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Roles of double salt formation and NaNO3 in Na2 CO3 -promoted MgO absorbent
for intermediate temperature CO2 removal
Keling Zhang a,b , Xiaohong S. Li c , Yuhua Duan d , David L. King c,∗ , Prabhakar Singh a,b , Liyu Li c
a
Center for Clean Energy Engineering, University of Connecticut, Storrs, CT 06269, USA
b
Department of Chemical, Materials and Biomolecular Engineering, University of Connecticut, Storrs, CT 06269, USA
c
Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P. O. Box 999, Richland, WA 99354, USA
d
National Energy Technology Laboratory, United States Department of Energy, Pittsburgh, PA 15236, USA
a r t i c l e i n f o a b s t r a c t
Article history: Absorption and desorption of carbon dioxide on Na2 CO3 -promoted MgO have been studied at temper-
Received 14 May 2012 atures compatible with warm gas cleanup (300–470 ◦ C) from a pre-combustion syngas. The absorbents
Received in revised form 5 October 2012 are synthesized through the formation and activation of the precipitate resulting from the addition of
Accepted 12 November 2012
sodium carbonate to an aqueous solution of magnesium nitrate. The absorbent, which comprises MgO,
Available online 3 January 2013
Na2 CO3 and residual NaNO3 after activation, forms the double salt Na2 Mg(CO3 )2 on exposure to CO2 .
The thermodynamic properties of the double salt, obtained through computational calculation, predict
Keywords:
that the preferred temperature range for absorption of CO2 with the double salt is significantly higher
CO2 absorption and desorption
Na2 CO3 promoted MgO
compared with MgO. Faster CO2 uptake can be achieved as a result of this higher temperature absorp-
Na2 Mg(CO3 )2 double salt tion window. Absorption tests indicate that the double salt absorbent as prepared has a capacity toward
Warm temperature CO2 capture CO2 of 15 wt.% (3.4 mmol CO2 /g absorbent) and can be easily regenerated through both pressure swing
Pre-combustion CO2 capture and temperature swing absorption in multiple-cycle tests. Thermodynamic calculations also predict an
NaNO3 facilitated CO2 capture important effect of CO2 partial pressure on the absorption capacity in the warm temperature range. The
impurity phase, NaNO3 , is identified as a key component in facilitating CO2 absorption by these materials.
The reason for reported difficulties in reproducing the performance of these materials can be traced to
specific details of the synthesis method, which are reviewed in some detail.
© 2012 Elsevier Ltd. All rights reserved.
1. Introduction employ the CO2 capture step with a catalytic reaction such as water
gas shift, to increase equilibrium conversion. This is only possi-
Fossil-fueled power plants are by far the largest CO2 emitters ble with warm CO2 capture in which the two functions operate
and major contributors to greenhouse gas emissions, making them in the same temperature range (Hufton et al., 2000; Sircar et al.,
obvious targets for the implementation of advanced carbon dioxide 1995). Most commercial processes for capturing CO2 use alkaline
capture and storage technologies. Three predominant technologies solutions such as various alkylamines, or physical solvents such as
that produce CO2 from coal power plants are oxy-combustion, post- glycol ethers (Blamey et al., 2010; Steeneveldt et al., 2006). Unlike
combustion and pre-combustion (Herzog, 2009). Pre-combustion liquid absorbents, solid sorbents can in principle be used over a
produces syngas, which may be used in a number of processes, wider temperature range, from ambient temperature to 700 ◦ C.
such as methane, methanol, and Fischer–Tropsch synthesis, and Unmodified MgO has a very low capacity of 0.24 mmol/g at 200 ◦ C
H2 production for fuel cell power production or for IGCC applica- (a preferred temperature for CO2 absorption based on thermody-
tions. In general, syngas must be cleaned of impurities such as sulfur namic considerations) (Gregg and Ramsay, 1970), indicating poor
gases prior to utilization, and their removal at warm tempera- absorption kinetics at that temperature. However, higher tempera-
tures (300–500 ◦ C) provides an efficiency improvement in avoiding ture operation is limited by thermodynamic equilibrium: according
cooling and reheating the syngas prior to use. However, if CO2 is to HSC Chemistry (V. 6.1, Qutotec), MgCO3 decomposes to MgO
also to be captured for subsequent sequestration, warm CO2 cap- and CO2 above 300 ◦ C (at 1 bar CO2 pressure). At higher pressures,
ture prior to syngas utilization is also necessary to maintain the higher operating temperatures are possible and the performance of
efficiency advantage. In some applications, an added benefit is to MgO could improve, but the observed low kinetic rates and capaci-
ties remain a concern. Recently, several MgO-based materials with
significantly better performance have been reported to selectively
∗ Corresponding author. Tel.: +1 509 375 3908; fax: +1 509 375 2186. and reversibly absorb CO2 . An absorption capacity of 3.37 mmol/g
E-mail address: David.King@pnnl.gov (D.L. King). was reported for Mg(OH)2 , however, the operation of this sorbent is
1750-5836/$ – see front matter © 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijggc.2012.11.013
352 K. Zhang et al. / International Journal of Greenhouse Gas Control 12 (2013) 351–358
2. Experimental
Fig. 3. First 3 cycles of (a) TSA and (b) PSA CO2 absorption tests of Na2 CO3 -promoted MgO absorbent.
of 380 ◦ C and a desorption temperature of 470 ◦ C were selected for 2.3. Characterization
TSA tests. Similarly, 400 ◦ C was selected for the PSA tests. The initial
heating from room temperature to the absorption temperature for The phase components of the absorbents were identified by
both TSA and PSA tests was conducted in 100% N2 to avoid absorp- X-ray diffraction (Bruker D8 ADVANCE) using both standard and
tion before reaching the desired temperature. For TSA, during each in situ measurements, with a scanning rate of 2◦ /min, using Cu K␣
cooling step from 470 ◦ C to 380 ◦ C, the surrounding gas was 100% radiation. CO2 absorption during in situ XRD measurements was
N2 . The remaining steps during the temperature swing between conducted through temperature swing between 380 ◦ C and 470 ◦ C
380 ◦ C and 470 ◦ C were in 100% CO2 . The absorption and desorp- in a 100% CO2 environment. Scanning electron microscopy (SEM)
tion time durations were 60 min and 10 min, respectively. The PSA analysis was conducted using a JEOL JSM-5900LV microscope.
tests were carried out by exposing the sample to alternating 100%
CO2 for 30 min and 100% N2 for 60 min at 400 ◦ C. The absorption 3. Results and discussion
heat was measured along with the TG tests through differential
scanning calorimetry (DSC). In order to calibrate the device, the 3.1. Absorbent chemistry during synthesis
heat of fusion of high purity NaNO3 (99.995%, Sigma–Aldrich) was
measured by heating to 400 ◦ C in N2 , and a correction factor was During the preparation of the absorbent, the phase compo-
obtained which was applied to the measured CO2 heat of absorption nents were identified by XRD: after filtration in the form of wet
value. paste; after drying in the form of a dry cake; and after activation
354 K. Zhang et al. / International Journal of Greenhouse Gas Control 12 (2013) 351–358
Fig. 5. In situ X-ray diffraction patterns of Na2 CO3 -promoted MgO absorbent during TSA (380/470 ◦ C) absorption cycles.
of the computational methods have been described and pre- shown in Fig. 7(b) Na2 CO3 contained in the synthesized sorbent
sented elsewhere (Duan and Sorescu, 2010; Duan et al., mixture will remain stable in its carbonate form. Though not con-
2011). tributing to CO2 absorption by itself, it activates MgO through
Calculated enthalpy and free energy changes for CO2 cap- Na2 Mg(CO3 )2 formation, thereby increasing the effective operating
ture reactions by MgO, Na2 O, and MgO + Na2 CO3 (double salt) temperature range for CO2 capture.
are shown in Fig. 7(a) and (b), respectively. It can be seen that
the double salt is thermodynamically more stable than MgCO3 , 3.2.2. Absorption heat measurement
with both a lower enthalpy (by ∼24 kJ/mol) and lower Gibbs Heat changes associated with the absorption reactions
free energy of formation (by ∼35 kJ/mol) over the warm tem- were measured through differential scanning calorimetric (DSC)
perature range of interest. As a result, the driving force for analysis in conjunction with the thermogravimetric measure-
Na2 Mg(CO3 )2 formation is larger than MgCO3 formation at equiv- ments. The DSC peak area associated with each absorption and
alent conditions. The Gibbs free energy changes of these CO2 desorption process is proportional to the change in enthalpy, the
capture reactions, provided in Fig. 7(b), show the temperature heat consumed or released by the sample. At 400 ◦ C, the absorption
at which G = 0 at 1 bar CO2 pressure. MgO can capture CO2 heat, which is also the formation heat of Na2 Mg(CO3 )2 , was calcu-
to form MgCO3 up to 300 ◦ C through reaction (c): lated by taking an average of the DSC results from 10 absorption
tests, yielding a value of −122.4 kJ/mol. We estimate this value to be
MgO + CO2 (g) = MgCO3 (c)
accurate within ±5%. According to Fig. 7(a), the theoretical enthalpy
Above 300 ◦ C, thermodynamically it is more favorable for for Na2 Mg(CO3 )2 formation is −121.6 kJ/mol at 400 ◦ C. The exper-
MgCO3 to dissociate to MgO. In the presence of Na2 CO3 , how- imental data is in accordance with theoretical predictions within
ever, as described in reaction (b), the thermodynamic data predict the uncertainty of the measurement.
that MgO can capture CO2 at temperatures up to 520 ◦ C by form-
ing double salt Na2 Mg(CO3 )2 , due to its greater stability. We note 3.3. Equilibrium pressure study of the absorbent
that in our TSA experiments, we employed 470 ◦ C for desorp-
tion, which should not be possible as predicted by computation. With the calculated thermodynamic data for Na2 Mg(CO3 )2 ,
Thus, we see some disparity between theory and experiment. As the predicted equilibrium of reaction (b) as a function of both
Fig. 6. The illustration of the conversions of compounds involved in absorption and desorption processes.
356 K. Zhang et al. / International Journal of Greenhouse Gas Control 12 (2013) 351–358
Fig. 8. CO2 partial pressure in equilibrium with the Na2 Mg(CO3 )2 double salt as a
function of temperature as predicted from ab initio calculation and after experimen-
tal correction.
4. Conclusions
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