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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 Science and 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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Page 1: DEVELOPMENT OF NANOCOMPOSITE MATERIALS FOR THE …prometia.eu/wp-content/uploads/2014/02/15_Clarens_UPC.pdf · (Vincent VanGogh) RECOVERY OF CESIUM BY PRUSSIAN BLUE. 7 Membrane. preparation

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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

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+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.

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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

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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.

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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)

17

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

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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