Article

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Phase Equilibrium for the Ternary Systems (KCl + K2SO4 + H2O) and
(KH2PO4 + K2SO4 + H2O) at 288.15 K and Atmospheric Pressure
Wei Liu,†,‡ Jun Zhou,*,§ Zi-wei Zhang,† Shuang Chen,† and Shang-yu Liu†
†
College of Energy Resources, Chengdu University of Technology, Chengdu, Sichuan 610059, P. R. China
‡
Post-Doctoral Research Cente, Tarim Oilfield Company, PetroChina, Korla, XinJiang 841000, P. R. China
§
Research Institute of Petroleum Engineering, Sinopec, Beijing 100101, P. R. China

ABSTRACT: The phase equilibrium of (KCl + K2SO4 + H2O) and

(KH2PO4 + K2SO4 + H2O) at 288.15 K is studied by isothermal solution
saturation method and wet residues. The equilibrium solid phases are
analyzed by the Schreinemaker’s method of wet residues and verified by X-ray
diffraction (XRD). On the basis of the experimental data, the diagram of
density versus composition and the phase diagram are plotted. The crys-
tallization regions are determined. In the two systems, KCl and KH2PO4 have
a strong salting-out effect on K2SO4, and the salting-out effect of KCl
on K2SO4 is stronger than that of KH2PO4 on K2SO4. There are in all
two crystalline regions, two univariant curves, and one invariant point.
The crystalline region of K2SO4 is the largest, whereas that of KCl is the
smallest. All results can offer fundamental data support for optimizing
processes and further theoretical studies.

■ INTRODUCTION
KH2PO4, as an important compound fertilizer and chemical
material, is widely applied in pharmaceutical, agricultural, and food
industries.1,2 Many processes, such as solvent extraction
technology, neutralization, ion exchange, and metathesis, are
applied to produce KH2PO4.2,3 In the solvent extraction
technology, the product often contains many impurities.4−8 The
Cl− and SO42− accumulate in the crystalline mother liquid and
cannot be removed after a series of removing impurity processes,
which brings about a low quality of potassium dihydrogen
phosphate. Therefore, to optimize the process and prepare a high
quality of potassium dihydrogen phosphate, it is essential to study
the phase equilibrium. Wang et al.9 reported the phase equilibrium
data of KH2PO4 + K2SO4 + H2O at 298.15 and 333.15 K. In the
literature,10 the phase equilibrium of K2SO4 + KCl + H2O at
303.15 K has been reported.
However, these data are insufficient to resolve the separation
above, and therefore, an extensive study at other temperatures needs
to be done. The phase equilibrium of the systems (KH2PO4 +
K2SO4 + H2O) and (K2SO4 + KCl + H2O) at 288.15 K have not
been reported yet. This paper is conducive to fill the blank of data
and new experimental data given in this study are useful for
optimizing the crystallization and separation processes. Additionally,
the research can offer fundamental data support for further theo-
retical studies.
Table 1. Purities and Suppliers of Chemicals
mass fraction
chemical purity source
KH2PO4 ≥0.995 Tianjin Bodi Chemical Holding Co. Ltd.,
China
K2SO4 ≥0.995 Tianjin Bodi Chemical Holding Co. Ltd.,
China
KCl ≥0.995 Chengdu Kelong Chemical Reagent Co. Ltd.,
China
work is purchased from Kelong Chemical Reagent Co. Ltd.,
Chengdu, China. The sources and purity of the chemicals are listed
in Table 1. Doubly deionized water (electrical conductivity ≤1 ×
10−4 S·m−1) is used in the work.
Apparatus. ASHZ-88 type constant temperature water bath
oscillator with a precision of 0.3 K is employed to measure phase
equilibrium and made in Jintan Medical Instrument Corporation,
Jiangsu, China. The Philips X Pert Pro MPD X-ray diffraction
(XRD) analyzer is employed for XRD characterizations.
Experimental Methods. The method of isothermal solution
saturation11−13 is employed to determine the solubility of the
ternary system. The famous Schreinemaker’s method of moist
residues13−15 is applied to determine the equilibrium solid phase
in the experiments indirectly, and the solid phase is also tested by
XRD to verify the crystalloid composition.

■
On the basis of a fixed ratio and ensuring that one of the compo-
METHODOLOGY nents is excessive, the experimental components are added into a
Materials. Potassium dihydrogen phosphate (KH2PO4, ≥0.995
mass fraction) and potassium sulfate (K2SO4, ≥0.995 mass fraction) Received: December 31, 2015
are purchased from Bodi Chemical Holding Co. Ltd., Tianjin, Accepted: May 17, 2016
China. Potassium chloride (KCl, ≥0.995 mass fraction) used in the

© XXXX American Chemical Society A DOI: 10.1021/acs.jced.5b01111

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series of conical flasks (250 mL) gradually, and the sealed flask is Table 2. Mass Fraction Solubility of the Ternary KCl +
placed into the oscillator. The oscillator vibrates continuously at K2SO4 + H2O System at Temperature = 288.15 K and
288.15 K (the standard uncertainty of 0.3 K). In a pre-experiment, Pressure = 0.1 MPaa
the liquid phase of the samples is analyzed at every 2 h. It
composition of densities of
demonstrates that the equilibrium is reached when the analytical liquid phase, composition of wet liquid
results keep constant. It is shown that the phase equilibrium is 100w residue phase, 100w phase
reached in 10 h. After equilibrium, the oscillation is stopped and equilibrium
the system is allowed to stand for 2 h to make sure that all no.d 100w1b 100w2 100w1 100w2 ρ/(g·cm−3) solid phase
the suspended crystals settle. The wet residues and liquid phase 1, N 0.00 9.12 c c
1.0756 K2SO4
are transferred to a 250 mL volumetric flask, respectively. 2 2.29 7.44 1.25 51.39 1.0765 K2SO4
Simultaneously, some other liquid phases are used to determine 3 4.45 5.98 2.19 54.00 1.0783 K2SO4
density individually. Finally, these samples are quantitatively 4 6.58 4.63 3.39 50.63 1.0814 K2SO4
analyzed by chemical methods. 5 8.98 3.83 4.45 52.49 1.0897 K2SO4
More details of the experimental method and the procedure of 6 10.64 3.19 5.52 50.46 1.0969 K2SO4
the transfer, collection and preparation of samples are presented 7 12.93 2.70 6.14 54.00 1.1080 K2SO4
in the previous papers.9,10,12 8 16.30 1.98 7.65 53.92 1.1258 K2SO4
Analysis. The concentration of H2PO4− is analyzed by the 9 19.43 1.51 9.09 54.09 1.1437 K2SO4
quinoline phosphomolybdate gravimetric method,16 and the 10 22.84 1.16 10.53 54.59 1.1651 K2SO4
relative standard uncertainty is 0.01. The sulfate concentration is 11, F 24.21 1.01 27.33 45.24 1.1746 K2SO4 + KCl
determined by the gravimetric method of barium chloride,17,18 12, F 24.21 1.01 43.89 14.32 1.1742 K2SO4 + KCl
and the relative standard uncertainty is 0.01 by this method. The 13 24.45 0.51 57.61 0.29 1.1711 KCl
chloride is measured by Volhard method,19,20 and the relative 14, E 24.72 0.00 ND ND 1.1682 KCl
standard uncertainty is 0.02. The density is measured by a specific a
Standard uncertainties u(T) = 0.3 K, ur(p) = 0.05, ur(w1) = 0.02,
weighing bottle method, and the relative standard uncertainty is ur(w2) = 0.01, ur(ρ) = 0.001. bw1, mass fraction of KCl; w2, mass
0.001. Each experimental result is achieved from the average fraction of K2SO4. cNot determined. dE, F, and N have the same
value of three parallel measurements. The equilibrium solid meaning as described in Figure 2.
phase is analyzed by XRD characterizations.

■ RESULTS AND DISCUSSION

In Figure 1, the experimental data is compared with litera-
ture data21,22 and it is found that the experimental values coincide
Figure 1. Solubility for KH2PO4, KCl, or K2SO4 in pure water at 288.15 K.
with the values from the references, which demonstrates that the
experimental devices and methods are feasible.
Solid−Liquid Phase Equilibrium for (KCl + K2SO4 +
H2O). The experimental data is listed in Table 2, and the phase
diagram is plotted in Figure 2.
As indicated in Figure 2, A, B, and W denote solid K2SO4, solid
KCl, and H2O, respectively; Point F, an invariant point, reflects
the cosaturated solution of K2SO4 and KCl at 288.15 K; N and E
represent the solubility of K2SO4 and KCl in water at 288.15 K,
respectively. The saturated liquid line EFN consists of two
branches. Branch EF corresponds to the saturated KCl solution
and visualizes changes of the KCl concentration with increasing
the K2SO4 concentration. Branch NF corresponds to the
saturated K2SO4solution and indicates changes of the K2SO4
B DOI: 10.1021/acs.jced.5b01111
concentration with the KCl concentration increasing in the
equilibrium solution. The K2SO4 concentration decreases
sharply with increasing the KCl concentration, which illustrates
that KCl has a strong salting-out effect on K2SO4.
As indicated in Figure 2, along the curve EF, we connect the
composition points of wet residue phase with liquid phase and
then extend, the intersection of these straight lines is
approximately the equilibrium solid phase for KCl. The same
method is utilized to analyze the equilibrium solid phase of NF,
and the intersection is K2SO4. As indicated in Figure 3, the
equilibrium solid phase of F is analyzed by XRD and verified to
be coexistence of K2SO4 and KCl. Consequently, the ternary
system is a simple eutectic type at 288.15 K.
Figure 2 shows that WEFN denotes unsaturated region at
288.15 K. AFN denotes crystallization region of K2SO4, while
BFE denotes crystallization region of KCl. Zone AFB represents
the mixed crystalline region of K2SO4 + KCl. It is obvious that
crystallization region of KCl is much smaller than that of K2SO4.
Figure 4 indicates the relationship between the mass fraction
of KCl and the density in the solution. With increasing the KCl
concentration, the density has the tendency to increase and then
the density declines slightly afterward. At the cosaturated point F,
the density reaches a maximum value.
Solid−Liquid Phase Equilibrium for (KH2PO4 + K2SO4 +
H2O). The phase equilibrium experimental data is shown in
Table 3, and the ternary phase diagram is drawn in Figure 5.
As indicated in Figure 5, A, C, and W denote solid K2SO4,
solid KH2PO4, and H2O, respectively; Point D, an invariant
point, reflects the cosaturated solution of K2SO4 and KH2PO4 at
288.15 K; N and M represent the solubility of K2SO4 and
KH2PO4 in water at 288.15 K, respectively. The saturated liquid
line MDN consists of two branches. Branch MD corresponds to
the saturated KH2PO4 solution and visualizes changes of the
KH2PO4 concentration with increasing the K2SO4 concen-
tration. Branch ND corresponds to the saturated K2SO4 solution
and indicates changes of the K2SO4 concentration with
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Figure 2. Equilibrium phase diagram of the ternary system KCl + K2SO4 + H2O at 288.15 K: ■, equilibrium liquid phase composition; ●, moist solid
phase composition; A, pure solid of K2SO4; B, pure solid of KCl; W, water; E, solubility of KCl in water; N, solubility of K2SO4 in water; F, cosaturated
point of KCl and K2SO4.
Figure 3. X-ray diffraction pattern of the invariant point F.
Figure 4. Density vs 100w (KCl) in the ternary system (KCl + K2SO4 +
H2O). N, F, and E have the same meaning as described in Figure 2.
increasing the KH2PO4 concentration. The solubility of K2SO4
decreases sharply with increasing the concentration KH2PO4,
which illustrates that KH2PO4 has a strong salting-out effect on
K2SO4. In the two ternary systems, the salting-out effect of KCl
on K2SO4 is stronger than that of KH2PO4 on K2SO4.
C DOI: 10.1021/acs.jced.5b01111
Article
As indicated in Figure 5, along the curve MD, we connect the
composition points of wet residue phase with liquid phase and
then extend, the intersection of these straight lines is
approximately the equilibrium solid phase for KH2PO4. The
same way is utilized to analyze the equilibrium solid phase of DN,
and the intersection is K2SO4. As indicated in Figure 6, the
equilibrium solid phase of D is analyzed by XRD and verified to
be coexistence of K2SO4 and KH2PO4. Consequently, the ternary
system is a simple eutectic type at the investigated temperature.
Figure 5 shows that WMDN denotes unsaturated region at
288.15 K. ADN denotes crystallization region of K2SO4, while
MDC denotes crystallization region of KH2PO4. Zone ADC
denotes the mixed crystalline region of K2SO4 + KH2PO4. It is
obvious that crystallization region of KH2PO4 is much smaller
than that of K2SO4. In the two systems, the crystalline region of
KCl is the smallest, while that of K2SO4 is the largest.
Figure 7 indicates the relationship between the mass fraction
of KH2PO4 and the density in the solution. With an increase of
the concentration of KH2PO4, the density has the tendency to
increase and then the density declines slightly afterward. At the
cosaturated point D, the density reaches a maximum value.
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Table 3. Mass Fraction Solubility of the Ternary KH2PO4 + K2SO4 + H2O System at Temperature = 288.15 K and Pressure =
0.1 MPaa
composition of wet residue phase,
composition of liquid phase, 100w 100w densities of liquid phase
no.d 100w1b 100w2 100w1 100w2 ρ/(g·cm−3) equilibrium solid phase
c c
1, N 9.12 0.00 1.0756 K2SO4
2 8.33 2.07 50.41 1.26 1.0843 K2SO4
3 7.62 4.39 45.83 2.70 1.0952 K2SO4
4 6.73 6.48 48.90 3.62 1.1049 K2SO4
5 6.08 8.51 51.03 4.55 1.1151 K2SO4
6 5.64 10.36 47.84 5.81 1.1255 K2SO4
7 5.30 12.14 45.33 7.08 1.1365 K2SO4
8, D 5.00 14.33 35.74 17.61 1.1502 KH2PO4 + K2SO4
9, D 5.00 14.33 16.11 51.14 1.1504 KH2PO4 + K2SO4
10 3.53 14.82 2.00 52.99 1.1425 KH2PO4
11 1.94 15.55 1.13 55.18 1.1332 KH2PO4
c c
12, M 0.00 16.53 1.1229 KH2PO4
a
Standard uncertainties u(T) = 0.3 K, ur(p) = 0.05, ur(w1) = 0.01, ur(w2) = 0.01, ur(ρ) = 0.001. bw1, mass fraction of K2SO4; w2, mass fraction of
KH2PO4. cNot determined. dN, D, and M have the same meaning as described in Figure 4.

Figure 5. Equilibrium phase diagram of the ternary system KH2PO4 + K2SO4 + H2O at 288.15 K: ■, equilibrium liquid phase composition; ●, moist
solid phase composition; A, pure solid of K2SO4; C, pure solid of KH2PO4; W, water; M, solubility of KH2PO4 in water; N, solubility of K2SO4 in water;
D, cosaturated point of KH2PO4 and K2SO4.

Figure 6. X-ray diffraction pattern of the invariant point D.

D DOI: 10.1021/acs.jced.5b01111
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Figure 7. Density vs 100w (KH2PO4) in the ternary system (KH2PO4 +
K2SO4 + H2O). N, D, and M have the same meaning as described in
Figure 4.
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■
CONCLUSIONS
The phase equilibrium of (KH2PO4 + K2SO4 + H2O) and (KCl +
K2SO4 + H2O) at 288.15 K is investigated. The solubility and
density of the ternary systems are obtained. The ternary phase
diagrams are plotted, the equilibrium solid phase is analyzed, and
the crystallization regions are determined. There are in all two
crystallization regions, one invariant point, and two univariant
curves in the ternary phase diagrams. In the two ternary systems,
KH2PO4 and KCl have a strong salting-out effect on K2SO4, and
the salting-out effect of KCl on K2SO4 is stronger than that of
KH2PO4 on K2SO4. The crystallization regions of K2SO4 in the
two systems are much larger than crystallization regions of
KH2PO4 and KCl. The crystallization region of K2SO4 is the
largest, whereas that of KCl is the smallest. All results can offer
fundamental data support for optimizing the processes and
further theoretical studies.
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AUTHOR INFORMATION (22) Deng, T. L.; Zhou, H.; Chen, X. The Phase Diagram of Salt−Water
System and its Application; Chemical Industry Press: Beijing, 2013.
Corresponding Author
*E-mail: zhoujun1121LG@163.com.
Notes
The authors declare no competing financial interest.

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E DOI: 10.1021/acs.jced.5b01111
J. Chem. Eng. Data XXXX, XXX, XXX−XXX