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DEVELOPMENT OF NANOCOMPOSITE MATERIALS FOR THE RECOVERY OF CESIUM AND URANIUM
J. Mora (1), J. Bastos-Arrieta (1), I. Casas (1), F. Clarens(2) and J. de Pablo (1,2)
(1) Department of Chemical Engineering and Barcelona Research Center for Multiscale Scienceand Engineering, UPC-Barcelona Tech, Av. Eduard Maristany, 10-14, 08019 Barcelona, Spain(2) Fundació CTM Centre Tecnològic, Plaça de la Ciència 2. 08240 Manresa, Spain
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EURECAT-CTM
An Advanced Technology Centre, a highly qualified worldleader in the technologies of the center, renowned inboth the scientific and industrial sectors. R&D+I AppliedResearch, Technological Development and Innovation forour own projects and for those of the world of business.
Areas of excellence: Metallic and Ceramic Materials, Environmental and Energy Sustainability and Process Modelling and Simulation.
The unit has experience in R&D in the fields of:
• Water technologies: treatment, reutilization, recovery of nutrients• Waste: management technologies, recycling, recovery of raw materials• Soil and groundwater remediation• Energy efficiency• Renewable energies• Industrial ecology, optimization of processes and equipment
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New UPC-Barcelona Tech Campus in Diagonal Besòs
Engineering School of Barcelona (EEBE)Barcelona Research Center for Multiscale Science and Engineering
• New space for innovation and knowledge
• High quality academic center in the field of the engineering for the industry
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1) Development of two nanostructured hybrid nanocomposite:
Cellulose TriAcetate (CTA) + Prussian Blue (PB)
CTA + graphite
2) Characterization of these nanocomposites
3) Recovery capacity of Cesium and Uranium
OBJECTIVES
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RECOVERY OF URANIUM BY GRAPHITE/ACTIVATED CARBON
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Prussian Blue (PB): Iron(III) hexacyanoferrate(II)
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Figura 1: Chemical structure of PB.https://chemicalstructure.net
Figure 2: Starry night(Vincent Van Gogh)
RECOVERY OF CESIUM BY PRUSSIAN BLUE
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Membranepreparation
CHLOROFORM
CTA
NPOE (plasticizer agent)
Polymeric InclusionMembranes
(PIM)
GRAPHITE (GR)
PRUSSIAN BLUE (PB)
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Amounts of1, 3 & 10 mg
EXPERIMENTAL PROCEDURE
Average raw membranesweight 100mg
%wt
88
+25 mL solution from,
1 g CTA100 mL Chloroform
0,5mL2-Nitrophenyl octyl ether
(NPOE)
+25 mL
Chloroformo
=50 mL
PIM Solution
6 mL on a plate
PIM SYNTHESIS
The optimal amount of the membranesolution was 6 mL.
99
+ =8 mL
Polyvinylpyrrolidone (PVP) / FeCl2·4H2O (ratio 20:1)
10mM FeCl2·4H2O
2 mL10mM K3[Fe(CN)]6
10 mLPB
25 mLKetone
+
Stirring 2 hours
60ºC24 hours
NPs of PB
PRUSSIAN BLUE SYNTHESIS
1500 rpm5 min
1010
PIM Solution
+
NPs of PB
+
Comercial nanolayers of graphite
CTA membrane doped with NPsof PB
PIM Solution
MODIFIED MEMBRANE SYNTHESIS
CTA membrane doped withnanolayers of graphite
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[U] = 10-6M
+
PB MEMBRANES
+
GRAPHITE MEMBRANES
Membrana de CTA dopada con nanopartículas de PB[Cs] = 10-5M
SORPTION TESTS
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Stirring 24 hours
pH = 7
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SEM RAW MEMBRANE CONTROL
Well defined porous
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SEM PB MEMBRANE
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• Doped membranes clearlyshow porous on the surface.
• This is due to use of ketoneduring the synthesis
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SEM GRAPHITE MEMBRANE
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• Doped membranes are wellcovered by nanolayers ofgraphite.
TEM GRAPHITE MEMBRANE
• It is possible to see the profile of theatomic planes forming the skeleton ofthe atoms.
• Interatomic space is 0.3335 nm
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0100000200000300000400000500000600000700000800000900000
1000000
800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000
Cont
aje
Raman shifts (cm-1)C-O-C Bonds (CTA& NPOE)
Acetate groups(CTA) NO2 groups(NPOE)
C-C (CTA & NPOE)
CH2 and CH3 groups (CTA & NPOE)
RAMAN RAW MEMBRANE CONTROL
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RAMAN GRAPHITE MEMBRANE AFTER URANIUM SORPTION
5000
5500
6000
6500
7000
7500
8000
350 450 550 650 750
Cont
aje
Raman shifts (cm-1)
5000
9000
13000
17000
21000
25000
750 850 950 1050
Cont
aje
Raman shifts (cm-1)
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A B
Vibrations of the crystal latticeSymmetry of the U-O double bond
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Cs SORPTION ON PB MEMBRANES
IONIC EXCHANGE MECHANISM OF Cs
EXPERIMENTS [Cs] (µg/L) RECOVERY (%)Initial Cesium 1072 -
Raw Membrane control 1046 2Membrane PB1 810 24Membrane PB3 188 82
Membrane PB10 120 89
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Experiments [U] (µg/L) Recovery (%)
Initial uranyl 120 -Raw Membrane
control 65 46
Membrane GR1 43 64
Membrane GR3 32 73
Membrane GR10 27 78
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Physical sorption+
Redox Reaction
U SORPTION ON GRAPHITE MEMBRANES
CONCLUSIONS
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Two nanostructured hybrid nanocomposite materials were prepared using cellulose triacetatemembranes as support matrix. Polymeric Inclusion Membranes (PIM) were prepared mixingcellulose triacetate (CTA), chloroform and 2-Nitrophenyl octyl ether (NPOE).
Some Membranes were modified with Prussian blue (PB) nanoparticles (NPs) protected bypolyvinylpyrrolidone (PVP) and Other Membranes were modified with Graphite.
The nanocomposites were characterised by Scanning Electronic Microscopy (SEM),Transmission Electronic Microscopy (TEM) and Raman spectroscopy to obtain detailedinformation about the morphology, chemical funcional groups and composition of theSamples
For the system graphite-U, the raw membrane showed a recovery of 46%, the maximum was found to be 78% of recovery when a 10% w/w of graphite was used
For the PB-Cs, the raw membrane did not present a significant! capacity to adsorb Cs, in contrast to the 89% sorption of Cs for nanocomposite with 10% w/w of PB.
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ACKNOWLEDGMENTS
THIS WORK WAS SUPPORTED BY
PROJECT: ENE2014R54299RC2R1RR
THANK YOU FOR YOUR ATTENTION