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Recycling of
sargassum for
activated carbon
production
Sarra Gaspard, Université des Antilles,
Laboratoire COVACHIMM2E
25/10/2019
Annual needs
1.9 Mio Tons
Many applications
Water, air treatment, Food processing
Pharmaceutical applications, energy storage
ACTIVATED CARBON ?
Carbon material
Previously produced from mineral carbon
Nowadays mainly produced from biomass
(mostly from coconut)
Porous material
Energy
storage
Biomass
valorization
AC synthesis
COVACHIMM2E
BIOMASS VALORIZATION FOR REMEDIATION
AND ENERGY STORAGE
Pesticide
sequestration
In animals
Capacitive
deionization for water
treatment
PhD, S. Roche
PhD, Yeray Alvarez
ANR project
PhD, Marckens Francoeur
PhD, Michel Manduca
Water treatment
Pharmaceutical
compound,
WHY PRODUCING CARBON MATERIAL FROM ALGA FOR
CARBON MATERIAL PRODUCTION
Due to their chemical composition, seaweeds are fantastic precursors for
nanotextured carbons preparation. Depending of pyrolysis conditions,
oxygen enriched carbons, with tuned micro/mesoporosity can be
obtained.
Natural
Carbon
source
High chemical
variety Highly available
and cheap
HOW TO PREPARE ACTIVATED CARBON ?
Fabrication
 pyrolysis
 Physical activation
 Chemical activation
 Hydrothermal carbonizatin
Precursor
Chemical Impregnation (ac. Phos) + pyrolysis
Physical activation
Chemical activation
500 - 700°C Activation (H2O, CO2)
BIOCHAR
ACTIVATED
CARBON
ACTIVATED
CARBON
Pyrolysis
hydrothermal carbonization+ imprégnation + pyrolysis
HTC
a
Supercapacitors are composed of:
• Electrode made of Highly porous materials
• such as carbon materials
• A separator
• An electrolyte -
-
+
+
+
+
+
+
+
+
+
+ +
+
-
-
-
-
-
-
-
-
- -
-
- - -
- -
-
-
--
-
-
-
-
-
+
+
+
+
+
+ +
+
+
++++
+
+
+
+
-
-
Current collector
Active material
Electrolyte
Electrode
Separator
-
-
-
-
- +
+
+
+
+
t
By applying a potential: positive charges remain on one plate, and negative charge on
the other plate = charged state
During discharge: negative and positive charges are released
Batteries : called also electrochemical
capacitors
Able to store and release energy in a
short time (few seconds)
Used for electric vehicles, tramways,
wind turbines, computers, for ex..
CARBON ELECTRODES FOR SUPERCAPACITORS
 Textural characteristics
 Nitrogen adsorption
 BET surface area
 Porous Volume
 Surface chemistry
 Xray photo-électron spectroscopy
 Elemental Analysis
 Surface functionnal groups
 Electrochemical properties
Cyclic voltametry
Galvanometry measurement
Carbon sample characterization
Adsorption studies
kinetic
Isotherm
Thermogravimetric analysis of Sargassum
-3
-2.5
-2
-1.5
-1
-0.5
0
0.5
-40
-20
0
20
40
60
80
100
40 240 440 640 840 1040
Weightloss(%)
Temperature (°C)
TG sarg_brut
dTG_sarg_brut
Laminarin , first stage fucoidan
Water, alginate
Second decomposition stage fucoidan
Mannitol
EDX Analysis
CS 800
30 m
CS 700
30 m
CS 900
30 m
30 m
CS 600
100 m
CSraw
30 m
CSraw
surface elemental composition obtained by XPS analysis
Atom CS600 CS700 CS800 CS900
O 1s (%) 7.98 10 4.54 2.76
C 1s (%) 91.57 87.16 93.68 96.33
C2p (%) nd nd nd 0.32
S 2p nd 0.75 1.78 0.59
Si 2p 0.5 1.19 nd nd
N 1s nd 0.71 nd nd
O/C 0.09 0.12 0.05 0.03
● The carbon samples contain different heteroatoms, O, Si,
● CS900 samples contain higher amount of oxygen
● CS700 samples contain higher amount of oxygen
● CS600 et CS700 contain Si
● CS700 and CS800 samples contain sulfur
0
200
400
600
800
1000
0 0,2 0,4 0,6 0,8 1
P/P0
Textural analysis
● Rectangular chape: capacitive
behaviour
● No faradic reactions
● CS 700, CS 800, have the better
chapes
Electrochemical study cyclic
-0.5
0
0.5
1
1.5
-300
-200
-100
0
100
0 200 400 600 800 1000
(i): Voltage
(ii): Current
Cellvoltage/V
Cyclingcurrent/mAg
-1
Time / s
(ii)
Cellvoltage/V
-1
-0.5
0
0.5
1
1.5
2
2.5
3
-400
-200
0
200
400
6500 7000 7500 8000
(i): Voltage
(ii): Current
Cellvoltage/V
Cyclingcurrent/mAg
-1
Time / s
(ii)
(i)
Cellvoltage/V
Charge/discharge galvanostatic cycling at 2.5 V of
the seaweed carbon supercapacitorCyclic voltammograms of symmetric two-electrode
capacitors (Roche et al, submitted)
Electrochemical results
● For CSN a higher capa and CT samples optimal temperature is 800°C
● Higher capacitance, lower resistance
Samples Capacitance
(F/g)
Electrolyte
CS600 84,4 1mol.L-1
H2SO4
CS700 83,7 1mol.L-1
H2SO4
CS800 95,1 1mol.L-1
H2SO4
CS900 47,8 1mol.L-1
H2SO4
CSN 141,78 6M KOH
PhD S. Roche
Material Capacitance
(F g-1)
BET surface
area (m2 g-1)
Electrolyte
Cassava
peel
153 1352 H2SO4
Coffee shells 150 842 KOH
Cherry
stones
232 1292 H2SO4
Bamboo 68 1251 H2SO4, KOH
Fir wood 197 2821 H2SO4
Banana fiber 74 1079 Na2SO4
Rubber
Wood Saw
Dust
138 912 H2SO4
Argan
(Argania
spinosa)
259-355 2100 H2SO4
Compared physical properties and electrochemical properties of different
carbonized biomass precursors (Gaspard & Taberna, in Biomass for
sustainable applications, RSC book series)
● Our values are similar to those obtained in the literature for lignocelulosic precursors
Treatment of water contaminated with micropollutant pharmaceutical
Compounds, diazepam, caffeine
Caffeine
Diazepam
Qmax(mg g-1) = 212 mg/gQmax(mg g-1) = 190 mg/g
PhD M. Francoeur
PhD M. Manduca
Chromium adsorption
Qmax(mg g-1) = 57 mg/g
PhD Y. Alvarez
AC can be prepared from sargassum by different
procedure
Sargassum AC has good electrochemical properties
Sargassum AC has good adsorptive properties for organic
compounds and chromium
CONCLUSION
ACKNOLEDGMENTS
 Enseignants-chercheurs
Ulises Jaurégui-Haza
Christelle Yacou
Nady Passé-Coutrin
Valérie Jeanne-Rose
MM Titirici
 Personnel technique
Corine Jean-Marius
• Financeurs
SYMEG, ANRT (CIFRE)
FCR Région Guadeloupe,
MECYST République
dominicaine
ANR, Amb France à Cuba
• Doctorants
Sandra Roche
Yeray Alvarez
Markens Francoeur
Michel Manduca
Kénia Melchor
Suly Rambinaising
• Post-doc/Ingénieur de
recherche
Ronald Ranguin
• Institutions partenaires
INRA Guadeloupe, Nancy
INRA INSTEC Cuba
INTEC St Domingue
Queen Mary University
• Entreprises
NBC (Guyane), TECMALAB
(Rep Dominicaine), NST
(Guadeloupe), Phytobokaz
THANK YOU FOR YOUR
ATTENTION
19

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Activated Carbon from Sargassum for Water Treatment and Energy Storage

  • 1. Recycling of sargassum for activated carbon production Sarra Gaspard, Université des Antilles, Laboratoire COVACHIMM2E 25/10/2019
  • 2. Annual needs 1.9 Mio Tons Many applications Water, air treatment, Food processing Pharmaceutical applications, energy storage ACTIVATED CARBON ? Carbon material Previously produced from mineral carbon Nowadays mainly produced from biomass (mostly from coconut) Porous material
  • 3. Energy storage Biomass valorization AC synthesis COVACHIMM2E BIOMASS VALORIZATION FOR REMEDIATION AND ENERGY STORAGE Pesticide sequestration In animals Capacitive deionization for water treatment PhD, S. Roche PhD, Yeray Alvarez ANR project PhD, Marckens Francoeur PhD, Michel Manduca Water treatment Pharmaceutical compound,
  • 4. WHY PRODUCING CARBON MATERIAL FROM ALGA FOR CARBON MATERIAL PRODUCTION Due to their chemical composition, seaweeds are fantastic precursors for nanotextured carbons preparation. Depending of pyrolysis conditions, oxygen enriched carbons, with tuned micro/mesoporosity can be obtained. Natural Carbon source High chemical variety Highly available and cheap
  • 5. HOW TO PREPARE ACTIVATED CARBON ? Fabrication  pyrolysis  Physical activation  Chemical activation  Hydrothermal carbonizatin Precursor Chemical Impregnation (ac. Phos) + pyrolysis Physical activation Chemical activation 500 - 700°C Activation (H2O, CO2) BIOCHAR ACTIVATED CARBON ACTIVATED CARBON Pyrolysis hydrothermal carbonization+ imprégnation + pyrolysis HTC a
  • 6. Supercapacitors are composed of: • Electrode made of Highly porous materials • such as carbon materials • A separator • An electrolyte - - + + + + + + + + + + + + - - - - - - - - - - - - - - - - - - -- - - - - - + + + + + + + + + ++++ + + + + - - Current collector Active material Electrolyte Electrode Separator - - - - - + + + + + t By applying a potential: positive charges remain on one plate, and negative charge on the other plate = charged state During discharge: negative and positive charges are released Batteries : called also electrochemical capacitors Able to store and release energy in a short time (few seconds) Used for electric vehicles, tramways, wind turbines, computers, for ex.. CARBON ELECTRODES FOR SUPERCAPACITORS
  • 7.
  • 8.  Textural characteristics  Nitrogen adsorption  BET surface area  Porous Volume  Surface chemistry  Xray photo-électron spectroscopy  Elemental Analysis  Surface functionnal groups  Electrochemical properties Cyclic voltametry Galvanometry measurement Carbon sample characterization Adsorption studies kinetic Isotherm
  • 9. Thermogravimetric analysis of Sargassum -3 -2.5 -2 -1.5 -1 -0.5 0 0.5 -40 -20 0 20 40 60 80 100 40 240 440 640 840 1040 Weightloss(%) Temperature (°C) TG sarg_brut dTG_sarg_brut Laminarin , first stage fucoidan Water, alginate Second decomposition stage fucoidan Mannitol EDX Analysis CS 800 30 m CS 700 30 m CS 900 30 m 30 m CS 600 100 m CSraw 30 m CSraw
  • 10. surface elemental composition obtained by XPS analysis Atom CS600 CS700 CS800 CS900 O 1s (%) 7.98 10 4.54 2.76 C 1s (%) 91.57 87.16 93.68 96.33 C2p (%) nd nd nd 0.32 S 2p nd 0.75 1.78 0.59 Si 2p 0.5 1.19 nd nd N 1s nd 0.71 nd nd O/C 0.09 0.12 0.05 0.03 ● The carbon samples contain different heteroatoms, O, Si, ● CS900 samples contain higher amount of oxygen ● CS700 samples contain higher amount of oxygen ● CS600 et CS700 contain Si ● CS700 and CS800 samples contain sulfur
  • 11. 0 200 400 600 800 1000 0 0,2 0,4 0,6 0,8 1 P/P0 Textural analysis
  • 12. ● Rectangular chape: capacitive behaviour ● No faradic reactions ● CS 700, CS 800, have the better chapes Electrochemical study cyclic -0.5 0 0.5 1 1.5 -300 -200 -100 0 100 0 200 400 600 800 1000 (i): Voltage (ii): Current Cellvoltage/V Cyclingcurrent/mAg -1 Time / s (ii) Cellvoltage/V -1 -0.5 0 0.5 1 1.5 2 2.5 3 -400 -200 0 200 400 6500 7000 7500 8000 (i): Voltage (ii): Current Cellvoltage/V Cyclingcurrent/mAg -1 Time / s (ii) (i) Cellvoltage/V Charge/discharge galvanostatic cycling at 2.5 V of the seaweed carbon supercapacitorCyclic voltammograms of symmetric two-electrode capacitors (Roche et al, submitted)
  • 13. Electrochemical results ● For CSN a higher capa and CT samples optimal temperature is 800°C ● Higher capacitance, lower resistance Samples Capacitance (F/g) Electrolyte CS600 84,4 1mol.L-1 H2SO4 CS700 83,7 1mol.L-1 H2SO4 CS800 95,1 1mol.L-1 H2SO4 CS900 47,8 1mol.L-1 H2SO4 CSN 141,78 6M KOH PhD S. Roche
  • 14. Material Capacitance (F g-1) BET surface area (m2 g-1) Electrolyte Cassava peel 153 1352 H2SO4 Coffee shells 150 842 KOH Cherry stones 232 1292 H2SO4 Bamboo 68 1251 H2SO4, KOH Fir wood 197 2821 H2SO4 Banana fiber 74 1079 Na2SO4 Rubber Wood Saw Dust 138 912 H2SO4 Argan (Argania spinosa) 259-355 2100 H2SO4 Compared physical properties and electrochemical properties of different carbonized biomass precursors (Gaspard & Taberna, in Biomass for sustainable applications, RSC book series) ● Our values are similar to those obtained in the literature for lignocelulosic precursors
  • 15. Treatment of water contaminated with micropollutant pharmaceutical Compounds, diazepam, caffeine Caffeine Diazepam Qmax(mg g-1) = 212 mg/gQmax(mg g-1) = 190 mg/g PhD M. Francoeur PhD M. Manduca
  • 16. Chromium adsorption Qmax(mg g-1) = 57 mg/g PhD Y. Alvarez
  • 17. AC can be prepared from sargassum by different procedure Sargassum AC has good electrochemical properties Sargassum AC has good adsorptive properties for organic compounds and chromium CONCLUSION
  • 18. ACKNOLEDGMENTS  Enseignants-chercheurs Ulises Jaurégui-Haza Christelle Yacou Nady Passé-Coutrin Valérie Jeanne-Rose MM Titirici  Personnel technique Corine Jean-Marius • Financeurs SYMEG, ANRT (CIFRE) FCR Région Guadeloupe, MECYST République dominicaine ANR, Amb France à Cuba • Doctorants Sandra Roche Yeray Alvarez Markens Francoeur Michel Manduca Kénia Melchor Suly Rambinaising • Post-doc/Ingénieur de recherche Ronald Ranguin • Institutions partenaires INRA Guadeloupe, Nancy INRA INSTEC Cuba INTEC St Domingue Queen Mary University • Entreprises NBC (Guyane), TECMALAB (Rep Dominicaine), NST (Guadeloupe), Phytobokaz
  • 19. THANK YOU FOR YOUR ATTENTION 19