Nanoparticle Enhanced

Nanoparticle-
enhanced CO
2
capture
Introduction
Objectives
Materials and
Methods
G-L Systems and
nanouids
Nanoparticles
Characterization
Apparatus
Experiments
Results
Diusion is
Fickian
Parameters
aecting E
p
Correlation of
results
Conclusions
Acknowledgments
Nanoparticle-enhanced capture of
carbon-dioxide with amine solvents
Srinivas Komati, Syam Sundar and A. K. Suresh
aksuresh@iitb.ac.in
Department of Chemical Engineering, IIT Bombay.
Powai, Mumbai 400076, INDIA.
Symposium on the Global energy future
(IIT Bombay) Nanoparticle-enhanced CO
2
capture Oct 04, 2010 1 / 20
Nanoparticle-
enhanced CO
2
capture
Introduction
Objectives
Materials and
Methods
G-L Systems and
nanouids
Nanoparticles
Characterization
Apparatus
Experiments
Results
Diusion is
Fickian
Parameters
aecting E
p
Correlation of
results
Conclusions
Acknowledgments
Outline
1 Introduction
Objectives
2 Materials and Methods
Gas-liquid systems and nanouids
Nanoparticles
Characterization
Experimental apparatus
Experiments: Regimes and Hydrodynamic conditions
3 Results
Diusion is Fickian
Parameters aecting E
p
Correlation of results
4 Conclusions
5 Acknowledgments
2
capture Oct 04, 2010 2 / 20
Nanoparticle-
enhanced CO
2
capture
Introduction
Objectives
Materials and
Methods
G-L Systems and
nanouids
Nanoparticles
Characterization
Apparatus
Experiments
Results
Diusion is
Fickian
Parameters
aecting E
p
Correlation of
results
Conclusions
Acknowledgments
Introduction
Introduction
Proven and currently practiced processes for CO
2
capture
in power generation from coal are based on gas absorption:
Conventional plants - chemical absorption based on amine
(MEA/MDEA/hindered amines) solvents
Gasication - physical absorption (Selexol/Rectisol
processes)
The gas-liquid mass transfer step is an important
determinant of the rate at which CO
2
can be captured,
and hence, of equipment size. Intensication of this step is
therefore of interest.
2
capture Oct 04, 2010 3 / 20
Nanoparticle-
enhanced CO
2
capture
Introduction
Objectives
Materials and
Methods
G-L Systems and
nanouids
Nanoparticles
Characterization
Apparatus
Experiments
Results
Diusion is
Fickian
Parameters
aecting E
p
Correlation of
results
Conclusions
Acknowledgments
Introduction
Why nanoparticles?
Literature claims anomalous eects of nanoparticles on
transport rates in heat transport and momentum transport.
Eect of nanoparticles on mass transport: Literature
suggests an enhancement in rates, but is not conclusive
convective mass transport:
often studied in bubbling equipment, and interpreted in
terms of an overall eect on the rate eect on k
L
is
dicult to assess.
Particles of Fe
3
O
4
, CuO, Al
2
O
3
, SiO
2
, Cu and Au, of
dierent sizes (10 to 200 nm) and in dierent
concentrations (< 1 to 40%w) have been used.
conicting results results of dierent groups dicult to
compare.
Molecular transport: Limited data; qualitative and dicult
to interpret.
if proven, could have potential in the CO
2
capture
context!
2
capture Oct 04, 2010 4 / 20
Nanoparticle-
enhanced CO
2
capture
Introduction
Objectives
Materials and
Methods
G-L Systems and
nanouids
Nanoparticles
Characterization
Apparatus
Experiments
Results
Diusion is
Fickian
Parameters
aecting E
p
Correlation of
results
Conclusions
Acknowledgments
Introduction Objectives
Objectives of the present study
The objectives stem from the need
for systematic studies and to unify results from the few
such studies which exist in the literature
conduct studies in model contactors and model systems;
compare eects in dierent contactors
interpret the observations using the established theories of
interphase transport
Establish and validate a basis for process design.
also to examine the systems relevant to CO
2
capture.
to distinguish the eect from those that ne particles are
known to cause in gas-liquid transport,
Use well characterized particles so that enhancements due
to the grazing eect can be calculated
2
capture Oct 04, 2010 5 / 20
Nanoparticle-
enhanced CO
2
capture
Introduction
Objectives
Materials and
Methods
G-L Systems and
nanouids
Nanoparticles
Characterization
Apparatus
Experiments
Results
Diusion is
Fickian
Parameters
aecting E
p
Correlation of
results
Conclusions
Acknowledgments
Materials and Methods G-L Systems and nanouids
Gas-liquid systems studied and absorption regimes
Absorption of CO
2
in
Water: Physical absorption.
Methyldiethanolamine(MDEA) solutions: slow fast
transition, and Fast reaction regimes
Monoethanolamine(MEA) solutions: Instantaneous
reaction regime.
2
capture Oct 04, 2010 6 / 20
Nanoparticle-
enhanced CO
2
capture
Introduction
Objectives
Materials and
Methods
G-L Systems and
nanouids
Nanoparticles
Characterization
Apparatus
Experiments
Results
Diusion is
Fickian
Parameters
aecting E
p
Correlation of
results
Conclusions
Acknowledgments
Nanoparticles and their characteristics
Magnetic Iron oxide: ferrouids: Liquid phase co-precipitation
followed by stabilization by various means
L: stabilized by Lauric acid: Size 7-13 nm (average 10.1nm);
Stable for short times in tert-amines; not very
stable in primary and secondary amines.
T: stabilized by TMAOH: Size 10-35 nm (average 21.1 nm);
better stability than L.
P: stabilized by grafted polymer: Size 10-16 nm (average 13.2
nm); excellent stability.
Gold colloid: Made from HAuCl
4
; broad size distribution
(12-250 nm; average 110 nm).
Silica: Sigma-Aldrich; broad size distribution (6-240 nm;
average 110 nm); also Ludox HS-40 (14.7 nm) and Ludox
SM-30 (11.3 nm).
2
capture Oct 04, 2010 7 / 20
Nanoparticle-
enhanced CO
2
capture
Introduction
Objectives
Materials and
Methods
G-L Systems and
nanouids
Nanoparticles
Characterization
Apparatus
Experiments
Results
Diusion is
Fickian
Parameters
aecting E
p
Correlation of
results
Conclusions
Acknowledgments
Particle and system characterization
Particle size, its distribution and stability:
DLS
TEM
XRD and Debye-Scherrer equation
BET
Reactivity of the particles towards the solute.
Solubility of the gas (for CO
2
).
Specic surface: BET.
Surface tension (in the presence of P nanoparticles).
2
capture Oct 04, 2010 8 / 20
Nanoparticle-
enhanced CO
2
capture
Introduction
Objectives
Materials and
Methods
G-L Systems and
nanouids
Nanoparticles
Characterization
Apparatus
Experiments
Results
Diusion is
Fickian
Parameters
aecting E
p
Correlation of
results
Conclusions
Acknowledgments
Materials and Methods Apparatus
Apparatus Wetted wall column
Known hydrodynamics; conforms to penetration theory precepts.
short contact times (order of a sec); dead-end operation.
Experimental setup
Wetted wall
2
capture Oct 04, 2010 9 / 20
Nanoparticle-
enhanced CO
2
capture
Introduction
Objectives
Materials and
Methods
G-L Systems and
nanouids
Nanoparticles
Characterization
Apparatus
Experiments
Results
Diusion is
Fickian
Parameters
aecting E
p
Correlation of
results
Conclusions
Acknowledgments
Materials and Methods Apparatus
Apparatus Liquid lled capillary
Unsteady state absorption into quiescent liquid.
(See gure) Shrinkage of gas slug A gives the rate of mass
transfer.
Long contact times (tens of minutes).
2
capture Oct 04, 2010 10 / 20
Nanoparticle-
enhanced CO
2
capture
Introduction
Objectives
Materials and
Methods
G-L Systems and
nanouids
Nanoparticles
Characterization
Apparatus
Experiments
Results
Diusion is
Fickian
Parameters
aecting E
p
Correlation of
results
Conclusions
Acknowledgments
Materials and Methods Experiments
Experiments: Systems, regimes and Hydrodynamic
conditions
The systems, apparata and literature results allow a study under
dierent hydrodynamic conditions, and
dierent levels of diusion limitations.
Apparatus System Regime Nanoparticles
WWC CO
2
MDEA SlowFast Fe
3
O
4
(L,T,P)
Fast
CO
2
MEA Instantaneous Fe
3
O
4
(L,T,P)
O
2
dithionite SlowFast Fe
3
O
4
(P)
Capillary CO
2
water Physical Fe
3
O
4
(P); Au; Silica
CO
2
MEA Instantaneous Fe
3
O
4
(P)
Stirred cell O
2
water Physical Fe
3
O
4
Olle et al, 2006
Bubble column CO
2
MDEA Instantaneous Fe
3
O
4
(L,T)
Rajagopal et al, 2007
2
capture Oct 04, 2010 11 / 20
Nanoparticle-
enhanced CO
2
capture
Introduction
Objectives
Materials and
Methods
G-L Systems and
nanouids
Nanoparticles
Characterization
Apparatus
Experiments
Results
Diusion is
Fickian
Parameters
aecting E
p
Correlation of
results
Conclusions
Acknowledgments
Results
Enhancement E
p
due to nanoparticles
From the measured absorption rates, using the theory of
mass transfer with chemical reaction, the physical mass
transfer coecient k
L
is calculated.
Between WWC and capillary, a range of contact times
(hence k
L
values) can be obtained.
The values in the presence (k
L,p
) and absence (k
L
) of
nanoparticles are compared to dene an Enhancement
Factor E
p
due to particles:
%E
p
=
k
0
l ,p
k
0
l
100
2
capture Oct 04, 2010 12 / 20
Nanoparticle-
enhanced CO
2
capture
Introduction
Objectives
Materials and
Methods
G-L Systems and
nanouids
Nanoparticles
Characterization
Apparatus
Experiments
Results
Diusion is
Fickian
Parameters
aecting E
p
Correlation of
results
Conclusions
Acknowledgments
Results Diusion is Fickian
Is the diusion in nanouids Fickian?
Capillary: Fickian diusion into a stagnant uid
L
1
L
2
=
D
A
A
c
G
t =
Ek
L
c
A
Sc
G
square root dependence of (L
1
L
2
) on time.
Figure: (a) Fe
3
O
4
; CO
2
MEA Figure: (b) Gold, phys. absorp.
2
capture Oct 04, 2010 13 / 20
Nanoparticle-
enhanced CO
2
capture
Introduction
Objectives
Materials and
Methods
G-L Systems and
nanouids
Nanoparticles
Characterization
Apparatus
Experiments
Results
Diusion is
Fickian
Parameters
aecting E
p
Correlation of
results
Conclusions
Acknowledgments
Results Parameters aecting E
p
E
p
: Eect of particle hold-up and size
Size and hold-up matter
(dierent uids in WWC)
but so does the depth of
diusion! (P: Capillary)
2
capture Oct 04, 2010 14 / 20
Nanoparticle-
enhanced CO
2
capture
Introduction
Objectives
Materials and
Methods
G-L Systems and
nanouids
Nanoparticles
Characterization
Apparatus
Experiments
Results
Diusion is
Fickian
Parameters
aecting E
p
Correlation of
results
Conclusions
Acknowledgments
Results Correlation of results
A normalized particle size . . . and a correlation
It is the particle size d
p
in relation to the depth of
penetration of solute that is of importance!
Penetration theory: penetration depth with reaction
D
A
t
c
E
d
p
=
k
L
d
p
E
D
A
= Sh
m
a modied Sherwood number!
Processing the data to seek a correlation between E
p
in
terms of and Sh
m
gives:
E
p
= 1.519
0.17
Sh
0.16
m
2
capture Oct 04, 2010 15 / 20
Nanoparticle-
enhanced CO
2
capture
Introduction
Objectives
Materials and
Methods
G-L Systems and
nanouids
Nanoparticles
Characterization
Apparatus
Experiments
Results
Diusion is
Fickian
Parameters
aecting E
p
Correlation of
results
Conclusions
Acknowledgments
Results for Fe
3
O
4
this work
Conditions: 0.02% < < 1%; 4 10
6
< Sh
m
< 1.8 10
3
2
capture Oct 04, 2010 16 / 20
Nanoparticle-
enhanced CO
2
capture
Introduction
Objectives
Materials and
Methods
G-L Systems and
nanouids
Nanoparticles
Characterization
Apparatus
Experiments
Results
Diusion is
Fickian
Parameters
aecting E
p
Correlation of
results
Conclusions
Acknowledgments
Results: Comparison for Fe
3
O
4
with literature
data are from Olle et al., I&EC Research, 45,4355, 2006.
2
capture Oct 04, 2010 17 / 20
Nanoparticle-
enhanced CO
2
capture
Introduction
Objectives
Materials and
Methods
G-L Systems and
nanouids
Nanoparticles
Characterization
Apparatus
Experiments
Results
Diusion is
Fickian
Parameters
aecting E
p
Correlation of
results
Conclusions
Acknowledgments
Results: Comparison for other nanoparticles
Figure: (a) Wide PSD (10-250
nm) gold and silica
Figure: (b) Ludox HS-40 (14.7
nm) and SM-30 (11.3 nm).
2
capture Oct 04, 2010 18 / 20
Nanoparticle-
enhanced CO
2
capture
Introduction
Objectives
Materials and
Methods
G-L Systems and
nanouids
Nanoparticles
Characterization
Apparatus
Experiments
Results
Diusion is
Fickian
Parameters
aecting E
p
Correlation of
results
Conclusions
Acknowledgments
Conclusions
Conclusions
Nanoparticles in suspension enhance lliquid phase mass transfer
coecients. This work establishes this across several gas-liquid
systems, regimes, in the presence and absence of reaction, and
in the presence and absence of ow, for several types of
nanoparticles.
Extant theories for the eect of ne particles do not explain the
enhancements (large and inconsistent values of solute
partitioning on nanoparticles required to t the data).
The extent of enhancement depends on particle holdup and
particle size in relation to the depth of penetration in any
circumstance.
The results suggest that the nanoparticles inuence molecular
transport rates.
Taylor dispersion studies to measure liquid phase diusivities
and validation in a bubbling type contactor are in progress.
2
capture Oct 04, 2010 19 / 20
Nanoparticle-
enhanced CO
2
capture
Introduction
Objectives
Materials and
Methods
G-L Systems and
nanouids
Nanoparticles
Characterization
Apparatus
Experiments
Results
Diusion is
Fickian
Parameters
aecting E
p
Correlation of
results
Conclusions
Acknowledgments
Acknowledgments
Acknowledgments
Financial assistance:
Newreka (Pvt.) Ltd.
Ministry of Human Resource Developments Thrust area
funding.
C3U
2
capture Oct 04, 2010 20 / 20

Nanoparticle Enhanced

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