Separation Techniques for Landfill Gas Mixtures and Economic Analysis

The Pennsylvania State University Chemical Engineering 410
By: Kevin Frasca Monica Patel Andrew Plowman Anthony Vaz Friday, December 10, 2010

Executive Summary The goal of this project is to weigh the relative benefits that are obtained from four different methods of recovering methane from a mixture of landfill gas containing 45% methane in carbon dioxide. These four processes are cryogenic distillation, absorption using water as the absorbent, absorption using methyldiethanolamine (MDEA) as the absorbent, and gas separation membranes. The purity of the methane gas that can be recovered from these mixtures determines the amount of money that can be made, but each process will have its own economic barriers of production. The available feed stream is already concentrated enough to be sold as is as medium energy gas, so it will need to be determined which, if any, of the four separation methods will be the most beneficial for energy efficient and economic purposes. The cost of increasing the quality of the methane to high energy gas, pipeline quality gas, or liquefied natural gas may exceed the amount that can be made from selling the final product. After thorough research of all four separation techniques it was decided that absorption using MDEA as the absorbent would be the most economical and reasonable method. While the other three separation techniques proved to have some economical gain, these methods have concerns. For cryogenic distillation the initial start up costs for materials and tower costs would be too expensive. Also, when using gas separation membranes as you increase the product purity the cost of the membrane hinders net profits. Finally, absorption using water doesn¶t appear propable due to the excessive tower heights in order to complete the separation. Moreover, MDEA increases the absorption capacity for carbon dioxide providing for a more efficient separation method. Therefore, choosing absorption using MDEA as the absorbant was the best choice.

Table of Contents Introduction Cryogenic Distillation Absorption: Water as absorbent Absorption: MDEA Gas Separation Membranes Recommendations Appendix

Page 3 5 10 15 22 28 30

Introduction With the recent concerns of global warming and the expected depletion of fossil fuel supplies, it is becoming increasingly important to not let any potential use of energy go to waste. Mixtures of methane and carbon dioxide are commonly found in a number of different fields. Such mixtures have in the past been simply vented to the atmosphere, which not only worsens global warming by some theories, but it wastes opportunities to produce efficient energy as well as potential profits. Separating these mixtures into their respective components can become extremely profitable if done properly. The purer the methane, the more money can be made off of each BTU combusted. This project examines four different methods of accomplishing such a separation, and how each can be modified to maximize the purity and the value of the product so that no gas is wasted. The gas feed in each of the four processes came from a landfill well. Significant amounts of methane gas can be generated by landfills as solid waste decomposes anaerobically. This methane is usually in a close to 50/50 mixture with carbon dioxide at roughly atmospheric pressure. This is one area where venting this excess gas to the atmosphere can be particularly common. It would be extremely beneficial, then, to recycle this gas for resale. Each separation process was done using the same initial feed conditions. Table 1 below displays the compositions and properties of the feed operation. Property Mol% CO2 Feed Pressure (psig) 50 Feed Flow (MMSCFD) 15 Operating Time (hours per year) 4500 Feed Stream



Landfill Gas

Table 1: Feedstock Specifications

The goal is to purify methane, but in purifying methane, the carbon dioxide will also reach higher purity levels. As shown in Table 2 below, methane is clearly much more valuable, though minor profits may be able to be made from carbon dioxide by selling it for dry ice if it is almost 100% pure. The price methane can be sold for increases with each tier of purity listed in the table below. Additionally, for methane mixtures 98% and above, the product must be compressed to 600 psi which will cause additional considerations.

Product High Purity CO2 Waste Gas Low Energy Gas Medium Energy Gas High Energy Gas Pipeline Quality Gas Liquefied Natural Gas

Methane Mol% <1 <10 10 ± 40 40 ± 70 70 ± 90 98 >99.995

Price per MMBTU $0.0015 (per cubic ft) -$2.60 $3.30 $4.10 $5.10 $6.10

Specifications -----600 psi 600 psi

Table 2: Pricings for Various Gas Compositions

The four processes that will be analyzed in this project are cryogenic distillation, absorption using water as the absorbent, absorption using methyldiethanolamine (MDEA) as the absorbent, and gas separation membranes. From these analyses, it will be determined both how each can best be utilized to maximize profit as well as which overall process will be the most feasible, both physically and economically and can thus be the recommended process.

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.


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


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 cost = $.11/ KW-hour 934.2 HP 696.6328466 kW $76.63 per hour $344,833.26 per year
Table 1: Inherent Cost

HEATER cost = $3.2/MMBTU 4153000 BTU/h 18688500000 BTU/year 18688.5 MMBTU/year $59,803.20 per year



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)


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.

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.


Mole Fraction 0.5 0.65 0.8 0.9 0.998

Income 5332628.539 6595246.753 8447535.088 8,039,801.30 8873874.473

Cost 8596684 6348058 5061239 4535235 3826842

Profit - 3,264,055.39 $247,188.79 $3,386,295.67 $3,504,566.55 $5,047,032.72

$1,436.12 per hour $6,462,558 75 p r y ar

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).

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$313.34 per hour $1,410,044 13 p r y ar

$2,972 16 p r y ar



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cost = $.11/ K -hour 3820 P 2848.574

cost = $3.2/ B U 206400 B U/h 928800000 B U/year B U/year 928.8



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selling price = $5.10/ B U molar flow out 333400 mol/h n rgy out 281592974 B U/h

selling price = $.0015/ft^3 olar flow out 413700 mol/h Volume out (standa 10115.68257 m^3/h Volume out (standa 357231.9584 ft^3/h $535.85 per hour $2,411,315 72 p r y ar DISTILL TI N B IL   

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MDEA: In the analysis of using a MDEA/water mixture for purifying a CH4/CO2 stream, it was determined that with the given parameters, the system would be cost productive, neglecting employee salaries and water costs. Shown in the graphs below are the equilibrium and operating data for what are believed to be the four key variable changes, which were temperature, pressure, purity of Methane, and concentration of MDEA.

Figure 1: MDEA 23.3 wt.% water mixture, 446.1 kPa

Figure 2: MDEA 23.3 wt.% water mixture, 1000 kPa

Figure 3: MDEA 23.3 wt.% water mixture, 1000 kPa

Figure 4: MDEA 48.9 wt.% water mixture, 1930 kPa

Figure 5: MDEA 23.3 wt.% water mixture, 1000 kPa Methane concentration of 98%

The choice of the pressures was based primarily on how the equilibrium line fit with the data. The overall effect of pressure on the system, as shown between figures 1 and 2, was found to be beneficial economically, however each of them reached a point where a pressure increase became counterproductive in maximizing profit. Calculations and Explanations: In this section of the report, a thorough explanation of the various calculations can be found. The section is split up into two sections, which are cost calculations and then the actual problem calculations. Cost Calculations:
Cost of tower, it was the area of the tower multiplied by the cost per ft³ and then multiplied by the unit conversion from m³, which was used in the calculations to ft³, which was used in the cost. Total profit was calculated by the total hours of operation per year multiplied by price per MMBtu. This was then multiplied by the energy per mol expended per Btu, and then by the total molar flow rate out (V2). The units were then corrected. Methane does 891 kJ/gmol[4] of work, which is equal to 844.5 Btu/gmol. The flow rate however was in lbmol, so the equation was multiplied by 453.6 in order to account for that. The percentage of methane must also be accounted for in the equation, which was 0.7. Cost of MDEA: L1 multiplied by the mol fraction of MDEA ( 0.0476), which was calculated by using the molarity of MDEA. There was either 2 or 4.28 mols of MDEA in solutions, which took up 0.238324 L in the 2M mixture. The difference in the volume remaining was then used to calculate the total mols of water remaining in the container. Then from here the molar composition was determined.

Problem Calculations:
Mol Fraction of MDEA: 23.3 wt% = 2 M = 2 mol/L 48.9 wt% = 4.28 M = 4.28 mol/L p = 1.038 g/cm^3 so 2 mols of MDEA take up 229.6 mL which leaves 770.4 mL of water, which is 42.447 mols at 40°C and 40.35 mols at 120°C. Divide the mols MDEA, by the calculated mols of water to get the mol fraction. Mass Transfer coefficients: H' is the slope of the equilibrium line approximately, and ya1 and ya2 are the mol fractions in the vapor. Using mass transfer relations in Geankoplis, the values of k'y and k'x can be calculated. Na = k'y (ya1-ya2) Na = k'x (xa1-xa2) Na is dependent on the diffusivity, which with changing temperature alters the viscosities, which are two things that diffusivity is dependent on. From the reference[3] below however, it shows that the viscosity of MDEA is relatively unchanging between the two temperatures, so we assume they are roughly equal. Because liquids are essentially incompressible, pressure difference will not have a significant effect on the mass transfer coefficients. Using these known values, a ratio can be set up assuming everything else stays constant in the equations while holding the other values constant i.e. the mol fractions. The fraction between the new temperature ( 393 K ) and the old one (313 K) is 1.2556, therefore, by multiplying this by the original mass transfer coefficients we have the new coefficients at the new temperature. M.W. = xmdea*M.W.mdea + (1-xmdea)*M.W.water 313°K 23.3 wt% = 0.04712*(238.324/2) + (1-0.04712)*(18.01) = 22.7762 g/mol 393°K 23.3 wt% = 0.04957*(238.324/2) + (1-0.04957)*(18.01) = 23.024 g/mol 313°K 48.9 wt% = 0.1527*(238.324/2) + (1-0.1527)*(18.01) = 33.456 g/mol Compression Costs Power = RT ln(P2/P1) Power =(((R*T)/LN(1000/446.1))*Molar flow rate(lb-moles/day)/24 hours)*(453.6 gmol/lbmol)*(2.778*10^-7 (kW-hr/J))*$0.11*4500 hours/year Heating/Temperature Costs: Estimate an average temperature of 68°F

W = Cp delt T in units of Btu/lb Multiply the work by the varying M.W. in order to eliminate the mass, then you have Btu/lb-mol; this can then be multiplied by the annual flow rate out (V2). This total number must then be multiplied by $3.2/10^6, which is the cost/MMBtu. The specific heats can be seen in Table (1). Conditions wt% MDEA in water 23.3 wt. % 120°C 23.3 wt. % 40°C 48.9 wt.% 40°C Specific Heat (Btu/lb*°F) 1.05[1] 0.94[2] 0.86[2]

Table [1]: Specific Heat of MDEA in Water

Calculating V1 (initial molar flow rate of the gas inlet): The molar flow rate was found using the ideal gas equation. n = PV/RT = (64.7 psi * 15,000,000 ft^3/day)/(10.7316 (psi*ft^3/°R*lbmol)* 563.4°R) or in the case of the higher temperature 707°R. This gives an answer of lb-mol/day. The mass transfer coefficients are then divided by 453.35 in order to convert from gram moles to lb moles, and the seconds are multiplied out for units of days. Meters are kept in the solution to simplify the units. Calculating x: Using the mass balance of the system A was calculated for simplifying the calculation of x at each given y

The calculation of x then becomes,

Calculating y*: This was accomplished by using a best fit line on the equilibrium line; the equation from this best fit line was then used for much more accurate interpolation than using a ruler. The way this worked was by plugging the value of x in at a given y on the operating line, and replacing the equilibrium line x. This gave the value of y* Calculating (1-y)*m:

Calculating V(y):

Calculating the Integrand: By using Excel® a spreadsheet was made up with the following variables below as they changed with the concentration of CO2 in the flow stream.

From this, numerical integration was used in order to integrate between concentrations of 0.55 (initial CO2) concentration to a given purity. The sum of this gave the tower height from the equation below.

Results: Running each of the models, showed that the most cost efficient method was running the system at 1000 kPa and purifying the methane stream to 98%. Each of the three variables that were changed had different effects, which can be seen in Table (2). Variable Change Effect Pros Cons Heating requires money, and also did not affect the required liquid flow rate enough to be beneficial Compression of the stream costs money MDEA is expensive, so prices increase with concentration Requires compression to 600psi, and Larger tower, which both increase cost


Steeper Equilibrium Line

Less MDEA needed

Pressure Concentration of MDEA

Lower Equilibrium Line More absorption faster Larger tower, more feed required

Require less MDEA Lower liquid flow rate required for operation Sell the product for a greater profit

Purity of Methane

Table (2): Variable Effects

Looking at the system strictly from an economic view was probably the best way for optimizing the system, because it summarized the effects of every aspect of the system. By maximizing the profit, the size of the towers and liquid flow rates were minimized. A complete economic breakdown of the absorption process can be seen in Table (3).
MDEA Conc. Methane Conc. Operating Pressure (kPa) Temperature (K) Tower Height (m) Tower Area (m²) Cost of Tower Cost of Packing Cost of MDEA Compression Cost Temperature Cost Total Cost Gross Profit (yr) Net Profit (yr) 23.3 wt% 0.7 446.1 313 3.25 2 $459,296.48 $459,296.48 $1,389,691.08 $319,641.91 $75,731.63 $2,703,657.59 48.9 wt% 0.7 1930 313 3.07 2 $433,739.22 $433,739.22 $2,435,994.51 $1,022,210.67 $55,050.97 $3,834,981.33 23.3 wt% 0.7 1000 393 4.36 2 $615,600.96 $615,600.96 $2,305,890.61 $1,085,532.49 $134,879.23 $4,757,504.25 23.3 wt% 0.7 1000 313 11.81 0.55 $458,647.02 $458,647.02 $1,351,790.41 $864,558.95 $73,666.23 $3,207,309.62 23.3 wt% 0.98 1000 313 8.68 2 $1,226,540.51 $1,226,540.51 $2,021,368.84 $1,088,360.67 $110,155.11 $4,812,920.61

$21,270,836.17 $21,270,836.17 $21,270,836.17 $21,270,836.17 $26,458,844.99 $18,567,178.58 $16,890,101.35 $16,891,540.74 $18,063,526.55 $20,785,879.36
Table (3): Economic Breakdown of the Systems

[1] Gas Spec MDEA Specialty Amine.´ Ineos inc. 9. December, 2010. <> [2]´MDEA Proven Technology for Gas Treating Systems.´Arkema inc. 9. December, 2010. <> [3] Maham, Y.; Teng, T.T; Mather, A; Hepler, L. Volumetric properties of (water + diethanolamine) Systems. Can. J. Chem. 73: 1514-1519 (1995). Printed in Canada / Imprimt au Canada. < 3291&volume=73&issue=9&startPage=1514> [4] Methane´. Wikipedia the Free Encyclopedia. 9. December, 2010

Gas Separation Membranes Membranes can be a very useful separation processes if applied properly to mixtures. Much like how the membrane of a cell works, a membrane is a selectively permeable material; it acts as a barrier to one mixture component while letting the other pass through, effectively creating two streams of purer products from one entering stream. The feed stream is usually a pressurized mixture. From this mixture, molecule A will permeate through the membrane and is then swept away by gas on the other side, known as the permeate stream, which is of lower pressure than the feed. Membranes will not provide perfect separation, the selective permeability rather refers to the fact that different molecules will permeate through the membrane at different rates, depending on a property called permeability. A pressure gradient across the membrane drives the permeation process. Membranes may also be staged, so that the permeate of one membrane is then fed through another membrane, further purifying the two final products. The staging of membranes follows similar principles to other processes in that the number of stages must be optimized to see when additional stages are no longer economically worth the higher purity it would produce. Separation In this process, polysulfone membranes are used to remove carbon dioxide methane. The gas properties with respect to the membrane, which include permeability and permeance (P¶/t) are shown in the table below. The cost of the membrane per square foot is also noted. In this system, carbon dioxide, which has a larger permeability, will diffuse through the membrane material 55 times more readily than methane. A feed of 55% carbon dioxide is introduced at a pressure of 334 cmHg. The retentate stream is examined after each individual separation to determine the degree of methane purity that has been achieved. Product High Purity CO2 Waste Gas Low Energy Gas Medium Energy Gas High Energy Gas Pipeline Quality Gas Liquefied Natural Gas Methane Mol% <1 <10 10 ± 40 40 ± 70 70 ± 90 98 >99.995 Price per MMBTU $0.0015 (per cubic ft) -$2.60 $3.30 $4.10 $5.10 $6.10 Specifications -----600 psi 600 psi

Table 3: Properties of the Polysulfone Membrane

Design Parameters and Assumptions Membrane separations are governed by several codependent parameters. With respect to the equations used for the design, relatively little information was known, so several of the parameters needed to be either calculated from given information, or simply assumed after

testing at several different values. The first assumption that was made was for the entering pressure. It was determined that higher pressure allowed for quicker permeation of carbon dioxide and thus, with the much lower permeability of methane, allowed for a more efficient separation. Cost analysis, which will be discussed later, proved that the benefit of pressurizing the stream to just below the critical pressure outweighed the cost of having to run a compressor. The low pressure was assumed to remain at atmospheric except for in the stages involving high purities, in which 600 psi was taken as the pressure. The first parameter, which has already been referenced, is the membrane selectivity, which is simply the ratio of the permeabilities of each gas: E =PCO2/PCH4 (1)

This value is used in conjunction with the ratio of the pressures of the reject stream, the feed carbon dioxide composition, and an additional parameter, , to calculate yp, the mole fraction of carbon dioxide in the permeate stream. represents the cut fraction of the feed permeated and is a ratio of the permeate and feed flow rates. The higher that is, the more carbon dioxide that is removed. However the membrane area will increase as well. Am= ULf yp (PA/t)(phxo-plyp) Here, xo is the mole fraction of carbon dioxide in the reject stream. Since carbon dioxide is not wanted in the reject stream, this needs to be minimized. The minimum possible achievement of this mole fraction can be found using the following equation: xoM = xf [1+ (E-1)pl/ph(1-xf)] E (1-xf)+ xf Since the feed was already at a concentration at which it could be considered medium level gas that could be sold for $3.30 per MMBTU, the analyses were run to determine the benefits of creating high energy gas and pipeline quality gas. Liquefied natural gas was not considered due to the immense losses of creating pipeline quality gas, which will be discussed later. Three single-stage processes were examined. The first, a simple separation in which the mole fraction of methane was determined by other parameters, a second in which the mole fraction was fixed within the high energy range, and a third in which the mole fraction was fixed within the pipeline quality range. A fourth process, in which staged membranes were used, was then looked at to determine if any number of stages would result in better separation. After testing several ways to reach high concentrations, it was determined two stages produced the best separation, yielding a very high energy gas that was not quite pipeline quality. Economic Analysis (3) (2)

An analysis of the economics of each process was conducted after the separation properties were calculated to determine which scenario best utilized the polysulfone membranes to obtain a maximum profit of the purest possible natural gas. The costs that went into this analysis are shown in the table below:

Polysulfone Membrane Electricity

Cost $3/square foot surface area $0.11/kilowatt-hour

Table 4: Operating Costs for Membrane Separation

As discussed earlier, it was determined that an increase in pressure did not have a significant impact on the cost of any of the processes examined. This is due to the low cost of electricity required to run the compressor. The cost of the compressor use was determined using the following equation: Power = RT ln (P2/P1)*flow rate*time needed (4)

Here, the temperature was taken to be 273 Kelvin due to all other calculations being run at STP. This yielded the power in joules which needed simply to be converted to kilowatt hours, then multiplied by 11 cents and 4500 hours for the year. For the selected pressures, this resulted in costing just $260 per separation stage that was pressurized from atmospheric to the critical point, and just $120 for pressurization involving the two high pressures´. The cost of the membrane depended only on its area, which even at $3 per cubic foot added up to the vast majority of the cost in every separation that was run. Determination of Profits Each individual scenario was run in such a way that maximized its own profit by changing the appropriate parameters. In each single stage trial, as shown in the table below, the mole fraction of methane was steadily increased. The first run brought the gas into the highenergy range, but as the gas went beyond 70% purity, membrane costs began to drag down the profit. Major losses were realized when attempting to bring the gas directly from 45% to 98% methane, as can be shown from the enormously negative profit, and the membrane size increasing by several degrees of magnitude. Methane Mol% 70 74 Membrane Area (cm2) 3.78x108 4.91x108 Membrane Cost (Millions) $1.220 $1.585 Methane Cost $261.14 $261.14 Profit/year (Millions) $3.703 $3.267

90 98

1.40x109 1.08x1011

$4.505 $348.9

$261.14 $119.68

$1.628 -$421.6

Table 5: Summary of Profits for Single-Stage Separations to Various CH4 Concentrations

The multistage process proved to be more profitable, but with the same comparative result: purifying beyond the 70% high-energy barrier increased the costs and drove down profits, with large losses coming from trying to purify the gas to pipeline quality. As a result, it was determined that this membrane system is suitable for producing high-energy gas at a reasonable profit, which is increased using staged membranes. Methane Membrane Membrane Methane Total Total Profit Mol% Area (cm2) Cost Cost Cost Accumulated (Millions/year) (Millions) (Millions) Cost (Millions) 70 1.02x106 $0.0033 $261.14 $0.0036 $0.0036 $7.939 90 8.05x108 $2.599 $261.14 $2.599 $2.603 $5.340 10 98 1.18x10 $38.26 $119.68 $38.26 $40.87 -$30.92
Table 6: Summary of Profits for Multiple Membrane Separation Stages

The graph below shows the relationship between the size of the membrane and the overall profit achieved. It is noteworthy that while the overall trend is downward, there is a spike indicating it may be worthwhile to determine an optimum reject stream fraction to design the system for.

Figure 1. The profit, in dollars, plotted against the membrane area in square centimeters.

Even though the selling price greatly increases by producing pipeline quality gas, the membrane area needed for such a high purity is massive, and results in exorbitant costs that not only drive

profit down, but result in major losses. If the feed stream was less concentrated with carbon dioxide from the start, it may have been more possible to generate profit beyond the high-energy range.

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. Using water as an absorbent is not recommended as a possible solution for separation of carbon dioxide and methane. Water does not have a high absorption capacity for carbon dioxide. This is transparent from the excessive heights of the tower needed in order to perform the separation. Although, at increased flow rates a net profit was achievable, absorption using water as an absorbent is not feasible. It is improbable to have tower heights miles long. Taking a further look at the accuracy of the cost analysis may provide some additional insight. In fact, the amount of power/electric was neglected in calculating the total cost of the operation, which would affect the net profits. By increasing the flow rates more power/electric would be needed to pump the stream in at faster rates. Also, for 98 % methane a process specification was required which was not accounted for. The pressure of the stream is required at a pressure of 600 psi, while the calculations only accounted for a stream entering the packed tower at 50 psig. Therefore, an additional cost to pressurize the stream for 98 % methane would decrease the net profit. However, further development of this project should look more in detail to absorption, just not using water as the absorbent. From the results found using MDEA, it seems that running the system to gain a 98% purity of methane would be a cost effective endeavor. As shown in the data above, using the less concentrated solution (2M) allows for the best results. Increasing the temperature was also an impractical option because of an increased required amount of MDEA, increased temperature costs, and above all the increased difficulty in working with the higher temperature. For the

highest profit operation, pressure and practicality come into play. Operating at a higher pressure, with a larger area means that the associated costs will be greater than working with 50psi, which was done in the first system. Overall, I believe that we can conclusively say that using MDEA absorption for purifying a landfill gas is a profitable, and worthwhile system. Using gas separation membranes as the desired method would require a lower purity of methane. A higher purity of methane would require a larger membrane area. Since there is a large cost associated with membranes this is not feasible. Purifying beyond the 70% high-energy barrier increased the costs and drove down profits. Therefore, optimization of this process would require a lower purity to have economical gain. In addition, the benefit of pressurizing the stream to just below the critical pressure outweighed the cost of having to run a compressor. Cost analysis is fairly accurate due to the incorporation of re-pressurization for streams. This added cost was factored into net profits. To conclude, this method only proves beneficial for lower purities of methane.

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