Adsorption with Water

1. Introduction
Water can be used to purify gas streams in a packed tower by flowing the water down
the tower and counter-currently bubbling the gas stream up through the tower. This idea was
used to purify a gas stream of carbon dioxide and methane. Because a system of CO2 and water
has larger mass transfer coefficients than CH4 and water, it is assumed that only CO2 is
adsorbed in the water. This will lower the concentration of CO2 in the final gas stream, thus
making it more pure in CH4.
The entering gas stream has a CO2 mole fraction of 0.28 and a CH4 mole fraction of 0.72
so it can be sold as High Energy Gas ($4.10/MMBtu). Water adsorption was used to purify the
stream to Pipeline Quality Gas ($5.10/MMBtu) and Liquefied Natural Gas ($6.10/MMBtu). In
order to find the best profit, both levels of purification were looked at for different
temperatures; the entering temperature (assumed to be 303 K) and the lowest temperature
(273 K – freezing point of water).

2. Mass Transfer Calculations

The equilibrium data was assumed to be represented by Henry’s Law.
y(CO2)*P = H*x(CO2)

Where y(CO2) and x(CO2) are the mole fractions of CO2 in the gas and liquid phase respectively,
P is the total pressure of the system, and H is the Henry’s law constant for CO2 gas in water
(shown in Table 1 below).

Temperature (K) Henry’s Law Constant (H atm)

303 K 1860 atm
273 K 728 atm
Table 1. Henry’s law constant for temperatures used

The minimum liquid flow rate was calculated by using the equilibrium data with xo equal to
zero, y2 equal to the entering concentration, y1 equal to the exiting concentration (.02 for
Pipeline and .00005 for LNG), and x1 calculated from Henry’s Law. The exiting liquid flow rate
(L1) was then found by using the mass balance below.

L1 = (V2y2 – V1y1) / x1

Lo,min = L1 * (1-x1)

The flow rate of water used in the tower is equal to 1.5 times L1 to ensure the purification
reaches the desired levels. The same balance was then used to find the actual x1. A table of the
flow rates and mole fractions can be found in Table 2.

Process V2 y2 V1 y1 Lo xo L1 x1
 PL (303) 1052.82 0.28 773.50 0.02 1570152 0 1570432 1.78E-4
PL (273) 1052.82 0.28 773.50 0.02 614301 0 614580 4.54E-4
LG (303) 1052.82 0.28 758.03 0.00005 662937040 0 662937335 4.45E-7
LG (273) 1052.82 0.28 758.03 0.00005 259472587 0 259472882 1.14E-6
Table 2. Flow rates and mole fractions into and out of reactor (kgmol/hr)

Next the mass transfer coefficients were found by assuming that the ky from the MDEA
solution could be used (0.56 mol/m^2*sec @ 313 K) and that one tenth of the kx value for
MDEA could be used (0.086 mol/m^2*sec @ 313 K). The lower kx value for water is because
CO2 does not adsorb as well in pure water when compared to a mixture of MDEA and water.
These values were converted to units of kgmol/m^2*hr to match the units of the flow rates and
corrected for each temperature by the Cussler correlations by assuming the only term that
changes is the Diffusivity (D).

k(T1) = k(To)*( D(T1)/D(To) )^(2/3)

Then the overall mass transfer coefficient was found by using the equation below with m’ being
equal to the slope of the equilibrium line (H/P).

1/Ky = 1/kx + m’/ky

After this was known, along with the interfacial area for 1” Raschig Rings (a=190 m^2/m^3) and
the cross-sectional area (set to – S=1 m^2), the following equation could be numerically
integrated to find the height of the tower.

z= ∫ V/((KyaS(1-y)(y-y*))/(1-y)*M)dy

Because the cross-sectional area is equal to 1 m^2, the reactor volume (m^3) is equal to the
reactor height. The results of the integration (converted to ft^3) are shown below in Table 3.

Process Reactor Volume (ft^3)

Pipeline (303) 113995.8951
Pipeline (273) 49678.68744
LNG (303) 387161.1376
LNG (273) 168720.948
Table 3. Reactor Volumes for each process

The volumes for the reactors in the LNG process are larger than the Pipeline process because
the gas has to reach a higher purity so the reactor needs to be larger. Also, the volume
decreases when the temperature is lowered because Ky gets smaller and it is in the
denominator of the integral.

3. Cost Analysis
 The cost for each process was calculated for one year by adding the cost of the reactor to the
cost per hour to operate the system by the time it will be running in the course of a year (5000
hrs). For the processes at 303 K, the costs were the cost of the reactor, the cost of the water
needed in the process, and the cost to pressurize the product stream to 600 psi. The processes
at 273 K had the same costs except there was an extra cost of cooling both the liquid and gas
streams to 273 K.

The total value of the product was calculated by multiplying the flow rate of gas out of
the reactor by the heat of combustion of CH4 (assumed the heat of combustion was only of CH4
because there is very little CO2) and then multiplied it by the price. The heat of combustion of
methane was found to be 844.5 Btu/mol1. The total cost for each process, as well as the value of
the product and profit, is shown in Table 4.

Process Total Cost ($/year) Value ($/year) Profit ($)

Pipeline (303) $ 235,619,287.08 $ 16,657,005.98 $ -218,962,281.11
Pipeline (273) $ 123,473,919.67 $ 16,657,005.98 $ -106,816,913.69
LNG (303) $ 3,927,152,371.16 $ 19,524,633.63 $ -3,907,627,737.53
LNG (273) $ 10,455,846,312.74 $ 19,524,633.63 $ -10,436,321,679.11
Table 4. Summary of cost analysis for one year

4. Conclusion

From the profit column of Table 4 it is easy to see that it is not feasible to use adsorption
with water to purify the CH4 – CO2 gas mixture because there is no profit to be made. Lowering
the temperature cut the cost of the pipeline process almost in half but you would still lose over
$100 million over the course of a year. Lowering the temperature of the LNG process raised the
cost substantially because cooling the large flow rate of water that would be needed to
complete the purification was very expensive. The best option is to either sell the gas at its
current purity (72% CH4  High Energy Gas) or use a different method of purification.