Article pubs.acs.org/jced
Phase Equilibria of the NaOH−NaBO2−Na2CO3−H2O System at 30 °C, 60 °C, and 100 °C Shiyue Qin,† Baowen Yin,†,‡ Yifei Zhang,*,† and Yi Zhang† †
National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China ‡ School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China ABSTRACT: Equilibrium data of the NaOH−NaBO2−Na2CO3−H2O quaternary system at 30 °C, 60 °C, and 100 °C were measured by an isothermal method. The phase diagrams at 30 °C and 100 °C were constructed, and the crystallization zones were discussed. In the phase diagram, the quaternary system has two invariant points, five univariant curves, and four crystallization zones corresponding to NaBO2·4H2O (NaBO2·2H2O at 100 °C), NaBO2·2H2O (NaBO2·1/3H2O at 100 °C), Na2CO3· H2O, and NaOH·H2O (NaOH at 100 °C). In addition, the solubility isotherms of NaBO2 in Na2CO3-saturated NaOH solution and the solubility isotherms of Na2CO3 in NaBO2-saturated NaOH solution were plotted. The solubility of Na2CO3 in NaOH solution was compared with that in NaBO2-saturated NaOH solution. On the basis of the solubility data, a strategy for the effective separation of NaBO2 and Na2CO3 from the NaOH−NaBO2−Na2CO3−H2O quaternary system was proposed.
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INTRODUCTION Boron is widely used in metallurgical and chemical industries due to its properties such as high hardness, wear resistance, fire retardant, heat resistance, and catalytic performance. China is rich in boron resources with boron reserves ranking next to Turkey, the U.S.A., and Russia, and szaibelyite ore is one of the most important source of boron in China.1 The traditional production process to extract boron from szaibelyite ore is the CO2−soda process, in which the ore is activated by roasting at 700 °C and then decomposed in soda solution with CO2 in autoclave.2,3 However, this process suffers from low boron extraction efficiency, its high energy consumption and environmental problems for the calcination of szaibelyite ore and limestone. Recently, we have investigated the synthesis of sodium metaborate by the direct leaching of szaibelyite ore in NaOH solution at 140 °C without calcination and the boron extraction rate was higher than the CO2-soda process. Sodium metaborate is a common raw material for chemical industries, used to produce, for example, sodium perborate tetrahydrate (NaBO2·H2O2·3H2O),4,5 sodium borohydride (NaBH4),6−8 and photographic and textile chemicals.9 As the szaibelyite ore is mainly consisted of szajbelyite (Mg2(OH)[B 2 O 4 (OH)]), magnesite (MgCO 3 ), and lizardite (Mg3Si2O5(OH)4), Na2CO3 is obtained as a byproduct besides NaBO2. The main reaction can be expressed as follows:
To separate NaBO2 and Na2CO3 from the NaOH solution effectively, it is necessary to study the phase diagram of the NaOH−NaBO2−Na2CO3−H2O quaternary system. There is some research on the phase equilibria with borate-bearing systems: Na+ + K+ + CO32− + B4O72− + H2O at 273.15 K,10 Na+, K+//Cl−, SO42−, B4O72−−H2O at 323 K,11 Li+, Na+//Cl−, B4O72−−H2O at 273 K,12 Na+, K+//Cl−, B4O72−−H2O at 323 K,13 Na+, K+//Br−, B4O72−−H2O at 298 K,14 Li + + K+ + Cl− + CO32− + B4O72− + H2O at 273.15 K,15 K2SO4−K2B4O7−H2O and Na2SO4−Na2B4O7−H2O at 348 K,16 KCl−KBr−K2B4O7− H2O at 323 K and 373 K,17,18 NaCl−NaBr−Na2B4O7−H2O at 348 K,19 KBr−K2SO4−K2B4O7−H2O and NaBr−Na2SO4− Na 2 B4O 7−H 2O at 298 K,20 Na 2B 4O 7−NaBr−H 2 O and Na 2B 4O 7−Na 2 SO 4−NaBr−H 2O at 323 K,21 Li2 B4O 7 + Na2B4O7 + K2B4O7 + Li2SO4 + Na2SO4 + K2SO4 + H2O at 273.15 K,22 NaBO2−H2O,23,24 and NaBO2 + NaOH + H2O within the range (263.15 to 323.15) K.25−27 The phase equilibria of the NaOH−NaBO2−Na2CO3−H2O quaternary system have not been reported, so an effective separation method with respect to NaBO2 and Na2CO3 from the quaternary system is yet to be established. In this work, the phase equilibria of the quaternary system at 30 °C, 60 °C, and 100 °C were studied for the separation of NaBO2 and Na2CO3.
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EXPERIMENTAL SECTION Apparatus and Reagents. An HZ-9612K-type thermostatic shaking incubator (Taicang Technology Equipment Factory) was used for the equilibrium measurements. The
Mg 2(OH)[B2O4 (OH)] + 2NaOH → 2NaBO2 + 2Mg(OH)2 ↓ MgCO3 + 2NaOH → Na 2CO3 + 2Mg(OH)2 ↓ © XXXX American Chemical Society
(1) Received: May 27, 2015 Accepted: September 23, 2015
(2) A
DOI: 10.1021/acs.jced.5b00443 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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chemicals used in the experiments, including NaOH (≥98.0%), NaBO2·4H2O (≥99.0%), and Na2CO3 (≥99.8%), were analytical grade and manufactured by the Xilong Chemical Co., Ltd. All chemical reagents were used without further purification. The sample description was provided in Table 1. Anhydrous sodium metaborate used was obtained by heat treatment of NaBO2·4H2O at 300 °C for 72 h in a tubular oven under nitrogen flow. Experimental Method. The solubility was determined by an isothermal method. A certain amount of sodium hydroxide, sodium metaborate, and sodium carbonate was mixed
Table 1. Chemical Samples chemical name
formula
sodium hydroxide
NaOH
sodium metaborate tetrahydrate sodium carbonate
NaBO2· 4H2O Na2CO3
a
source Xilong Chemical Co., Ltd. Xilong Chemical Co., Ltd. Xilong Chemical Co., Ltd.
initial mass fraction puritya 98.0 % 99.0 % 99.8 %
All chemical reagents were used without further purification.
Table 2. Solubility Data of the NaOH−NaBO2−Na2CO3−H2O System at p = 0.1 MPaa
a
composition of liquid phase
composition of liquid phase
100w(b)
g/100 g of dry salt
NaOH
NaBO2
Na2CO3
NaOH
NaBO2
0.00 3.91 7.70 11.33 15.20 19.85 21.89 23.93 27.20 34.88 38.65 39.54 51.26 19.54
12.53 11.54 10.59 9.62 8.91 8.30 8.09 7.63 5.94 4.49 3.25 5.85 0.00 10.00
19.59 16.17 12.85 9.52 6.61 3.25 2.28 1.69 1.51 1.66 1.45 0.00 3.10 0.00
0.00 12.37 24.74 37.11 49.48 63.21 67.85 71.98 78.50 85.02 89.17 87.12 94.30 66.15
39.00 36.50 34.00 31.50 29.01 26.45 25.07 22.94 17.14 10.94 7.49 12.88 0.00 33.85
0.00 5.37 10.19 14.26 22.56 25.76 32.72 37.29 43.68 44.92 45.98 37.99 59.21 37.53
29.87 24.43 20.32 17.08 12.37 10.17 9.30 9.20 7.75 7.05 4.52 9.50 0.00 10.27
12.03 8.68 6.03 4.62 1.66 1.41 1.21 1.14 1.13 1.03 1.04 0.00 2.60 0.00
0.00 13.95 27.89 39.66 61.65 68.98 75.69 78.29 83.11 84.75 89.22 79.99 95.79 78.51
71.29 63.50 55.60 47.50 33.81 27.24 21.51 19.32 14.74 13.31 8.76 20.01 0.00 21.49
0.00 5.93 10.91 13.42 16.99 20.75 25.34 28.87 32.73 45.52 72.30 49.85 12.91
50.56 41.99 38.61 34.03 30.43 26.83 18.94 15.87 12.03 9.19 0.00 3.42 39.10
4.34 2.36 1.63 1.55 1.52 1.47 1.41 1.31 1.28 1.14 1.53 0.00 0.00
0.00 11.80 21.33 27.38 34.71 42.31 55.46 62.70 71.09 81.51 97.93 93.58 24.82
92.10 83.50 75.48 69.45 62.18 54.69 41.45 34.46 26.13 16.45 0.00 6.42 75.18
Na2CO3 t = 30 °C 61.00 51.13 41.26 31.19 21.51 10.34 7.07 5.08 4.36 4.05 3.34 0.00 5.70 0.00 t = 60 °C 28.71 22.56 16.50 12.84 4.54 3.78 2.80 2.39 2.15 1.94 2.02 0.00 4.21 0.00 t = 100 °C 7.90 4.70 3.18 3.16 3.11 3.00 3.09 2.84 2.78 2.04 2.07 0.00 0.00
equilibrium solid phase
H2O 211.37 216.16 221.13 227.80 225.62 218.49 209.96 200.74 188.61 143.74 130.70 120.34 83.96 238.52
Na2CO3·H2O NaBO2·4H2O + Na2CO3·H2O NaBO2·4H2O + Na2CO3·H2O NaBO2·4H2O + Na2CO3·H2O NaBO2·4H2O + Na2CO3·H2O NaBO2·4H2O + NaBO2·2H2O + Na2CO3·H2O NaBO2·2H2O + Na2CO3·H2O NaBO2·2H2O + Na2CO3·H2O NaBO2·2H2O + Na2CO3·H2O NaBO2·2H2O + Na2CO3·H2O NaBO2·2H2O + Na2CO3·H2O + NaOH·H2O NaOH·H2O + NaBO2·2H2O NaOH·H2O + Na2CO3·H2O NaBO2·4H2O + NaBO2·2H2O
138.70 159.87 173.65 178.06 173.35 167.83 131.32 109.96 90.25 88.68 94.02 110.55 61.79 109.21
NaBO2·2H2O + Na2CO3·H2O NaBO2·2H2O + Na2CO3·H2O NaBO2·2H2O + Na2CO3·H2O NaBO2·2H2O + Na2CO3·H2O NaBO2·2H2O + Na2CO3·H2O NaBO2·2H2O + Na2CO3·H2O NaBO2·2H2O + Na2CO3·H2O NaBO2·2H2O + NaBO2·1/3H2O + Na2CO3·H2O NaBO2·1/3H2O + Na2CO3·H2O NaBO2·1/3H2O + Na2CO3·H2O NaBO2·1/3H2O + Na2CO3·H2O + NaOH·H2O NaOH·H2O + NaBO2·1/3H2O NaOH·H2O + Na2CO3·H2O NaBO2·2H2O + NaBO2·1/3H2O
82.15 98.85 95.51 104.12 104.37 103.87 118.86 117.17 117.23 79.06 35.45 87.73 92.27
NaBO2·2H2O + Na2CO3·H2O NaBO2·2H2O + Na2CO3·H2O NaBO2·2H2O + Na2CO3·H2O NaBO2·2H2O + NaBO2·1/3H2O + Na2CO3·H2O NaBO2·1/3H2O + Na2CO3·H2O NaBO2·1/3H2O + Na2CO3·H2O NaBO2·1/3H2O + Na2CO3·H2O NaBO2·1/3H2O + Na2CO3·H2O NaBO2·1/3H2O + Na2CO3·H2O NaBO2·1/3H2O + Na2CO3·H2O + NaOH NaOH + Na2CO3·H2O NaOH + NaBO2·1/3H2O NaBO2·2H2O + NaBO2·1/3H2O
Note: w(b) is the mass fraction of b. Standard uncertainties u are u(t) = 0.1 °C, u(p) = 0.4 kPa, and u(w) = 0.01. B
DOI: 10.1021/acs.jced.5b00443 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Figure 1. Dry-salt phase diagram for the NaOH−NaBO2−Na2CO3−H2O quaternary system at 30 °C (a) and 100 °C (b). Points P1 and P2 are the invariant points, points F1, F2, F3, and F4 represent the equilibrium compositions of the solid phases at the two extremes of the corresponding sides, and areas A, B, C, and D are the crystallization zones.
Figure 2. X-ray diffraction patterns of the equilibrium solids at the invariant point. (a−b) P1 and P2 at 30 °C, (c−d) P1 and P2 at 100 °C, respectively.
analyzed by acid−base titration with HCl (0.1 mol L−1) using phenolphthalein solution as the indicator with the relative standard deviation less than 0.5 %. The CO32− concentration was determined by the charge balance of the solution with the relative standard deviation less than 1.0 %.
homogeneously in a given amount of water and then added into sealed polyethylene bottles. The bottles were placed in the thermostatic vibrator, with a temperature standard uncertainty of ± 0.1 °C. The experiments were performed at ambient pressure, and the temperature was fixed at three specific values: 30, 60, and 100 °C. Experimental results demonstrated that the equilibrium states could be established in 2 days. The sealed bottles needed stay still for 1 day. After the liquid was clarified, the solution and wet crystals could be taken out for physicochemical analysis. The composition of the solution was analyzed quantitatively, and the solid phase was analyzed by X-ray diffraction (XRD, Siemens D500 X-ray diffractometer). Analytical Methods. The Na+ and BO2− in solution were measured by an Optima 5300DV ICP-AES with the relative standard deviation (RSD) less than 0.06 %. The OH− was
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RESULTS AND DISCUSSION
Phase Equilibria of the NaOH−NaBO2−Na2CO3−H2O Quaternary System. The solubility data of the NaOH− NaBO2−Na2CO3−H2O quaternary system at 30 °C, 60 °C, and 100 °C were measured and presented in Table 2. The data are the average values of three measurements, with the relative standard deviation values of less than 2%. The dry-salt phase diagram was plotted in Figure 1. The phase diagram at 60 °C is similar to that at 100 °C and, therefore, is not shown in this paper. C
DOI: 10.1021/acs.jced.5b00443 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Figure 3. Solubility isotherms of NaBO2 in Na2CO3-saturated NaOH solution.
Figure 5. Solubility of Na2CO3 at 100 °C in NaOH solution and NaBO2-saturated NaOH solution.
Figure 4. Solubility isotherms of Na2CO3 in NaBO2-saturated NaOH solution.
Figure 6. Na2CO3 and NaBO2 crystallization process depicted in the phase diagram.
Table 3. Comparison of Solubility of Na2CO3 in NaOH Solution with That in NaBO2-Saturated NaOH Solution at 100 °C solubility in NaOH solution without NaBO2
solubility in NaOH solution saturated with NaBO2
wt %
wt %
NaOH
Na2CO3
NaOH
Na2CO3
NaBO2
0.00 4.60 10.50 13.80 17.10 19.00 24.20 27.00 29.70 35.00 43.75 52.04 71.66
30.80 23.80 16.60 12.80 9.40 7.60 4.80 3.60 2.70 1.50 1.45 1.14 1.51
0.00 5.93 10.91 13.22 16.99 20.75 25.34 28.87 32.73 45.52 71.66
4.34 2.36 1.63 1.20 1.22 1.23 1.41 1.31 1.28 1.14 1.51
50.56 41.99 38.61 34.03 30.43 26.83 18.94 15.87 12.03 9.19 0.00
larger than the other three, and the NaOH crystallization zone is the smallest. The NaBO2 crystallization zones at 100 °C are much smaller than those at 30 °C, but the Na2CO3·H2O crystallization zone at 100 °C is far larger than that at 30 °C. Figure 2 is the X-ray diffraction patterns of the equilibrium solids at the invariant points in the quaternary system. Solubility Isotherms of NaBO2 from 30 °C to 100 °C. To study the impact of the temperature on the solubility of NaBO2, the solubility isotherms of NaBO2 in Na2CO3-saturated NaOH solution from 30 °C to 100 °C was shown in Figure 3. The solubility of NaBO2 decreases strongly with a decrease of temperature. For example, the concentration of NaBO2 in Na2CO3-saturated NaOH solution is 26.82 wt % at 100 °C when the NaOH concentration is 20.00 wt %, whereas that at 30 °C is only 8.30 wt %. So, the solubility of NaBO2 is sensitive to temperature and it can be separated from the NaOH− NaBO2−Na2CO3−H2O system by cooling crystallization. Solubility Isotherms of Na2CO3 from 30 °C to 100 °C. As shown in Figure 4, when NaBO2 is saturated the solubility isotherms of Na2CO3 decline sharply with the increase of the NaOH concentration initially and change negligibly thereafter. For example, when the NaOH concentration increases from 0.00 wt % to 23.93 wt % at 30 °C, the Na2CO3 concentration decreases from 19.59 wt % to 1.69 wt %; then, the Na2CO3 solubility shows no obvious decrease. That is, the salting-out effect of NaOH on Na2CO3 is obvious. On the other hand, the solubility of Na2CO3 decreases significantly with the increase of
Figures 1a−b show that the NaOH−NaBO2−Na2CO3−H2O quaternary system has two invariant points, five univariant curves, and four crystallization zones, which are NaBO2·4H2O (NaBO2·2H2O at 100 °C), NaBO2·2H2O (NaBO2·1/3H2O at 100 °C), Na2CO3·H2O, and NaOH·H2O (NaOH at 100 °C). Among the four zones, the Na2CO3·H2O crystallization zone is D
DOI: 10.1021/acs.jced.5b00443 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Figure 7. X-ray diffraction patterns of the products obtained: (a) Na2CO3·H2O and (b) NaBO2·2H2O.
cooling crystallization. This study provides a theoretical basis for the separation of NaBO2 and Na2CO3 from NaOH solution.
temperature when the concentration of NaOH is below 25 wt %, which is due to the increase of the NaBO2 solubility with the increase of temperature, as shown in Figure 3. Comparison of the Solubility of Na2CO3 in NaOH Solution with That in NaBO2-Saturated NaOH Solution. To evaluate the salting-out effect of NaBO2 on Na2CO3 in NaOH solution, the equilibrium data of Na2CO3 in NaOH solution28 and in NaBO2-saturated NaOH solution at 100 °C are compared and presented in Table 3. The isotherms plotted in Figure 5 show that the solubility of Na2CO3 in NaBO2saturated NaOH solution decreases significantly as compared with NaOH solution without NaBO2. For example, Na2CO3 solubility decreases from 16.60 to 1.63 wt % when the NaOH concentration is around 10.50 wt %. The existence of NaBO2 shows a significant salting-out effect on Na2CO3 especially in the low alkali region. There are similar results at other temperatures. Therefore, it can be concluded that Na2CO3 could be separated from the quaternary solution by evaporative crystallization. Separation of NaBO 2 and Na 2 CO 3 from NaOH solution. The graphical description of the separation process is shown in Figure 6. Point A represents the original solution with the concentration of NaOH 11 wt %, NaBO2 8 wt %, and Na2CO3 6 wt %. With the continuous evaporation of the NaOH solution at 100 °C, the concentration of NaBO2 and Na2CO3 increases and Na2CO3·H2O begins to salt out along the line A−B. Then, the cooling crystallization of NaBO2·2H2O at 30 °C will be operated and NaBO2·2H2O starts to crystallize along the line B−C. The obtained Na2CO3·H2O and NaBO2· 2H2O crystals are analyzed by XRD as shown in Figure 7a−b. Therefore, Na2CO3·H2O and NaBO2·2H2O could be separated from the quaternary system by evaporative crystallization and cooling crystallization, respectively.
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AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. Tel./Fax: +86 10 82544826. Funding
We acknowledge the financial support from the National 863 Project of China (Grant No. 2011AA060701) and the National Natural Science Foundation of China (Grant No. 21276258). Notes
The authors declare no competing financial interest.
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REFERENCES
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CONCLUSIONS Phase equilibria of the NaOH−NaBO 2 −Na 2 CO 3 −H 2O quaternary system from 30 °C to 100 °C were studied. The phase diagrams of the system and the solubility isotherms of NaBO2 and Na2CO3 were plotted. The results show that the solubility isotherms of Na2CO3 decline sharply with an increase of the concentration of NaOH and NaBO2, and evaporative crystallization is an efficient way to separate Na2CO3 from the solution. The solubility of NaBO2 decreases strongly with a decrease of temperature, and NaBO2 can be separated by E
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