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The physicochemical data of extraction with the mixed solvent of NOA and MIBK from hydrochloric acid route phosphoric acid
Accepted Manuscript The physicochemical data of extraction with the mixed solvent of NOA and MIBK from hydrochloric acid route phosphoric acid Weiqing Li, Ruicao Peng, Peng Ye, Xianhe lv, Tianrong Zhu, Zhanfang Cao, Yuan-Hang Qin, Jiayu Ma, Tielin Wang, Cunwen Wang, Zaikun Wu PII: DOI: Reference:
S0021-9614(18)31146-7 https://doi.org/10.1016/j.jct.2018.11.012 YJCHT 5613
To appear in:
J. Chem. Thermodynamics
Received Date: Revised Date: Accepted Date:
3 September 2018 31 October 2018 14 November 2018
Please cite this article as: W. Li, R. Peng, P. Ye, X. lv, T. Zhu, Z. Cao, Y-H. Qin, J. Ma, T. Wang, C. Wang, Z. Wu, The physicochemical data of extraction with the mixed solvent of NOA and MIBK from hydrochloric acid route phosphoric acid, J. Chem. Thermodynamics (2018), doi: https://doi.org/10.1016/j.jct.2018.11.012
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The physicochemical data of extraction with the mixed solvent of NOA and MIBK from hydrochloric acid route phosphoric acid Weiqing Lia,#, Ruicao Peng b,#, Peng Yea, Xianhe lva, Tianrong Zhu c, Zhanfang Caod, Yuan-Hang Qina, Jiayu Maa, Tielin Wanga, Cunwen Wanga, Zaikun Wua,* a
Key Laboratory of Green Chemical Process of Ministry of Education, Key Laboratory of Novel
Reactor and Green Chemical Technology of Hubei Province, School of Chemical Engineering & Pharmacy, Wuhan Institute of Technology, Wuhan 430205, P. R. China b
College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, P.R. China
c
Key Laboratory of Optoelectronic Chemical Materials and Devices
of
Wuhan
(Jianghan University), Ministry of Education, Jianghan University, Wuhan 430072, P. R. China d
Hunan Provincial Key Laboratory of Efficient and Clean Utilization of Manganese Resources,
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, P. R. China
ABSTRACT: In this study, the mixed solvent of octanol (NOA) and methyl isobutyl ketone (MIBK) was used as extractant to purify wet process phosphoric acid from hydrochloric acid route. Densities and viscosities of leachate, extraction phase and raffinate phase were determined at 293-333K, respectively. And the relation between density and temperature or phosphoric acid concentration can be expressed as a linear equation, with the maximum deviation of 0.0011 and 0.0027 g.cm-3, respectively. Meanwhile, the viscosity of leachate, extraction phase and raffinate phase were measured since its importance on mass transfer occurred in the process of phosphoric acid extraction. And the relation between viscosity and temperature or phosphoric acid concentration can be summarized as a unitary quadratic equation, with the maximum deviation of 0.4489 and 0.1122 mPa·s, respectively. The results show that the densities and viscosities from experiment are generally in good agreement with 1
calculated values from those equations obtained by regression analysis. The combined expanded uncertainty in the reported densities and viscosities are 0.3% and 5.5% of the measured values respectively, each with a coverage factor, k = 2. Keywords: Physicochemical data, Hydrochloric acid, Extraction, Wet process phosphoric acid
1. INTRODUCTION Commercial phosphoric acid is an important basic material and is widely used in various industrial branches, such as additive to food or medicine, fertilizers, catalysts for producing phenolic resin, detergents, coatings and integrated circuit, et al [1-4]. At present, phosphoric acid is mainly prepared by high grade phosphate rock in chemical industry. However, high-grade phosphate rock is gradually being exhausted with the development of phosphorus chemical industry in China. Therefore, it is inevitable trend that the mid-low grade phosphate rock was exploited more widely for producing phosphoric acid [5-9]. As usual, thermal process, kiln process and wet process are well established to manufacture phosphoric acid in chemical industry [10-13]. Among these production technologies, thermal process is used for long time because of high product quality, kiln process is limited to use because of high energy consumption [1,2,10]. In recent years, wet process phosphoric acid (WPA) is developing quickly, in that the energy consumption and production cost of wet process are lower than thermal process. According to the raw material of the production, wet process can be divided into hydrochloric acid, sulfuric acid and nitric acid method. H2SO4-route is the most widely used in WPA production. However, it has some drawbacks, such as the high requirement for phosphate rock grade, heavily dependence upon sulfur resources and high energy consumption, et al [1,14]. Moreover, lots of phosphogypsum is produced and the waste residue is difficult to utilize, which cause environmental pollution and partial phosphorus loss [1,15]. Hydrochloric acid can be used to prepare wet process phosphoric acid by dissolving phosphate rock. Compare to H2SO4 technology, the HCl-route was known 2
as a novel technology in the preparation of WPA because of no phosphogypsum, low requirement for the phosphorus rock grade, less waste, low production cost and high dissolution fraction of phosphorus, et al. [16-18]. However, there is no industrial device for preparing wet-process phosphoric acid by HCl-route, and related reports are rare. Therefore, this process has aroused many researchers’ great interest in the case of increasingly environmental requirements and the gradual depletion of high-grade phosphorus resources. However, there are lots of impurities in HCl-route WPA, especially when using medium and low grade phosphate rock. So it is important to choose a suitable method to purify phosphoric acid. At present, solvent extraction was regarded as efficient method of purifying wet process phosphoric acid in H2SO4 technology. And aliphatic alcohols, tributyl phosphate (TBP) and ketone have been reported as the extraction agent of phosphoric acid in the wet process of phosphoric acid [1,3,19-22]. Therefore, it is a trend to study the application of solvent extraction on the HCl-route wet process phosphoric acid. This leads to the need for a lot of data to be determined. So it is important to study the physicochemical data of wet process phosphoric acid owing to their impact on solvent extraction. At present, relative research was only focus on the field of H2SO4-route. Zheng et al.[23] measured the viscosities and densities of tributyl phosphate (TBP) + kerosene + phosphoric acid at 20-60 K. Huang et al.[21] determined the viscosity of mixed solvent composed by phosphoric acid + TBP + methyl isobutyl ketone (MIBK) and its performance on extracting phosphoric acid. Guendouzi et al.[24] studied the thermodynamic properties of fluoride in WPA and described the activity and osmotic coefficients of binary solution. And the study on the basic data of HCl-route has not reported yet. In this paper, wet process phosphoric acid was prepared with low grade phosphate rock and hydrochloric acid, then the densities and viscosities of leachate, raffinate phase and extraction phase were determined at different condition. Based on the data of experiment, the relation of density, viscosity, temperature and phosphoric acid concentration were established, respectively. These basis data are necessary for 3
studying the solvent extraction of HCl-route and will also be helpful for guiding the design of equipment and pipe in chemical industry.
2. EXPERIMENTAL SECTION 2.1. Chemicals. The rock particles were crushed and sieved with a 180 mesh sieve to collect some size fractions for further analysis after drying at 80°C. The chemical analysis of experimental samples taken from Hubei dayukou chemical co., LTD in China was presented in Table 1. The specifications and sources of the chemicals used in this work are summarized in Table 2. Table 1 The chemical analysis of phosphate rock Componentsa
P2O5
SiO2
CaO
MgO
Fe2O3
Al2O3
Mass percent (%)
22.93
9.83
40.41
4.50
2.93
1.83
a
Major elemental content in phosphate rock was stated in the form of their oxides
Table 2 Specifications and sources of chemicals used in this work
Chemical name
CAS registry number
Mass fraction puritya
Purification method
Methyl isobutyl ketone
108-10-1
>0.98
No further purification
Octanol
111-87-5
>0.98
No further purification
Hydrochloric acid
7647-01-0
36.0～38.0%
No further purification
Water
7732-18-5
>18MΩ.cm
HHitech laboratory water purification system
a
Source Sinopharm Chemical Reagent Co., Ltd., China Sinopharm Chemical Reagent Co., Ltd., China Sinopharm Chemical Reagent Co., Ltd., China
The purity was stated by the supplier
2.2 Experimental procedure Hydrochloric acid with a mass percentage of 15%, 20%, 25%, 30% was prepared for obtaining different concentration of raw phosphoric acid (RPA), respectively. After the optimization experiment of process condition, phosphate rock was reacted with 4
hydrochloric acid in a three-necked flask at 50°C for 0.5 h in order to leachate completely leaching phosphorus from phosphoric rock. The raw phosphoric acid (wet process phosphoric acid) was obtained by filtering insoluble matter. After the extraction process was optimized, the extraction experiment of this work was carried out at optimal condition. So RPA was extracted for equilibrated 15 minutes by the mixture solvent of MIBK and NOA (the volume ratio of MIBK and NOA is 1:1.) at organic/aqueous phase ratio of 1:1 in a reciprocating thermostatic oscillator. And phase separation was carried out with a separating funnel. In addition, the concentrations of all ions in leachate, raffinate phase and extraction phase were determined by Ion Chromatography System (DIONEX ICS-1100, USA), respectively. Referred to the methods in previous literatures [25, 26], Density (ρ) and viscosity of the solution were measured by pycnometer and Ubbelohde viscometer method at 293-333 K, respectively. In order to obtain densities precisely, the volume of the pycnometer was calibrated with pure water before experiment. All samples were measured repeatedly for three times at constant temperature. The viscosity (μ) was measured by Ubbelohde viscometer in a thermostat water bath in which temperature fluctuation was controlled in ±0.3°C.
3. RESULTS AND DISCUSSION The leachates were prepared by phosphate rock (cellophane) and different concentration (mass percentage: 15%, 20%, 25%, 30%) hydrochloric acid solution, respectively. And the main ions of initial solution, raffinate phase and extraction phase were also measured, as listed in Table 3. Based on the corresponding data, phosphoric acid concentrations in the leachate were measured to be 69.94, 92.27, 109.60 and 123.91 mg.ml-1, respectively. Depend on pycnometer and Ubbelohde viscometer method, the densities and viscosities of leachate, raffinate and extract liquor were determined at 293-333 K, respectively, as shown in Table 4. According to Eq. (1), the standard deviation (s) of densities and viscosities was calculated by different values of three replicate measurements, as shown behind positive and negative sign in Table 4. 5
xi i n
s
x
1
(1)
n 1
Where x i and x are the value of each measurement and the mean of the n measurements, respectively. Table 3 Ions concentration (Ci) of initial solution and raffinate phase in the leachate obtained from different hydrochloric acid solution of different mass fractions (ωHCl)
ωHCl
Ci (mg.ml-1) PO43-
15% 20% 25% 30%
67.798 89.443 106.247 120.115
15% 20% 25% 30%
57.758 80.905 85.989 90.863
15% 20% 25% 30%
10.040 8.538 20.258 29.252
Cl-
F-
initial 156.062 4.246 208.032 4.700 225.302 5.380 255.970 6.535 raffinate phase 141.421 4.047 180.523 4.331 195.428 4.826 217.186 5.465 extraction phase 14.641 0.199 27.509 0.369 29.874 0.554 38.784 1.070
Mg2+ 6.815 9.330 10.855 11.575
65.195 86.855 99.115 105.445
6.609 8.353 9.297 9.723
59.747 72.010 83.275 90.621
0.206 0.977 1.558 1.852
5.448 14.845 15.840 14.824
The determination of ions concentration was conducted at a pressure of 101.10 kPa. Standard uncertainties u are u(ωHCl) = 0.005, u(P)=1.0kPa, u(Ci) = 0.020mg.ml-1.
6
Ca2+
Table 4 Densities (ρ) and Viscosities (μ) of leachate, raffinate phase and extraction phase for hydrochloric acid route phosphoric acid systema leachate
raffinate phase
extraction phase
T
ρi
μi
ρr
μr
ρo
μo
K
g·cm-3
mPa·s
g·cm-3
mPa·s
g·cm-3
mPa·s
15% (wt) hydrochloric acid 293
1.2056±0.0004
2.2542±0.0159
1.2046±0.0007
2.4234±0.0111
0.8255±0.0001
1.9497±0.0110
303
1.2008±0.0008
1.7615±0.0083
1.2007±0.0009
1.8763±0.0050
0.8182±0.0004
1.5062±0.0053
313
1.1956±0.0003
1.4182±0.0081
1.1947±0.0005
1.4787±0.0089
0.8096±0.0005
1.1899±0.0029
323
1.1917±0.0005
1.1513±0.0108
1.1905±0.0007
1.2158±0.0056
0.8021±0.0011
0.9570±0.0013
333
1.1856±0.0005
0.9741±0.0084
1.1840±0.0007
1.0017±0.0023
0.7941±0.0011
0.7771±0.0034
293
1.2653±0.0003
3.1645±0.0012
1.2594±0.0006
3.2619±0.0068
0.8361±0.0005
2.4328±0.0025
303
1.2610±0.0006
2.4290±0.0048
1.2553±0.0003
2.5098±0.0113
0.8297±0.0002
1.8414±0.0035
313
1.2548±0.0002
1.9330±0.0203
1.2500±0.0001
1.9771±0.0082
0.8210±0.0004
1.4315±0.0015
323
1.2501±0.0005
1.5472±0.0142
1.2446±0.0003
1.6021±0.0024
0.8143±0.0006
1.1360±0.0057
333
1.2444±0.0004
1.3049±0.0058
1.2393±0.0004
1.3067±0.0039
0.8048±0.0006
0.9179±0.0051
20% (wt) hydrochloric acid
25% (wt) hydrochloric acid 293
1.3165±0.0006
4.4589±0.0232
1.3075±0.0007
4.3127±0.0309
0.8530±0.0002
3.2639±0.0034
303
1.3114±0.0004
3.3664±0.0074
1.3034±0.0003
3.2770±0.0079
0.8459±0.0002
2.4113±0.0098
313
1.3049±0.0004
2.6114±0.0074
1.2963±0.0001
2.5342±0.0144
0.8381±0.0003
1.8462±0.0104
323
1.2999±0.0005
2.0852±0.0040
1.2916±0.0003
2.0223±0.0153
0.8304±0.0003
1.4530±0.0006
333
1.2932±0.0005
1.6974±0.0171
1.2847±0.0001
1.6395±0.0025
0.8216±0.0008
1.1580±0.0020
30% (wt) hydrochloric acid 293
1.3621±0.0008
6.2839±0.0188
1.3456±0.0002
5.8485±0.0160
0.8668±0.0006
4.1184±0.0028
303
1.3556±0.0003
4.6557±0.0202
1.3401±0.0005
4.4231±0.0119
0.8593±0.0011
3.0246±0.0240
313
1.3480±0.0001
3.5429±0.0124
1.3338±0.0003
3.3980±0.0088
0.8519±0.0004
2.2506±0.0102
323
1.3430±0.0004
2.7870±0.0191
1.3285±0.0004
2.6931±0.0150
0.8450±0.0002
1.7292±0.0062
333
1.3368±0.0011
2.2711±0.0179
1.3213±0.0002
2.1592±0.0003
0.8363±0.0001
1.3627±0.0092
a
The extraction experiment and the determination of physicochemical data were conducted at a pressure of 101.10 kPa . Standard uncertainties u are u(T) = 0.10 K and u(P) = 1.0 kPa (0.68 level of confidence). The combined expanded uncertainties Uc are Uc(ρ) = 0.003·ρ·g·cm-3, and Uc(μ) = 0.055·μ·mPa·s, each with a coverage factor, k = 2.
3.1 Density In Table 4, as hydrochloric acid concentration is constant, it is obvious that the densities of all tested solution decrease with the increasing of temperature, and the densites of extraction phase and raffinate phase reduce faster than the densites of leachate. After adopting linear regression analysis, it is found that there is a linear 7
relation between density and temperature, as expressed by Eq. (2), and the related coefficients are shown in Table 5.
=a bT
(2)
Where ρ represents the density, T is temperature, a and b are coefficients of linear equation. The average absolute deviation (AAD) was calculated as Eq. (3). Where X i ,cal and X i,exp represent the calculated and experimental values, respectively, for individual point i and n represent the number of data points. By comparing the X i ,cal values from the models of different coefficients and the X i,exp values from experiment, the maximum deviation of this model including the densities of leachate, raffinate phase and extraction phase can be calculated as 0.0011g·cm-3. It proved that the result of models is in good agreement with the experimental measurements. n
AAD
i 1
X i ,cal X i ,exp n
(3)
Table 5 The Coefficients a, b in Eq. (2) a CP b (mg.ml-1)
a
b*10
69.94 92.27 109.60 123.91
1.3495 1.4201 1.4870 1.5469
-4.91 -5.27 -5.81 -6.32
leachate 4
raffinate phase 4
AAD
a
b*10
0.0003 0.0003 0.0003 0.0003
1.3560 1.4090 1.4764 1.5223
-5.14 -5.09 -5.74 -6.02
extraction phase
AAD
a
b*104
AAD
0.0006 0.0003 0.0006 0.0004
1.0569 1.0653 1.0829 1.0876
-7.89 -7.80 -7.83 -7.53
0.0002 0.0007 0.0004 0.0003
a
Standard uncertainty u is u(Cp) = 0.02 mg.ml-1 , u(P)=1.0kPa
b
CP, phosphoric acid concentration
Meanwhile, it can be seen that the densities of all tested solution increase with the increasing of hydrochloric acid concentration at a constant temperature. This result can be explained that more components will be extracted into extractant with the increasing of phosphoric acid in leachate. So it can be concluded that the extraction performance will be improved by increasing phosphoric acid concentration. By plotting the curve of density and phosphoric acid concentration, it is clear that 8
there is a linear relation, and the relation of the density and phosphoric acid concentration can be described by the following equation.
=mCP n
(4)
Where CP is phosphoric acid concentration. m, n are the coefficients of Eq. (4), and are listed in Table 6. The results show that the slope of density changing with temperature is almost the same. Depended on Eq. (3), the average absolute deviation of Eq. (4) was calculated, the values of AAD were also listed in Table 6. The maximum deviation of this model (including three kinds of solution in Table 6) is 0.0027g·cm-3. It concluded that Eq. (4) can better reflect the law of experimental data. Table 6 The Coefficients m, n in Eq. (4) a Tb
leachate
raffinate phase
extraction phase
(K）
m*103
n
AAD
m*103
n
AAD
m*103
n
293 303 313 323 333
2.90 2.87 2.83 2.81 2.80
1.0004 0.9982 0.9959 0.9933 0.9878
0.0023 0.0018 0.0016 0.0018 0.0018
2.62 2.60 2.58 2.57 2.55
1.0198 1.0179 1.0132 1.0098 1.0052
0.0014 0.0010 0.0009 0.0009 0.0004
0.7731 0.7677 0.7918 0.7965 0.7866
0.7689 0.7623 0.7518 0.7442 0.7364
a b
AAD 0.0024 0.0020 0.0022 0.0022 0.0026
Standard uncertainty u is u(T) = 0.10 K, u(P)=1.0kPa T, Kelvin temperature
3.2 Viscosity The viscosities of leachate, raffinate phase and extraction phase were determined at different temperatures, as shown in Fig.1-3. It shows that viscosity reduces with the increasing of temperature. Based on polynomial fitting, the relationship between viscosity and temperature can be described by the following equation.
pT 2 qT r
(5)
Where μ represents the viscosity of solution. p, q and r are coefficients of Eq. (5), their values are listed in Table 7. And the average absolute deviation of Eq. (5) for different phosphoric acid was analyzed and the result was also listed in Table 7. After referring to the above related method, the maximum deviation of this model is 0.4489 mPa·s. There has some error in that a small amount of water was evaporated from 9
tested solution. But those models are still able to correctly express the relation to viscosity and temperature. Table 7 The Coefficients q, p, r in Eq. (5) a CP b
leachate -1
(mg.ml )
p*10
4
q
r
raffinate phase AAD
p*10
4
q
extraction phase
r
AAD
p*10
4
q
r
AAD
69.94
5.0529
-0.3480
60.8365
0.0078
5.7193
-0.3931
68.4833
0.0128
4.3614
-0.3020
52.9767
0.0122
92.27
7.8329
-0.5364
93.0579
0.0213
7.6507
-0.5271
92.0124
0.0180
6.1500
-0.4223
73.3710
0.0917
109.60
11.7000
-0.8006
138.5447
0.0344
11.0000
-0.7531
130.7340
0.2425
-0.6272
108.0935
0.0233
123.91
18.4000
-1.2532
215.1563
0.03725
15.0000
-1.0315
179.0913
0.2191
143.0247
0.0656
a
Standard uncertainty u is u(Cp) = 0.02 mg.ml-1, u(P)=1.0kPa
b
CP, phosphoric acid concentration
9.1936 12.2000
-0.8314
Fig. 1. The relation between viscosity of leachate and temperature at different phosphoric acid concentration: (■) CP=69.94 mg.ml-1; (●) CP=92.27 mg.ml-1; (▲) CP=109.60 mg.ml-1; (▼) CP=123.91 mg.ml-1
10
Fig. 2. The relationship between viscosity of raffinate phase and temperature at different phosphoric acid concentration: (■) CP=69.94 mg.ml-1; (●) CP=92.27 mg.ml-1; (▲) CP=109.60 mg.ml-1; (▼) CP=123.91 mg.ml-1
Fig.3. The relationship between viscosity of extraction phase and temperature at different phosphoric acid concentration: (■) CP=69.94 mg.ml-1; (●) CP=92.27 mg.ml-1; (▲) CP=109.60 mg.ml-1; (▼) CP=123.91 mg.ml-1
In general, the viscosity of solution is related to the concentration of components in solution. Therefore, in order to investigate the relation of viscosity and phosphoric acid concentration, the viscosity of leachate, raffinate phase and extraction phase were tested with mass concentration 69.94-123.91mg.ml-1 phosphoric acid at 293-333K, respectively. Plotted the curve of
vs C in Fig. 4-6, the results showed that
viscosity increased with the increasing of phosphoric acid concentration. And the viscosities of all determined solution can be described as Eq. (6) by polynomial fitting. Where Cp represents the concentration of phosphoric acid in wet process phosphoric acid. And the coefficients a, b, d and average absolute deviation of this eqation are listed in Table 8. Through error analysis, it can be see that the maximum deviation of Eq. (6) is 0.1122 mPa·s. Therefore, based on the concentration of phosphoric acid in 11
the solution, the regression models can get data that is almost identical to the experimental values. 2
aC p bC p d
(6)
Table 8 Coefficients a, b, d in Eq. (6) a Tb
leachate
raffinate phase
extraction phase
(K）
a*104
b
d
AAD
a*104
b
d
AAD
a*104
293
11.6000
-0.1506
7.1428
0.0480
9.1336
-0.1146
5.9878
0.0532
5.5539
-0.0672
3.9238
0.0169
303
8.0557
-0.1032
5.0464
0.0321
6.7203
-0.0839
4.4715
0.0435
4.0045
-0.0493
2.9956
0.0085
313
5.5938
-0.0695
3.5531
0.0244
4.8656
-0.0595
3.2712
0.0385
2.5874
-0.0303
2.0387
0.0114
323
4.2216
-0.0518
2.7130
0.0140
3.7540
-0.0460
2.6076
0.0321
1.7486
-0.0193
1.4494
0.0138
333
3.2869
-0.0401
2.1765
0.0212
2.8852
-0.0349
2.0413
0.0236
1.2505
-0.0132
1.0847
0.0104
a b
b
Standard uncertainty u is u(T) = 0.10 K, u(P)=1.0kPa T, Kelvin temperature
Fig.4 The curve of the viscosity vs phosphoric acid concentration at different temperatures for leachate: (□)333K; (○)323K; ( )313K; ( )303K; ( )293K 12
d
AAD
Fig.5 The curve of the viscosity vs phosphoric acid concentration at different temperatures for raffinate phase: (□)333K; (○)323K; ( )313K; ( )303K; ( )293K
Fig.6 The curve of the viscosity vs phosphoric acid concentration at different temperatures for extraction phase: (□)333K; (○)323K; ( )313K; ( )303K; ( )293K
13
4. Conclusions In this work, physicochemical data has been obtained for the leachate, raffinate phase and extraction phase of hydrochloric acid route phosphoric acid system. The densities of all determined solution reduce with the increasing of temperature but increase with increasing of phosphoric acid concentration. And it can be expressed as a linear equation of temperature or phosphoric acid concentration. Meanwhile, the viscosities of all determined solution have a quadratic function relationship with temperature or phosphoric acid concentration, respectively. And the values of viscosities reduce as temperature increases but increases with the increasing of phosphoric acid concentration. Those equations from data regression analysis can correctly reflect the relationship between physicochemical data (density and viscosity) and temperature, phosphoric acid concentration. It will be helpful for the further study of the hydrochloric acid route phosphoric acid. Notes The authors declare no competing financial interest. Corresponding Author: [email protected] (Zaikun Wu) First Author: Weiqing Li, Ruicao Peng
Acknowledgments The authors are grateful for the financial support from the Scientific Research Plan Guidance Project of Hubei Education Department in China (B2017054), Open Fund from Key Laboratory of Green Chemical Process of Ministry of Education in Wuhan Institute of Technology (201714), the Scientific Research Fund of Wuhan Institute of Technology (k201641), the Training Program of College Students Innovation and Entrepreneurship in Hubei province (201710490030), the Technology Innovation Project of Hubei province (2018ACA156) and Dean’s Fund for Students 14
of School of Chemical Engineering & Pharmacy in Wuhan Institute of Technology (2017027) .
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[18] R. Perez-Lopez, J. M. Nieto, I. Lopez-Coto, J. L. Aguado, J. P. Bolivar, M. Santisteban, Appl. Geochem. 25 (2010) 705-715. [19] M. I. Amin, M. M. Ali, H. M. Kamal, A. M. Youssef, M. A. Akl, Hydrometallurgy 105 (2010) 115-119. [20] A. Hannachi, D. Habaili, C. Chtara, A. Ratel, Sep. Purif. Technol. 55 (2007) 212-216. [21] M. Huang, B. Zhong, J. Li, J. Chem. Eng. Data 53 (2008) 2029-2032. [22] D. Beltrami, G. Cote, H. Mokhtari, B. Courtaud, B. A. Moyer, A. Chagnest, Recovery of uranium from wet phosphoric acid by solvent extraction processes. Chem. Rev. 114 (2014) 12002-12023. [23] D-s. Zheng, J. Li, K. Zhou, J. H. Luo, Y. Jin, J. Chem. Eng. Data 55 (2010) 58–61. [24] M. E. Guendouzi, A. Rifai, M. Skafi, Fluid Phase Equilibr. 396 (2015) 43-49. [25] Z. K. Wu, Z. L. Huang, Y. Zhang, Y-H. Qin, J. Y. Ma, Y. B. Luo, Chem. Eng. J. 295 (2016) 64-72. [26] Z. K. Wu, W. Q. Li, T. R. Zhu, Y. Zheng, T. L. Wang, C.W. Wang, Y.B. Luo, Energ. Fuel. 32 (2018) 6934−6942
HIGHLIGHTS The physicochemical data of extraction with mixed solvent from the WPA of hydrochloric acid route was studied in our work. The effect of temperature and phosphoric acid concentration on the density and viscosity of solution were discussed, respectively. The relation of density, temperature and phosphoric acid concentration was expressed by one-dimensional linear equation. The relation of viscosity, temperature and phosphoric acid concentration was expressed by one-quadratic equation.
16
S0021-9614(18)31146-7 https://doi.org/10.1016/j.jct.2018.11.012 YJCHT 5613
To appear in:
J. Chem. Thermodynamics
Received Date: Revised Date: Accepted Date:
3 September 2018 31 October 2018 14 November 2018
Please cite this article as: W. Li, R. Peng, P. Ye, X. lv, T. Zhu, Z. Cao, Y-H. Qin, J. Ma, T. Wang, C. Wang, Z. Wu, The physicochemical data of extraction with the mixed solvent of NOA and MIBK from hydrochloric acid route phosphoric acid, J. Chem. Thermodynamics (2018), doi: https://doi.org/10.1016/j.jct.2018.11.012
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The physicochemical data of extraction with the mixed solvent of NOA and MIBK from hydrochloric acid route phosphoric acid Weiqing Lia,#, Ruicao Peng b,#, Peng Yea, Xianhe lva, Tianrong Zhu c, Zhanfang Caod, Yuan-Hang Qina, Jiayu Maa, Tielin Wanga, Cunwen Wanga, Zaikun Wua,* a
Key Laboratory of Green Chemical Process of Ministry of Education, Key Laboratory of Novel
Reactor and Green Chemical Technology of Hubei Province, School of Chemical Engineering & Pharmacy, Wuhan Institute of Technology, Wuhan 430205, P. R. China b
College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, P.R. China
c
Key Laboratory of Optoelectronic Chemical Materials and Devices
of
Wuhan
(Jianghan University), Ministry of Education, Jianghan University, Wuhan 430072, P. R. China d
Hunan Provincial Key Laboratory of Efficient and Clean Utilization of Manganese Resources,
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, P. R. China
ABSTRACT: In this study, the mixed solvent of octanol (NOA) and methyl isobutyl ketone (MIBK) was used as extractant to purify wet process phosphoric acid from hydrochloric acid route. Densities and viscosities of leachate, extraction phase and raffinate phase were determined at 293-333K, respectively. And the relation between density and temperature or phosphoric acid concentration can be expressed as a linear equation, with the maximum deviation of 0.0011 and 0.0027 g.cm-3, respectively. Meanwhile, the viscosity of leachate, extraction phase and raffinate phase were measured since its importance on mass transfer occurred in the process of phosphoric acid extraction. And the relation between viscosity and temperature or phosphoric acid concentration can be summarized as a unitary quadratic equation, with the maximum deviation of 0.4489 and 0.1122 mPa·s, respectively. The results show that the densities and viscosities from experiment are generally in good agreement with 1
calculated values from those equations obtained by regression analysis. The combined expanded uncertainty in the reported densities and viscosities are 0.3% and 5.5% of the measured values respectively, each with a coverage factor, k = 2. Keywords: Physicochemical data, Hydrochloric acid, Extraction, Wet process phosphoric acid
1. INTRODUCTION Commercial phosphoric acid is an important basic material and is widely used in various industrial branches, such as additive to food or medicine, fertilizers, catalysts for producing phenolic resin, detergents, coatings and integrated circuit, et al [1-4]. At present, phosphoric acid is mainly prepared by high grade phosphate rock in chemical industry. However, high-grade phosphate rock is gradually being exhausted with the development of phosphorus chemical industry in China. Therefore, it is inevitable trend that the mid-low grade phosphate rock was exploited more widely for producing phosphoric acid [5-9]. As usual, thermal process, kiln process and wet process are well established to manufacture phosphoric acid in chemical industry [10-13]. Among these production technologies, thermal process is used for long time because of high product quality, kiln process is limited to use because of high energy consumption [1,2,10]. In recent years, wet process phosphoric acid (WPA) is developing quickly, in that the energy consumption and production cost of wet process are lower than thermal process. According to the raw material of the production, wet process can be divided into hydrochloric acid, sulfuric acid and nitric acid method. H2SO4-route is the most widely used in WPA production. However, it has some drawbacks, such as the high requirement for phosphate rock grade, heavily dependence upon sulfur resources and high energy consumption, et al [1,14]. Moreover, lots of phosphogypsum is produced and the waste residue is difficult to utilize, which cause environmental pollution and partial phosphorus loss [1,15]. Hydrochloric acid can be used to prepare wet process phosphoric acid by dissolving phosphate rock. Compare to H2SO4 technology, the HCl-route was known 2
as a novel technology in the preparation of WPA because of no phosphogypsum, low requirement for the phosphorus rock grade, less waste, low production cost and high dissolution fraction of phosphorus, et al. [16-18]. However, there is no industrial device for preparing wet-process phosphoric acid by HCl-route, and related reports are rare. Therefore, this process has aroused many researchers’ great interest in the case of increasingly environmental requirements and the gradual depletion of high-grade phosphorus resources. However, there are lots of impurities in HCl-route WPA, especially when using medium and low grade phosphate rock. So it is important to choose a suitable method to purify phosphoric acid. At present, solvent extraction was regarded as efficient method of purifying wet process phosphoric acid in H2SO4 technology. And aliphatic alcohols, tributyl phosphate (TBP) and ketone have been reported as the extraction agent of phosphoric acid in the wet process of phosphoric acid [1,3,19-22]. Therefore, it is a trend to study the application of solvent extraction on the HCl-route wet process phosphoric acid. This leads to the need for a lot of data to be determined. So it is important to study the physicochemical data of wet process phosphoric acid owing to their impact on solvent extraction. At present, relative research was only focus on the field of H2SO4-route. Zheng et al.[23] measured the viscosities and densities of tributyl phosphate (TBP) + kerosene + phosphoric acid at 20-60 K. Huang et al.[21] determined the viscosity of mixed solvent composed by phosphoric acid + TBP + methyl isobutyl ketone (MIBK) and its performance on extracting phosphoric acid. Guendouzi et al.[24] studied the thermodynamic properties of fluoride in WPA and described the activity and osmotic coefficients of binary solution. And the study on the basic data of HCl-route has not reported yet. In this paper, wet process phosphoric acid was prepared with low grade phosphate rock and hydrochloric acid, then the densities and viscosities of leachate, raffinate phase and extraction phase were determined at different condition. Based on the data of experiment, the relation of density, viscosity, temperature and phosphoric acid concentration were established, respectively. These basis data are necessary for 3
studying the solvent extraction of HCl-route and will also be helpful for guiding the design of equipment and pipe in chemical industry.
2. EXPERIMENTAL SECTION 2.1. Chemicals. The rock particles were crushed and sieved with a 180 mesh sieve to collect some size fractions for further analysis after drying at 80°C. The chemical analysis of experimental samples taken from Hubei dayukou chemical co., LTD in China was presented in Table 1. The specifications and sources of the chemicals used in this work are summarized in Table 2. Table 1 The chemical analysis of phosphate rock Componentsa
P2O5
SiO2
CaO
MgO
Fe2O3
Al2O3
Mass percent (%)
22.93
9.83
40.41
4.50
2.93
1.83
a
Major elemental content in phosphate rock was stated in the form of their oxides
Table 2 Specifications and sources of chemicals used in this work
Chemical name
CAS registry number
Mass fraction puritya
Purification method
Methyl isobutyl ketone
108-10-1
>0.98
No further purification
Octanol
111-87-5
>0.98
No further purification
Hydrochloric acid
7647-01-0
36.0～38.0%
No further purification
Water
7732-18-5
>18MΩ.cm
HHitech laboratory water purification system
a
Source Sinopharm Chemical Reagent Co., Ltd., China Sinopharm Chemical Reagent Co., Ltd., China Sinopharm Chemical Reagent Co., Ltd., China
The purity was stated by the supplier
2.2 Experimental procedure Hydrochloric acid with a mass percentage of 15%, 20%, 25%, 30% was prepared for obtaining different concentration of raw phosphoric acid (RPA), respectively. After the optimization experiment of process condition, phosphate rock was reacted with 4
hydrochloric acid in a three-necked flask at 50°C for 0.5 h in order to leachate completely leaching phosphorus from phosphoric rock. The raw phosphoric acid (wet process phosphoric acid) was obtained by filtering insoluble matter. After the extraction process was optimized, the extraction experiment of this work was carried out at optimal condition. So RPA was extracted for equilibrated 15 minutes by the mixture solvent of MIBK and NOA (the volume ratio of MIBK and NOA is 1:1.) at organic/aqueous phase ratio of 1:1 in a reciprocating thermostatic oscillator. And phase separation was carried out with a separating funnel. In addition, the concentrations of all ions in leachate, raffinate phase and extraction phase were determined by Ion Chromatography System (DIONEX ICS-1100, USA), respectively. Referred to the methods in previous literatures [25, 26], Density (ρ) and viscosity of the solution were measured by pycnometer and Ubbelohde viscometer method at 293-333 K, respectively. In order to obtain densities precisely, the volume of the pycnometer was calibrated with pure water before experiment. All samples were measured repeatedly for three times at constant temperature. The viscosity (μ) was measured by Ubbelohde viscometer in a thermostat water bath in which temperature fluctuation was controlled in ±0.3°C.
3. RESULTS AND DISCUSSION The leachates were prepared by phosphate rock (cellophane) and different concentration (mass percentage: 15%, 20%, 25%, 30%) hydrochloric acid solution, respectively. And the main ions of initial solution, raffinate phase and extraction phase were also measured, as listed in Table 3. Based on the corresponding data, phosphoric acid concentrations in the leachate were measured to be 69.94, 92.27, 109.60 and 123.91 mg.ml-1, respectively. Depend on pycnometer and Ubbelohde viscometer method, the densities and viscosities of leachate, raffinate and extract liquor were determined at 293-333 K, respectively, as shown in Table 4. According to Eq. (1), the standard deviation (s) of densities and viscosities was calculated by different values of three replicate measurements, as shown behind positive and negative sign in Table 4. 5
xi i n
s
x
1
(1)
n 1
Where x i and x are the value of each measurement and the mean of the n measurements, respectively. Table 3 Ions concentration (Ci) of initial solution and raffinate phase in the leachate obtained from different hydrochloric acid solution of different mass fractions (ωHCl)
ωHCl
Ci (mg.ml-1) PO43-
15% 20% 25% 30%
67.798 89.443 106.247 120.115
15% 20% 25% 30%
57.758 80.905 85.989 90.863
15% 20% 25% 30%
10.040 8.538 20.258 29.252
Cl-
F-
initial 156.062 4.246 208.032 4.700 225.302 5.380 255.970 6.535 raffinate phase 141.421 4.047 180.523 4.331 195.428 4.826 217.186 5.465 extraction phase 14.641 0.199 27.509 0.369 29.874 0.554 38.784 1.070
Mg2+ 6.815 9.330 10.855 11.575
65.195 86.855 99.115 105.445
6.609 8.353 9.297 9.723
59.747 72.010 83.275 90.621
0.206 0.977 1.558 1.852
5.448 14.845 15.840 14.824
The determination of ions concentration was conducted at a pressure of 101.10 kPa. Standard uncertainties u are u(ωHCl) = 0.005, u(P)=1.0kPa, u(Ci) = 0.020mg.ml-1.
6
Ca2+
Table 4 Densities (ρ) and Viscosities (μ) of leachate, raffinate phase and extraction phase for hydrochloric acid route phosphoric acid systema leachate
raffinate phase
extraction phase
T
ρi
μi
ρr
μr
ρo
μo
K
g·cm-3
mPa·s
g·cm-3
mPa·s
g·cm-3
mPa·s
15% (wt) hydrochloric acid 293
1.2056±0.0004
2.2542±0.0159
1.2046±0.0007
2.4234±0.0111
0.8255±0.0001
1.9497±0.0110
303
1.2008±0.0008
1.7615±0.0083
1.2007±0.0009
1.8763±0.0050
0.8182±0.0004
1.5062±0.0053
313
1.1956±0.0003
1.4182±0.0081
1.1947±0.0005
1.4787±0.0089
0.8096±0.0005
1.1899±0.0029
323
1.1917±0.0005
1.1513±0.0108
1.1905±0.0007
1.2158±0.0056
0.8021±0.0011
0.9570±0.0013
333
1.1856±0.0005
0.9741±0.0084
1.1840±0.0007
1.0017±0.0023
0.7941±0.0011
0.7771±0.0034
293
1.2653±0.0003
3.1645±0.0012
1.2594±0.0006
3.2619±0.0068
0.8361±0.0005
2.4328±0.0025
303
1.2610±0.0006
2.4290±0.0048
1.2553±0.0003
2.5098±0.0113
0.8297±0.0002
1.8414±0.0035
313
1.2548±0.0002
1.9330±0.0203
1.2500±0.0001
1.9771±0.0082
0.8210±0.0004
1.4315±0.0015
323
1.2501±0.0005
1.5472±0.0142
1.2446±0.0003
1.6021±0.0024
0.8143±0.0006
1.1360±0.0057
333
1.2444±0.0004
1.3049±0.0058
1.2393±0.0004
1.3067±0.0039
0.8048±0.0006
0.9179±0.0051
20% (wt) hydrochloric acid
25% (wt) hydrochloric acid 293
1.3165±0.0006
4.4589±0.0232
1.3075±0.0007
4.3127±0.0309
0.8530±0.0002
3.2639±0.0034
303
1.3114±0.0004
3.3664±0.0074
1.3034±0.0003
3.2770±0.0079
0.8459±0.0002
2.4113±0.0098
313
1.3049±0.0004
2.6114±0.0074
1.2963±0.0001
2.5342±0.0144
0.8381±0.0003
1.8462±0.0104
323
1.2999±0.0005
2.0852±0.0040
1.2916±0.0003
2.0223±0.0153
0.8304±0.0003
1.4530±0.0006
333
1.2932±0.0005
1.6974±0.0171
1.2847±0.0001
1.6395±0.0025
0.8216±0.0008
1.1580±0.0020
30% (wt) hydrochloric acid 293
1.3621±0.0008
6.2839±0.0188
1.3456±0.0002
5.8485±0.0160
0.8668±0.0006
4.1184±0.0028
303
1.3556±0.0003
4.6557±0.0202
1.3401±0.0005
4.4231±0.0119
0.8593±0.0011
3.0246±0.0240
313
1.3480±0.0001
3.5429±0.0124
1.3338±0.0003
3.3980±0.0088
0.8519±0.0004
2.2506±0.0102
323
1.3430±0.0004
2.7870±0.0191
1.3285±0.0004
2.6931±0.0150
0.8450±0.0002
1.7292±0.0062
333
1.3368±0.0011
2.2711±0.0179
1.3213±0.0002
2.1592±0.0003
0.8363±0.0001
1.3627±0.0092
a
The extraction experiment and the determination of physicochemical data were conducted at a pressure of 101.10 kPa . Standard uncertainties u are u(T) = 0.10 K and u(P) = 1.0 kPa (0.68 level of confidence). The combined expanded uncertainties Uc are Uc(ρ) = 0.003·ρ·g·cm-3, and Uc(μ) = 0.055·μ·mPa·s, each with a coverage factor, k = 2.
3.1 Density In Table 4, as hydrochloric acid concentration is constant, it is obvious that the densities of all tested solution decrease with the increasing of temperature, and the densites of extraction phase and raffinate phase reduce faster than the densites of leachate. After adopting linear regression analysis, it is found that there is a linear 7
relation between density and temperature, as expressed by Eq. (2), and the related coefficients are shown in Table 5.
=a bT
(2)
Where ρ represents the density, T is temperature, a and b are coefficients of linear equation. The average absolute deviation (AAD) was calculated as Eq. (3). Where X i ,cal and X i,exp represent the calculated and experimental values, respectively, for individual point i and n represent the number of data points. By comparing the X i ,cal values from the models of different coefficients and the X i,exp values from experiment, the maximum deviation of this model including the densities of leachate, raffinate phase and extraction phase can be calculated as 0.0011g·cm-3. It proved that the result of models is in good agreement with the experimental measurements. n
AAD
i 1
X i ,cal X i ,exp n
(3)
Table 5 The Coefficients a, b in Eq. (2) a CP b (mg.ml-1)
a
b*10
69.94 92.27 109.60 123.91
1.3495 1.4201 1.4870 1.5469
-4.91 -5.27 -5.81 -6.32
leachate 4
raffinate phase 4
AAD
a
b*10
0.0003 0.0003 0.0003 0.0003
1.3560 1.4090 1.4764 1.5223
-5.14 -5.09 -5.74 -6.02
extraction phase
AAD
a
b*104
AAD
0.0006 0.0003 0.0006 0.0004
1.0569 1.0653 1.0829 1.0876
-7.89 -7.80 -7.83 -7.53
0.0002 0.0007 0.0004 0.0003
a
Standard uncertainty u is u(Cp) = 0.02 mg.ml-1 , u(P)=1.0kPa
b
CP, phosphoric acid concentration
Meanwhile, it can be seen that the densities of all tested solution increase with the increasing of hydrochloric acid concentration at a constant temperature. This result can be explained that more components will be extracted into extractant with the increasing of phosphoric acid in leachate. So it can be concluded that the extraction performance will be improved by increasing phosphoric acid concentration. By plotting the curve of density and phosphoric acid concentration, it is clear that 8
there is a linear relation, and the relation of the density and phosphoric acid concentration can be described by the following equation.
=mCP n
(4)
Where CP is phosphoric acid concentration. m, n are the coefficients of Eq. (4), and are listed in Table 6. The results show that the slope of density changing with temperature is almost the same. Depended on Eq. (3), the average absolute deviation of Eq. (4) was calculated, the values of AAD were also listed in Table 6. The maximum deviation of this model (including three kinds of solution in Table 6) is 0.0027g·cm-3. It concluded that Eq. (4) can better reflect the law of experimental data. Table 6 The Coefficients m, n in Eq. (4) a Tb
leachate
raffinate phase
extraction phase
(K）
m*103
n
AAD
m*103
n
AAD
m*103
n
293 303 313 323 333
2.90 2.87 2.83 2.81 2.80
1.0004 0.9982 0.9959 0.9933 0.9878
0.0023 0.0018 0.0016 0.0018 0.0018
2.62 2.60 2.58 2.57 2.55
1.0198 1.0179 1.0132 1.0098 1.0052
0.0014 0.0010 0.0009 0.0009 0.0004
0.7731 0.7677 0.7918 0.7965 0.7866
0.7689 0.7623 0.7518 0.7442 0.7364
a b
AAD 0.0024 0.0020 0.0022 0.0022 0.0026
Standard uncertainty u is u(T) = 0.10 K, u(P)=1.0kPa T, Kelvin temperature
3.2 Viscosity The viscosities of leachate, raffinate phase and extraction phase were determined at different temperatures, as shown in Fig.1-3. It shows that viscosity reduces with the increasing of temperature. Based on polynomial fitting, the relationship between viscosity and temperature can be described by the following equation.
pT 2 qT r
(5)
Where μ represents the viscosity of solution. p, q and r are coefficients of Eq. (5), their values are listed in Table 7. And the average absolute deviation of Eq. (5) for different phosphoric acid was analyzed and the result was also listed in Table 7. After referring to the above related method, the maximum deviation of this model is 0.4489 mPa·s. There has some error in that a small amount of water was evaporated from 9
tested solution. But those models are still able to correctly express the relation to viscosity and temperature. Table 7 The Coefficients q, p, r in Eq. (5) a CP b
leachate -1
(mg.ml )
p*10
4
q
r
raffinate phase AAD
p*10
4
q
extraction phase
r
AAD
p*10
4
q
r
AAD
69.94
5.0529
-0.3480
60.8365
0.0078
5.7193
-0.3931
68.4833
0.0128
4.3614
-0.3020
52.9767
0.0122
92.27
7.8329
-0.5364
93.0579
0.0213
7.6507
-0.5271
92.0124
0.0180
6.1500
-0.4223
73.3710
0.0917
109.60
11.7000
-0.8006
138.5447
0.0344
11.0000
-0.7531
130.7340
0.2425
-0.6272
108.0935
0.0233
123.91
18.4000
-1.2532
215.1563
0.03725
15.0000
-1.0315
179.0913
0.2191
143.0247
0.0656
a
Standard uncertainty u is u(Cp) = 0.02 mg.ml-1, u(P)=1.0kPa
b
CP, phosphoric acid concentration
9.1936 12.2000
-0.8314
Fig. 1. The relation between viscosity of leachate and temperature at different phosphoric acid concentration: (■) CP=69.94 mg.ml-1; (●) CP=92.27 mg.ml-1; (▲) CP=109.60 mg.ml-1; (▼) CP=123.91 mg.ml-1
10
Fig. 2. The relationship between viscosity of raffinate phase and temperature at different phosphoric acid concentration: (■) CP=69.94 mg.ml-1; (●) CP=92.27 mg.ml-1; (▲) CP=109.60 mg.ml-1; (▼) CP=123.91 mg.ml-1
Fig.3. The relationship between viscosity of extraction phase and temperature at different phosphoric acid concentration: (■) CP=69.94 mg.ml-1; (●) CP=92.27 mg.ml-1; (▲) CP=109.60 mg.ml-1; (▼) CP=123.91 mg.ml-1
In general, the viscosity of solution is related to the concentration of components in solution. Therefore, in order to investigate the relation of viscosity and phosphoric acid concentration, the viscosity of leachate, raffinate phase and extraction phase were tested with mass concentration 69.94-123.91mg.ml-1 phosphoric acid at 293-333K, respectively. Plotted the curve of
vs C in Fig. 4-6, the results showed that
viscosity increased with the increasing of phosphoric acid concentration. And the viscosities of all determined solution can be described as Eq. (6) by polynomial fitting. Where Cp represents the concentration of phosphoric acid in wet process phosphoric acid. And the coefficients a, b, d and average absolute deviation of this eqation are listed in Table 8. Through error analysis, it can be see that the maximum deviation of Eq. (6) is 0.1122 mPa·s. Therefore, based on the concentration of phosphoric acid in 11
the solution, the regression models can get data that is almost identical to the experimental values. 2
aC p bC p d
(6)
Table 8 Coefficients a, b, d in Eq. (6) a Tb
leachate
raffinate phase
extraction phase
(K）
a*104
b
d
AAD
a*104
b
d
AAD
a*104
293
11.6000
-0.1506
7.1428
0.0480
9.1336
-0.1146
5.9878
0.0532
5.5539
-0.0672
3.9238
0.0169
303
8.0557
-0.1032
5.0464
0.0321
6.7203
-0.0839
4.4715
0.0435
4.0045
-0.0493
2.9956
0.0085
313
5.5938
-0.0695
3.5531
0.0244
4.8656
-0.0595
3.2712
0.0385
2.5874
-0.0303
2.0387
0.0114
323
4.2216
-0.0518
2.7130
0.0140
3.7540
-0.0460
2.6076
0.0321
1.7486
-0.0193
1.4494
0.0138
333
3.2869
-0.0401
2.1765
0.0212
2.8852
-0.0349
2.0413
0.0236
1.2505
-0.0132
1.0847
0.0104
a b
b
Standard uncertainty u is u(T) = 0.10 K, u(P)=1.0kPa T, Kelvin temperature
Fig.4 The curve of the viscosity vs phosphoric acid concentration at different temperatures for leachate: (□)333K; (○)323K; ( )313K; ( )303K; ( )293K 12
d
AAD
Fig.5 The curve of the viscosity vs phosphoric acid concentration at different temperatures for raffinate phase: (□)333K; (○)323K; ( )313K; ( )303K; ( )293K
Fig.6 The curve of the viscosity vs phosphoric acid concentration at different temperatures for extraction phase: (□)333K; (○)323K; ( )313K; ( )303K; ( )293K
13
4. Conclusions In this work, physicochemical data has been obtained for the leachate, raffinate phase and extraction phase of hydrochloric acid route phosphoric acid system. The densities of all determined solution reduce with the increasing of temperature but increase with increasing of phosphoric acid concentration. And it can be expressed as a linear equation of temperature or phosphoric acid concentration. Meanwhile, the viscosities of all determined solution have a quadratic function relationship with temperature or phosphoric acid concentration, respectively. And the values of viscosities reduce as temperature increases but increases with the increasing of phosphoric acid concentration. Those equations from data regression analysis can correctly reflect the relationship between physicochemical data (density and viscosity) and temperature, phosphoric acid concentration. It will be helpful for the further study of the hydrochloric acid route phosphoric acid. Notes The authors declare no competing financial interest. Corresponding Author: [email protected] (Zaikun Wu) First Author: Weiqing Li, Ruicao Peng
Acknowledgments The authors are grateful for the financial support from the Scientific Research Plan Guidance Project of Hubei Education Department in China (B2017054), Open Fund from Key Laboratory of Green Chemical Process of Ministry of Education in Wuhan Institute of Technology (201714), the Scientific Research Fund of Wuhan Institute of Technology (k201641), the Training Program of College Students Innovation and Entrepreneurship in Hubei province (201710490030), the Technology Innovation Project of Hubei province (2018ACA156) and Dean’s Fund for Students 14
of School of Chemical Engineering & Pharmacy in Wuhan Institute of Technology (2017027) .
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HIGHLIGHTS The physicochemical data of extraction with mixed solvent from the WPA of hydrochloric acid route was studied in our work. The effect of temperature and phosphoric acid concentration on the density and viscosity of solution were discussed, respectively. The relation of density, temperature and phosphoric acid concentration was expressed by one-dimensional linear equation. The relation of viscosity, temperature and phosphoric acid concentration was expressed by one-quadratic equation.
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