Separation Techniques for Landfill Gas Mixtures

and Economic Analysis

The Pennsylvania State University

Chemical Engineering 410
By:

Monica Patel

Friday, December 10, 2010

Cryogenic Distillation
 Cryogenic distillation is used to separate components of a gaseous mixture. This
process requires extremely low temperatures (around 100 K) and is energy demanding.
Cryogenic distillation is commonly used to remove nitrogen from natural gas, but can
be used to remove other components as well. In cryogenic distillation, heat is added to
the reboiler of the distillation column to evaporate the mixture. The heat is them
removed from the top of the column to condense the unwanted substance.

Design

By using a simulator such as HYSYS, a cryogenic distillation can be mimicked

and used to collect useful information. Before beginning this process, an XY graph was
plotted to determine the plausibility of the separation. Figure 1 shows the equilibrium
diagram of methane and carbon dioxide. This plot shows that the mixture can be easily
separated into its separate components.

Figure 1: Equilibrium Graph

Cryogenic distillation is used in this situation because the boiling points are 112
K (methane) and 216 K (carbon dioxide). Therefore the condenser must operate at the
lower boiling of 112 K. With the given data of 45% methane along with 50 psi entering
feed pressure, a distillation tower was created via HYSYS. The minimum reflux rate
able to reach the desired methane mol fraction was found to be 3. This was found
through variation of the reflux rate on HYSYS. The same was done for the amount of
trays necessary for the desired molar fraction. The number of trays was determined to
be 4.

Since methane vaporizes at a lower temperature than carbon dioxide, methane

was chosen to come out of the top of the distillation tower. While holding the reflux
ratio and the amount of trays constant, the flow of the entering feed was adjusted to
reach a preferred mole fraction of methane. The highest purity of methane (.998) was
desired since, as will be discussed later on, it proved to be the most profitable.

As explained previously, cryogenic distillation requires that the temperature of

the mixture be very low. The entering temperature required of the feed into the
distillation tower is -97 degrees Fahrenheit. Therefore, a cooler was added to the
process to make the gas mixture the correct temperature to be used in the distillate
column. The gas was assumed to be at standard temperature (293 K) to begin with.
Also, the temperature of the out-stream gas to be sold would be at an extremely low
temperature if sold right out of the distillation column. For this reason, the product is
heated to reach standard temperature (293K). To account for this, a heater was added
to the methane stream, making the final product stream ready to be sold.

Figure 2: HYSYS Replica

Costs
 Some costs are inherent with the process of cryogenic distillation. Since four
trays were used to create the optimum mol fraction, there is an automatic cost of
$2,000,000. The cost of cooling the gas to the temperature needed for cryogenic
distillation was equal for every mole fraction of methane possible, as was the cost of
heating the product gas to room temperature for resale. Table 1 displays these two
unvarying costs.

REFRIGERATION HEATER

cost = $.11/ KW-hour cost = $3.2/MMBTU

energy 934.2 HP energy 4153000 BTU/h
696.6328466 kW 18688500000 BTU/year
18688.5 MMBTU/year
$76.63 per hour
$344,833.26 per year $59,803.20 per year

Table 1: Inherent Cost

The following table (Table 2) shows the income, cost and profit of several
different mole fractions of methane. Of the mole fractions shown, .5 and .65 are
considered medium energy gas while .8 and .9 are considered high energy gas. Finally,
the mole fraction of .998 methane is considered to be pipeline quality. Pipeline quality
gas must be under 600 psi, therefore I must compress my outlet stream of 50 psi to 60
psi required. To account for this cost, equation 1 was used.

Power = VL(P2-P1) (1)

Using this equation, the estimated cost of the power needed to pump the gas at 600 psi
(HYSYS gave a value of a 17.7 m3/hour) and for it to be converted to the pressure
needed for the gas to be sold. At the rate of $ .11 per kilowatt-hr, the total extra cost of
converting the pressure is $9189.00 per year.
 Figure 2 shows the mole fraction of methane vs. the profit. By using this plot, a
rough estimation of profit can be determined for any mole fraction of methane.

Mole Fraction Income Cost Profit

0.5 5332628.539 8596684 -$3,264,055.39
0.65 6595246.753 6348058 $247,188.79
0.8 8447535.088 5061239 $3,386,295.67
0.9 8,039,801.30 4535235 $3,504,566.55
0.998 8873874.473 3826842 $5,047,032.72

Table 2: Comparison of Mole Fractions

Figure 4: Comparison of Mole Fractions

The graph predicts that with a starting mol fraction of .63 methane, cryogenic
distillation would provide $0 in profit. The pipeline quality gas proved to be the most
profitable, even with the extra power needed to the pressure conversion.
 METHANE CARBON DIOXIDE

selling price = $5.10/MMBTU selling price = $.0015/ft^3

molar flow out 333400 mol/h Molar flow out 413700 mol/h
energy out 281592974 BTU/h Volume out (standard)10115.68257 m^3/h
Volume out (standard)357231.9584 ft^3/h
$1,436.12 per hour
$6,462,558.75 per year $535.85 per hour
$2,411,315.72 per year
DISTILLATION CONDENSER DISTILLATION REBOILER

cost = $.11/ KW-hour cost = $3.2/MMBTU

energy 3820 HP energy 206400 BTU/h
2848.574 kW 928800000 BTU/year
928.8 MMBTU/year
$313.34 per hour
$1,410,044.13 per year $2,972.16 per year

Table 3: Cost Information of .998 mol Fraction of Methane

Cryogenic distillation is an option to make a profit for the given conditions. If

considering this process to separate carbon dioxide and methane, the specifications of
the process that will make the greatest profit include distilling the mixture to pipeline
quality (.98 mol).

Recommendations
 Using cryogenic distillation to separate the gaseous mixture is not recommended.
Even though distilling pipeline quality gas would be profitable, estimating about $5
million a year, this method may not be worth the trouble. While cryogenic distillation
seems like a viable option, the initial costs of setting up the plant are great, and would
take a long time to pay back this debt with the predicted profit made each year.
Another, more profitable option may be more practical for a start up. There can also be
some improvements made within the profit determination. Carbon dioxide was
assumed to be an ideal gas for its profit calculation. This is not an accurate assumption,
especially because the gas needed to be at an extremely low temperature, and a high
pressure to enter the distillation column. To provide a more accurate determination of
the profit made from CO2, the viral equation of state should be used. HYSYS was used
to predict almost every other aspect of the distillation process, including the feed flow
rate, temperature required for the distillation column, and the heat flow of the reboiler.
The accuracy of these factors depends on the accuracy of the HYSYS computer
program.