development of composite and hybrid materials from
TRANSCRIPT
CYPRUS2016
P.M. NIGAY1, C. WHITE 2,W. SOBOYEJO 3, A. NZIHOU1
Development of composite and hybrid materials from
gasification biochar and clay
1 Mines Albi, RAPSODEE Research Center, CNRS, France2 Princeton University, Civil and Environmental Engineering, USA3 Princeton University, Mechanical and Aerospace Engineering, USA
4th International Conference on Sustainable Solid Waste Management‐ Limassol, CYPRUS, 23‐25 June 2016
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OUTLINE
I. Introduction
II. Biochar
III. Clay
IV. Applications
V. Conclusions
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Carbonaceous materials including carbon black, carbon fibers, carbon nanotubes (CNTs) and graphenes are of great interest
Carbonaceous materials can derive from renewable resources such as Biomass and Biogenic waste
New momentum for clay energy based materials, clay bricks, clay geopolymer mortars, clay sorbents, clay biopolymer fillers
Raw natural clay from deposite sites or processed by chemical/thermal/mechanical treatment with additives
Engineered biochars / clays composites for various applications
Widespread utilization of Carbonaceous and Clay materials
I. Introduction
Hybrid: mixture of two or more materials to obtain a material with new propertiesComposite: mixture of carbon materials with inorganic or organic matter to produce a new material with structural and functional properties
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OUTLINE
I. Introduction
II. Biochar
III. Clay
IV. Applications
V. Conclusions
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Thermochemical conversion – range of applicationsB I O G R E E N ® i n t r o d u c t i o n
conversion most of the feedstock into
methane-rich syngas which can be
valorized into energy by using it CHP
unit or steam boiler. Yield of syngas
ranges from 50 and 95%
HT pyrolysis & gasification
SYNGASSYNGAS
a mild form of pyrolysis dedicated only
for biomass conversion. Torrefaction
leads to obtaining dry product with
higher energy content. Main product is
biocoal - yield between 70 and 80%
Torrefaction
BIOCOALBIOCOAL
enables chemical conversion of
products like biomass, plastic, or rubber
into a solid, liquid or gas phase. Enables
valorization to biooil and biochar. Yield
of biooil ranges from 30 to 60%.
Yield of biochar 25 to 35%
MT pyrolysis
BIOOIL, BIOCHARBIOOIL, BIOCHAR
600 ‐ 900°C300 ‐ 550°C250 ‐ 280°C
www.etia.fr
100‐ 150°C
Drying
A dehydration with the release of light
hydrocarbons
GASGAS
CO+H2
II. Biochar - Biochar production
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By-product for plant extract Wood sawdust Crop residue Green waste
BIOCHAR PROPERTIES DEPENDS ON BIOMASS AND OPERATING CONDITIONS
Biochar is biomass dependant !B I O G R E E N ® B i o m a s s c o n v e r s i o n I. Biochar
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Energy Fuel cellsphotovoltaicSupercapacitors
ChemistryCatalystAdsorbentWater treatment
Agronomy Water retentionPlant nutrientsSoil conditioner
EnvironmentCarbon sequestrationCO2 StorageSensors
Reinforcing materialsin polymer composites.Biocomposites
Other usesBiomedical use Pharmaceutical Gas storage
II. Biochars
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Van Krevelen plot for biocharStructure Various material forms within the black carbon defined
by the range in the oxygen to carbon (O/C) ratio :
Exposition of Carbon atoms
MgMg
KKCaCa
NiNi
FeFe
ZnZn
NaNaPbPb
AsAs
Mass loss,
Structure of chars vs temperatures towards graphitic structures
Carbonaceous matrix: Aromatic units /O within heterocyclic and phenolic group /Aromatic units cross-linked by ether and olefine
II. Biochar
Biochar stability
Biomass (O/C > 0.6)
Biochar (0.4 < O/C < 0.6)
Charcoal (0.2 < O/C < 0.4)
Soot (0 < O/C < 0.2)
Graphite (O/C = 0)Incr
easi
ng O
/C ra
tio
T
150°C
1000°C
H/C
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Carbon structure of the raw biochar
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0.8
0.9
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800 1000 1200 1400 1600 1800 2000
Normalized
intensity
Raman shift (cm‐1)
• Raw biochar complex carbon containing:
‐ Ordered structures
‐ Disordered structures
• turbostratic carbon:
‐ Diffuse SAED
‐ No organization of the graphene layers
HRTEM
Raman spectrum
II. Biochar
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OUTLINE
I. Introduction
II. Biochar
III. Clay
IV. Applications
V. Conclusions
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KAl3Si3O10(OH)2 → KAl3Si3O11 + H2O
CaCO3 + SiO2 → CaSiO3 + CO2
Dehydroxylation of clay minerals at 500°C:
Degradation of calcium carbonates at 700°C:
Combination as stable silicates up to 1200°C
Stability and structure
Stacking of alumina and silica sheets
III. Clay
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OUTLINE
I. Introduction
II. Biochar
III. Clay
IV. Applications
V. Conclusions
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0 200 400 600 800 1000 1200
Poro
sity
(%)
Temperature (°C)
Clay + 15% Biomass (N2)Clay + 10% Biomass (N2)Clay + 5% Biomass (N2)Clay (N2)
[*] Calculation of the porosity via experimentalcoupling between TGA and TMA
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0 200 400 600 800 1000 1200Po
rosit
y(%
)Temperature (°C)
Clay + 15% Biochar (N2)Clay + 10% Biochar (N2)Clay + 5% Biochar (N2)Clay (N2)
Control of the porosity rate and morphology of the composites
IV. Applications
Release of H2O and CO2
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0 200 400 600 800 1000 1200
Poro
sity
(%)
Temperature (°C)
Clay + 15% Biochar (Air)Clay + 10% Biochar (Air)Clay + 5% Biochar (Air)0
10
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0 200 400 600 800 1000 1200
Poro
sity
(%)
Temperature (°C)
Clay + 15% Biochar (N2)Clay + 10% Biochar (N2)Clay + 5% Biochar (N2)Clay (N2)
Control of the porosity rate and morphology of the composites
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Spec
ific
surfa
ce a
rea
(m²/
g)
Biochar rate (%)
Clay + Biochar
Clay-Biochar composites
Filters for effluents treatment Sensors for pollutants removal
IV. Applications
SensorInlet gas Outlet gas
Inlet gas
Outlet gas
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Sensors
0
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60
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Claymaterials
Clay + 5%Biomass
Clay + 5%Biochar
Clay + 10%Biomass
Clay + 10%Biochar
Clay + 15%Biomass
Clay + 15%Biochar
Colle
ctio
n of
Cd
(%)
Collection of Cadmium into the composite[*]
[*] Concentration of cadmium using ICP
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Intermittent nature of the renewable energy sources
Exclusive production of energy with sun or wind ...
Grading of the excess by means of a storage
Storage by sensible heat (Q) of materials
Q=m.cp.∆T
Require materials with a high thermal capacity (cp)
Addition of organics and firing under inert atmosphere (N2)
Conservation of organics with a high cp in inorganic structure
IV. Applications – Energy storage
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1,2
1,3
1,4
1,5
0 5 10 15 20
Ther
mal
cap
acity
(kJ/
kg.K
)
Addition rate (%)
Clay + Biochar (300°C)Clay + Biomass (300°C)
Improvement of thermal capacity with biochar addition of 15% Easy production and handling in comparison to rivals (molten salts)
[*] Thermal properties of the materials fired to 950°C using hot disk method at 300°C
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1,0
1,2
1,4
1,6
Ther
mal
cap
acity
(kJ/
kg.K
) Ceramics
Concrete
Clay/Biochar
Molten Salts
Clay-Biochar compositesIV. Applications
Materials for energy storage
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OUTLINE
I. Introduction
II. Biochar
III. Clay
IV. Applications
V. Conclusions
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Advantages using carbon additives Improvement of the reactivity Increase of the functionnality
Motivation for further studiesProduction of advanced composites from biochar and clay : Sensors Catalysts Materials for insulation Materials for energy storage Soil amendement
V. Conclusions
Wide range of possibilities for biochar / clay composites
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ACKNOWLEDGMENTS
My group:
CYPRUS2016
Thank you for your attention!
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Contact:ange.nzihou@mines‐albi.fr
Institut Mines‐Télécom
4th International Conference on Sustainable Solid Waste Management‐ Limassol, CYPRUS, 23‐25 June 2016