An Economic Cost Evaluation of Landfill Gas

Kyle Zezenski Absorption with MDEA Jeffrey Zugates Absorption with Water Sagarika Badyal Cryogenic Distillation Anuj Upadhyay Gas Separation Membranes

ChE 410 Mass Transfer Operations Dr. Michael Janik December 09, 2011

Table of Contents Introduction...3 Executive Summary..4 Separation Processes A. Absorption with MDEA5 B. Absorption with Water..10 C. Cryogenic Distillation....16 D. Gas Separation Membranes21 Overall Recommendation...24 Appendix/References..25

Introduction In todays world, people are progressively looking for alternative forms of energy, and one interesting source is the use of landfill gas. This rise in the use of landfill gas can be attributed to a variety of factors: High energy prices make landfill gas economical compared to other sources of renewable energy There is a demand from consumers for a greener form of energy.

Landfill gas is generated when microorganisms in the ground break down organic material in the landfill, and this gas contains approximately fifty to sixty percent methane and forty to fifty percent carbon dioxide. This gas is eventually released into the air. At certain times, it could enter buildings, houses, even those that are not directly over buried waste. In rare cases, high levels of landfill gas may cause a fire if a spark were present. The gas from the decomposition of waste in the landfill gas can be used as a source of fuel and can eventually be converted to electricity. For our project, we were given the following parameters Landfill gas with a carbon dioxide mole percent of 62, a feed flow rate of 10 MMSCFD, a feed pressure of 25 psig and an operating time of 2000 hr/yr.

Executive Summary

Adsorption of CO2 from a CH4/CO2 mixture into an MDEA solution was found to be the most profitable process for producing liquefied natural gas (LNG). This process resulted in a methane revenue of 421,936,104/yr and a CO2 revenue of $46,315/yr. The operating costs required for this process include the cost for a resupply of MDEA each year which was determined to be $2,085,000/yr and the compression costs to bring the LNG up to pressurized standards (600psi) which was determined to be $865,000/yr. The capital investment required for this process includes only the cost of the 1 Rashig rings to fill the adsorption column which was calculated to be $733,000. Therefore, the total revenue for this process is $19,032,153/yr and will pay for its initial investment in about 27 days of time. Absorption using water to produce a medium energy gas yielded the most profitable separation process with respect to investment costs. The revenue associated with this product is $1.1 million per year. The absorption tower requires $221,648 each year for operation and $8.3 million in packing material. An income of $893,305 could be acquired each year. The separation process requires a tower height of approximately 15 m and a pure water flow rate of 64 gallons/second. Pressurizing the gas feed to 10 atm provided the best separation. Increasing the feed pressure beyond this value would not be feasible for this process. Absorption towers were designed for high energy, pipeline quality, and liquefied natural gas products. These separation units were not possible due to the high water flow rates and excessive tower heights needed. The costs associated with operating these towers were much greater than the costs required to produce a medium energy gas. The distillation process used 2 trays to produce a fractional concentration of 0.98 of methane. An XY equilibrium plot of Methane depicts this is a one stage easy separation process. This pipeline quality gas can be produced using a two stage process and generating a profit of $964,129.5 while taking operating costs into considerations. Although, selling the initial unprocessed low energy gas would be more profitable since it does not take the operating costs into the consideration while generating high revenue. The distillate product flow is 427.3lbmol/hr and methane fraction of 0.98 is produced. The membrane separation for the landfill gas stream ran on an annual loss of $204,363.00 per year. This loss is due to the fact that the membrane area was 234,683.08 ft2 which greatly increased the cost. The total cost of production was the cost of the membrane and was $ 938,732.34. The permeate stream did not have a concentration of methane that was high enough to be sold commercially so the revenue from that stream was $0. The retentate stream as sold as a Medium Energy gas at $3.3/MMBTU and the revenue was $734,369.34.

Adsorption with MDEA Solutions

Overview The use of methyldiethanolamine (MDEA) solutions in the process industries for absorbing gasses such as carbon dioxide from bulk gas streams is a very popular alternative to other processes such as absoption with water, distillation, and gas separation membranes for many reasons. MDEA solutions has a very high solubility for carbon dioxide, are less prone to evaporative losses, and are resistant to thermal and chemical degradation. These traits make MDEA an ideal choice when choosing an adsorbent for carbon dioxide and allowing the process to bring the product gas to be brought to very high concentrations. Bringing the product gas to a high purity is fundamental in creating the most valuable product from your process and therefore producing a high profit. Mass Transfer Model In this process the inlet gas feed flow is specified as 10MMSCFD with a carbon dioxide mole fraction of 0.62 and a methane mole fraction of 0.38. The MDEA liquid feed flow was not specified, however, four assumptions are made regarding the MDEA entering the column: The MDEA feed contains no carbon dioxide. Methane does not readily adsorb into the MDEA solution. The MDEA solution is 23% wt in water (2M) Regeneration of the MDEA solution costs no money and recovers 100% of the CO2 from the leaving MDEA stream.

Equilibrium data was found at a temperature of 313K (1) and a model assuming a concentrated gas mixture was used. There were originally two choices as to the adsorption column design. A counter current design and a concurrent design were both plausible options. However, the counter-current gives the maximum concentration gradient and in turn provides a higher separation in a shorter column length. The following equations 1 and 2 provide the equations for the operating line of the adsorption column ( ) ( ) ( ) ( ) (A-1) (A-2)

L2*x2 + V1*x1 = L1*x1 + V2*y2

Equations 1 and 2 provide a method for calculating the CO2 mole fraction in the exit gas stream, y2, when the other variables are either known are assumed to be some value. One assumption that eases with the optimization of this process is the calculation of Lmin. Lmin is the minimum amount of MDEA liquid flow that will produce a column that has an x1 in equilibrium
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with y1. According to the equilibrium data for MDEA at 313K, x1,eq was equal to 0.4617 when it was in equilibrium with y1 of 0.62. Using this equilibrium data a function of Lmin was created that was dependent upon y2. This equation is listed as equation 3.
( )

(A-3) L values could then be estimated using equation 3 and in turn all of the variables listed in equations 1 and 2 became dependent on only one variable, y2. Once the gas/liquid feed/exit streams were specified a long with their corresponding mole fractions of CO2 it was possible to begin the iterative calculation of the adsorption column volume. Using the equilibrium data and the following equations one can determine the final volume of the column. First equation 4 is used to determine the slope of the line that will pass through a given x,y point on the operating line. This allows for the interface compositions, xi and yi, to be calculated then using equations 5 and 6. Finally the volume of the column is calculated by integrating equation 7 from the starting composition y1 to the final composition y2. A more detailed listing of all the variables can be viewed in table M-1. (A-4) (A-5)

(A-6) (A-7)

(A-8)

Table M-1 - Variables L' (mol/s) V' (mol/s) V (mol/s) x x1 x2 xi 55.60 0 MDEA solution Liquid Flow Rate Methane Gas Flow Rate Total Gas Flow Rate Operating Line Liquid Mole Fraction CO2 Exit Liquid Mole Fraction CO2 Feed Liquid Mole Fraction CO2 Interface Liquid Mole Fraction CO2

Y y1 y2 yi k'x (mol/m2 s) k'y (mol/m2 s) K'y (mol/m2 s) a (m2/m3) S (m2) Z (m) vol (m3)

0.62 0.86 0.56 0.412 206.7 -

Operating Line Gas Mole Fraction CO2 Feed Gas Mole Fraction CO2 Exit Gas Mole Fraction CO2 Interface Gas Mole Fraction CO2 Liquid Film Mass Transfer Coefficient Gas Film Mass Transfer Coefficient Total Film Mass Transfer Coefficient Interfacial Area between Phases Tower Cross Sectional Area Tower Height Tower Volume

Economic Assumptions and Conditions: Costs include: o The post-tower pump power for the exiting gas stream. The power calculation and pricing information can be found in the appendix. The post-tower pump is only used to pressurize the 98% methane and the 99.9995% methane from the initial 39.7psia to 600psia. o Yearly replacement of the MDEA solution at $1.6/lb for a 1day stock that is continuously used for one year. o The initial purchase of the Rashig rings at $2,200/ft3 of tower volume. Profits o The price of methane is varying according to its purity. The prices can be reviewed in the appendix. o The price of CO2 is constant and can be reviewed in the appendix.

Economic Maximizations The adsorption process economic efficiency was maximized by modifying the desired product composition and the liquid flow rate in the column while adhering to the previously stated assumptions. As the desired product composition was increased, the compression costs of the exit gas increased, the amount of MDEA required increased, and the column volume increased. These three factors surely took away from the total profit but the reduction was small in comparison to the large gain in profit from purifying the methane as much as possible. The increase in profit being directly proportional to the increase in methane purity can be seen in figure 1. It should be noted that for figure 1, all of the profits are based on a liquid MDEA flow rate equal to 1.5*Lmin.
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Profit vs. Methane Purity

20000000 18000000 16000000 14000000 12000000 10000000 8000000 38 48 58 68 78 88 98 Methane Purity (%) Profit ($/yr)

Figure M-1. Profit vs. Methane Purity As can be seen in figure 1, the maximum profit occurs when the CH4/CO2 stream is purified to 99.9995% CH4. This is a clear indication that in order to optimize the profit of this process, the liquid MDEA flow must be altered at the point of 99.9995% CH4 product composition. According to Transport Processes and Separation Process Principles by Geankoplis, the most economically efficient adsorption column is produced when the liquid MDEA flow is 1.2-1.6x greater than the minimum liquid MDEA flow required for x1 to be in equilibrium with y1. The correlation between the profit and the liquid MDEA flow can be viewed in figure 2.

Profit vs Liquid MDEA flow

19200000 Profit ($/yr) 19000000 18800000 18600000 18400000 18200000 1.2 1.3 1.4 L'=x*L'min 1.5 1.6

Figure M-2. Profit vs. Liquid MDEA Flow Rates It should be noted that the profit is inversely proportional with the liquid MDEA flow rate. This is because as you increase the MDEA flow rate it will cost more money to supply the increased amount of MDEA. However, the liquid MDEA flow rate is also inversely proportional to the tower volume. As the MDEA flow rate increases, the tower volume decreases. It just so happens that the tower volume decreases by such a small amount in comparison to the increase in the MDEA flow rate that it is more economically efficient to use the minimum operating
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liquid MDEA flow rate of 1.2*Lmin. It should be noted that Lmin was determined to be 105.46mol/s when y2 was equal to 0.0005. This corresponds to a liquid MDEA flow rate of 126.55mol/s. You could mathematically go below 1.2*Lmin and keep increasing your profit but this is not a realistic solution because as you approach Lmin the concentration gradients become less and less and the tower height becomes larger and larger. Recommendations Comparing the initial cost of this process to the profit of the process shows that this is a highly valuable process. With an initial cost of a little over $700,000, this process could begin making $19,000,000/yr with an operating time of only 2000 hours/yr. This is a very low risk process because of the fact that the profit is so much higher than the initial cost.
Table M-2 - 99.9995% purity CH4, 1.2*L'min V1 (MMSCFD) 10 L' (mol/s) 126.5 MDEA ($/yr) 2085278 V' (mol/s) 55.6 CH4 ($/yr) 21936104 Volume (ft3) 333.2506 Rashig Rings ($) 733151 V1 - V2 (mol/s) 90.6 CO2 ($/yr) 46315 Feed Pressure (psia) 39.7 Compression Pressure (psia) 600 Compression Costs ($/yr) 864988 Profit ($/yr) 19032153 Initial Cost ($) 733151

Future Improvements Due to the assumptions made during the calculations of this process, the profitability could vary greatly in a declining manner. It is almost certain that some methane will adsorb into the MDEA solution which will mean a loss in profit. Also, the MDEA regeneration will never actually be free. Some cost will always be associated with the regeneration of anything and that will reduce the profitability also. Lastly, the column may not actually be at 313K so there will be a deviation from the equilibrium data used in the calculations which corresponded to 313K. Experimentation should be conducted to determine the equilibrium data at a temperature closer to the columns operating temperature. Another improvement would be to increase the columns operating time/yr. Increasing the amount of hours the column operates will always increase the profitability of it but may take away from time to perform important maintenance work. In the end, the adsorption of CO2 from methane into an MDEA solution is a viable separation process with a high profitability associated with it.

Absorption using Water as the Absorbent Overview The separation of a carbon dioxide/methane stream generated by a landfill was assessed using a packed absorption tower. The feed stream contained a 62 mole percent carbon dioxide composition, a pressure of 25 psig (2.701 atm), and a flow of 10 MMSCFD. The operating time of the absorption tower was 2000 hr/yr. An analysis using these feed conditions with changes in temperature and pressure was conducted to determine the optimum absorption tower. In addition to altering the feed stream properties, the methane concentration of the gas product was varied to determine which product concentration yielded the greatest profit. A series of calculations were evaluated, and the results were translated into revenue, capital, and operating costs. Engineering Analysis The equations used to design the packed absorption column were based on certain assumptions. Even though the inlet gas stream was concentrated, it was assumed to be dilute in order to use Henrys law (Equation B-1). (B-1) The Henrys law constants (H) of 1860 and 2330 atm/mol frac were used when evaluating the effects of raising the feed stream temperature from 30C to 40C. The pressure (P) in Henrys law was varied from 2.701-10atm to determine the advantages or disadvantages of compressing the CO2/CH4 inlet stream. The overall mass transfer coefficient, , was determined from a series of calculations. The Cussler mass transfer correlations and Equation B-2 taken from Geankoplis were used to obtain an approximate overall mass transfer coefficient of 0.005 mol/m2 s. It was assumed this value remained constant in all of the calculations. However, in actuality the value will vary at different positions in the column and fluctuations will occur in response to temperature, pressure, and liquid velocity changes. (B-2) The packing material used in the tower was one inch ceramic Raschig rings with a surface area per unit volume of 190 m2/m3. The pressure drop at flooding ( ) was considered to be 2.00 in. of water/ft height of packing since the packing factor was greater than 60. The tower cross sectional area was set to 7m2 for each proposed column design. The overall mass balance around the absorption column was evaluated using the expression in Equation B-3 (taken from Geankoplis).
( ) ( ) ( ) ( ) (B-3)

It was possible to calculate the process water flow rate from Equation B-3 using the minimum liquid . The optimum liquid flow rate was taken as 1.2 times the minimum flow, , where liquid flow. The optimum liquid flow rate of pure water was used in the calculation of process water cost. 10

The Raschig ring packing material was assessed using Equation B-4 to calculate the column height. (B-4)

Equation B- 4 (taken from Geankoplis) was integrated numerically using the inlet and outlet mole fractions of carbon dioxide as the bounds of integration. The height was multiplied by the cross sectional area to obtain the tower volume, and this value was used to calculate the cost of packing material needed for the desired separation to occur. However, the actual cost of packing material would not be based on the total column volume. In actuality, there would be allotted space at the top and bottom of the tower to permit the liquid inlet to enter at the top and the gas inlet to enter at the bottom. Equations B-1, B-2, and B-4 were the key equations used in the evaluation of the product gas. Four product gas options were considered in the calculations: medium energy gas, high energy gas, pipeline quality gas, and liquefied natural gas. The equations were applied at temperatures of 30C and 40C. The gas released from the landfill is typically at ambient temperature (25C). Raising the temperature of the gas stream was considered to demonstrate how gas solubility changes based on increasing temperature. Pressures of 2.701, 5, 7.5, and 10 atm were used to evaluate the possibility of using a compressor.

Cost Analysis The costs associated with each absorption separation process were determined to obtain the most profitable scenario with respect to investment costs. The cost analysis was conducted by generating the revenue, operating costs, and capital costs of each tower. Revenue was calculated based on the outlet CH4 gas concentration. Process water cost was assessed using the pure water flow rate in the top of column. The electrical cost of operating a compressor was determined from the inlet CO2/CH4 gas flow rate and the power requirements for a gas compressor. The heating cost for raising the temperature of the gas stream was obtained by calculating the energy required to change the temperature. This expression is presented in Equation B-5. (B-5) The cost obtained from Equation B-5 was divided by the capital costs to acquire the return on investment (ROI). The ROI of each absorption process was compared to conclude which method provided the best gains from investment. Equation B-6 demonstrates a simple calculation for the ROI expressed as a percentage. (B-6) It must be noted that the only capital cost considered in the ROI calculation was the cost of packing. The cost of Raschig rings was specified as $2200/ft3 which is most likely an inflated value. It is assumed additional fees such as installation costs attributed to the high value.

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Results The results of the four processes were analyzed using an Excel spreadsheet. The cost calculations associated with product purity at varying pressure and temperature conditions are provided for each scenario. The absorption tower that yielded the highest ROI is highlighted in yellow. A summary of the specific design and cost aspects of the best column were gathered from Excel and presented in Tables B-4 and B-5. Scenario 1 The first scenario considered was designing an absorption tower that could generate a liquefied natural gas product. The target methane concentration in the outlet gas stream was 99.995%. The cost data associated with this scenario is presented in Table B-1.
CH4 Conc (mole fraction) P (atm) T (K) Raschig Rings ($) Process Water ($/yr) Electric ($/yr) Heating ($/yr) Revenue ($/yr) 0.99995 2.701 303.2 718797625.8 859825.068 83690.67 0 2196121.2 0.99995 5 303.2 718819081 464121.24 114651.7 0 2196121.2 0.99995 7.5 303.2 718842463.2 309155.88 135037.1 0 2196121.2 0.99995 10 303.2 718792547.7 231673.2 149500.7 0 2196121.2 0.99995 2.701 313.2 718792547.7 1077288.492 86450.92 1530.1047 2196121.2 0.99995 5 313.2 718809662.9 581594.976 118433.1 1530.1047 2196121.2 0.99995 7.5 313.2 718828307 387471.708 139490.8 1530.1047 2196121.2 0.99995 10 313.2 718846985.2 290410.08 154431.5 1530.1047 2196121.2 Income ($) -7.18E+08 -7.17E+08 -7.17E+08 -7.17E+08 -7.18E+08 -7.17E+08 -7.17E+08 -7.17E+08 ROI (%) -99.8257 -99.775 -99.7563 -99.7475 -99.8564 -99.7919 -99.7678 -99.7564

Table B-1: Cost Analysis of Liquefied Natural Gas Product The column needed to conduct the separation was outside the realm of possibility. The possible revenue that could be generated for the outlet stream was $2.2 million per year. This was the highest revenue value of all the scenarios, but the income and ROI are negative. This operation requires a large tower height (1321 m) and a realistic target is in the range of 9-21 meters. The large column height requires an unrealistic amount of packing material which results in a negative ROI. In addition to the high cost of Raschig rings, an electric cost for compressing the product to 600 psi adds to the operating costs. This only contributes to a diminishing income. It was evident from the design and economic data that this process would not be feasible due to its immense size and cost.

Scenario 2 The second scenario was aimed at producing a pipeline quality gas containing a 98% methane concentration. An additional compression cost for the gas product was considered in the electric cost analysis. A summary of this data is shown in Table B-2.

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CH4 Conc (mole fraction) P (atm) T (K) Raschig Rings ($) Process Water ($/yr) Electric ($/yr) Heating ($/yr) Revenue ($/yr) Income ($) 0.98 2.701 303.2 39279139.91 849096.204 85394.37 0 1824469.9 889979.3 0.98 5 303.2 39294749.99 458329.944 115969.1 0 1824469.9 1250171 0.98 7.5 303.2 39311760.17 305298.252 136100.1 0 1824469.9 1383072 0.98 10 303.2 39328807.28 228782.4 150383.3 0 1824469.9 1445304 0.98 2.701 313.2 39275445.05 1063846.116 88210.81 1530.1047 1824469.9 670882.9 0.98 5 313.2 39287897.94 574337.856 119793.9 1530.1047 1824469.9 1128808 0.98 7.5 313.2 39301462.05 382636.848 140588.9 1530.1047 1824469.9 1299714 0.98 10 313.2 39315049.65 286786.344 155343.1 1530.1047 1824469.9 1380810

ROI (%) 2.265781 3.181521 3.518213 3.674925 1.708148 2.87317 3.307037 3.512167

Table B-2: Cost Analysis of Pipeline Quality Gas The best option for this scenario is to compress the gas to 10 atm and enter the feed into the column at ambient temperature. However, the cost of the Raschig rings inflates the capital cost and yields a low ROI percentage. A desirable income of $1.4 million is possible for this separation, but it is not feasible to acquire due to high investment costs. The tower height required to operate this separation unit is 72 meters which is above the desired interval.

Scenario 3 The third scenario was designed to release a high energy gas product. The desired outlet concentration of methane was considered to be 80%. The cost analysis for this separation process is shown in Table B-3.
CH4 Conc (mole fraction)P (atm) T (K) Raschig Rings ($) Process Water ($/yr) Electric ($/yr) Heating ($/yr) Revenue ($/yr) Income ($) ROI (%) 0.8 2.701 303.2 19901063.15 728100 0 0 1486605.1 758505.1 3.81138 0.8 5 303.2 19908712.59 393017.928 49938.71 0 1486605.1 1043648.5 5.24217 0.8 7.5 303.2 19917046.48 261793.248 82819.33 0 1486605.1 1141992.5 5.733744 0.8 10 303.2 19925396.74 196180.908 106148.5 0 1486605.1 1184275.7 5.943549 0.8 2.701 313.2 19899252.35 912248.052 0 1530.1047 1486605.1 572826.94 2.878636 0.8 5 313.2 19905355.04 492494.712 51585.77 1530.1047 1486605.1 940994.51 4.727344 0.8 7.5 313.2 19912001.27 328111.104 85550.84 1530.1047 1486605.1 1071413.1 5.38074 0.8 10 313.2 19918657.91 245919.288 109649.4 1530.1047 1486605.1 1129506.3 5.670594

Table B-3: Cost Analysis of High Energy Gas The ROI obtained from this process is approximately 6% which is still not an ideal investment. However, decreasing the methane purity in the exiting gas stream lowers the overall operating and capital costs. The column height of the absorption tower was 36 meters, and the Raschig ring cost was around $19 million. The capital cost is still too high relative to the income. It was observed from the first three scenarios that this process would need to be constructed to purify a medium energy product.

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Scenario 4 The fourth scenario was based on building an absorption column to purify a medium energy gas product. The target methane concentration in the product stream was 55%. This purification was best scenario out of the four evaluated. The data is summarized in Table B-4.
CH4 Conc (mole fraction)P (atm) T (K) Raschig Rings ($) Process Water ($/yr) Electric ($/yr) Heating ($/yr) Revenue ($/yr) Income ($) ROI (%) 0.55 2.701 303.2 8278636.46 428664.9325 0 0 1114953.8 686288.87 8.289878 0.55 5 303.2 8281510.019 231387.1808 49938.71 0 1114953.8 833627.91 10.06613 0.55 7.5 303.2 8284640.164 154129.356 82819.33 0 1114953.8 878005.11 10.59799 0.55 10 303.2 8287775.9 115500.4464 106148.5 0 1114953.8 893304.85 10.77858 0.55 2.701 313.2 8277956.149 537081.096 0 1530.1047 1114953.8 576342.6 6.962378 0.55 5 313.2 8280248.793 289953.6 51585.77 1530.1047 1114953.8 771884.33 9.321994 0.55 7.5 313.2 8282745.289 193173.636 85550.84 1530.1047 1114953.8 834699.22 10.07757 0.55 10 313.2 8285245.342 144783.648 109649.4 1530.1047 1114953.8 858990.65 10.36772

Table B-4: Cost Analysis of Medium Energy Gas The tower would have to be operated at 10 atm, and the inlet stream temperature would need to remain at ambient air temperature (30C). The revenue generated from this methane product was $1.1 million, but considering each operating cost the income would be $893,304. The capital costs were around $8.3 million and the ROI was around 11%. The ROI is within the acceptable range (8-12%) which means the absorption tower is worth the investment. Within 5 years the ROI will increase by 43% and in 15 years this number will increase by 119%. This short term and long term projection is based on a one time Raschig ring cost. The specifications of the absorption tower are presented in Table B-5.

Design Parameter P = 10 atm T = 30C Inlet Gas Flow = 146 mol/s Inlet Water Flow = 64 gal/s Column Height = 15 m Column Cross Sectional Area = 7 m2 Table B-5: Column Design Specifications Compressing this gas at high pressure causes an increase in the temperature of the feed. It was assumed the feed temperature did not increase drastically, but an additional heat exchanger cost would be needed to accommodate for temperature change. Heating the gas for each separation unit proved to be a waste in the operating costs. Increasing the temperature of the gas feed will decrease the solubility of carbon dioxide in the water stream. Cooling the inlet gas was considered when evaluating temperature effects. Lowering the temperature by 10C decreased the process water costs. This was expected since a lower temperature increases the solubility of carbon dioxide in water. However, the column height did not change significantly. The reason this was observed can be attributed to the fixed value. Ideally, the overall mass transfer coefficient should be calculated for each temperature and pressure change. These changes affect
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Henrys law constant, H, which will in turn influence the value of the mass transfer coefficient However, the procedure used to obtain was very detailed and fallible with many iterations. Therefore, the value was kept constant for all of the calculations. Another aspect of the design that was analyzed involved the tradeoff between a large tower height and a low water flow rate and vice versa. Figure B-1 displays the relationship between tower height and water flow rate for scenarios 2, 3, and 4. The figure clearly shows the water flow rate increasing with increasing height. It was expected that the water flow rate would decrease as height increases and the opposite case would be observed. Upon further analysis, the pressure and temperature values varied with each specified methane outlet concentration. Competing pressure and temperature effects resulted in the correlation shown in Figure B-1. Therefore, the column with the shortest height and lowest water flow rate proved to be the most cost effective process. The shorter tower requires less packing and less process water to achieve the desired separation. Therefore, the capital and process water operating costs decrease, which yields the highest ROI.

80 Tower Height (m) 60 40 20 0 15000

20000

25000

30000

35000

Water Flow Rate (mol/s)

Figure B-1: Tower Height vs. Water Flow Rate

Conclusion/Recommendation An absorption tower that can concentrate the 62 mole percent carbon dioxide/methane stream to a medium energy gas product was the ideal design. This conclusion was based on the economic evaluation of the data. The focus of the economic analysis was in the operating costs since these costs were the most accurate relative to capital costs. The only specified capital cost were Raschig rings. A further analysis of all the capital costs would have to be conducted to obtain more accurate ROI values. Such considerations would be concentrated in the construction aspects. These types of aspects include civil, mechanical, and electrical areas. The site excavation, concrete, structural steel, and roofing contribute to civil costs. Auxiliary equipment such as pumps, compressors, filters for the inlet streams prior to entering the column, piping, and valves are mechanical costs. The electrical costs associated with operating the column are motor controls, motor starters, transformers, field instrumentation, overall process control system, and lighting.
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Cryogenic Distillation Overview

Normally, gaseous mixtures are separated by cryogenic distillation where the feed is allowed to enter the column at low temperatures. The distillation of carbon dioxide and methane is a known and used process due to the large difference in the boiling points of the two components. The aim of cryogenic distillation is to produce high-purity steams. On a large scale, gaseous separations are accomplished economically by cryogenic distillation. Cryogenic separation unit are operated at extremely low temperature and high pressure to separate components according to their different boiling temperatures. A good economic and less costly scenario would be to have a high inlet flow rate, high mole percent methane and a feed at low temperature.

Separation of Carbon Dioxide and Methane by Cryogenic Distillation

The HYSYS program was used to create a PFD for the separation process. Separators were used to separate the two components. Methane has a higher boiling point of 87K and carbon dioxide has a boiling point of 243K. Therefore, methane is vented off through the overhead of the separator and is called the distillate. Liquid carbon dioxide is collected at the bottom of the separator and is called the bottoms product. An XY plot of Methane and Carbon dioxide is shown below. A McCabe Thiele Analysis shows that this is a one stage easy separation process.

Figure (C-1). Equilibrium plot for methane.

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First Compressor

First Separator

Second Separator Compressor

Second Compressor

Figure (C-2). The PFD on HYSYS. Assumptions The inlet temperature for the feed was assumed to be 0F. The feed pressure of 39.70 psia was increased by 200 psi for first compressor. The first cooling heat exchanger is used to cool the gas mixture to -120F. The second cooling heat exchanger is used to cool the gas mixture to -175F, since at this temperature the maximum methane is collected in the vapor form. The heat exchanger works at 100% efficiency.

Second heat exchanger First heat exchanger

Figure (C-2). First and second cooling heat exchangers

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The landfill feed( CO2 and Methane) containing 62 mole percent carbon dioxide and an inlet molar flow rate of 10 MMCSFD was allowed to enter a compressor at temperature of 0F in order to compress the gas to a pressure 239.7 psia. A low temperature was assumed so as to have favorable economic condition. The compressed gas was then cooled in a cooling heat exchanger to a temperature of -120F. The exiting gas was then sent to the first separator where the mixture was separated and the fractional concentration of methane and carbon dioxide produced was found to be 0.88 and 0.11 respectively. In order to get a more purified concentration of methane, the methane product from the first separator was sent into another separator passing through a cooling heat exchanger again. The purpose of using a 2 stage process is to increase purity while simultaneously keeping the operating costs at minimum. This exiting gas from the first reflux drum was further sent to a cooling heat exchanger and cooled to a temperature of -175F. The mixture was then sent to a second separator and methane was compressed to the given specification of 600 psi to produce methane gas at a fractional concentration of 0.98 and carbon dioxide was produced at a fractional concentration of 0.0186. The two separators can be assumed to be two trays where the gas mixture is being separated. The use of two separators instead of one was to get a higher purity concentration for methane. Cost/Data Analysis In order to calculate the operating cost for the entire system, the electric costs are taken into consideration since the system is dominated by the cost of refrigeration. The electric costs if the two heat exchangers and the two compressors to get the operating cost. The two tables below show the cooling duty and the compressor duty electric cost. Heat Exchanger Duty (Btu/hr) 8781000 Heat Exchanger Electric Duty (kwh/hr) Cost ($/yr) 0.11 0.11 Operating Time (hr/yr) $2,000 $2,000 Cooling Duty Electric cost ($/yr) $566,023.3 $39,862.1

2572.833 Heat Exchanger 1 618400 181.1912 Heat Exchanger 2 Table (C-1). Heat Exchangers Cost Analysis Compressor Duty (Btu/hr) Compressor Duty (kwh/hr)

Electric Cost ($/yr) 0.11 0.11

Operating Time (hr/yr) $2,000 $2,000

2900000 849.7 Compressor 1 618400 49.1654 Compressor 2 Table (C-2). Compressors Cost Analysis

Compressor Electric cost ($/yr) $186,934 $10,816.388

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The total operating cost is the sum of the cooling duty electric cost of the two heat exchangers and the compressor electric cost of the two compressors.

Total Operating Cooling Duty Cost Electric cost $803,635.7 ($/yr) $566,023.3

Cooling Duty Electric cost ($/yr) $39,862.1

Compressor Electric cost ($/yr) $186,934

Compressor Electric cost ($/yr) $10,816.388

The end methane product is of 98% purity, which is a pipeline quality gas and can be sold at a price of $5.4/MMBtu. From the HYSYS simulation the flow rate of methane gas from the second separator was found to be found to be 427.7 lbmol/hr. Using the following data, the total cost of selling the methane per year was calculated using the heat of combustion of methane to be 0.383061MMBtu/lbmol.

(Equation C-1) Therefore, at a total operating cost of $803,635.7, the total cost of selling a feed of 98% methane would cost $964,129.5 (Total cost at 98% purity Total operating cost). The total cost of selling methane at the feed concentration was calculated to be $2,271,865.84 without any operating costs. The bar chart below shows the cost analysis of selling the methane product at 98% purity and 38% purity.

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Cost Analysis
$2,500,000.0 $2,000,000.0 $1,500,000.0 $1,000,000.0 $500,000.0 $0.0 $5.4/MMBtu $2.7/MMBtu

Figure (C-4). Cost Analysis Bar Graph. Therefore, even though a profit is generated using cryogenic distillation, there is net loss of $1,307,736.3 is generated when compared to selling the landfill feed methane. This proves that Distillation would not be an ideal process. Recommendations With the feed conditions given, using cryogenic distillation is a profitable process for separating methane and carbon dioxide but selling methane from the landfill feed was calculated to be more profitable. Therefore, a net loss of $1,307,736.3 was generated if distillation was used as a separation process. Therefore, Distillation may not be an ideal choice of process and the landfill gas (feed) can be sold a higher price without purifying it.

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Gas Separation

Overview Membrane filtration is a very important process for separating a gaseous mixture into two components which are purer streams. Modern examples of membrane separation in industry other than methane and carbon dioxide include removal of H2S from natural gas, recovery of H2 in oil refinery processes, as well oxygen enrichment for metallurgical processes. Gas separation using membranes utilize three streams; the inlet feed, and the outlet retentate and permeate. The driving force through the membrane is a pressure difference which provides the separation.

Low Pressure

High Pressure

Figure D-1 The amount of separation depends on the selectivity of the membrane and the Permeability of each component to the membrane. The membranes can be selective based on molecule size, polarity, and volatility. The permeablities for each component through the membrane are given as P(CH4) and P(CO2). Throughout this process, it was assumed that the contents of every stream was completely mixed, which made the calculations of exit values feasible.

Design In the situation presented, a 62% by mole mixture of carbon dioxide was fed into the separator at a flow rate of 10 MMSCFD. The rest of the mixture consisted of methane and the pressure of the feed was 25 psig. The goal of the process was to separate the feed stream into two streams that were high in methane content. Based on the concentration methane in the exit streams, a certain price could be demanded for the cost of the natural gas.
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Calculations With the specified conditions given in the scenario, the amount of methane in each exit stream needed to be calculated in order to do cost analysis. As an intermediate calculation, the Yp is determined. This is found using intermediate values of a, b, and c which are in turn calculated from r = p(l)/p(h), Xo, and * = P(CH4)/P(CO2). Yp is found using the quadratic formula with a, b, and c. From this theta can be found and then the area of the membrane needed is calculated. The area of the membrane is found using the following equation:

Am = ___LfYp______ Pat (PhXoPlyp) Process Analysis

(D-1)

When pressure on the permeate side is lower, the driving force is greater which means the separation is greater. Calculations were performed with varying pressures on the permeate side but as expected, the smallest membrane area was achieved when the pressure was lowest. Physically, the lowest pressure possible for the permeate side is 1/10 of the high pressure because anything more would cause too much strain on the membrane and blow it out. Using the minimum pressure, the following values were determined:

Xo 0.1 0.4 0.7 0.9

Yp Theta CH4 0.002262 -2.8648 0.014247 0.051847 0.057793 0.498282 0.32602 0.905956

Process Analysis Am Lo Vp ft^2 mol/s mol/s -8224264 373.3718 -276.763 234683.1 91.59959 5.008816 5253116 48.47019 48.13822 43121722 9.085475 87.52294

CH4 in Lo mol/s 37.33718 36.63984 33.92914 8.176927

CH4 in Vp mol/s -0.62599 0.071358 2.782061 28.53427

Table D-1

Table D-1 shows that the renentate methane concentration (Xo) cannot be less than feed methane concentration (Xf) because that would then mean the membrane area would be negative. Also, if Xo was less than Xf it would not make sense to use a membrane process and just selling the straight feed stream would make more money. Other than the exit concentration
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being 10% methane, every other concentration is possible, but in order to determine which is best, an economic analysis of the costs and revenues must be done. Another method that could be utilized would be a multiple-stage membrane process. In this scenario, the retentate stream is then put into another shell where another membrane is present to purify the stream even more. The retentate stream from the second shell will be more purified than the feed; this could be done as many times as needed to get a desired methane concentration. However this is an interesting idea, the feed flow rate already started very low and each subsequent stream would only be lower. When a necessary concentration is achieved, the flow rate would be so low that barely any money could be made from it. Also, the costs of each shell is not known so that would need to be accounted for before proceeding with this idea.

Economic Analysis In any process there are certain fixed and variable costs. With this separation, the fixed cost is only the area of the membrane, which is $4/ft2. Each membrane needs to be replaced annually, so that cost will be incurred every year this process is conducted. Additionally, there are various variable costs that may need to be attributed to the overall cost of the process. For this situation, those variable costs are heating, cooling, electric, and steam. These costs need to be evaluated if the feed or exit streams need to be pressurized to meet certain conditions. Pressurizing the inlet feed would increase the driving force and separation but that would increase the costs and ultimately diminish the profits, so that was not done in this process. Revenue is made by selling the exit streams which are at certain concentrations. The above table shows those concentrations with Xo and Yp. For given conditions, the permeate stream does not have a high enough methane concentration to sell for any value.

Cost Analysis Xo .4 .7 .9 Membrane cost $938,732.34 $21,012,462.16 $172,486,888.73 Retentate Revenue $734,369.34 $906,718.60 $218,519.33 Profit ($204,363.00) ($20,105,743.56) ($172,268,369.40) Return on Investment (21.77) (95.68) (99.87)

Table D-2

From Table D-2, the exit stream cannot achieve a profit at any of these exit concentrations. This is due to the fact that there was not enough of a pressure gradient to drive the feed through the membrane. This caused the area of the membrane to be very large, making it more expensive than the exit streams could be sold for. When an exit stream of 70% is demanded
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with all other conditions constant, the area of the membrane must increase substantially. With this increase, there was a slight increase in the price it could be sold for but it was not enough to offset the costs. With then the increase to 90% methane, there is yet another increase in the area of membrane needed but there is no increase in selling price so the profit decreases dramatically. The only scenario where this process could be profitable at any concentration methane is if the low pressure was extremely close to a vacuum. Theoretically, that would mean that the permeate side would have maximum ability to pull the feed stream through the membrane. If this maximum pulling was available, the membrane would not have to be so big and the fixed costs would greatly decrease. This vacuum idea is not physically possible due to the restrictions of the membrane as described above.

Recommendation With the feed already having a concentration of 38%, it is able to be sold for $3.3/MMBTU and $602,017.83 could be made without any processes done to the feed. Due to the tables and data above, using membrane separation to purify the given feed with given conditions should not be done. By trying to purify the feed to a point where it could be sold at a higher price is not worth it because of the price of the membrane. This process runs at a loss even when conditions like low pressure are optimized. Even though no single-stage process proved to be profitable, a multi-stage process could be investigated as a possible way to turn a profit. Cost research for shells must be done and a second analysis of costs as determined by area, shells, and pressurization.

Overall Recommendation Of all four separation processes analyzed the gas membrane separation was the least effective in producing a profitable exit stream. The minimum loss of the membrane unit was $204,366. The cryogenic distillation unit generated less profit than selling the initial unprocessed gas. The distillate contained 98% methane and the profit obtained from this separation was $964,000. The profit obtained from the unprocessed gas was $2.3 million. Therefore, it was unreasonable to design a distillation unit. The absorption processes both generated a considerable profit. However, the absorption process using MDEA yielded the highest profit possible at $19 million per year for a liquefied natural gas product. Therefore, the final consensus of constructing an absorption column using MDEA solutions would be the most economical option.

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Appendix

1. Product CH4 concentration Price Waste Gas < 10% Low Energy Gas 10 - 40% $2.7/MMBtu Medium Energy Gas 40 - 70% $3.3/MMBtu High Energy Gas 70 - 90% $4.4/MMBtu Pipeline Quality Gas 98% $5.4/MMBtu Liquified Natural Gas <50 ppm CO2 $6.5/MMBtu Price estimates are in the range of $0.002/SCF (SCF = standard cubic feet). Specifications 600 psi 600 psi

2. Definitions Heat Exchanger: A piece of equipment used in many chemical plants that is built for efficient heat transfer from one medium to another (i.e. from liquid to gas or vice versa). Separator: A piece of equipment that makes the necessary separation between a gas/ liquid mixture giving a one gaseous and one liquid product. Compressor: A mechanical device that is used to compresses a gas to a higher pressure.

References

Athanassios Vrachnos, Georgios Kontogeorgis, Epaminodas Voutsas, Thermodynamic Modeling of Acidic Gas Solubility in Aqueous Solutions of MEA, MDEA, and MEA-MDEA Blends, Ind. Eng. Chem. Res. 2006, 45, 5148-5154. "Carbon Dioxide Properties." Engineering ToolBox. Web. 06 Dec. 2011. <http://www.engineeringtoolbox.com/carbon-dioxide-d_1000.html>. "Cryogenic Distillation." Don't Waste Your Green Beer. Web. 05 Dec. 2011. <http://students.chem.tue.nl/ifp33/Purification/Cryogenic%20Distillation.htm>. Rousseau, Ronald W. "Distillation." Handbook of Separation Process Technology. New York: J. Wiley, 1987. 230. Print. Geankoplis, C. J. Transport Processes and Separation Process Principles: (includes Unit Operations). Upper Saddle River, NJ: Prentice Hall Professional Technical Reference, 2003. Print.

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Heat of Combustion of methane: http://www.wolframalpha.com/. "Landfill Gas." Illinois Department of Public Health Home Page. Web. 06 Dec. 2011. <http://www.idph.state.il.us/envhealth/factsheets/landfillgas.htm>. "Landfill Gas to Energy: A Growing Alternative Energy Resource." TreeHugger. Web. 07 Dec. 2011. <http://www.treehugger.com/renewable-energy/landfill-gas-to-energy-a-growingalternative-energy-resource.html>. "Methane - Specific Heat." Engineering ToolBox. Web. 6 Dec. 2011. <http://www.engineeringtoolbox.com/methane-d_980.html>. Photo courtesy: "Landfill Gas to Energy Overview." ACUA Home Page. Web. 05 Dec. 2011. <http://www.acua.com/acua/content.aspx?id=506>. Photo courtesy: "Looks Into The Carbon Offset Project At The Tontitown Landfill." TreeHugger. Web. 05 Dec. 2011. <http://www.treehugger.com/corporateresponsibility/treehugger-looks-into-the-carbon-offset-project-at-the-tontitown-landfill.html>. "Return on Investment (ROI) Definition." Business & Small Business / News, Advice, Strategy / Entrepreneur.com. Entrepreneur Media, Inc. Web. 07 Dec. 2011. <http://www.entrepreneur.com/encyclopedia/term/82570.html>. Solomon, Stephen M. Plural Stage Distillation of a Natural Gas Stream. The Lummus Company; 1976. Bloomfield, NJ. Pat# - 3983711. "Water - Density and Specific Weight." Engineering ToolBox. Web. 6 Dec. 2011. <http://www.engineeringtoolbox.com/water-density-specific-weight-d_595.html>.

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