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VOL. 41, NO. 21, 2007 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 7559
TABLE 1. Reaction Cycle for Na/Ca Air Capture
reaction ∆H° (kJ/mol) name type
2 NaOH(aq) + CO2(g) f Na2CO3(aq) + H2O(l) -109.4 absorption gas/liquid
Na2CO3(aq) + Ca(OH)2(s) f 2 NaOH(aq) + CaCO3(s) -5.3 causticization aqueous
CaCO3(s) f CaO(s) + CO2(g) +179.2 calcination gas/solid
CaO(s) + H2O(l) f Ca(OH)2(s) -64.5 hydration liquid/solid
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FIGURE 3. Evolution of CO2 flux of 1 M NaOH at 380 ppm CO2.
VOL. 41, NO. 21, 2007 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 7561
TABLE 4. Comparison of Energy Requirements (in kJ/mol) for TABLE 5. Mass Ratio for Components of Air Capture Reference
Air Capture System
item Zeman Keith et al. Baciocchi et al. CO2 CaO Ca(OH)2
energy required 1 1.3 1.7
air contacting 88 12 30 CaCO3 sorbent solution ambient air
causticization 0 96 0
evaporation 63 180 202 2.3 190 3,000
calcination (eff.) 256 (70%) 204 (88%) 239 (75%)
CO2 purificationa 16 168 27
CO2 compression 19 19 18 TABLE 6. Moles of CO2 Released from Electricity Generation
total 442 679 516 Per Mole Captured
energy available
heat of hydration 105 0 0 air movement total
a O2 production (Zeman, Baciocchi et al.), MEA capture (Keith et al.) electricity oxygen and forced 50% forced 50%
source compression draft passive draft passive
natural gas 0.08 0.20 0.10 0.28 0.18
to elevate the CO2 concentrations in the process. Keith et al. coal 0.17 0.42 0.21 0.59 0.38
chose to add an amine scrubbing process, effectively a second
gas-separation process. Baciocchi et al. and our analysis used system is presented in Table 5. The comparison shows that
high-purity oxygen to avoid the amine process with a much air movement and sorbent recirculation dominate the mass
lower energy penalty. The reason is related to the origin of balance.
the CO2 in the kiln. During calcination, CO2 is released from One mass flow not considered is evaporative losses. Dry
the calcium carbonate and produced from the oxidation of air can hold 17 g of water vapor per m3 at 20 °C (35). The total
the fuel. For an oxygen system, electrical energy is required water loss associated with capturing 1 ton of CO2 based on
to produce sufficient oxygen to combust the fuel. In contrast, a 3,000,000 m3 throughput could be 50 tons. This is indeed
amine systems must capture all of the CO2, both calcination significant. The water loss assumes 0% relative humidity,
and oxidation. Considering a kiln running at 90% efficiency and any background humidity would reduce it proportionally.
and fired by natural gas, we can see that amine scrubbing By comparison, the equivalent maximum water loss at 10 °C
is concerned with five times the CO2 of an oxygen system. would be 26 tons and further reduced to 13 tons if the relative
Essentially, in an oxygen system, the calcination CO2 is along humidity is 50%. This suggests that placement of any Air
for the ride and is not a penalty. The energy penalty for oxygen Capture device would include average annual temperature,
production in Baciocchi et al. is higher than that in this paper relative humidity, and rainfall in the location criteria.
because of the extra heat required for drying. Increasing the alkalinity of the absorbing solution can further
The total energy required for Air Capture is similar among reduce the water losses although this would complicate the
the three analyses, especially if the causticization and amine process by introducing a dilution/concentration step between
penalties are removed from Keith et al. It is important to the capture device and causticizer (36).
note that the reason is coincidental offsets, which highlights 5.3 Emissions from Electricity Generation. The net
the need for future work on the concept. It also suggests the amount of CO2 sent to storage by such a facility, disregarding
most important unknowns are the moisture content of the leakage, will depend on the source of the electricity. Renew-
filter cake and feasibility of oxygen calcination. While neither able energy, such as wind, could be used and the negligible
is conceptually difficult, experimental results will determine emissions would be balanced against higher cost and
which assumption was correct. Reviewing Table 4 we can intermittency. The emissions from fossil fuel electricity plants
see that calcination, oxygen production, and CO2 compres- can be estimated by using the representative values contained
sion cannot be avoided. These three processes require a in Table TS.3 of the IPCC Special Report (1). The listed value
minimum of 230 kJ/mol of CO2 captured, assuming a 90% for a natural gas combined cycle plant is 0.367 kg CO2/kWh,
efficient, coal fired kiln. The other penalties must be which can be converted to 2.3 mmol/kJe. Similarly, a
minimized to optimize the process. The heat released by conventional pulverized coal plant produces 0.762 kg CO2/
steam hydration is not trivial and could ensure that no kWh or 4.8 mmol CO2/kJe. The emissions for any combination
additional heat is required for drying. can be obtained by multiplying the fraction of generation
5.2 Relative Mass Flows. This paper outlines the mass capacity by the representative emissions factor.
flows associated with capturing CO2 from the air. The The electricity consumption of the process can be divided
complete system will also be required to move air through into process needs and air movement. The first, CO2
the device and provide a wetted surface area. Assuming a compression and oxygen production, cannot be avoided.
50% capture rate, we are required to move 3,000,000 m3 of The electricity consumption associated with the air blowers
air over 315,000 m2 of surface for each ton of CO2 captured. can be reduced or eliminated by using passive air movement
The total volume of sorbent required is dependent on its or newer, more efficient tower designs. Table 6 shows the
capacity to hold CO2 and the film thickness, as the efficient CO2 emissions due to electricity generation for each mole of
use of surface area requires that it is constantly wetted. CO2 captured.
Chemically, we require 45 m3 of 1 mol/L NaOH solution to 5.4 Thermodynamic Efficiency. The feasibility of air
hold 1 ton of CO2. Physically, we require 190 m3 of solution capture can be quantified using the concept of thermody-
to wet the surface, using a minimum film thickness of 0.6 namic efficiency. This refers to the ratio of the thermodynamic
mm (34). Distributing 1 ton of CO2 evenly throughout the minimum energy requirement to the actual amount of energy
larger volume results in a 0.75 mol/L NaOH solution, which used in the process. We will compare air capture to
maintains high flux values (eq 5). established capture technologies, not as a direct comparison,
The mass balance for such an Air Capture system is rather how well each achieves its objective. MEA flue gas
available by including the solids handling component. Recall, scrubbing is considered the industry standard and consumes
from Table 1, that the mass of lime and limestone relate to roughly 172 kJ/mol CO2 of thermal energy and 9 kJe/mol of
the CO2 captured through their molar mass. The relative mass electrical energy (37). Advanced amine sorbents, such as KS-
of the CO2, lime, limestone, sorbent solution, and air for this 1, require only 132 kJ/mol CO2 of thermal energy for
7562 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 41, NO. 21, 2007
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Center, Oak Ridge National Laboratory, U.S. Department of Received for review April 13, 2007. Revised manuscript re-
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