that of Fe.
When the pH increased to 7, the P and Fe concentrations decreased Ca2 + + HPO24 + 2H2 O = CaHPO4 2H2 O G2° = 37183 J/mol (8)
significantly compared with the Si and Mn concentrations. Their con-
centrations in the leachate were only 9.3–24.4 mg/L, respectively, in- Ca2 + + H2 PO4 + 2H2 O = CaHPO4 2H2 O + H+ G3° = 3822 J/mol (9)
dicating that the precipitation of the phosphate and Fe2+ ions pre-
ferentially occurred.
G1°
HPO42− and H2PO4− are the major phosphate ions in the aqueous log K1 = = log C Ca2 + log Ca2 + log CHPO24 log HPO24
2.303RT
solution whose pH ranges from 3 to 9 (Recillas et al. 2012). The re-
lationship between HPO42− and H2PO4− ions is described in Eq. (7). (10)

6
C.-M. Du, et al. Hydrometallurgy 189 (2019) 105109

G2°
log K2 = = log C Ca2 + log Ca2 + log CH2 PO4 log H2PO4
2.303RT
—pH (11)

Az i2 I
log i =
1 + Ba0 I (12)

3Fe2 + + 2HPO24 + 8H2 O = Fe3 (PO4 )2 8H2 O + 2H+ G4°

= 36919 J/mol (13)

3Fe 2+ + 2H2 PO4 + 8H2 O = Fe3 (PO4 ) 2 8H2 O + 4H+ G5° = 45091 J/mol
(14)
where R is a gas constant, and T is the leachate temperature. In addi-
tion, A and B are constants that depend on the temperature and solvent,
z is the valence of dissolved substances, a0 is the ion-size parameter (Å),
and I is the ionic strength of the solvent. Because the leachate is a di-
luted solution, the values of A, B, and I applied in the present work were
0.509, 0.329, and 0.676, respectively (Okabe et al., 1980).
Using the above equations, we calculated the solubility lines of Fig. 12. Solubility lines of Fe3(PO4)2·8H2O under various pH conditions and
CaHPO4·2H2O at different pH conditions and compared the results with experimental results.
the experimental results of leachate A, as shown in Fig. 11. The cal-
culated P concentration in the solution was equal to the sum of the
determine its formation, we also calculated the relationship between
HPO42− and H2PO4− concentrations. With an increase in the pH and Ca
the concentrations of Fe2+ and phosphate ions under various pH con-
concentration, CaHPO4·2H2O will precipitate, accounting for a decrease
ditions using Eq. (13) and Eq. (14) (Futatsuka et al. 2004; Iglesia 2009).
in the P concentration. This confirms that the dissolved P can be ex-
As displayed in Fig. 12, the experimental result for the leachate B was
tracted from the leachate through a chemical precipitation. At a lower
located below the solubility line of Fe3(PO4)2·8H2O at pH 3, indicating
pH condition, the pH had a significant influence on the P concentration.
that Fe3(PO4)2·8H2O did not precipitate, and that Fe2+ and phosphate
However, the Ca concentration principally affected the P concentration
ions can coexist. When the pH increased to 7, the solubility of
at a higher pH condition. Because the solubility of CaHPO4·2H2O was
Fe3(PO4)2·8H2O decreased significantly. The P concentration in the
high at pH 3, the P concentration in the original leachate did not reach
leachate was higher than its saturation concentration. Meanwhile, the
saturation, and the Ca2+ and phosphate ions could stably coexist. When
experimental result at pH 7 was also located above the corresponding
the pH increased, the P concentration in the original leachate was far
solubility line of CaHPO4·2H2O in Fig. 11. These results indicate that
higher than its saturation concentration. Thus, CaHPO4·2H2O pre-
Fe3(PO4)2·8H2O and CaHPO4·2H2O both precipitated in leachate B at
cipitated and the P concentration decreased to a lower level. The ex-
pH 7. The existence of the insoluble ferric phosphate is a disadvantage
periment result for the leachate at pH 7 was located slightly above the
to the utilization of this precipitate as a fertilizer.
corresponding solubility line, indicating the supersaturation of P in this
Following the calcination of the precipitate separated from the
solution. At pH 8–9, the experimental results for the leachates also lay
leachate, the final phosphate product was obtained, as shown in Fig. 13.
near the solubility lines. In summary, the majority of the soluble P was
Table 5 lists the compositions of the phosphate products produced from
precipitated and the solubility of CaHPO4·2H2O determined the P
different leachates under various pH conditions. These products mainly
concentration in the leachate.
consisted of CaO, SiO2, and P2O5, which is similar with the C2S–C3P
In the leachate B containing a higher Fe2+ concentration, the pre-
solid solution. The SiO2 content was the highest among these compo-
cipitation of Fe3(PO4)2·8H2O (vivianite) may occur (Iglesia 2009). To
nents, accounting for nearly half of each product. The P2O5 content in
product A (obtained from leachate A at pH 9) was only 12.95 mass%. As

Fig. 11. Solubility lines of CaHPO4·2H2O under various pH conditions and

experimental results. Fig. 13. Image of the phosphate product obtained in this process.

7
C.-M. Du, et al. Hydrometallurgy 189 (2019) 105109

Table 5
Compositions of the product under various pH conditions (mass%) and P precipitation ratio.
Sample CaO SiO2 P2O5 Fe2O3 MnO MgO Al2O3 Others P precipitation ratio

Product A (Leachate A, pH = 9) 25.77 50.80 12.95 0.33 2.38 2.37 0.59 4.81 0.959
Product B (Leachate A, pH = 8) 24.08 52.70 13.11 0.32 2.25 1.13 0.59 5.82 0.921
Product C (Leachate A, pH = 7) 28.90 41.88 20.17 0.49 2.76 0.89 0.71 4.20 0.863
Product D (Leachate B, pH = 7) 18.12 49.35 13.76 10.22 3.37 0.84 0.81 3.53 0.888

the product, and M is the molar mass. As listed in Table 5, most of the
soluble P in the leachate was precipitated during the chemical pre-
cipitation. The P precipitation ratio in leachate A increased from 86.3%
to 95.9% when the pH changed from 7 to 9. Using the product of the P
extraction efficiency from slag and the P precipitation ratio, we esti-
mated the total recovery ratio of P from the steelmaking slag in this
selective leaching–chemical precipitation process. When a chemical
precipitation was conducted at pH 7, this process provided more than a
70% P recovery from steelmaking slag. The P2O5 content in the product
obtained reached 20.2 mass%, which can be applied as a fertilizer.
A novel process for P recovery and waste-free steelmaking was
proposed on the basis of this study, as displayed in Fig. 15. Following
dephosphorization of hot metal, a P-bearing steelmaking slag is gen-
erated and then treated through selective leaching. The P in steel-
making slag is leached and concentrated in the leachate. Through
chemical precipitation, most of the P in the leachate is precipitated
under a nearly neutral condition. The phosphate product obtained with
a higher content of citrate-soluble P2O5 has the potential to be utilized
as a fertilizer in agriculture. The P-removed residue with a higher Fe2O3
content can be reutilized in steelmaking process. No extra slag is dis-
charged, and the P contained in the steelmaking slag is recovered
through an efficient and low-cost process.
Fig. 14. X-ray diffraction patterns of the phosphate products obtained under
different conditions.
4. Conclusions

the pH decreased to 7, the precipitation of silicate ions was significantly Selective leaching and chemical precipitation were adopted to re-
suppressed compared with that of phosphate ions, resulting in an in- cover P from the normal steelmaking slag. The effects of the acid, pH,
crease in the P2O5 content in the product. The P2O5 content in product and valence of Fe in slag on the leaching characteristics of P were first
C exceeded 20 mass%, and the CaO content was 28.9 mass%. Fig. 14 investigated. The P precipitation in the leachate and the characteristics
shows X-ray diffraction patterns of the phosphate products. The peaks of the final product were then evaluated. The following conclusions
of Ca5(PO4)3(OH) were clearly found in products A and C. This is be- were drawn:
cause the CaHPO4·2H2O that precipitated during the chemical pre-
cipitation was transformed into thermodynamically stable (1) The P-concentrated solid solution was readily leached whereas the
Ca5(PO4)3(OH) after calcination (Valsami-Jones 2001). The intensity of Fe-rich magnesioferrite was resistant to dissolution in each acid
these peaks was higher in product C than in product A, indicating a solution. In view of reducing the production costs and utilizing the
higher content of calcium phosphate. Furthermore, an amorphous
phase was also confirmed in the X-ray diffraction patterns of these
products, with the broad peaks at between 20° and 35° being attributed
to an amorphous nature of the silicates (Jo et al. 2017). The P avail-
ability was measured using the solubility of P compounds in a 2% citric
acid solution (Shiba and Ntuli, 2017). Approximately 85% of the P2O5
in product C was leached, although the leaching of SiO2 was extremely
low. It can therefore be concluded that the majority of P in the product
is bioavailable for plant uptake. To produce a high-quality fertilizer,
future studies will focus on the removal of SiO2 from the product.
The Fe2O3 content in product D was higher because a large amount of
Fe was precipitated in leachate B. However, the P2O5 and CaO contents
were lower. As shown in Fig. 14, the peaks associated with
Ca5(PO4)3(OH) was extremely weak in product D, whereas some peaks of
Fe2O3 (hematite) were observed. The formation of Fe2O3 may be caused
by the decomposition of Fe(OH)3 during calcination. This product with
lower P2O5 and higher Fe2O3 amounts is not suitable as a fertilizer.
2MP m wP2O5
PR =
MP2O5 V CP (15)
The P precipitation ratio (PR) in the leachate was evaluated using
Eq. (15), where m is the total product mass, wP2O5 is the P2O5 content in Fig. 15. A novel process for P recovery and waste-free steelmaking.

8
C.-M. Du, et al.
residue, hydrochloric acid was considered the optimum leaching
agent to dissolve the steelmaking slag.
(2) The dissolution of steelmaking slag in the hydrochloric acid solu-
tion increased with a decrease in pH. In addition, 81.6% of the P in
the slag was dissolved at pH 3, whereas the Fe leaching was negli-
gible, exhibiting an improved selective leaching. A residue con-
taining lower P2O5 and higher Fe2O3 amounts can be reutilized in
the steelmaking process.
(3) The FeO-containing slag showed a lower extraction efficiency of P
and a higher extraction efficiency of Fe in the hydrochloric acid
solution, which is a disadvantage to the P recovery. Thus, an oxi-
dization treatment is necessary to transform the FeO in slag into
Fe2O3.
(4) During chemical precipitation at pH 7, most of the soluble P in the
leachate was transformed into an insoluble calcium phosphate. A
higher pH resulted in a higher P precipitation ratio, whereas the
P2O5 content in the product decreased. This process provides more
than a 70% P recovery from steelmaking slag. The P2O5 content in
the product obtained reached 20.2 mass%, which can be applied as
a fertilizer.
Declarations of Competing Interest
None.
Acknowledgment
This work was supported by JST-Mirai Program Grant Number
JPMJMI17C2, Japan.
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