Christian Walleck

Absorption with Water as the Absorbent

The absorption tower was designed to run at the conditions of the feed stream: 20C, 500psig, and 80 MMSCFD. Optimization of the absorption tower depended mostly on the tower volume and water flow rate. The tower height was determined by numerical integration while adjusting the water flow rate, area of the column, and purity of the methane exit stream. Once the tower height was calculated, costs for packing, water, compression energy, and the value of the original stream were removed from income to determine total profit. Before calculations could be run, equilibrium data and the mass transfer coefficient for carbon dioxide needed to be determined. Equilibrium data for carbon dioxide and methane in water at ambient temperature is shown below. Separation of carbon dioxide from methane by absorption works well because only a small amount of methane dissolves in water. (appendix A 3-18) Table 1. Henrys Law Coefficients for Carbon Dioxide and Methane in Water Species H H CO2 1420 40.6 CH4 37600 1070

Mass transfer coefficients were calculated from correlations for gas and liquid phases in a packed tower. For gas in a packed tower, ( For liquid in a packed tower, ( ) ( ) ) ( ) ( )

Where D is the diffusion coefficient, k is mass transfer coefficient, v is kinematic viscosity, is packing area per bed volume, d is nominal packing size, and v0 is fluid velocity. The diffusion coefficient was also calculated from an experimental correlation. ( ( ) )

Where M is the atomic mass of a molecule and V is the structural volume increments of the molecules. After the mass transfer coefficients were determined, they were converted to an overall mass transfer coefficient (Ky) used in all calculations of tower height. Initial calculations were run with an exit methane purity of 70%. With purity set, the other two variables were tower diameter and water flow rate. The tower diameter was initially set at 0.75 meters because it is approximately thirty times the diameter of the raschig rings used to pack the tower (1 inch). This is the minimum tower diameter that still creates random flow patterns resulting in proper mass transfer. The effect of water flow rate on tower cost was then determined; a flow rate of 1.02 times the minimum flow rate was the most efficient. Similar profit calculations at 40% purity and 95% purity also revealed maximum profit at 1.02 the minimum water flow rate. Total profit is calculated by finding the amount of BTUs contained in the exit stream and multiplying by the appropriate price, then subtracting all costs. Figure 1

5 Profit (million $/yr) 4.5 4 3.5 3 2.5 2 1

Net Profit Varying Flow Rate

No CH4 loss

1.2

1.4 Multiple of Lmin

1.6

The amount of methane lost in water was first ignored because its Henrys law coefficient was so high, but even the small amount of methane clearly impacts profit. Therefore, profit is reported including the cost of methane lost in the liquid stream in all subsequent data. The best flow multiple is very low because the price of water greatly outweighs the price of packing on a yearly basis. Water is the overwhelming cost unless the water flow rate is very

close to Lmin. Even though the mass transfer coefficient goes up as the flow rate increases, this effect is not enough to overcome the prohibitive cost of water. The decrease in packing cost does not offset the increase in water cost as shown in figure 2. Figure 2

Expenses at 70% Purity

70 Cost ( 10 Thousand $/yr) 60 50 40 30 20 10 0 1 1.1 1.2 1.3 1.4 1.5 1.6 Multiple of Lmin Packing Water

Packing and water are the only costs considered at 70% purity because there are no pressure specifications set on the product. The stream is sold at the outlet temperature and pressure. Water is sold by the gallon at a flat rate. Packing needs to be bought once every thirty years so the cost was adjusted to a yearly average by dividing by thirty. After an ideal flow rate was determined, the effect of tower diameter on profit at 70% purity was investigated with water flow rate set at 1.02Lmin shown in figure 3. Figure 3

Effect of Diameter on Profit at 1.02Lmin

Profit (Million $/yr) 3.85 3.845 3.84 3.835 3.83 3.825 0 0.5 Diameter (m) 1 1.5 profit

The smallest diameter tower was the cheapest. This is likely the case because the smallest tower diameter forces the water and gas velocity to be the highest. Higher velocities lead to a higher mass transfer coefficient, so the tower volume is smaller and less packing is needed to complete the separation. With ideal conditions found for each methane purity level, profit generated in each case was finally compared. Figure 4 shows the profit generated from each level of methane purity at the optimal conditions, diameter of 0.75m and flow rate of 1.02Lmin. Figure 4

Profit at Different Purities

6 Profit (Million $/yr) 5 4 3 2 1 0 40 70 Purity Level 95 99.9995

99.9995 data shown without refrigeration costs included.

It should be noted that costs for 99% and 95% methane streams differ from lower quality methane streams. Pipeline and liquefied gas streams need to be sold at 600psi. Therefore, pressure drop through the absorption tower must be accounted for to ensure accurate compression costs are included. Pressure drop through the tower was estimated as 0.5in H20 per foot. Pressure drop in the tower producing pipeline gas was 1.90atm. The cost of compressing the methane stream to 600psi needed to be calculated based on the energy required to reach the target pressure. The equation below gave the amount of energy necessary to reach 600psi. ( )

Energy costs were $.08/kWhr for electricity to run the compressor.

The liquefied gas stream also required refrigeration because it was still a gas at outlet conditions. However, refrigeration costs were not included in the analysis because 99.9995% purity could not be reached while still making a profit. The most profit occurs at 95% methane; however, liquefied methane is a close second. Tower heights were compared to determine the more reasonable option. Clearly, the tower size is too large for liquefied methane to be a viable option. Even with a much larger diameter and flow rate, the tower is still quite tall and the extra water and packing expenses incurred make the liquefied methane unprofitable. Figure 5

Tower Height at 0.75m Diameter

500 Height (m) 400 300 200 100 0 40 70 Purity Level 95 99.9995

As a final summary, figure 6 compares net profit and each individual cost for 40%, 70%, and 95% methane. Liquefied methane is left off the chart because it was not profitable. Figure 6

Max Profit and Cost at Different Purities

6 5 Profit (Million $/yr) 4 3 2 1 0 40 70 Purity Level 95 600000 500000 Cost ($/yr) 400000 300000 200000 100000 0

Water Cost Packing Cost Compression Cost Profit

Net profit rose with each increasing purity level because the product was sold at a higher price while costs remained relatively low. 95% methane and lower could be achieved with an absorption tower of reasonable dimensions. Trying to improve above 99% purity led to excessively large and expensive towers. Water was the dominant cost for all three levels of purity because carbon dioxide is not very soluble in water. Even close to the minimum theoretical flow rate, the cost of water was significantly higher than packing or compression costs. 220 gallons per second are required to reach 95% purity and even at 40% purity 66 gallons per second are needed. This is an extremely large quantity of water that makes water a very impractical absorbent. Absorption with water will yield a profit. A tower producing pipeline quality gas 0.75m in diameter with a flow rate of 1.02Lmin (13200 gal/min) generates $5.47million/year; however, the amount of water required to run the tower makes the process impractical to implement. A tower generating medium density gas can generate 2.25 $million/year using 3960 gal/min of water. This amount of water is a slightly more reasonable value but profit is reduced. Other methods are better for separating carbon dioxide and methane. Absorption with water as an absorbent is not recommended.