Materials Chemistry A: Journal of
Materials Chemistry A: Journal of
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Removal of acidic gases such as H2S and CO2 is performed during the purication of raw natural gas, most
commonly using amine gas treatment. However, this industrially entrenched method is limited by
signicant shortcomings including low operational capture eciency, amine pipeline corrosion and a
large energy penalty due to the sorbent regeneration process. To address these shortcomings, we have
studied the use of peruorinated silica-stabilized dry alkanolamines (DAf) for CO2 capture. Due to their
micronized liquid domains, DAf display high operational CO2 capture eciency. Further, to minimize
energy requirements for sorbent regeneration, microwave-assisted regeneration of the spent DAf
Received 18th November 2014
Accepted 16th February 2015
sorbent was also studied and shown to decrease the energy requirements by about ten times. In
contrast to very recent work, our results show that the use of DAf exhibits extraordinary recyclability,
DOI: 10.1039/c4ta06273f
with a negligible decrease in absorption capacity over at least ten absorptionregeneration cycles,
www.rsc.org/MaterialsA indicating the potential of this material for gas treatment applications.
a
Institute of Materials Research and Engineering, Agency for Science Technology and
Research, 3 Research Link, Singapore 117602, Singapore. E-mail: j.chin@hull.ac.uk
b
Surfactant & Colloid Group, Department of Chemistry, University of Hull, HU6 7RX,
UK. E-mail: b.p.binks@hull.ac.uk
Electronic supplementary information (ESI) available: Detailed experimental Scheme 1 Reaction of (a) monoethanolamine (MEA) and (b) dieth-
procedures, ESI Fig. S1S4 and ESI Tables S1S3. See DOI: 10.1039/c4ta06273f anolamine (DEA) with CO2 to form the corresponding carbamate salts.
6440 | J. Mater. Chem. A, 2015, 3, 64406446 This journal is The Royal Society of Chemistry 2015
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We herein report the use of dry, undiluted alkanolamines for to dry water (DW) which has received signicant attention in
CO2 capture whereby instead of hydrocarbon-functionalized, recent years.2731
hydrophobic fumed silica, peruoroalkyl-functionalized oleo- For dry liquid formation to occur, the stabilizing particles
phobic fumed silica was utilized for dry alkanolamine, DA, must be hydrophobic towards the encapsulated liquid, other-
formation. These ndings were previously outlined in our wise a foam or paste may ensue.27 Generally, for a at surface to
patent led in May 2013,26 prior to the work being reported by be hydrophobic towards a liquid (contact angle > 90 ), the solid
Dawson et al. We refer to this DA as DAf. In contrast to the surface tension gS must be gS gL/4, where gL is the surface
ndings by Dawson et al.,25 we found that DAf showed excellent tension of the liquid.32 It has recently been demonstrated that
recyclability and stability. Studies were conducted on mono- the formation of dry oils with liquids of decreasing surface
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ethanolamine (MEA) and diethanolamine (DEA) due to their tension requires the use of nanoparticles with increasing
degrees of uorination on their surfaces.33 Based on the surface
Open Access Article. Published on 17 February 2015. Downloaded on 30/11/2015 13:47:43.
Methods
Synthesis of peruoroalkyl-functionalized oleophobic SiO2
nanoparticles. 10 g of fumed SiO2 was added to a well-mixed
solution of 220 mL ethanol, 11 mL of 28% aqueous NH3 and 2
mL of 1H,1H,2H,2H-peruorooctyltriethoxysilane, which was
then homogenized (using an IKA T18 basic Ultra Turrax digital
homogenizer) for 30 min until a homogeneous suspension was
obtained. The resulting dispersion was stirred at 400 50 rpm
at room temperature overnight, aer which the dispersion was
heated on a hot plate to evaporate the solvents and subse-
quently dried in an oven at 80 C for 12 days to collect the dry
peruorinated silica powder. Thermogravimetric analysis (TGA)
was performed using a TGA Q500 v6.7 Build 203 instrument,
from room temperature to 800 C at a rate of 20 C min1 with
40 mL min1 of nitrogen gas as the balance gas and 60 mL
min1 of air as the sample gas. TGA of peruorinated silica
versus unmodied fumed silica particles showed that the per-
uorocarbon groups comprised approximately 35 wt% of the
functionalized silica (Fig. S2). Dynamic Light Scattering (DLS)
studies were performed with a Brookhaven ZetaPlus Zeta
Potential Analyzer to determine the size distribution of
Fig. 1 (a) Sketch of a liquid droplet in air encapsulated by particles of unmodied fumed silica particles versus peruorinated fumed
low surface energy. Since the particles form a porous shell on the
silica particles aer dispersing them in ethanol. DLS studies
surface of the liquid, there is rapid diusion of gases into and out of the
liquid through the particle interstices. (b) Sketch of a dry liquid (left) and showed that the average aggregate size of peruorinated silica
bulk liquid (right) in round-bottomed asks. (c) Photograph of the DAf particles was smaller than that of unmodied fumed silica
powder containing DEA. particles (282 nm vs. 367 nm, see Table S2).
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Results and discussion In this equation, Dij is the diusion coecient of solute i in
pure solvent j, k is the Boltzmann constant, T is the tempera-
BrunauerEmmettTeller (BET) analysis performed on per- ture, nSE is the StokesEinstein number, hj is the solvent
uorinated SiO2 particles showed that CO2 adsorption on these viscosity, Ri is the radius of the solute molecule and Rj is the
particles at room temperature was negligible (Fig. 2), because 1 radius of the solvent molecule. According to eqn (1), the diu-
g of peruorinated SiO2 nanoparticles absorbed approximately sion coecient of CO2 gas in the amine sorbent decreases with
6 mg of CO2 at atmospheric pressure while 1 g of DAf (con- increasing solvent viscosity. Further, given that the system
taining 0.48 g of peruorinated silica) absorbed approximately studied is stationary and unagitated, the increased viscosity also
100 mg of CO2. Of this 100 mg, about 3% is attributed to signicantly aects the replenishing of the unreacted amine
adsorption by silica. Hence, the mass increase is largely due to near the gasliquid interface, which is dependent upon the
CO2 uptake by the alkanolamine.
6442 | J. Mater. Chem. A, 2015, 3, 64406446 This journal is The Royal Society of Chemistry 2015
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Fig. 3 Results of the absorption prole of CO2 into bulk alkanolamine or DAf for (a) MEA and (b) DEA at room temperature and pressure.
movement of alkanolamine molecules towards the interface via regenerate the alkanolamines. The decrease in mass was
convection currents or diusion. attributed to both CO2 and H2O release, which was veried by
However, due to the small domain sizes within DAf thermogravimetric mass spectroscopy (TG-MS) analysis
(approximate diameter of a microscopic liquid marble is 80 (see Fig. 4).
30 mm, as measured by cryo-SEM), the required distance of CO2 For each sample of bulk alkanolamine and DAf, three cycles
diusion within the droplets to contact the unreacted alkanol- of absorption and desorption of CO2 were performed (Fig. 5). As
amine is signicantly less than for the bulk liquid. This helps to shown in Fig. 5, DEA appears to be more recyclable than MEA,
explain why the DAf achieve a much larger gas absorption with a negligible change in CO2 uptake capacity over three
relative to the theoretical capacity within the timeframe of the cycles. This is because secondary amines like DEA form weaker
experiment than do the bulk amines. In addition, the reason for bonds with CO2 than primary amines like MEA, allowing for
the slightly higher absorption capacity of dry MEA compared to easier regeneration of the free amines.37 This is supported by
dry DEA is due to the inherently lower viscosity of the former the ndings of McCann et al., where the enthalpy of carbamate
compared to the latter. formation for MEA and DEA was found to be 29.7 kJ mol1
Based on the work of Wang et al.,31 who postulated that the and 23.7 kJ mol1, respectively.38 Moreover, MEA has a lower
higher methane gas hydrate formation rate in dry versus bulk boiling point than DEA (170 C vs. 271 C) and a much higher
water was due to the higher surface area to volume ratio in dry vapour pressure, leading to a greater degree of sorbent loss per
water, and taking the view that the rate of gas uptake is cycle.
dependent upon the gasliquid interfacial area, we expect that As heating is essential for the sorbent regeneration process,
the CO2 absorption rate by DAf would follow a similar trend it is imperative to maximize the heat transfer eciency within
(estimated surface area to volume ratio in DAf is 75 000 m1 the amine sorbents. This is dependent on the three main
based on the volume of alkanolamine present). Nevertheless, mechanisms of heat transfer, namely conduction, convection
the gasliquid interfacial area of the microscopic liquid drop- and radiation. In the case of DAf, these three mechanisms
lets is reduced by the presence of the silica shell around each happen to be hindered by the silica shell encasing the
droplet; CO2 must diuse across this porous shell to react with micronized alkanolamine droplets and the air pockets
the encapsulated alkanolamines. throughout the dry liquids. For heat transfer via conduction,
Our CO2 uptake studies showed that for MEA, the absorption fumed silica particles exhibit low thermal conductivity due to
rate by the bulk liquid in the rst minute was faster than that by the nanoscale pores among them in their fractal arrange-
dry MEA (Fig. S4). This is presumably because the lower liquid ment,39,40 causing the silica shell to block eective heat
viscosity of MEA compared with DEA means that CO2 mass conduction from the heat source to the droplets. Importantly,
transfer eects do not outweigh the eect of the silica barrier many air pockets between the microscopic particle-coated
initially. However, as carbamate formation proceeds, the liquid marbles in DAf also limit heat conductivity. With regard
viscosity of the liquid mixture increases (Table S3), and mass to convection, the liquid in DAf exists as dispersed microscopic
transfer eects become more important. The rate of CO2 uptake droplets, thereby limiting convective heat transfer. As for radi-
therefore becomes faster for dry over bulk MEA. For DEA, dry ative heat transfer, Taylan and Berberoglu have shown that the
DEA exhibits faster CO2 absorption than bulk DEA throughout silica shell in dry water greatly attenuates infrared radiative heat
the entire absorption cycle (Fig. S4), because the mass transfer transfer due to its high single-scattering albedo, i.e. a signi-
rate in the more viscous DEA liquid was much slower and hence cantly larger proportion of heat radiation is scattered compared
the eect of higher surface area to volume ratio of dry DEA was to that absorbed by the silica shell,41 thus preventing infrared
more prominent. radiative heat transfer from the heat source to the droplets.
Since the carbamate salts decompose in the temperature Since the three major forms of heat transfer are signicantly
range of 100150 C,35,36 the CO2-loaded bulk alkanolamines inhibited for DAf, we turned to microwave heating as an alter-
were heated to 120 C to release the absorbed CO2 gas and native method to improve the eciency of heat transfer during
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Fig. 4 (a and b) TG-MS graphs of CO2-loaded bulk DEA, and (c and d) TG-MS graphs of bulk DEA without CO2 loading. (a) The black line shows a
decrease of 18.92% of the initial sample mass for CO2-loaded bulk DEA with a concomitant increase in the sample temperature from 30 to 120 C
as depicted by the blue line, (b) graph corresponding to (a), depicting ion current detection of both CO2 and H2O. (c) The black line shows a
decrease of 16.03% of the initial sample mass for bulk DEA, (d) graph corresponding to (c) depicting detection of only H2O but not CO2.
the regeneration process. This method is dependent on the approximately 1 h until no further mass loss occurred. To test
ability of the irradiated material, e.g. a solvent, to absorb the recyclability of the sorbent and conrm that the observed
microwave energy and convert it to heat, which is quantied by mass loss was correctly attributed to the CO2 loss, 10 repeated
a dielectric parameter called the loss factor tan d. This loss cycles of CO2 absorption and removal were carried out, as
factor is expressed as:42 shown in Fig. 6. The level of CO2 uptake by dry DEA was found to
300 be stable over at least 10 cycles, showing an excellent recycla-
tan d (2) bility of dry DEA. Similar regeneration results were obtained
30
using a simple household microwave instrument, although the
where 300 is the dielectric loss, which is indicative of the e- heating periods were limited to 1020 s in order to avoid
ciency with which electromagnetic radiation is converted into overheating.
heat, and 30 is the dielectric constant describing the ability of Regeneration of DAf via microwave heating was found to be
molecules to be polarized by the electric eld. A solvent with a more ecient than conventional hotplate heating under the
high tan d value of more than 0.5 is required for ecient same conditions (whereby no purge gas was used). Conven-
microwave absorption. DEA, with a high tan d value of 0.6 at tional hotplate heating took more than 3 h and consumed about
2.45 GHz at 278 K can be rapidly heated to temperatures >100 C 0.38 kW h per cycle on average. Microwave heating on the other
within a minute when irradiated under microwave hand took about 1 h and consumed about 0.034 kW h per cycle
conditions.43 on average, which is less than 10% of the energy consumption
Owing to the higher recyclability of DEA over MEA, we chose by conventional hotplate heating.
to study DEA for microwave heating-based regeneration. Finally, the recyclability of the peruorinated silica particles
Samples of approximately 10 g of dry DEA containing 5 mL of was investigated. Alkanolamines typically undergo degradation
liquid DEA were loaded with CO2 until the absorption pla- over multiple absorption and regeneration cycles aer which
teaued, and the CO2-loaded samples were subsequently heated they must be replaced.44 Nevertheless, the peruorinated silica
in a programmable microwave synthesizer at 120 C for particles could be separated from the amines by dispersion of
6444 | J. Mater. Chem. A, 2015, 3, 64406446 This journal is The Royal Society of Chemistry 2015
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Conclusions
In conclusion, the dry alkanolamines described herein
demonstrate signicantly enhanced performance with regard to
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Acknowledgements
JMC would like to acknowledge the Institute of Materials
Research and Engineering, Agency for Science Technology and
Research (A*STAR) for funding this work. The authors thank Mr
Anthony Sinclair for the cryo-SEM analysis, Ms Sophie A. Dar-
ragh, Dr Michael R. Reithofer, Dr Tommy S. Horozov, Dr Robert
A. Lewis and Dr R. McDonald for helpful discussions.
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6446 | J. Mater. Chem. A, 2015, 3, 64406446 This journal is The Royal Society of Chemistry 2015