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A non-aqueous phase extraction system using tributyl phosphate for H3PO4 separation from wet-process superphosphoric acid: Extraction equilibrium and mechanism

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Abstract

Conventional wet-process phosphoric acid (WPA) extraction route encounters unsatisfactory extraction efficiency, phosphorus yield, and raffinate utilization. Herein, a new extraction route for H3PO4 separation from wet-process superphosphoric acid (WSPA) is proposed to improve these dilemmas. We focus on the equilibrium of H3PO4 extraction by tributyl phosphate (TBP) from WSPA and the extraction mechanism of TBP under high H3PO4 loading conditions. Several critical factors affecting the extraction equilibrium were investigated to optimize the extraction process, including the initial phase ratio (R0), the volume fraction of TBP in extradant (φTBP), temperature (T), and the crosscurrent extraction stages. The results show that the single-stage extraction rate of H3PO4 reaches 70% at R0=6, φTBP=80% and T=80oC with separation factors βP/Fe, βP/Al, βP/Mg, and βP/Ca of 12.48, 21.66, 47.57, and 8.89, respectively. In addition, Fourier transform infrared spectroscopy and Raman spectroscopy enlighten the extraction mechanism at high loading conditions. The characteristic peak positions of P=O, P=O⋯H2O, and P=O⋯H3PO4 in the infrared spectra are determined to be centered at 1,283, 1,267, and 1,233 cm−1, respectively. The semi-quantitative analysis implies that the self-polymerization behavior of the extraction complex TBP·H3PO4 and the mutual attraction of reverse micelles (RMs) through their polar cores is the trigger for the formation of a third phase. Furthermore, the red shift of P-(OH)3 asymmetrical stretching vibration in the Raman spectrum indicates the formation of hydrogen bonds among H3PO4 molecules in the organic phase, which corroborates the formation of RMs. Conclusions can be obtained that H3PO4 enters the organic phase under high loading capacity by reversed micellar extraction. The feasibility of this extraction process is further tested by scrubbing, stripping, and cycling performance experiments. The results are promising for the design of a new efficient route for separating H3PO4 from WPA.

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Abbreviations

A:

peak area

C:

concentration of component i [mol/L]

C:

constant

D:

distribution ratio

Ei :

extraction rate of component i

FWHH:

full width of half height

g:

gravitational acceleration [9.80 m/s2]

∆H:

molar enthalpy of reaction [kJ/mol]

h:

heavy phase

k:

mole ratio of H3PO4 to TBP

l:

light phase

LRP:

H3PO4 loading ratio of TBP

m:

mass [kg]

M:

moles per litre

[i]:

concentration of component I [mol/L]

n:

mole number

q(i):

mass flow rate of component I [kg/s]

R:

universal gas constant [J/(mol·K)]

R:

volumetric phase ratio of organic phase to inorganic phase [Vorg/Vino]

R0 :

initial volumetric phase ratio of organic phase to inorganic phase before extraction or stripping [Vorg/Vino]

Re :

volumetric phase ratio Vorg/Vino at extraction equilibrium

Re:

removal rate

T:

temperature [oC]

V:

volume [m3]

w(i):

mass fraction of component i

Xc :

peak position

Xn :

the mass ratio of H3PO4 to TBP in organic phase at the nth stage

Xf :

the mass ratio of H3PO4 to TBP in feed loading organic phase

Y0 :

the mass ratio of H3PO4 to H2O in feed aqueous phase

Yn+1 :

the mass ratio of H3PO4 to H2O in aqueous phase at the stage (n+1)

β i/f :

separation factor of component i towards component j

γ :

out-of-plane bending vibration

δ :

scissoring vibration

ρ :

rocking vibration

φ i :

volume fraction of component i

v :

stretching vibration

aq:

aqueous solution

as:

asymmetrical vibration

f:

feed state

tl:

total liquid collected at the end by stripping

ino:

inorganic phase

org:

organic phase

r:

raffinate phase

s:

symmetrical vibration

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Acknowledgement

This work was financially supported by National Key R&D Program of China (2016YFD0200404).

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Authors and Affiliations

  1. School of Chemical Engineering, Sichuan University, Research Center for Comprehensive Utilization and Clean Processing Engineering of Phosphorus Resources, Ministry of Education, Chengdu, 610065, China

    Haozhou Liu, Jingxu Yang, Xiuying Yang, Chao Hu & Lin Yang

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  1. Haozhou Liu
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  2. Jingxu Yang
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  3. Xiuying Yang
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  4. Chao Hu
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  5. Lin Yang
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Correspondence to Lin Yang.

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A non-aqueous phase extraction system using tributyl phosphate for H3PO4 separation from wet-process superphosphoric acid: Extraction equilibrium and mechanism

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Liu, H., Yang, J., Yang, X. et al. A non-aqueous phase extraction system using tributyl phosphate for H3PO4 separation from wet-process superphosphoric acid: Extraction equilibrium and mechanism. Korean J. Chem. Eng. 39, 1659–1672 (2022). https://doi.org/10.1007/s11814-021-1021-z

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  • DOI: https://doi.org/10.1007/s11814-021-1021-z

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