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Presented by
Wasamon Konaem
Simulation for synergistic extraction of
neodymium ions with hollow fiber supported
liquid membrane
Department of Chemical Engineering
Faculty of Engineering, Chulalongkorn University
2
Neodymium is the raw material used in high-strength permanent
magnets (Nd–B–Fe)
Rare earth elements (REEs) have similar chemical and physical
properties. Separation of individual REE was a difficult.
The high value of REE depends on their effective separation
into high purity compounds
HFSLM is an effective method to treat a very low concentration
of metal ions
 Inside that shell, there are many thin fibers running the length
of the shell, all in nice, neat rows
 The HFSLM system composed of feed phase, liquid phase and
stripping phase.
 Feed and stripping phase are separated by a membrane
embedded with extractant.
Figure 1 HFSLM module
1.Very small and low release of extractant.
2.Extraction and stripping can be carried
out simultaneously in one equipment.
3.High contact surface are a per unit
extract or volume.
4.Independent control of process flow
rates eliminating loading and flooding.
5.Lower capital and operating costs.
6.Lower energy consumption.
Figure 2 schematic representation of mass transfer through a liquid membrane
Co-operative effect of two (or
more) extractants where the efficiency
for the combination is greater than the
largest individual distribution.
The first, is major extractant and
the other is donor electron.
Feed : Nd(III) 100 mg/L in nitric acid
solution, pH = 4.5, on tube side
Extractants :
Acidic extractant was 0.5 M D2EHPA
(A)
Neutral donor was 0.5 M TOPO (B)
Stripping : 1 M H2SO4, on shell side
Mode : Once through, countercurrent
flow
Figure 3 schematic representation of the counter
current flow diagram in HFSLM
Figure 4 The molecular structure of extractants (A)
D2EHPA and (B) TOPO
Step 1: Nd(III) ion in the feed
solution is transport to feed-
membrane interface.
Nd(III) ion is reacted with
D2EHPA and TOPO yields a
stable complex compound
(1)
(2)
(3)
Figure 5 Schematic of Nd(III) transport across HFSLM.
Step 2: neodymium complex
compound diffuses from
membrane phase to stripping
phase.
Step 3: neodymium complex react
with stripping solution (H2SO4)
at the membrane-stripping
interface
Step 4: Nd3+is transferred into the stripping
solution the extractant diffuses back to the
feed phase to react again with Nd3+ In feed
solution
(4)
(5)
(6)
Assumption :
 The physical properties in feed phase are constant.
 The concentration of neodymium ions in the radial
direction is constant because the inside diameter of
hollow fiber is very small. Therefore means that the
diffusion fluxes of neodymium ions in the feed phase exist
only in the axial direction.
 Perfect mixing occur in the small cross sectional area of
the inner tube. Therefore the concentration of neodymium
ions in the radial direction is constant.
 Only complex species, not neodymium ions, are transport
through the liquid membrane phase.
 The forwards reaction is dominant.
(7)( , ) ( , ) ( ( , )
f f Af
f Af f Af f Af Af f
A D C
q C x t q C x x t xA r C x x t xA
x t

          
 
3
8 0.5
0.6
7.4 10 ( )w
f
w Nd
M T
D

  



2
f iA N r 
( , )n
Af Ex Afr k C x t (8)
(9)
(10)
3 3
f,in f,out
3
f,in
Nd Nd
Extraction(%) 100
Nd
 

      
 
  
3 3
exp
3
exp
Nd Nd
Absolute error (%) = 100
Nd
cal
 

      

  
(11)
(12)
Figure 6 Experimental and model of concentration of Nd(III) in feed solution
Figure 7 Experimental and model of percentage extraction of Nd(III) in feed solution
Figure 8 Effect of volumetric flowrate in feed solution on percentage extraction of Nd(III)
 A hollow fiber supported liquid membrane
system using 0.5M D2EHPA and 0.5M TOPO
mixtures as the synergistic extractant
 Simulation results of the developed models
are in good agreement with the experimental
data reported.
 The average percentage of absolute error is
8.95%.
Grds conferences icst and icbelsh (2)

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  • 1. 1 Presented by Wasamon Konaem Simulation for synergistic extraction of neodymium ions with hollow fiber supported liquid membrane Department of Chemical Engineering Faculty of Engineering, Chulalongkorn University
  • 2. 2 Neodymium is the raw material used in high-strength permanent magnets (Nd–B–Fe) Rare earth elements (REEs) have similar chemical and physical properties. Separation of individual REE was a difficult. The high value of REE depends on their effective separation into high purity compounds HFSLM is an effective method to treat a very low concentration of metal ions
  • 3.  Inside that shell, there are many thin fibers running the length of the shell, all in nice, neat rows  The HFSLM system composed of feed phase, liquid phase and stripping phase.  Feed and stripping phase are separated by a membrane embedded with extractant. Figure 1 HFSLM module
  • 4. 1.Very small and low release of extractant. 2.Extraction and stripping can be carried out simultaneously in one equipment. 3.High contact surface are a per unit extract or volume. 4.Independent control of process flow rates eliminating loading and flooding. 5.Lower capital and operating costs. 6.Lower energy consumption.
  • 5. Figure 2 schematic representation of mass transfer through a liquid membrane
  • 6. Co-operative effect of two (or more) extractants where the efficiency for the combination is greater than the largest individual distribution. The first, is major extractant and the other is donor electron.
  • 7. Feed : Nd(III) 100 mg/L in nitric acid solution, pH = 4.5, on tube side Extractants : Acidic extractant was 0.5 M D2EHPA (A) Neutral donor was 0.5 M TOPO (B) Stripping : 1 M H2SO4, on shell side Mode : Once through, countercurrent flow Figure 3 schematic representation of the counter current flow diagram in HFSLM Figure 4 The molecular structure of extractants (A) D2EHPA and (B) TOPO
  • 8. Step 1: Nd(III) ion in the feed solution is transport to feed- membrane interface. Nd(III) ion is reacted with D2EHPA and TOPO yields a stable complex compound (1) (2) (3) Figure 5 Schematic of Nd(III) transport across HFSLM.
  • 9. Step 2: neodymium complex compound diffuses from membrane phase to stripping phase. Step 3: neodymium complex react with stripping solution (H2SO4) at the membrane-stripping interface
  • 10. Step 4: Nd3+is transferred into the stripping solution the extractant diffuses back to the feed phase to react again with Nd3+ In feed solution (4) (5) (6)
  • 11. Assumption :  The physical properties in feed phase are constant.  The concentration of neodymium ions in the radial direction is constant because the inside diameter of hollow fiber is very small. Therefore means that the diffusion fluxes of neodymium ions in the feed phase exist only in the axial direction.  Perfect mixing occur in the small cross sectional area of the inner tube. Therefore the concentration of neodymium ions in the radial direction is constant.  Only complex species, not neodymium ions, are transport through the liquid membrane phase.  The forwards reaction is dominant.
  • 12. (7)( , ) ( , ) ( ( , ) f f Af f Af f Af f Af Af f A D C q C x t q C x x t xA r C x x t xA x t               3 8 0.5 0.6 7.4 10 ( )w f w Nd M T D        2 f iA N r  ( , )n Af Ex Afr k C x t (8) (9) (10)
  • 13. 3 3 f,in f,out 3 f,in Nd Nd Extraction(%) 100 Nd                3 3 exp 3 exp Nd Nd Absolute error (%) = 100 Nd cal               (11) (12)
  • 14. Figure 6 Experimental and model of concentration of Nd(III) in feed solution
  • 15. Figure 7 Experimental and model of percentage extraction of Nd(III) in feed solution
  • 16. Figure 8 Effect of volumetric flowrate in feed solution on percentage extraction of Nd(III)
  • 17.  A hollow fiber supported liquid membrane system using 0.5M D2EHPA and 0.5M TOPO mixtures as the synergistic extractant  Simulation results of the developed models are in good agreement with the experimental data reported.  The average percentage of absolute error is 8.95%.

Editor's Notes

  1. Good afternood everybody. I’m wasamon konaem. Today I would like to present Simulation for synergistic extraction of neodymium ions with hollow fiber supported liquid membrane.
  2. For introduction Neodymium was used functionalized in permanent magnets in computer hard drives, mobile phones, wind turbines, and electric motors neodymium is classed as a "rare earth element’ that have similar chemical and physical properties. Separation of individual REE was a difficult. The high value of REE depends on their effective separation into high purity compounds. Separating individual REE from concentrates is a very difficult process due to their similar chemical properties. Therefore the separation process for REE need to high separation performance. Therefore HFSLM was applied to separate neodymium from wastewater because effective method to treat a very low oncentration of metal ions.
  3. The characteristic of hollow fiber is show in this picture1. Inside that shell, there are many thin fibers. Hollow fiber supported liquid membrane system composes of a feed solution and a stripping solution. Both feed and stripping phase are separated by a supported liquid membrane impregnate with one type of organic extractant or a mixture of two types of extractant to enhance the separation.
  4. Hollow fiber supported liquid membrane (HFSLM) based separation methods have several advantages over conventional solvent extraction method such as Very small and low release of extractant. Extraction and stripping can be carried out simultaneously in one equipment. High contact surface are a per unit extract or volume. Independent control of process flow rates eliminating loading and flooding. Lower capital and operating costs. Lower energy consumption.
  5. The counter transport is the flux of two ions moves counter to each other across the membrane by the driving force. เขียน
  6. The synergistic extraction is the extract metal ion species which use two extractants taken together with much higher efficiency as compared to the normal additive effect of these extractants separately. The first, is major extractant and the other is donor electron.The optimal extraction of neodymium ion occurred at the mixture of 0.5M D2EHPA and 0.5 M TOPO in heptane served as the extractants. D2EHPA is a proton acceptor and TOPO is a proton donor
  7. The transportation of neodymium ion through the HFSLM can be described by Figure First step Nd(III) ion in the feed solution is transport to a contact surface between feed phase and liquid membrane phase and reacted with D2EHPA show in equation 1, reacted with TOPO show in equation 2 and reacted with mixture of D2EHPA and TOPO show in equation 3 yields a stable complex compound.
  8. Second step : neodymium complex compound diffuses from membrane phase to stripping phase. Third step : neodymium complex react with stripping solution at the membrane-stripping interface
  9. Forth step Nd3+is transferred into the stripping solution while the extractant diffuses back to the feed phase. the stripping reaction are shown in equation 4-6.
  10. The laminar transport of neodymium ion in feed phase with reaction flux, diffusion and axial convection influence. The concentrations of neodymium ion along the hollow fiber tube vary depending on the axial direction and the extraction time corresponding to the accumulation of neodymium ions in the feed phase. The model in feed phase is made according to the following assumption: - The physical properties in feed phase are constant. - The concentration of neodymium ions in the radial direction is constant because the inside diameter of hollow fiber is very small. Therefore means that the diffusion fluxes of neodymium ions in the feed phase exist only in the axial direction. - Perfect mixing occur in the small cross sectional area of the inner tube. Therefore the concentration of neodymium ions in the radial direction is constant. - Only complex species, not neodymium ions, are transport through the liquid membrane phase. - The forwards reaction is dominant.
  11. Mathematical models have been developed based on material balance. Rate of mass transport into the system by convection minus Rate of mass transport out of the system by convection Minus Rate of mass extracted by extraction reaction Plus Rate of mass transport through the system by diffusion Equal Rate of mass accumulation within the system. Where extraction reaction was calculated by equation 8 small n is the order of reaction kex is the reaction rate constants Diffusion was calculated by equation 9 And the inside cross-sectional area of the hollow fibers was calculated by equation 10. Capital N is the number of hollow fiber
  12. The percentages of Neodymium ion extraction from experiments was calculated by Eqs. 11 The absolute error percentage of the removal efficiency of Neodymium ion in the feed solution obtained by experimental runs and model simulation is defined as by Eqs. 12
  13. Figure. 6 is shown the concentration of Nd(III), at any time, from feed solution as calculated in Eq. 7 – 10 shows the comparison of concentration of Nd(III) in feed solution obtained from experimental results and from the models. It was found that the model provides good estimates of the concentration of Nd(III) in feed solution; the absolute error is 15.68%.
  14. The percentage of Nd(III) extraction was plotted in Figure 7 by compare the experimental with predictive by model. The percentage of extraction was calculated by Eq. 11. The modeled results were in good agreement with the experimental data at the average percentage of deviation about 8.37%.
  15. The volumetric flowrate has an effect on the efficiency of Nd(III) extraction because the residence time and the formation rate of Neodymium complex will be decrease if the volumetric flowrate increase, and the efficiency of extraction will be also decrease. Figure 8 was plotted in feed phase by comparing the extraction results by experiment and predicted by model. We can see that the plot of neodymium extraction in this work predicted by the proposed model had the good agreement with the experiment data. The absolute error is 2.79%.
  16. - A hollow fiber supported liquid membrane system that studied in this work has using 0.5M D2EHPA and 0.5M TOPO mixtures as the synergistic extractant and once-through-mode operation Mathematical models considering the term of axial convection, axial diffusion, chemical reaction at the feed-liquid membrane and accumulation of neodymium ions Simulation results of the developed models are in good agreement with the experimental data reported. The average percentage of absolute error is 8.95%.