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Hydrometallurgy: Sciencedirect
Hydrometallurgy: Sciencedirect
Hydrometallurgy: Sciencedirect
Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet
a
School of Metallurgy, Northeastern University, Shenyang 110819, China
b
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577, Japan
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 plants and is one of the significant strategic sources of fertilizer pro-
duction (Abelson, 1999). Although phosphate ores are the main raw
Steelmaking slag, which is produced to remove the impurities of hot material for industrial phosphate, they are not evenly distributed
metal through oxidation and the addition of lime, is a significant by- worldwide. For example, Japan has no natural phosphate ores
product of the steelmaking process. The productivity of steelmaking (Matsubae-Yokoyama et al., 2009). Because the high-grade phosphate
slag is approximately 0.11 tons per ton of molten steel (Nippon Slag ore reserves are decreasing and the demand for fertilizer is strong, the
Association, 2018). Because the global output of steel has exceeded 1.5 price of phosphate ore is continually increasing. To secure a sustainable
billion tons (World Steel Association, 2018), the disposal and utilization supply of P, it is critical to either recover P from waste wherever pos-
of such large amounts of steelmaking slag is an enormous challenge to sible or develop alternative sources of P (Budhathoki et al. 2018). Al-
society and the environment. The major components in steelmaking though P is vital for the chemical industry and agriculture, it is detri-
slag are CaO, SiO2, and FetO. Steelmaking slag also contains some va- mental to steel products. Most of the P in hot metal needs to be removed
luable oxides such as P2O5 and MnO, which are considered potential and concentrated in slag. P-bearing steelmaking slag is regarded a po-
sources. However, steelmaking slag is normally applied as a concrete tential P source owing to the extremely large amount produced
material, or in road construction and landfills (Miki and Kaneko, 2015). (Matsubae et al. 2016).
The intrinsic value of steelmaking slag has yet to be properly exploited. To increase the efficiency of P removal and reduce the consumption
With an increase in the environmental burden and depletion of natural of lime, hot metal dephosphorization is generally carried out using a
resources, the extraction of valuable elements from steelmaking slag converter during the steelmaking process. During this process, the slag
has drawn significant attention. is saturated with dicalcium silicate (2CaO∙SiO2) in a coexisting solid and
Phosphorus is an essential element for the growth of animals 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. Hydrometallurgy 189 (2019) 105109
reacts with the 2CaO∙SiO2, leading to the formation of a solid solution Table 1
of 2CaO∙SiO2–3CaO∙P2O5 (C2S–C3P) in the liquid phase (Suito et al. Actual composition of steelmaking slag with different valence of Fe (mass%).
1977). Ito et al. (1982) confirmed that the majority of P2O5 in steel- CaO SiO2 Fe2O3 FeO P2O5 MgO MnO Al2O3
making slag was enriched in a C2S–C3P solid solution, whereas the
other phases showed a lower P2O5 content. Thus, P recovery sub- 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
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
solution was then precipitated from the liquid slag during cooling. Fi-
P recovery, the P-removed steelmaking slag, which contains higher
nally, the sample was removed from the furnace at 1273 K. The atmo-
amounts of FetO and MnO, can be reutilized in a steel plant. Therefore,
sphere while synthesizing the slag containing Fe2O3 and FeO was air
the extraction of the C2S–C3P solid solution from steelmaking slag is of
and Ar, respectively. Table 1 shows the actual composition of steel-
significance in both the steelmaking and phosphate industries.
making slag with different valence of Fe, which was determined using
Many studies have been conducted to separate the solid solution
inductively coupled plasma-atomic emission spectroscopy (ICP-AES).
from steelmaking slag using the difference in physicochemical proper-
The mineral constituent of steelmaking slag and the average composi-
ties between different mineralogical phases. Kubo et al. (2010) adopted
tion of the mineralogical phase were determined using X-ray diffraction
magnetic separation to extract the nonmagnetic solid solution from the
(XRD) analysis and electron probe micro analyzer (EPMA).
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) 2.2. Selective leaching
used CaO to absorb the Fe-rich liquid phase using the capillary phe-
nomenon to separate the solid solution. However, these methods are The synthesized slag was crushed and ground with a particle size of
costly in terms of energy and have a lower efficiency. smaller than 53 μm. A total of 4 g of steelmaking slag was added to a
Because the C2S–C3P solid solution dissolves readily in water com- Teflon container with 400 mL of distilled water. The solution was mixed
pared to other mineralogical phases, Teratoko et al. (2012) proposed using a rotary stirrer at 200 rpm for 2 h. All leaching experiments were
the recovery of P from steelmaking slag through selective leaching of conducted at 298 K. To achieve the selective leaching of P from steel-
the solid solution. Numata et al. (2014) confirmed this selective making slag, we need to control the pH of the solution at a constant
leaching for the quenched steelmaking slag, whereas the extraction value. In the present study, hydrochloric acid (HCl, 1.5 mol/L), sulfuric
efficiency of P was lower. Previously, our studies principally focused on acid (H2SO4, 0.75 mol/L), nitric acid (HNO3, 1.5 mol/L), and citric acid
the selective leaching of P from steelmaking slag with a high P2O5 (H3C6H5O7, 0.75 mol/L) were selected as the leaching agents. Acid was
content (8 mass%), which is generated from the utilization of high-P automatically pumped into the solution using a PC-controlled system
iron ores. The C2S–C3P solid solution in this slag contains a higher P2O5 which connects with a pH meter. To study the effects of the acid and
content, resulting in lower water solubility (Teratoko et al. 2012). To valence of Fe in slag, the pH was maintained at 3. During leaching, the
achieve an improved selective leaching, we should maximize the ex- solution was sampled and filtered through a 0.45 μm mixed cellulose
traction efficiency of the P-concentrated solid solution while mini- ester membrane filter. The concentration of each element released from
mizing the leaching of other phases. Through a series of fundamental the slag into the leachate was determined using ICP-AES. After the re-
studies, we determined that Na2O modification, a slow cooling of the action, the slurry was filtered. The leachate was then used for the fol-
molten slag, and the use of citric acid as a leaching agent are ad- lowing P recovery, and the dried residue was weighed and analyzed
vantageous to the selective leaching of P (Du et al. 2017a, b). For the P- using XRD and EPMA.
containing leachate, we proposed a novel method that makes the so-
luble P precipitate as calcium phosphate by adjusting the pH. It was 2.3. Chemical precipitation
confirmed that most of the P is precipitated and recovered (Du et al.
2018a, b). These studies presented an efficient and energy-saving Following leaching in the hydrochloric acid solution at pH 3, the
method for the comprehensive utilization of the slag with a high P2O5 leachates of slags A and B were used to extract P. The soluble P can be
content, although the process is complex and expensive. precipitated by adjusting the pH to a higher value, although it is ne-
To achieve a high value-added utilization of normal steelmaking cessary to transform the metal-P precipitates into a plant-available
slag (containing approximately 3 mass% P2O5), selective leaching and fertilizer by adding Ca2+ or NH4+ cations (Franz 2008). We selected a
chemical precipitation were applied to recover P from this slag. The saturated Ca(OH)2 solution as the source of Ca2+ ions and to adjust the
objective of this study is to reduce the production costs and realize an pH. When the pH of the leachate exceeded 7, a large amount of pre-
improved selective leaching of P. Specifically, the effects of the acid, cipitate was formed. The cloudy leachate was first settled to allow a
pH, and valence of Fe on the leaching characteristics of P from furnace- solid–liquid separation. A concentrated precipitate was then collected
cooled steelmaking slag were first investigated. Precipitation using an using centrifugal separation. After calcination at 773 K, a final phos-
alkaline solution was then adopted to extract P from the leachate under phate product was obtained. The mineral composition of the product
a nearly neutral condition. The characteristics of the final product and was characterized using XRD, and the contents of each component were
its available P2O5 content were evaluated. Finally, we proposed a low- determined using ICP-AES.
cost process for P recovery and waste-free steelmaking.
3. Results and discussion
2. Experimental method
3.1. Mineralogical composition of slag
2.1. Slag preparation
The mineralogical phases in slag with different valence of Fe were
The slag preparation method used in this study is almost the same as characterized using EPMA, as displayed in Fig. 1. Table 2 lists the
that described in previous papers (Du et al. 2017a, 2018c). Two types of average compositions of the mineralogical phase in different slags.
steelmaking slag containing Fe2O3 and FeO, respectively, were syn- Three major domains corresponding to three mineralogical phases were
thesized using chemical reagents. The mixing ratios of the total Fe and identified in each slag. The white phase with high FetO, MgO, and MnO
other oxides of each slag were virtually the same. The mixture of che- contents was magnesioferrite. In addition to the large particles of
mical reagents was first melted at 1823 K in a MgO crucible. The solid magnesioferrite, large amounts of fine particles are also present in the
2
C.-M. Du, et al. Hydrometallurgy 189 (2019) 105109
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.
3
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)
4
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
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
Fig. 6. Extraction efficiency of each element from slag with different valence of of P was performed at a lower pH, the residue showed a lower P2O5
Fe. 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
practical steelmaking slag, which contains both FeO and Fe2O3, an
61 mass%. It is possible to utilize such materials as a steelmaking flux or
oxidization treatment is necessary to make the FeO in the slag trans-
raw ironmaking material. Thus, the Fe2O3 and MnO remaining in the
form into Fe2O3. In general, steelmaking slag poured from a converter is
residue is recovered, and the maximum value of the steelmaking slag is
directly oxidized by blowing oxygen during the molten state.
exploited.
Using the phase fractions of each slag, we calculated the mass fractions
Fig. 8 shows a micrograph of the residue surface of the Fe2O3-con-
of P and Fe distributed in each phase, and compared them with the ex-
taining slag after leaching in the hydrochloric acid solution at pH 3. The
traction efficiencies of P and Fe. As shown in Fig. 7, P was only distributed
average compositions of the identified domains on the residue surface
in the solid solution and merwinite in each slag, whereas Fe was mostly
are listed in Table 4. There were many holes on the surfaces of the large
concentrated in the magnesioferrite. For the Fe2O3-containing slag, the
particles. The residual slag mainly consisted of Fe, Mn, and Mg, which
mass fraction of P distributed in the solid solution was approximately 80%.
was virtually identical to the magnesioferrite. In addition to the large
The extraction efficiency of P was comparable to this value, illustrating
particles, smaller particles without holes were also observed. These
that most of the solid solution was leached, although some of the extracted
particles rich in Fe and Mg were also magnesioferrite. The P-containing
P was supplied from the merwinite. Because only a small portion of Fe2O3
solid solution and merwinite were not detected on the residue surface.
was distributed in the solid solution and merwinite, the dissolution of Fe
This result demonstrates that the solid solution and merwinite were
was poor. For the FeO-containing slag, the extraction efficiency of P was
readily leached compared to the magnesioferrite. Most of the P could be
lower than the mass fraction of P distributed in the solid solution, showing
extracted from the steelmaking slag.
that the extraction efficiency of the solid solution was lower compared to
Fig. 9 shows X-ray diffraction patterns of the Fe2O3-containing slag
the Fe2O3-containing slag. The mass fraction of Fe distributed in the solid
and its residues after leaching at pH 3. Three crystalline phases were
solution and merwinite was approximately 8.4%, which was nearly equal
observed in the original slag, which was consistent with the above
to the Fe extraction efficiency. This indicates that the extracted Fe was
EPMA analysis. The peaks associated with the solid solution and mer-
supplied from the large leaching of the solid solution and merwinite, ra-
winite were almost the same owing to their similar structures. After
ther than the magnesioferrite.
leaching in the hydrochloric acid solution, the peaks associated with the
solid solution and merwinite weakened significantly, whereas the peaks
3.3. Residue composition of the magnesioferrite intensified. This demonstrates that the majority
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.
5
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
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)
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
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. Hydrometallurgy 189 (2019) 105109