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JCO2 ) CKH√D1k{OH-} (1) where N1 and N1 are the number densities of dl and d2 drops,
υt is the drop’s terminal velocity, and Ec is the collision
where C is the concentration of CO2 in bulk air, KH is the efficiency for drops of those sizes passing within geometric
Henry’s constant in the form of the ratio of CO2 concentration alignment (the odds that they will collide as opposed to slip
in air to CO2 concentration in water at equilibrium, D1 is the around each other). The collision rate for each drop size is
diffusion rate of CO2 in solution, and {OH-} is the activity of calculated by dividing a continuous distribution of drop sizes
hydroxide ions (primarily a function of NaOH concentration into discrete size bins and applying eq 4 for every possible
in solution). The reaction constant, k, refers to the reaction pair of sizes.
(12): To estimate the surface area of spray in a full-scale
contactor, we adapted and extended a numerical model
CO2(aq) + OH- f HCO-
3 (2) developed for cloud aerosol physics (24). The drop size
distribution of the spray nozzle is approximated as log-normal
This is a second-order reaction, however the concentration and represented by a number and mass of particles in 50 size
of OH- is so large in our system (>1 M) that it can be treated bins. At each time step, eq 4 is applied using empirical fitted
as a pseudo-first-order reaction in CO2. Each of the factors formulas for υt (20) and Ec (22). The mass and number of
KH, {OH-}, and Dl is a function of the species present in the drops in each bin is then updated by the method of Tzivion
solution (especially the ionic strength and viscosity) and et al. (25) as implemented by Adams and Seinfeld (24). The
temperature. In later calculations, we use the modified Pitzer distribution is then further updated to reflect addition of
model (16) to calculate {OH-} for a given concentration, adjust fresh spray, spontaneous breakup of drops having d > 5 mm,
KH for ionic strength based on data for NaCl solutions (17), and gravitational settling according to the terminal velocity
and adjust Dl for solution viscosity effects (18). We assume of each drop size.
Two spatial variants of the model were used to bound the For simplicity we assume that air and liquid reach the
problem, i.e. one case ignores vertical mixing and the second outlet of the contactor at the same temperature, so that an
assumes vertical mixing at a 1 m length scale. In the first, the energy balance yields the temperature at the outlet (assuming
contactor was approximated by a continuous-flow stirred contactor materials have reached thermal equilibrium and
tank reactor (CFSTR) in which drops are assumed uniformly neglecting the small contribution of the CO2 enthalpy of
distributed throughout; fresh spray addition and the rate of dissolution):
settling reflect uniform distribution. In the second variant,
the height dimension is resolved and the contactor is ∆CH2O∆Hvap
represented by a stack of layers, each of which is modeled Tout ) Tin - (7)
FairCp, air + Flcl
as a CFSTR. Air flow is purely horizontal (Figure 1b) so drops
move from one layer to the one beneath by gravitational where Cp,air and cl are the heat capacities of air and the liquid
settling at terminal velocity. Spray is added to the top layer, solution (assumed equivalent to water), and Fair and Fl are
and drops are removed when they settle from the bottom the bulk densities of air and suspended solution. The quantity
layer. Reality will be in between these two idealizations: some of water evaporated, ∆ CH2O, is the difference between the
mixing would occur due to turbulent diffusion, and vertical inlet water concentration and the water concentration
air flow would be induced by the falling drops. Our base case corresponding to the vapor pressure of the solution:
cost estimate uses the average of the two results.
This model yields spray surface area per unit contactor ∆CH2O ) Cs, H2O(T ) Tout) - CH2O, in (8)
volume, S. To estimate CO2 absorption from this, we define
the CO2 absorption rate constant, kspray, such that Equations 7 and 8 are solved simultaneously by iteration to
yield ∆ CH2O. Knowing the overall capture efficiency for the
dC
) SksprayC(t) (5) contactor of CO2 from air allows a calculation of water loss
dt per unit CO2 absorbed.
Then kspray is the absorption rate per unit CO 2 in air per unit Experimental Methods. We constructed a prototype
drop surface area, given by JCO2/C (eq 1). contactor to measure CO2 capture by NaOH spray and to
The rate of CO2 uptake depends on C, which changes measure the energy requirements in a way that is relevant
over time. To account for depletion of CO2 in air as it passes to full-size contactors.
through the contactor, we approximate S as uniform along Figure 1a shows a schematic drawing of the apparatus
the length of the contactor and use the concentration, Cavg, (see photographs in the SI, Figures SI3-SI4). NaOH solution
that yields the average rate of uptake over the contactor (see is sprayed through the tower, collected, and recirculated from
SI for the derivation of Cavg). For a full-scale contactor (Figure a 15 L reservoir while air is blown down through the tower
1b), the rate of CO2 capture of the contactor per unit floor cocurrently at approximately 0.4 m/s. Though it sacrificed
area (denote; Ṁ) is then (from eq 5) some efficiency over an upward-flow design, the downward-
flow, cocurrent design allowed for simpler construction and
Ṁ)ksprayCavgSH (6) maintenance of the particle trap system. CO2 concentration
in inlet and outlet air was measured using a LiCOR (Lincoln,
whereas in the height-resolved model, S is the average over NE) infrared gas analyzer. Carbonate (CO2) concentration
all cells. was measured in periodic liquid samples using a Shimadzu
Evaporative Water Loss. For the contactor designs studied (Kyoto, Japan) total carbon analyzer to corroborate the LiCOR
here, we will find that the rate of water loss is large enough measurements. Additionally, temperature, relative humidity,
that the air leaving the contactor would be saturated with and pressure drops were recorded. More detailed explanation
water vapor. In this case, we can estimate evaporative water of the experimental apparatus is given by Stolaroff (26).
loss by assuming the air leaving the contactor has water partial Two single-fluid spray nozzles producing uniform, full-
pressure equal to the vapor pressure of water at the surface cone spray patterns were used: a spiral-tip nozzle from
of the drops. This calculation provides an upper-bound on Allspray (Carol Stream, IL) with a higher flow rate and larger
evaporative water loss. drop size (the “high-flow nozzle”), and a swirl-chamber