CH E 410 Final Project

David Belias Cryogenic Distillation Mike McEldrew Gas Separation Membranes David Kozak MDEA Absorption Austin Goewert Water Absorption

4/25/2014

Contents
Executive Summary....................................................................................................................................... 3 Introduction .............................................................................................................................................. 3 Distillation Analysis ....................................................................................................................................... 6 Gas Separation Membranes ....................................................................................................................... 16 Model 1: .................................................................................................................................................. 17 Model 2: .................................................................................................................................................. 18 Model 3: .................................................................................................................................................. 21 Model 4: .................................................................................................................................................. 23 Absorption using MDEA .............................................................................................................................. 25 Introduction ............................................................................................................................................ 25 Calculations and Equations ..................................................................................................................... 26 Discussion................................................................................................................................................ 27 Conclusion ............................................................................................................................................... 31 Absorption using Water .............................................................................................................................. 33 Introduction ............................................................................................................................................ 33 Calculations ............................................................................................................................................. 35 Discussion................................................................................................................................................ 36 Conclusion ............................................................................................................................................... 40 Recommendation........................................................................................................................................ 41 Appendix A .................................................................................................................................................. 43 Appendix B .................................................................................................................................................. 46 Appendix B1 ............................................................................................................................................ 46 Appendix B2 ............................................................................................................................................ 47 Appendix B3 ............................................................................................................................................ 48 Appendix B4 ............................................................................................................................................ 49 Appendix C: ................................................................................................................................................. 50 Appendix C1 ............................................................................................................................................ 50 Appendix C2 ............................................................................................................................................ 50 Appendix C3 ............................................................................................................................................ 52 References .................................................................................................................................................. 53

Executive Summary
This report provides an analysis and evaluation of four separation unit operations. Cryogenic distillation, gas separation membranes, and absorption using water and MDEA were explored. Analysis for distillation utilized Aspen HYSYS, while the other three analyses utilized Wolfram Mathematica. Current market values for all prices were used in the cost analysis to find operational costs and revenues. All calculations can be found in the following discussions. The investigation found that absorption was the most profitable operation due to the highest purity product being sold. Specifically, absorption using water is the recommended option because it produced the greatest profit with the least uncertainty. Distillation had, by far, the greatest costs due to refrigeration and equipment prices. Gas separation membranes had much lower costs, but they were still triple those of absorption. The assumptions used in the analysis of absorption need to be explored further in subsequent examinations to more accurately examine the revenues and costs. In the future, changes in market prices and innovations in industry may yield different results in the capabilities of each unit operation.

Introduction
The separation of methane and carbon dioxide is a recurring industrial process that can be completed using numerous unit operations. In this analysis, Cryogenic distillation, gas separation membranes, and absorption using both water and methyl diethanolamine (MDEA) were investigated in great detail. The feed stream originated from a natural gas well and its properties are outlined in Table A below. Pressure (psia) Temperature (F) 77 Methane Concentration (mol%) 86 Carbon Dioxide Concentration (mol%) 14 Feed Flow (MMSCFD)

494.7

35

Table A. Properties of the feedstock from the natural gas well.

The feed flow was converted to a molar flow using the ideal gas law at standard temperature and pressure (14.7 psia, 459.67 R). Equation A below shows how the molar flow was calculated.
( ( ( ) ( )

Gases with varying energy levels could be sold for different prices, which are outlined in Table B below. Product Waste Gas Low Energy Gas Medium Energy Gas Methane Concentration (mol%) <10% 10-40% 40-70% 3 Price ($/MMBtu) 2.50 3.00 Specifications -

High Energy Gas Pipeline Quality Gas Liquefied Natural Gas High Purity Carbon Dioxide

70-95% 95% 99.995% 1%

3.50 4.00 5.20 0.003/SCF

600 psia 600 psia -

Table B. Product stream market prices based on purity.

Since the feed was already a high energy gas, pipeline quality gas and liquefied natural gas were explored as possible product streams. The revenue generated from selling the feedstock, pipeline quality gas, and liquefied natural gas were calculated using Equations B, C, and D. Selling the high purity carbon dioxide was also investigated for some unit operations. Calculating the revenue for this stream is outlined in equation E below. The operating time for this analysis was 7,000 hours per year.

The combustion value of methane was found in Btu per standard cubic feet and converted to MMBtu per pound mole using Equation F.1 Equation A was used to calculate the number of moles in one standard cubic foot. ( )

In order to calculate the high purity carbon dioxide flow rate used in Equation E, the ideal gas law was employed at standard temperature and pressure. There were also operational costs to consider, before calculating the net profit of a given system. Each of the aforementioned unit operations requires the pressurization of gas or liquid streams. The cost associated with this compression can be seen in Equations G and H.
( ) ( ( (

Each unit operation has its own unique operational costs, which will be discussed further in the subsequent sections. The net profit was calculated by subtracting the total operational costs from the revenue generated from the product and waste streams. Distillation was the first operation considered for this separation. The simulations were performed using Aspen HYSYS with the Peng-Robinson fluid package. The main factors investigated were number of stages, reflux ratio, column pressure, feed quality, and product streams. Costs for running the column included refrigeration, compression, heating, and equipment. The next unit operation examined was gas separation membranes. The primary elements explored were number of stages, recycling strategy, membrane area, feed entry stage, and outlet stream purity. The main costs associated with gas separation membranes are the cost of membranes, and the cost of gas compression. The calculations were performed using Wolfram Mathematica. The third operation that was investigated was MDEA absorption. The main variables of concern for the absorption involved Henrys Law constant, liquid flow rate, volume of the column, pressure of the column, and temperature of the column. The more substantial costs included the capital for building the column and the pressurization of the feed as well as heating and cooling the two feed streams. These calculations were performed in both Excel and Wolfram Mathematica.

Distillation Analysis
The first analysis was done on the output streams that could be produced. Since the gas that comes out of the well is already high energy gas, there were only two different products that could be produced. Pipeline quality gas needed a methane concentration of 95%, while liquefied natural gas needed a methane concentration of 99.995%. The first setup used a cooler to cool the gas to a saturated vapor that entered the column. The condenser was operated at a pressure of 480 psia. Since the specifications called for a product pressure of 600 psia, a pump was added at the outlet of the condenser to pressurize the liquid methane rich stream. At the outlet of the reboiler and condenser, heaters were added to bring the liquid streams back up to a vapor. No heater was required for the liquefied natural gas because the specifications required a liquid. This setup is displayed in Figure 1 below. The condenser and all heat exchangers were assumed to have a pressure drop of 5 psia. The reboiler was assumed to have no pressure drop and the distillation column was assumed to have a 3 psia pressure drop, on average, regardless of the number of stages.

Figure 1. Setup 1 for the methane/carbon dioxide cryogenic distillation. When producing the pipeline quality gas, there were two options considered for the bottoms stream. High purity carbon dioxide and low energy gas were both considered as the bottoms stream for distillation. To perform the comparison of the different scenarios, the distillate methane concentration was specified to be 95% and the bottoms stream was specified to be the two different options. This was also done for the liquefied natural gas, but changing the methane distillate concentration to 99.995%. The number of stages was changed during each simulation to find the optimum number of stages. The Fenske Equation was used as a starting point to estimate the minimum number of stages for each different scenario that would be expected. Table 1 below gives the values for minimum stages. The number of stages was increased until the reflux ratio did not change drastically.

Product Stream
Pipeline Quality Gas Liquefied Natural Gas

High Purity Carbon Dioxide 2.3061 4.4346

Low Energy Gas 1.5727 3.7012

Table 1. Minimum stages of different scenarios estimated using Fenske Equation.

Equations 1-4 below show the Fenske Equation and calculations of vapor pressures. The vapor pressures were calculated using the Antoine Equation at the temperature of the feed entering the column.2,3 The alpha value was assumed to be constant at each stage. (

There were four factors that contributed to the total cost of distillation. This included equipment costs, compression costs, refrigeration costs, and heating costs. Equations 5-8 below show how each of the costs were calculated. Energy and power values were calculated in HYSYS. The refrigeration costs were obtained from Figure A1 of Appendix A.
( ) #

( ( ( ) ( ( ( ( ) ( ) ( ) ( ( ) ( + ( ( ( +

)+

( (

( )

Table 2 below shows the optimal number of stages for each scenario, which was determined by minimizing total cost, which maximizes profit.

Product Stream
Pipeline Quality Gas Liquefied Natural Gas

High Purity Carbon Dioxide 4 26

Low Energy Gas 2 26

Table 2. Optimal stages of different scenarios from HYSYS analysis. After performing the analysis, it was determined that producing pipeline quality gas with high purity carbon dioxide in the bottoms was the most profitable scenario. The profit vs. number of stages plots are pictured below in Figure 2. There are several key points that can be learned from these plots. Appendix A provides plots of number of stages versus reflux ratio and total cost versus reflux ratio for these product streams.

The two main contributors to the changes in total cost are the reflux ratio and number of stages. At a very large reflux ratio, the amount of energy needed for the condenser is very large. This is because a higher reflux results in more liquid going back into the column, so there is more methane still in the column to allow the desired purities to be reached. This liquid eventually enters the reboiler at the bottom, which results in a higher vapor flow rate moving up the column. Finally, this vapor enters the condenser, so a higher vapor flow rate means more energy needs to be removed to fully condense 8

all of the vapor. The refrigeration costs increase due to this increased reflux ratio. Increasing the number of stages decreases the reflux ratio. Each stage is assumed to be 100% efficient in order to analyze the best profit that a distillation column can make. This means that the mixture reaches equilibrium at each stage. Going up the column, the temperature and pressure at each stage decrease, allowing the methane to transfer into the vapor phase more easily. The vapor phase goes to the condenser and becomes the distillate stream. More stages gives more opportunity for the methane to transfer into the vapor phase. However, increasing the number of stages also increases the equipment costs. The optimal number of stages allows the desired purities to be reached, while minimizing cost. By comparing all four figures, it is apparent that the pipeline quality gas with high purity carbon dioxide bottoms is the most profitable option, with a maximum profit of $31.52 million per year. For the pipeline quality gas with high purity carbon dioxide in the bottoms, seen in Figure 2a, there is a clear maximum and then a linear decline in profit as the number of stages is increased. The optimum number of stages is clearly 4 stages because that maximizes the profit. The minimum number of stages determined from the Fenske Equation was 2.3061, so at 3 stages, the reflux is beginning to grow very large. This is the reason for the decrease in profit. Above 4 stages, the reflux ratio begins to decrease due to the increase in stages. Refrigeration costs begin to decrease, but equipment costs increase. The profit decreases because the decrease in refrigeration costs is not enough to counteract the increase in equipment costs. The profit versus number of stages for pipeline quality gas with low energy gas bottoms plot is displayed in Figure 2b. The maximum profit for this scenario is $29.8 million per year. The optimal number of stages that gives the maximum profit is two. There is no maximum in the plot, so the maximum profit is at two stages and the profit decreases linearly with an increase in the number of stages. This could be because the reflux ratio is never large enough for the condenser refrigeration costs to outweigh the equipment costs. There is no minimum in the plot of total cost vs. reflux ratio seen in Figure A4 of Appendix A, so the equipment costs always outweigh the refrigeration costs. When simulating the production of liquefied natural gas, it is clear that this option is not as profitable as pipeline quality. Looking at Figure 2c, it is seen that the maximum profit for liquefied natural gas with high purity carbon dioxide bottoms is only $19.25 million per year. Figure 2d shows that the maximum profit for liquefied natural gas with low energy gas bottoms is $16.25 million per year. This is a little over half the maximum profit that can be achieved by the pipeline quality gas. Even though these result in a more pure stream that can be sold for $5.20 per million Btu versus $4.00 per million Btu for the pipeline quality, it requires many more stages. The optimal number of stages for both scenarios is 26, which is over six times as many as the pipeline quality requires. As a result, equipment costs are six times as high, so profits are much lower. Also, the refrigeration costs are higher because a higher reflux ratio is also needed to get to the desired purity. The required reflux ratio is very high at a lower number of stages, so the refrigeration costs greatly outweigh any money earned from selling the products. Below fifteen stages, this is the case, and money is actually lost from producing this liquefied natural gas. A heater is not needed for the distillate stream because the gas is sold as a liquid. Even though this is the case, heating costs are almost negligible, so it does not change the profit

drastically. Above the optimal number of stages, the profit begins to decrease again because equipment costs begin to dominate. After analyzing the data, it was determined that producing pipeline quality gas is much more profitable than liquefied natural gas. It was also determined that producing high purity carbon dioxide in the bottoms is more profitable than producing low energy gas. Generating the very pure liquefied natural gas requires many more stages and a higher reflux ratio in order to achieve the desired purity. The refrigeration and equipment costs outweigh the revenue from selling the product streams due to the high number of stages and reflux ratio. Producing the high purity carbon dioxide in the bottoms is more profitable than the low energy gas because of the flow rate that can be produced. Since the distillate is very pure with methane, the flow rate of methane in the bottoms is very low. As a result, not much money can be made from this stream. On the other hand, there is a large amount of carbon dioxide in the bottoms, so more money can be generated from this stream. Even though it takes several more stages to produce this, selling the carbon dioxide outweighs the cost. In the end, the best option was producing pipeline quality gas with high purity carbon dioxide in the bottoms. The next investigation was to determine the best pressure for operating the column to produce the pipeline quality gas with high purity carbon dioxide in the bottoms. Figure 3 below shows the xy diagram for the methane/carbon dioxide mixture at feed pressure (494.7 psia) and at 600 psia, which is required for the pipeline quality gas. It can be seen that the equilibrium curve at 494.7 psia has more separation from the y=x line than for 600 psia. This means that the separation is easier at 494.7 psia, so fewer stages are required. However, the operating costs may be lower for a setup with the condenser operating at a pressure of 600 psia, so this was investigated.

10

Setup 2 for the distillation column is outlined in Figure 4 and it uses a compressor to pressurize the feed that enters the column. At the outlet of the distillate, there is no pump required because the pressure of the stream is at the required pressure specification.

Figure 4. Setup 2 for the methane/carbon dioxide cryogenic distillation.

In order to find the effect of column pressure on maximum profit, the column pressure was increased to 605 psia to find the maximum profit at the highest logical pressure choice. Since the heater has a pressure drop of 5 psia, the distillate stream had to be at a pressure of 605 psia to maintain specifications for pipeline quality gas. There is no point in operating the column above 605 psia because the specifications only require a pressure of 600 psia. The analysis with setup 2 was performed, and the comparison with setup one is summarized below in Figure 5.

11

Comparing the results from Figure 5, there is not a drastic increase in the profit due to increasing the column pressure. The column at 605 psia results in a maximum profit of $32.1 million, while operating at 480 psia gives a maximum profit of $31.52 million. This is not a very drastic increase in maximum profit. This can be attributed to an increase in equipment costs because the optimal number of stages is 6 versus 4 for a column pressure of 480 psia. However, the required condenser energy decreases, so refrigeration costs decrease, outweighing the increase in equipment costs. Looking at both plots in Figure 5, it can be seen that there is a much smoother maximum in the profit for a pressure of 605 psia. This setup is better because there is more allowance in the variability of the number of stages in the column, and thus the reflux ratio. If five or seven stages are used, the profit will still be near the maximum profit. Other operating pressures were explored between 480 and 605 psia, but they did not considerably change the maximum profit. The problem with these operating pressures is that a compressor before the column and a pump after the column would be necessary to achieve the required pressure specifications. Adding an extra piece of equipment adds more complications and increases the chances of an equipment failure. In the first two analyses, the feed entered the column as a vapor, so the final analysis was for the effect of feed quality on profit. Setup two was used with the optimal range of stages for varying vapor fraction feeds until a maximum profit was found. The optimal number of stages was between 4 and 8, giving an unbiased comparison of the feed qualities. The maximum profit was plotted against the varying vapor fractions of the feed. The results are displayed below in Figure 6.

Pipeline Quality Gas with High Purity CO2 Bottoms

32.5 32 31.5 31 30.5 30 29.5 29 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 Vapor Fraction of Feed Profit ($M/yr)

Figure 6. Profit at varying feed qualities for producing pipeline quality gas with high purity carbon dioxide bottoms. Looking at Figure 6, it is apparent that the best feed quality is a saturated vapor. Again, the costs are dominated by the cost of refrigeration, which is determined by the reflux ratio. The higher the vapor fraction in the feed, the higher the required reflux ratio. This increases refrigeration costs in the

12

condenser. On the other hand, the higher the liquid fraction in the feed, the higher the refrigeration costs of the cooler because the feed needs to be cooled more. Judging by the plot, the energy requirements for the cooler are much higher than the condenser. The flow rate into the cooler is higher than the flow rate into the condenser, so more energy needs to be removed from the feed. The minimum in the plot occurs because once some vapor is introduced into the column from the feed, the condenser energy requirements increase due to the increase in reflux ratio. Table 3 below shows energy requirements of the condenser and cooler for a low and high vapor fraction in the feed. Vapor Fraction 0.1 0.1 0.1 0.1 0.1 0.5 0.5 0.5 0.5 0.5 0.9 0.9 0.9 0.9 0.9 Number of Stages 4 5 6 7 8 4 5 6 7 8 4 5 6 7 8 Reflux Ratio 2.02 0.748 0.323 0.296 0.207 2.18 0.808 0.46 0.411 0.348 2.41 1.05 0.726 0.63 0.564 Cooler Energy (Btu/hr) 1.78E+07 1.78E+07 1.78E+07 1.78E+07 1.78E+07 1.52E+07 1.52E+07 1.52E+07 1.52E+07 1.52E+07 1.19E+07 1.19E+07 1.19E+07 1.19E+07 1.19E+07 Condenser Energy (Btu/hr) 1.55E+07 8.96E+06 6.78E+06 6.65E+06 6.19E+06 1.63E+07 9.27E+06 7.49E+06 7.23E+06 6.91E+06 1.75E+07 1.05E+07 8.85E+06 8.35E+06 8.02E+06

As expected, an increase in the vapor fraction of the feed decreases the cooler energy requirements and increases the condenser energy requirements. After all of the analysis, it was determined that the optimal design was a distillation column operated with a condenser pressure of 605 psia and six stages. The feed is compressed to 620 psia and fed to the column as a saturated vapor. This design results in a maximum profit of $32.1 million. This analysis was not entirely comprehensive because there are other factors that could have been considered. To cut down on the costs of cooling the feed stream and heating up the distillate, the distillate could have been used to cool the feed. The distillate did not need to be sold at such a low temperature, and the feed needed to be cooled to a saturated vapor. Another factor that could have been considered was feeding the column with a superheated vapor. This would cut down on the refrigeration costs for the cooler, which could have potentially saved some money. However, the condenser would need to remove more energy since the vapor is superheated. In the end, these changes may not have increased profits by too much. Using a flash separator instead of an entire distillation column is another consideration that could be made for further analysis. This would cut

13

down on the equipment and heating costs of the column. However, refrigeration would be needed to cool the gas to a saturated liquid. Also, since the feed was very rich in methane, it would be difficult to reach pipeline quality gas and liquefied natural gas with a single flash separator. As a result, the profit would most likely not be any better than what was achieved with a full distillation column. The final question that needed to be considered was whether it was economically beneficial to purify the feed using distillation versus just selling the feed that came from the natural gas well. Figure 7 below shows the maximum profit from each of the different options explored, as well as the costs associated with each option.

Figure 7. Profit and costs in millions of dollars per year for producing varying product streams.

It can be inferred from Figure 7 that the most profit could be generated from selling the feedstock. The costs of purifying the stream into a higher energy gas outweighed the revenue generated. Refrigeration and equipment costs are the highest, with compression and heating costs being very marginal. Producing the liquefied natural gas almost doubled costs, so this was clearly not a viable option. Clearly, cryogenic distillation is a very expensive purification technique. As a result, it is more profitable to sell the feed gas, rather than selling the more pure pipeline quality gas with high purity 14

carbon dioxide in the bottoms. Refrigeration costs make up nearly 75% of the total costs, so it is the dominant factor in driving the profit down for this purification technique. Equipment costs are the second highest, so reflux ratio and number of stages determine the total cost. Higher reflux ratio results in fewer stages, but this increases the refrigeration costs. On the other hand, a lower reflux ratio results in more stages, so equipment costs increase and refrigeration costs decrease. Finding the optimum balance between the two gave the maximum profit. When trying to produce liquefied natural gas, six times as many stages were needed, as well as a higher reflux ratio. This drove refrigeration and equipment costs very high, so a lower profit was generated. When analyzing the operating pressure of the column, it was determined that increasing the pressure only increases profit minimally. Finally, the higher the vapor fraction in the feed, the higher the profit generated. This is due to the large refrigeration costs in the condenser for a more liquefied feed. After completing all of this analysis, distillation was most likely not the best option for purification of the feedstock.

15

Gas Separation Membranes

The separation of methane and carbon dioxide can also be performed using gas separation membranes. Separation is possible because the membrane permeability coefficient of methane is less than that of carbon dioxide for polysulfone membranes. This means that carbon dioxide will pass through the membrane more easily than the methane, creating a separation driving force. In this profitability analysis, four models of membrane gas separation were explored. The first model analyzed was a simple single stage process. The second model was a two stage process with the conventional recycling strategy, and configuration. The third model was a three stage process, where the feed entry stage was changed from the first stage to the second stage. The final model was a four stage process, where the feed entry stage was moved to the third stage. Each of these models was explored in detail, and the most profitable option proved to be the three stage process. However, the four stage model gave a much more stable maximum profit, while only sacrificing a small amount of profit. These models, as well as the net profits attained from each model are examined in a great amount of detail below. For any gas separation membrane process, there are four algebraic equations that can be written for each stage. The equations used in this analysis were 1) a total mass balance over the entire stage, 2) a methane mass balance over the entire stage, 3) a methane balance over the permeate section of the stage, 4) a carbon dioxide balance over the permeate section of the stage. These equations are written in mathematical form below:
1. 2. 3. 4. ( + ( +

It should be noted that when recycling streams are employed, which can be seen in Figure 10 and Figure 12, the mass balances on each stage or sub-stage changed and so the general mass balance equations above were altered accordingly. The type of balances used in the calculations were of the same form, just with additional terms where necessary. The goal of this analysis is optimizing profit, so it is important to explain how the numbers generated through the mass balance equations above translate into dollars. Calculating the value of a product stream, the value of the waste stream, and the general cost of compression can be seen above in the introduction section. The only additional cost in gas separation by membranes, is calculating the cost of the membranes, which can be seen below. The net profit is calculated by summing up the value of the product stream and the waste stream and then subtracting the costs of compression and membranes. It is important to note that for a given gas separation membrane process all these values can and will change, affecting the net profit in varying ways.
5.
( ) ( ( ) ( ) ( )

The feedstock is received at a relatively high pressure of 494.4 psia. The analyses were completed assuming that this pressure was high enough for the retentate, and no preliminary

16

compression was necessary. Altering the pressures of the retentates could be an area worth exploring, because pressure gradients are key driving forces in gas separation membrane processes. Increasing the pressure gradient will decrease the area necessary for a given gas separation job. However, it turns out that membrane and compressional costs are quite comparable, so increasing the price of one cost in order to save money on another would not be extremely meaningful. For the sake of simplifying the procedure of honing in on an optimal gas separation membrane model, the pressure was not modified.

Model 1:

Feed Retentate

Permeate

Figure 8: Simple One-Stage Gas Separation Membrane Process

The first analysis was completed using just one gas separation membrane stage, and can be seen outlined in Figure 8 above. In this simple analysis, the area of the membrane was varied, giving different product and waste streams. The goal of this analysis was to get an idea of the size of the gas membrane that would be needed for considerable gas separation, and to find the size of the gas membrane that would optimize profit. Area was varied from one million cm2 to one billion cm2, giving a wide range of product stream purities. However, achieving 99.995% methane (liquefied natural gas) was infeasible using this model of gas separation membranes. It was clear that as more membrane was used in the separation, the purity of the gas may increase, but the cost of membrane increases as well. Another competing factor involving the membrane size is that as the membrane size increases a higher fraction of the feed passes through the membrane into the permeate, and the retentate product stream will contain less material, albeit with higher purity. In fact, as the membrane area increases from one million cm2 to one billion cm2 the product stream decreases almost 100 lb-moles. Possibly the most important factor to consider is the value of the product stream. As was outlined in the introduction, the product stream can be sold at different rates, based on methane purity. Because the feed is already 86%, the goal of this separation is to create pipeline quality gas (95% methane) or liquefied methane (99.995% Methane), which was already determined to be impractical. The last factor to consider in optimizing profit is the value of the waste stream, also known as the carbon dioxide rich permeate stream. If this stream is rich enough in carbon dioxide (99% carbon dioxide), then it can be sold for 0.3 cents per standard cubic foot. Also if the waste gas is greater than 10% methane, then it can be sold as a low energy gas for 2.5 dollars per million BTU. When all of these factors are considered and calculated then the net profit can be optimized.

17

Net Profit vs Membrane Area For Single Stage Gas Separation Membrane
40 Net Profit ($ per year) 39 38 37 36 35 34 33 1000000

10000000 100000000 Membrane Area (cm^2)

1E+09

Figure 9: Graph of net annual profit versus membrane area for single stage gas membrane separation.

Figure 9 displays how the net annual profit changes with the membrane area. A clear maximum profit is seen for a membrane area of 115,560,000 cm2, which gives a methane purity of 95%. The large jump in profit occurs, when methane purity reaches 95%, and the stream can be sold for 4 dollars per million BTU. Apart from this jump, the graph tends downward as membrane area increases, due to the increase in the cost of the membrane. Also, it should be noted that when the product stream reaches 95% methane, there is an additional cost in compressing the product stream to 600 psia, in order to sell it as pipeline quality gas. This additional cost cannot be seen in the graph, because the increase in the value of the product stream greatly outweighs the cost of compression. Profit was also gained from selling the waste gas. As the area of the membrane increases, the methane content of the waste stream increases. At an area of around 50 million cm2, the waste gas stream methane fraction rose above 10%, and could be sold as a low energy gas. The waste stream never reached high enough purities in carbon dioxide, to sell it as production quality carbon dioxide. Overall, this single membrane analysis illustrated the importance of product stream value, and that attaining 95% purity in the product stream will most likely produce optimal results. A full summary of results for this model are tabulated in Appendix B1.

Model 2:
A two-stage gas membrane separation process was the next model to be analyzed. The recycling scheme and staging can be seen below in Figure 10. The goal of this analysis was to determine if additional staging would result in greater net profit. It was shown in the single stage analysis that the area that optimized profit was 115,560,000 cm2. In order to have an unbiased comparison between one and two stages, the area was kept constant at 115,560,000 cm2 for the first membrane. Initially, the calculations were done with both membranes at this same area. The results that followed were

18

unexpected. The product stream was calculated to be 95% methane, the same as with one stage. However, the retentate stream from the second stage tended toward zero, and the permeate stream from the first stage was identical to the permeate stream from the second stage. In other words, everything that entered the second stage tended to pass through the second membrane into the second permeate stream. The area of the second membrane was determined to be too large. For any meaningful calculation, the second membrane had to be considerably smaller.

Product Retentate Stream

Feed

Permeate Stream 1

Second Permeate Stream (Waste Gas)

Second Retentate Stream, (Recycle)

Figure 10: Two Stage Gas Membrane Separation Configuration

The domain of areas for the second membrane was particularly hard to find, so instead of varying the second membrane area, it would be easier to vary the retentate stream of the second stage, and record the changing areas of the second membrane. It is desirable to make the second retentate stream a finite fraction of the feed stream, in order to provide any considerable recycling within the system. The fraction of the feed that was recycled as the retentate from the second stage was named the reflux ratio. In this analysis, the reflux ratio was varied from 0.02 to just below 0.3. Once again, the area of the first membrane remained constant at 115,560,000 cm2. Using this domain of reflux ratios, the area of the second membrane ranged from a little over 33 million cm2 to 0 cm2. As the reflux ratio increased the area of the second membrane decreased. This tendency coincides with the previous conclusion that when the area of the second membrane becomes too great, the flow rate of the retentate in the second stream tends toward zero. The product stream purity varied from just below 95% to 86% as the reflux ratio changed from 0.02 to 0.2944. The latter reflux ratio dictates the highest possible second stage retentate flow rate permitted by material balances. In other words, it says that in order to have a recycle stream flow rate that high, none of the gas that enters the second stage can leave in the permeate stream. Because the area of the second membrane goes to zero at this reflux ratio, effectively this is the same as just recycling the permeate from the first stage back into the retentate of the first stage. This explains why the product stream has a mere 86% methane purity; in essence, this gas membrane configuration separates the methane and carbon dioxide only to mix them back up again. Another phenomenon that was observed was the lack of high purity in the methane rich product stream. The highest possible separation in the methane stream was 95% purity. This occurs as the area of the second membrane grows very large, and the reflux becomes very low. This limit on purity was essentially determined by the area of the first membrane. The recycle stream only adds more impurities back into

19

the first stage. Moreover, when the product stream is collected, it can never be as pure as the case when there is no recycling taking place. This means that for this area of the first membrane, the product stream could not be sold as pipeline quality gas. Also, another cost for additional stages is the compression that must occur in between stages. The permeate leaves the first stage at atmospheric pressure, and must be compressed to 494.7 psia before entering the second stage. The additional staging is not entirely useless. It does create a higher product stream flow rate, and purifies the carbon dioxide rich stream further. However, in order to maximize profit from the feed stock, a high purity carbon dioxide rich stream is not the answer.

Net Annual Profit Vs Area of the Second Membrane

37.5 Millions of Dollars per Year 37 36.5 36 35.5 35 34.5 34 33.5 0 10000000 20000000 30000000 40000000 Area of the Second Membrane (cm2)

Figure 11: Graph of Net Annual Profit plotted against the Area of the Second Gas membrane for a two stage gas membrane separation process.

From Figure 11, it can be seen that net profit for this two stage model was maximized when the area of the second membrane was slightly higher than 9 million cm2. This maximum occurred when the waste stream had a carbon dioxide purity of exactly 99%, and could be sold. The large drop that can be seen in Figure 11, occurs when the area of the second membrane is greater than the aforementioned optimal value. The reason for this drop is that the waste gas carbon dioxide purity dips below 99%, and cannot be sold. Net profit increases up until the peak area value, because the increase in purity increases the revenue generated by the product stream. The increasing value of the product stream outweighs the increasing membrane cost, thus increasing net profit. A full summary of the results for this model are tabulated in Appendix B2. When comparing the single stage gas membrane profit maximum to that of the two stage process, it is clear that the single stage process is better than the two stage process. The overall profit comparison is summarized in Table 4.

20

Area of the First Membrane (cm2) Single Stage Two Stage 115,560,000 115,560,000

Area of the Second Membrane (cm2) n/a 9,340,200

Waste Gas Value (millions of dollars per year) 0.663 2.684

Product gas Value (millions of dollars per year) 38.809 35.300

Compression Cost (millions of dollars per year) 0.194 0.540

Membrane Cost (millions of dollars per year) 0.373 0.403

Net Profit (millions of dollars per year) 38.906 37.041

Table 4: Tabulated summary comparing the optimized profits for single stage and two stage gas separation

The two stage analysis proved that additional staging with the current recycling strategy is not profitable. Because the methane rich product stream comes from the first stage, and the feed enters the first stage, there is not enough time for the feed to be considerably purified. The resolution occurs by considering a three stage gas membrane process, where the feed enters the second stage, instead of the first. This configuration, which can be seen in Figure 12, will theoretically allow enough time for the feed to be purified before leaving as the product gas in the first stage. Essentially, this configuration sacrifices the purity of the carbon dioxide rich waste gas, by increasing the purity of the methane rich product stream.

Model 3:
Product Stream Feed Permeate Waste Stream Permeate Retentate

Retentate

Figure 12: Three stage gas membrane separation configuration with altered feed stage

The final analyses would be of the three stage gas membrane configuration seen above in Figure 12, and a four stage gas membrane separation process, with the feed entering the third stage. It was evident from the analysis of the single and two stage gas separation membrane processes that 95% purity in the methane rich product stream reveals the greatest net annual profit. For the remaining analyses, the purity of the product stream was set at 95% methane, while the membrane areas, or reflux ratios would vary. The goal of this three stage gas separation membrane analysis was to determine if additional staging could be made more profitable than single staging, and to determine if changing the feed entry

21

stage would prove to provide more profitable results. The three stage gas membrane was analyzed by setting the area of the first two membranes equal to each other, but the third membrane left unconstrained. This method proved to give the best results after considerable exploration with the calculations. It turns out that when the feed enters a given stage, the following stage should be made with a smaller membrane than the others. This is very similar to the problem that occurred in the previous analysis of the two stage separation process, where the second membrane was determined to be optimal when smaller than the first membrane. Once again, instead of varying the membrane areas, reflux ratio was specified. In this case, the reflux ratio of the third stage would be varied as a finite fraction of the feed stream, and the rest of the variables would be solved for and recorded. The domain of input reflux ratios that provided meaningful results was 0.001 to 0.012. The results of these calculations were extremely promising, and are tabulated in Appendix B3. The flow rate of product stream was on average around 15 moles per second greater than the flow rates of the single stage and two stage gas separation processes. Also, when the reflux ratio was set above 0.011, the carbon dioxide rich waste gas reached 99% purity and could be sold. Figure 13 summarizes the effects of reflux ratio and total area on net annual profit. It is easy to see that as membrane area decreases and reflux ratio is increased the net profit increases. This tendency is a result of increased flow rate in the product stream. As reflux ratio increased and membrane area decreased. These trends can be seen in Figure 13, in the upward trend for reflux ratio, and the downward trend for membrane area.

Millions of Dollars per Year

Net Annual Profit Vs. Reflux Ratio of the Third Stage

42 41 40 39 38 37 0 0.005 0.01 0.015 Reflux Ratio of the Third Stage Millions of Dollars per year

Net Annual Profit Vs. Total Area of Gas Membrane

42 41 40 39 38 37 100000000

120000000

140000000

160000000

180000000

Total Area of Membrane

(cm2)

Figure 13: (Left) A plot of net annual profit versus the reflux ratio of the third stage, for the three membrane gas separation process. (Right) A plot of net annual profit versus the total area of membrane for the three membrane gas separation process.

The jump in the graph occurs when the purity of the waste stream is rich enough in carbon dioxide to be sold. The maximum profit for this analysis was slightly above 41.5 million dollars. This profit is considerably greater than any profit of the previous membrane configurations. It is clear that making the feed stage separate from the product stream stage is a viable option that deserves further exploration.

22

Model 4:
The final analysis would be to determine if the new process configuration would be profitable with additional staging. This was be done by analyzing a four stage process with the feed entering the third stage. The calculations for this model were completed in a very similar manner as the three stage process. The areas of the first three membranes were set equal to each other, and the fourth membrane was allowed to be unconstrained. In this analysis, the reflux ratio of the fourth stage would be varied, and the remaining variables could be calculated. The complete results for this model are tabulated in Appendix B4. The domain of reflux that provided meaningful results was 0.01 to 0.1. Across this domain of reflux ratios, the flow rate of the methane rich product stream increased very slightly, however the total membrane area increased much more rapidly. Ultimately, this means that the increased cost in membrane area will overpower the increased product stream value due to increased flow rate. The effects on Net Profit of the reflux ratio and total area of membrane can be seen in Figure 14.

Net Annual Profit Vs. Reflux Ratio

42 Millions of Dollars per Year 41 40 39 38 37 0 0.02 0.04 0.06 0.08 0.1 0.12 Reflux Ratio of Fourth Stage 42 41 40 39 38

Net Annual Profit Vs. Total Area of Membrane

Millions of Dollars per Year

37 150000000

170000000

190000000

210000000

230000000

Area of Membrane (cm2)

Figure 14: (Left) A plot of net annual profit versus the reflux ratio of the fourth stage, for the four stage separation process. (Right) A plot of net annual profit versus total area of membrane, for the four stage separation process.

Once again, the jumps in the graphs in Figure 14 occur because the waste gas becomes rich enough in carbon dioxide to be sold for profit. When the profit of the three stage process is compared to the profit of the four stage process, it is clear that the three stage process has the highest maximum profit. The higher profitability for the three stage process is due to a lower membrane and compression cost for the three stage process. Because there are only three membranes instead of four, there will be less membrane area for the three stage process, leading to less membrane cost. Also, there will be less compression cost, because there are less permeate streams in need of compression for the three stage process. Normally, increasing the number of stages increases recovery, which in turn increases the product stream flow rate. However, in this case, the increase in the number of stages only negligibly increases the flow rate of the product stream; not enough to make the additional stage profitable.

23

Total Area of 2 Membranes (cm ) 3 Stage 4 Stage 117312971 160737300

Product Stream Flow Rate (mol/s) 495.202 495.202

Waste Stream Value (Millions of Dollars per year) 2.903 2.932

Product Stream Value (Milllions of Dollars per year) 39.855 39.813

Compression Cost (millions of dollars per year) 0.868 1.205

Membrane Cost (millions of dollars per year) 0.379 0.519

Net Profit (millions of dollars per year) 41.51117082 41.02049259

Table 5: Tabulated summary comparing the optimized profits for three stage and four stage gas separation

Table 5 compares the profitability of the three and four stage processes. Even though the three stage process has a higher maximum profit, it is important to consider the stability of this profit. As can be seen in Figure 13, the peak profit occurs across a very small range of reflux ratio. In fact, the maximum reflux ratio for the third stage permitted by material balances, is only slightly greater than 0.012. This reflux ratio is the one that maximized profit for the three stage process. This means that the reflux ratio in the third stream must be kept between about 0.011 and 0.012. This really does allow any room for process error. When considering the instability of the maximum profit for the three stage process, it may very well be the rational decision to take the slight loss in profit and use the four stage design, which allows much more room for error. Overall, the separation of methane and carbon dioxide using polysulfone membranes proved to be a complicated task. There were many competing costs and calculation complications that muddled the optimization of profit. Still, gas separation membrane also proved to be a profitable option for this separation. As can be seen in Figure 15, each gas separation membrane model was profitable compared to the gross value of the feed. Figure 15 also reveals that selling the waste stream as high purity carbon dioxide, as in the 2, 3, and 4 stage models, is much more profitable than selling the waste gas as low energy gas, as in the single stage model. This analysis proved that additional staging will increase purity, but not always the purity of the desired outlet stream. It demonstrated that the entry stage of the feed has a very large effect in the purity of the outlet streams. Finally, this analysis verified that separating the gases, to achieve exactly pipeline quality gas is ultimately the most profitable. Any separation past pipeline quality, and any separation leading up to pipeline quality will not be profitable.

Monetary Comparison of Gas Separation Membrane Models

45 Millions of Dollars per year 40 35 30 25 20 15 10 5 0 Feed Single Stage Two Stage Three Stage Four Stage Gas Separation Membrane Models
Membrane Cost ($M/year) Compression Cost ($M/year) Waste Stream Value ($M/year) Product Stream Value ($M/year) Net Profit ($M/year)

Figure 15: A bar graph comparison of operational costs, stream revenues, and net profit for each gas 24 separation membrane model.

Absorption using MDEA

Introduction
The natural gas feed stream contained a very high concentration of CH4 before entering the absorption column. This concentration, 86% CH4, limited the possible end products to only three options. With this parameter set for possible products, several assumptions were then made to simplify calculations while still maintaining accuracy. 1. Only CO2 crosses the medium allowing for the masses of the CH4, water, and MDEA to be constant with their flows. 2. The system is gas phase controlled making the concentration in x uniform in the horizontal direction (i.e. xint = x). 3. The liquid solution coming in contains no CO2. 4. The CO2 is absorbed at a low enough concentration that the CO2 product stream is negated. 5. The CH4 and C02 mixture acted like an ideal gas. 6. It was taken that the weight percent of MDEA in the solution was constant at 23.3%. This allowed for constant molar composition of the liquid solution while also permitting the usage of the equilibrium data from problem set 4.6 7. It was assumed that the water/MDEA solution is recycled every day and the only costs are associated with the daily usage of the solution. 8. The cooling water is run in a countercurrent flow and the Ts are equal.7 9. The CO2 solubility in MDEA data is only given for temperatures of 313 K, 343 K, 373 K, and 393 K, but was assumed to be proportional to temperature. This conclusion was utilized to estimate CO2 solubility data for temperatures at 298 K and 275 K.4 Employing these assumptions allowed for the most thorough analysis of the system given. Without many of the assumptions, many more equations and variables would need to be involved and thus adding more error to the calculations. However, due to the necessity to interpret data for different temperatures, these numbers may have some error associated with them. Overall though, the data was scaled to the most accurate representation of the obtained data. Therefore, the differences in the obtained data versus experimental may differ slightly but the proportions should be similar enough that the calculations using these values will be reflective of the general trends within the changing variables.

Solubility of CO2 in MDEA vs Partial Pressure of CO2

10000 1000 100 10 1 0.1 0.01 0.001 0.0001 Partial Pressure CO2 (kPAa)

0.001

T = 275

0.01 T = 298

XC02 T = 313

25

0.1 T = 343

T = 373

T = 393

Figure 16: Interpreted data for CO2 solubility in MDEA (23.3%)6

Calculations and Equations

With the set of assumptions in place, the specific equations used to help find the different profits were then determined. These equations for the MDEA absorption account for the differing liquid flow rate, the pressure changes and temperature changes of the column, as well as volume of the column. Many of these equations are common among all absorption calculations but may be repeated due to consistency and their use for finding values for other calculations. 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. ( ( 11. ( ( 12. ( ( ( ( ) ( ) ( )+ ( ) ( ) ( ( ( ) )+ ( ( ( ( ) ) ( ( ) ( ) ( ( ) ( ) ( ) ( ( ) ( ) ( ) ( ) ) ( ) ( ( ) ) ( ( +( ( ( ( ) ( ( ( )
( ( ) ) ( ( ( )

L`= Lin

In examining the absorption with MDEA, the two key variables that needed to be determined were the volume of the column and the liquid flow rate (Lin) into the column. Using Equation 8 and Assumption 2, it was found that L` was equal to Lin. These are the two main variables that significantly affect the economics of the system. However, due to the use of MDEA in the aqueous solution, Equation 6 could not be used alone. Henrys law constant ( ) is related to the interface concentrations of CO2 in both the liquid and gas (shown in Equation 2). To accommodate for the changing Henrys law constant ( , the value must be set in terms of another variable. In this case, the was then put in terms of Calculating in terms of required utilization of Equation 2 and the interpreted data from Figure 16. Finding different and values from Figure 16, values were obtained at different values. The last step in was finding its relationship to x. Using excel, equations were discovered to reflect the overall relating and . This equation was then set as ( ) to distinguish its dependence on . Thus, the (in Equation 1) value was also put in terms of the ( ) variable. There were now two variables 26

for the single interval meaning that one has to be put in terms of the other. This was done by setting in terms of through the usage of the CO2 mass balances in each system. After determining the constants L` and V` and solving the mass balances, Equation 7 could be found. This let Equation 6 now become a function dependent on . With all variables specified in terms of , the integral for volume could be solved. The molar composition of the feed stream being 86% CH4 meant that there were only two sets of limits involved. ( was set at 0.14 for all calculations as the molar composition of the feed was constant.) The first choice for modifying the feed stream was to raise the purity of the gas stream to 95% CH4 to make it pipeline quality gas. The limit was set as which allowed the definite integral to be solved. Noting that L`= Lin (proven above), the volume could be found by estimated by inputting different values of Lin into Mathematica.2 Solving for volume and having a Lin value, all the necessary values for calculating costs were available. Entering the values of Lin and volume into Equations 10 and 11, respectively, the costs for building the column and the liquid solution were determined. Utilizing the heating, cooling, and pressurization costs, discussed in the introduction of this paper, the changes in temperature and pressure of the columns and streams could be calculated as well. These steps were then redone using for the 99.995% purity product stream to obtain the liquefied natural gas product. The overall profits were then determined using the costs subtracted from the revenue. To find the revenue, the flow rate had to first be evaluated. Using Assumption 1, it was found that the gas flow rate out ( ) of the column was equal to Equation 9. For both , the revenues were constant due to being a constant. The revenues, computed with the combustion of CH4 equation and the energy prices of each product stream, could then be compared with the overall costs.

Discussion
The first analysis for the entire system was to see the profit gained by just exporting the 86% CH4 for combustion. The feed was already within the purity range for high energy and therefore this would be the basis to see the potential consequences of adjusting the product stream purity. The revenue for the 86% CH4 was determined to be about $35.3 million. Since there were no costs for the feed stream, the profit was equal to the revenue. The base profit was then $35.3 million. This value was taken at ambient temperature (298 K) and feed pressure (480 psi). The next step was to analyze the profit for the 95% purity. This analysis required the utilization of the Henrys law constant and x. In this case, the ( ) equation was acquired through the interpreted data and inserted into the integral to find the different volumes. (6) Temperatures were varied in this calculation to attempt to isolate the variable and see how it affects the overall economics of the column. It can be assumed that lowering the temperature would raise the x values because the vapor pressure would be lower, so it has a lesser ability to escape the liquid phase. This in turn would lower the volume and liquid flow rate necessary for the column. On the contrary, raising the temperature of the column lowers the solubility of CO2 while increasing costs for heating, liquid flow rate, and volume. As seen in

27

Figure 17, the column temperature of 275 K produced the greatest profit. Yet, the difference between the profit at 275 K and 298 K was approximately $20,000. The costs of cooling the feed and solution were outweighed by the increased benefits of decreasing column volume and solution flow rate. As well, the increase in temperature brought smaller profits as predicted. The calculations were repeated for the 99.995% methane to assess the potential advantages of a liquefied nitrogen stream. As shown in figure 3, the data again supported the lowering of temperature for highest profits. Additionally, the increased purity contributes to an increased profit of approximately $12 million. The differing profits for one year did not vary enough to justify any conclusions. Thus, analysis of long term profits and pressurization of the column would have to be reviewed to provide a more concise understanding of the benefits of lowering the temperature within the column. However, several conclusions could still be drawn from this data. Raising the temperature within the column resulted in lower solubility and in turn, higher costs. Obtaining the highest purity of CH4, 99.995%, would involve minimal costs in comparison to the return revenue. Thus, further investigation into maximizing profit only included the recovery of 99.995% CH4.

39.8 39.6

Average Annual Profit of Pipeline Quality Gas (95% CH4) at Different Temperatures
39.64 39.62 39.54

Profit ( $ x 106)

39.4 39.2 39

39.31 39.13

38.83 38.8 38.6 38.4 T=275 K T=298 K T=313 K T=343 K T=373 K T=393 K

Figure 17: The effect of varying temperatures within the column versus the profit of the column for 95% CH4.

28

51.75 51.5 51.25 51 50.75 50.5

Average Profit of Liquified Natural Gas (99.995% CH4) at Different Temperatures

51.68 51.64 51.54

51.21 50.99

Profit ( $ x 106)

50.31 50.25 T=275 K T=298 K T=313 K T=343 K T=373 K T=393 K

Figure 18: The effect of varying temperatures within the column versus the profit of the column for 99.995% CH4. The discovery of increased profits with temperature was then investigated on a 30 year basis. This was performed to accommodate for a full use of the Raschig rings. To calculate the profits for this scenario, each annual cost was multiplied by 30 years except for the column volume and Raschig rings. In this situation, the results again supported decreasing the temperature within the column (illustrated in Figure 19).

30 Year Profit vs Temperatures at 480 psi

1.563E+09 T=275 T=298 K

Profit ($ 1 x 106)

1.558E+09

T=313 K T=343 K T=373 K

1.553E+09

T=393 K

1.548E+09

1.543E+09 100 200 300 400 500

L iquid Flow Rate (mol/s)

Figure 19: The overall profits over 30 years accounting for the annual heating, cooling, and pressurization costs along with the initial column costs.

29

After confirming the slight increase of both annual and 30 year profits with decreasing temperature within the column, the pressures were altered to investigate their possible effects. Utilizing Equations 2, 3, 4, and 5 from the Equations and Calculations sections (copied in Figure 20 too), the differing pressures could be evaluated according to their 2. changing partial pressures. These values were assessed at 3. constant temperatures so they assumption that 4. from Equation 5. Thus, the partial pressures would change 5. ( ( with changing pressures while still leaving constant for all pressures (validated by Equation 2). Leaving Figure 20: Different Henrys law constant constant allowed for the use of Equation 4 to find . equations relating to pressures7 With and the partial pressure found, a new x could be determined. Finally, with the new x and constant, a new could be found. The effect of changing pressure was hypothesized to alter the solubility of gas and thus changing the driving force, . An increase in x at constant would correspond to a decreasing and more importantly, a force to improve solubility of the CO2. This new data was again converted to a function, , with respect to x (data shown in appendix). The volume integral was then performed in Mathematica for five different pressures and compared to the original column at a pressure of 480 psi (The data is shown below in Figures 21 and 22).

5.18E+07 5.17E+07 5.17E+07 5.16E+07

Annual Profit vs Liquid Flow Rate for Different Column Pressures at T=275 K for 99.995% CH4.

P=697 P=640 P = 560 P=520 P=480 P=400 50 100 150 200 250

Profit $

5.16E+07 5.15E+07 5.15E+07 5.14E+07 5.14E+07

Liquid Flow Rate (mol/s)

Figure 21: The effect of changing the pressures within the columns compared to annual profits at a constant temperature of 275 K.

30

Annual Profit vs Liquid Flow Rate for Different Column Pressures (psi) at T=298 K for 99.995% CH4
51,700,000 P=697 P=640 51,500,000 P=560 P=520 P=480 51,300,000 P=400

51,600,000

Profit ($)

51,400,000

51,200,000 75 100 125 150 175 200 225 250 275 300

Liquid Flow Rate (mol/s)

Figure 22: The effect of changing the pressures within the columns compared to annual profits at a constant temperature of 298 K. As hypothesized above, increasing pressure did reduce the liquid flow rate and volumes necessary to accomplish the 99.995% CH4. However, the increased costs associated with pressurization of the feed and liquids outweighed the decrease in capital and liquid flow rate costs. The pressures chosen were used to show the effects of both expanding and compressing the column. Specifically, the pressure at 697 psi was chosen because it accommodated for the pressure drop across the column in the gas. This decrease in pressure resulted in the product leaving the column at 600 psi, precisely what is required for the liquefied natural gas to be used. As well, 400 psi was chosen to confirm that lowering pressure would not be beneficial. In all these cases, the major cost for the columns was pressurizing the feed. Therefore, the increase in pressure for the feed would provide a substantial cost for the system paralleled to the minor benefits of cost reduction in capital and liquid flow rate.5

Conclusion
Overall, the absorption column analysis provided clarity with regards to varying flow rate, volume, pressure, and temperature. Each was shown to have a clear effect on the how the system was run and its efficiency yet in the overall breakdown, only temperature played a clear role in varying from the norm. There are many possibilities as to why when changing the variables, only small differences were calculated. First, the feed stream came in at a very high purity which allowed for the obtainment of high purity CH4 with few costs. Secondly, the costs associated with the column were relatively insignificant. For example, in cooling the feed stream and liquid stream for the temperature at 275 K,

31

the amount of cooling water used became a nominal value due its absurdly low cost. The only two substantial costs were pressurization of the feed and the capital cost. Nonetheless, the capital cost only occurred every 30 years and became small around that time. With this data, it should be assumed then that obtaining a purity of 99.995% was not only a feasible operation but also provided the best profits. Altering pressure and temperature did affect the solubility of CO2 in the liquid. These alterations contributed minimal changes in the $100,000s range. The most cost-effective scenarios for the system were achieved when temperature was lowered from the original standard temperature (298 K) but the feed pressure was maintained. The recommendation for the best absorption column would then meet these 5 criteria: 1. 2. 3. 4. 5. Temperature is between 275 K and 298 K Pressure is maintained around 480 psi The purity of the product stream is at 99.995% The liquid flow rate is about 170 mol/s The volume of the column is about 5.57 m3

32

Absorption using Water

Introduction
The separation of carbon dioxide from methane can be accomplished by absorption of carbon dioxide into water. Several key equations are necessary to perform this analysis: 1. Volume of column: 2. ( +( ( ) ( + (
( (

( 3. Henrys Law constant : : vapor mole fraction at interface : liquid mole fraction at interface * ( )+

4. Henrys Law variation with8 T: : constant8 (=2400 Kelvin for CO2)

It is essential to derive an equation for the volume of the absorption column in order to calculate the capital cost for this process. Equation 1 is derived from a material balance within the column. Since liquid concentration varies throughout the column, equation 2 is necessary to evaluate the integral. The final step in solving for the volume of the column is the evaluation of H using solubility data for carbon dioxide in methane. Since the process is gas phase dominated (1/ky >> H/kx), the liquid composition is approximately uniform horizontally. Liquid composition is approximately 0.005 at the top of the column and 0.1 at the bottom. By using tabulated partial pressures, vapor composition and thereby H can be determined at the top and bottom of the column. Htop and Hbottom were calculated for all operating conditions tested. Since Htop/Hbottom is approximately one for all operating conditions(Table 6), it is valid to assume H is constant throughout the column.

33

Table 6 :Comparison of Henrys Law Constant Values at Top and Bottom of Column9,10 T (K) 298 298 298 298 273 Note: See Appendix C1 for H values P (psi) 480 520 590 660 480 Htop/Hbottom .9903 .9903 .9903 .9903 1.0022

Table 7: Solubility of Carbon Dioxide in Water at Various Temperatures and Pressures9,10

The solubility of a gas in a liquid depends on temperature, the partial pressure of the gas, the nature of the solvent, and the nature of the vapor. Lower temperatures and higher pressures increase solubility, therefore decreasing H. Particles at lower temperatures have less energy and thus are more inclined to the lower energy liquid phase. Higher pressures tend to force particles into the liquid phase in order to relieve the applied pressure. Equation 4 is used to calculate the effect of these changes on the liquid mole fraction of CO2, which in turn is used to calculate a new Henrys Law constant.

34

Table 8: Henrys Law Constants at Various Operating Conditions T (K) 298 298 298 298 273 P (psi) 480 520 590 698 480 H 1.20236 0.831172 0.73256 0.554863 0.430802

At this point, the solubility of methane in water must be considered. Numerous experimental sources show the Henrys law constant for methane in water is high compared to that of carbon dioxide11 (Hmethane 20). Therefore, 100% methane recovery is assumed.

Calculations
The calculations for each system were similar and proceeded as follows: 1. Assume equilibrium at bottom of column. Use Henrys law constant to calculate xout 2. Use CO2 species balance to calculate approximate Lmin 3. Generate table of Lin and column volume over range of Lmin 4. Calculate annual profit and capital cost for each value of L ( ) ** ( ( ( * ( 2.5Lmin

* See introduction for revenue calculations. Revenue values are constant due to 100% recovery. **4 Cpw = 4.183 Jg-1k-1 CpCO2= .846 Jg-1k-1 CpCH4=2.203 Jg-1k-1 CpFeed=0.86(CpCO2) +0 .14(CpCH4)= 2.0328 Jg-1k-1
12,13

35

Discussion
The inlet feed of 86% methane leaves only three product options: sell the feed as high energy gas (7095%), purify to pipeline quality gas (95%), or purify to liquefied natural gas (99.995%). Operating conditions of T=298K and P=480psi were chosen for the initial calculations since they require no change to the vapor feed. Annual profits were calculated over a range of liquid flow rates for both purities. Since the feed is high in methane concentration, the associated costs are minute in comparison to the revenue. As a result, profit values are approximately equal to revenue; profits therefore are quite consistent across all liquid flow rates. Average values of costs and profits are shown below in Figure 23. Figure 23

Variations in liquid flow rate have minimal impact on profit because the revenue outweighs all associated costs. High energy gas and pipeline quality gas products will be discarded at this point since the liquefied natural gas profit is clearly the highest. As discussed earlier, increasing pressure increases the solubility of carbon dioxide in water. Higher solubility will decrease both capital and water costs; however compression costs will increase. The liquefied gas product was examined at increased pressures, specifically 520 psi, 590 psi, and 698 psi. The pressure of 698 psi was chosen because the product stream will exit the column at 600 psi, eliminating the need for compression after the column.

36

Annual profit and costs were determined for each pressure over a range of liquid flow rates. The average costs and revenue are displayed below in Figure 24. Again, costs have minimal impact on profit. In order to determine the optimal pressure for the column, capital costs were plotted against annual profit. It is clear in Figure 25 below that increasing pressure has a negative financial impact. It is concluded that the optimal pressure is the feed pressure of 480 psi. Figure 24

Figure 25

Note: See Appendix C2 for exact profit values. 37

The next variable considered is decreased temperature. As discussed above, lowering temperature increases the solubility of carbon dioxide in water. This will decrease the capital cost and liquid flow rate; however an additional water stream is required to cool the gas. The most efficient method for this cooling stream is a countercurrent flow along the inlet stream. Assuming the cooling water is at 273 K, countercurrent over a long distance will decrease the inlet stream temperature to 273 K. Similarly, the temperature of the water on the other end will increase to 298 K. i.e. Tw= Tfeed.5 The liquid flow rate required for this heat exchange is calculated assuming all heat leaving the vapor goes into the water. The calculation is described below. (The feed saturation temperature at 480 psi was calculated in HYSYS as 188 K.)

Lw=250 mol/s is arbitrarily chosen to account for some heat loss to the surroundings. Assuming the temperature of the liquid flow into the column is also 273 K, the operating conditions for the process are T=273 K , P=480 psi. The decreased temperature increases solubility, resulting in a smaller H value (0.43). The liquid flow rates and corresponding column volumes at 273 K are noticeably smaller than those at 298 K. (The exact values can be seen in APPENDIX Iii). Figure 26

38

Figure 26 compares average costs associated with both temperatures. Despite the addition of a cooling stream, water costs are less at 273 K due to smaller liquid inlet requirements. Both liquid and vapor stream compression costs decrease at 273 K as liquid compression is proportional to liquid flow rate and vapor compression is proportional to temperature. Lastly, capital costs decrease due to higher solubility at lower temperatures.

Figure 27

Capital costs are plotted against annual profit across the range of liquid flow rates at both temperatures. It is apparent that higher profits are generated at a lower operating temperature. Note: See Appendix C3 for exact capital and liquid flow rate values

39

Figure 28

In order to determine the optimal liquid flow rate for the process, a long term profit analysis is conducted. 30 year profit is calculated and plotted against liquid flow rate. Since the Raschig rings require replacement every 30 years, a 50 year profit analysis is also conducted. The long term profit results are shown here.

Conclusion
It is apparent that operating conditions of T=273 K and P= 480 psi generate the highest profit for the absorption process. Short term profits are maximized due to relatively low capital costs. Low temperature and inexpensive cooling maximize long term profits. Both 50 and 30 year analyses(Figure 28) display liquid flow rate maxima in the range of 350-400 mol/s. It is therefore recommended to run the absorption column at T=273 K, P=480 psi, Lin = 375 mol/s, and Lcooling = 250 mol/s. Relaxation of cooling assumptions will likely require a higher cooling liquid flow rate.

40

Recommendation
After completion of the analysis of the four unit operations, absorption is clearly the best method. One of the main reasons for the higher profit is the ease with which liquefied natural gas is achieved. Distillation and gas separation membranes required immense operational costs when producing the liquefied natural gas. The increased revenue generated by producing the liquefied natural gas as opposed to pipeline quality made the absorption columns a much more profitable operation. In Figure 23, below, it is easy to see that not only was the net profit much greater in each of the absorption options, but the operational costs were also much lower than that of gas separation membranes and especially distillation. Gas separation membranes failed in producing liquefied natural gas, because the polysulfone membrane permeability coefficients of methane and carbon dioxide are not drastically different. The amount of membrane area needed to produce the required purity would be extremely high. For distillation, the operational costs are dominated by refrigeration and equipment costs. The cost of refrigeration was between $50 and $70 per million Btu. Each plate in the distillation column was $442,000. The refrigeration costs depended upon the reflux ratio, which depended upon the number of stages. When trying to produce the higher purity gas products, the number of stages required was very large, driving the operational costs way up. Even though both the distillate and bottoms streams were able to be sold, the operational costs greatly outweighed the revenue generated.

Maximum Profit and Total Costs for Different Operations

52 41.5 32.1 52.1

11.23 1.246 Distillation Gas Separation Maximum Profit ($M/yr) 0.4335 MDEA Absorption 0.3955 Water Absorption

Operational Costs ($M/yr)

Figure 23: Comparison of net profit and operational costs between each of the analyzed unit operations. The values presented in this graph are taken from the optimal design for each unit operation.

41

It can be seen in Figure 23, that the net profit generated from absorption using water slightly exceeds that of absorption using MDEA. Therefore, absorption using water is the suggested process. In order to affirm this suggestion further, the assumptions made during the MDEA absorption analysis must be revisited. In the MDEA absorption analysis, it was assumed that there was no cost involved with the regeneration of the MDEA after each day. This assumption is most likely not entirely true, and would need to be investigated further. This assumption also meant that the amount of MDEA needed for this absorption process would only be one days worth. It is reasonable to imply that the MDEA regeneration is not perfect, and that additional MDEA would most likely need to be purchased. When considering these uncertainties, absorption using water can be confidently suggested over absorption using MDEA. Absorption using water does not come without reservation as well. The calculations for both types of absorption were done assuming that methane was entirely insoluble in water. This assumption allowed methane recovery to be 100%. Obviously, methane is not entirely insoluble in water, and some of the water will absorb methane. In order to confidently assert the absorption process as the best, calculations would need to be completed without this assumption. Another hesitation involved with absorption using water is its dependence on the market for methane. Because the carbon dioxide leaves as waste in absorption processes, there is no revenue generated by carbon dioxide. This leaves the entire net profit dependent upon the revenue generated by the methane rich stream. In distillation and gas separation membranes, there is additional revenue generated by carbon dioxide rich outlet streams. This extra income diversifies the market for the feedstock, which could be very advantageous. Still, these doubts in absorption using water do not alter the final recommendation. Absorption will almost certainly have the least operational costs associated with it. Even if methane recovery cannot be assumed to be 100%, the revenue generated from the liquefied natural gas stream will exceed that of the pipeline quality gas by around 20%.

42

Appendix A

Figure A1. Effect of temperature level on cost of refrigeration for cooler and condenser.

Figure A2. Plots of a) Number of Stages vs. Reflux Ratio and b) Total Cost vs. Reflux Ratio for producing pipeline quality gas with high purity carbon dioxide bottoms with a condenser pressure of 605 psia.

43

Figure A3. Plots of a) Number of Stages vs. Reflux Ratio and b) Total Cost vs. Reflux Ratio for producing pipeline quality gas with high purity carbon dioxide bottoms with a condenser pressure of 480 psia.

Figure A4. Plots of a) Number of Stages vs. Reflux Ratio and b) Total Cost vs. Reflux Ratio for producing pipeline quality gas with low energy gas bottoms with a condenser pressure of 480 psia.

Figure A5. Plots of a) Number of Stages vs. Reflux Ratio and b) Total Cost vs. Reflux Ratio for producing liquefied natural gas with high purity carbon dioxide bottoms with a condenser pressure of 480 psia.

44

Figure A6. Plots of a) Number of Stages vs. Reflux Ratio and b) Total Cost vs. Reflux Ratio for producing liquefied natural gas with low energy gas bottoms with a condenser pressure of 480 psia.

Profit ($M/yr)

Refrigeration Cost ($M/yr) 0 8.11 9.83 9.35 12.48 12.32

Compression Cost ($M/yr) 0 0.325 0.0269 0.0274 0.01899 0.01899

Equipment Cost ($M/yr) 0 2.65 1.77 0.884 11.49 11.49

Feed 600 Psia Pipeline CO2 480 Psia Pipeline CO2 480 Psia Pipeline Low Energy 480 Psia Liquefied CO2 480 Psia Liquefied Low Energy

35.38 32.1 31.52 29.8 19.25 16.25

Heating Cost ($M/yr) 0 0.144 0.1799 0.192 0.0843 0.0763

Table A1. Profit and different costs in millions of dollars per year for the different product streams explored.

45

Appendix B: Gas Separation Membrane Additional Information

Appendix B1: Single Stage Gas Separation Membrane:
Area of Membrane (cm2) 0 1000000 3000000 5000000 8000000 10000000 50000000 80000000 100000000 115560000 300000000 500000000 1000000000 Product Stream Purity 0.8600 0.8620 0.8658 0.8695 0.8746 0.8779 0.9205 0.9374 0.9452 0.9500 0.9754 0.9806 0.9900 Molar Flow rate of Product Stream (mol/s) 547.64 546.26 543.61 541.10 537.56 535.34 505.96 493.39 487.01 482.73 449.04 435.19 362.41 Waste Stream purity 0.0000 0.0700 0.0730 0.0750 0.0780 0.0800 0.1245 0.1556 0.1758 0.1907 0.3345 0.3931 0.6020 Waste Stream Flow Rate (mol/s) 0.00 1.38 4.02 6.54 10.07 12.29 41.68 54.24 60.62 64.91 98.60 112.44 185.22

Table B11: Table of operational variables with respect to changing membrane area, for the single stage gas separation membrane process model. Area of Membrane (cm2) 0 1000000 3000000 5000000 8000000 10000000 50000000 80000000 100000000 115560000 300000000 500000000 1000000000 Waste Gas Value ($/year) 0.00 0.00 0.00 0.00 0.00 52691.75 278159.84 452272.18 571116.04 663335.81 1767555.90 2368842.65 5975778.56 Compression Cost ($/year) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 193871.28 180341.55 174781.15 145550.95 Membrane Cost ($/year) 0.00 3229.09 9687.28 16145.47 25832.76 32290.95 161454.73 258327.57 322909.46 373154.17 968728.38 1614547.30 3229094.59 Product Stream Value ($/year) 35336084.84 35329204.39 35313063.68 35300031.97 35273238.62 35261799.72 34943344.19 34701632.86 34536542.59 39322771.95 37555965.23 36592621.23 30765026.52 Profit $/year 35336084.84 35325975.29 35303376.40 35283886.50 35247405.87 35282200.52 35060049.30 34895577.47 34784749.17 39419082.31 38174451.20 37172135.43 33366159.53

Table B12: Table of operational costs and product stream revenues with respect to changing membrane area, for the single stage gas separation membrane process model.

46

Appendix B2: Two Stage Gas Separation Membrane Model:

Reflux Ratio (Fraction of Feed Recycled) 0.0200 0.0400 0.0471 0.0600 0.0800 0.1000 0.1200 0.1400 0.1600 0.1800 0.2000 0.2200 0.2400 0.2600 0.2800 0.2944 Flow Rate of Recycle Stream (mol/s) 10.953 21.905 25.810 32.858 43.811 54.764 65.716 76.669 87.622 98.574 109.527 120.480 131.432 142.385 153.338 161.230 Area of Second Membrane (cm2) 33979700 11110500 9340200 7568390 6097970 5165070 4445210 3829630 3271780 2784300 2246700 1758880 1280040 806923 337245 0 Total Area of Membrane (cm2) Product Stream Purity Molar Flow rate of Product Stream (mol/s) 492.805 498.000 499.635 502.104 505.866 509.618 513.388 517.185 521.012 524.872 528.766 532.696 536.661 540.663 544.702 547.635 Waste Stream purity 0.0585 0.0135 0.0100 0.0068 0.0045 0.0033 0.0026 0.0022 0.0019 0.0016 0.0014 0.0013 0.0011 0.0010 0.0010 0.0000 Waste Stream Flow Rate (mol/s) 54.830 49.425 48.000 45.531 41.769 38.017 34.247 30.450 26.623 22.763 18.869 14.940 10.974 6.972 2.933 0.000

149539700 126670500 124900200 123128390 121657970 120725070 120005210 119389630 118831780 118344300 117806700 117318880 116840040 116366923 115897245 115560000

0.949 0.944 0.942 0.937 0.931 0.924 0.917 0.911 0.904 0.897 0.891 0.884 0.878 0.871 0.865 0.860

Table B21: Table of operational variables with respect to changing reflux ratio, for the two stage gas separation membrane process model.
Reflux Ratio (Fraction of Feed Recycled) 0.0200 0.0400 0.0471 0.0600 0.0800 0.1000 0.1200 0.1400 0.1600 0.1800 0.2000 0.2200 0.2400 0.2600 0.2800 0.2944 Compression Cost ($/year) 481372.15 521964.21 540109.61 573617.52 626238.22 678926.23 729050.17 783851.50 835996.55 887900.13 939547.58 990938.92 1042066.83 1092931.31 1143525.03 1179812.90 Membrane Cost ($/year) 482877.84 409031.03 403314.56 397593.22 392845.09 389832.67 387508.17 385520.41 383719.06 382144.94 380408.98 378833.76 377287.54 375759.80 374243.17 373154.17 Waste Stream Value ($/year) 0.00 0.00 2684256.61 2546190.17 2335827.46 2125979.24 1915157.96 1702854.75 1488834.72 1272974.85 1055196.85 835450.39 613690.72 389898.29 164041.20 0.00 Product Stream Value ($/year) 35095620.31 35271255.34 35299973.05 35312872.72 35322057.00 35326558.26 35329277.20 35331128.85 35332417.22 35333365.40 35334058.51 35334687.63 35335164.77 35335559.94 35335890.63 35336084.84 Net Profit ($/year) 34131370.32 34340260.10 37040805.49 36887852.15 36638801.15 36383778.59 36127876.82 35864611.69 35601536.33 35336295.19 35069298.81 34800365.34 34529501.12 34256767.12 33982163.62 33783117.77

Table B22: Table of operational costs and product stream revenues with respect to changing reflux ratio, for the two stage gas separation membrane process model.

47

Appendix B3: Three Stage Gas Separation Model:

Reflux Ratio for The Second Recycle Stream 0.0010 0.0020 0.0030 0.0040 0.0050 0.0060 0.0070 0.0080 0.0090 0.0100 0.0110 0.0110 0.0120

Area of each of the First 2 Membranes (cm2) 58112500 58152700 58192800 58232900 58272800 58312700 58352500 58392200 58431900 58471400 58510000 58500000 58550300

Area of the third Membrane (cm2) 53249900 48427700 43605600 38783600 33961800 29140000 24318400 19496900 14675500 9854340 5144690 5033270 212371

Total Area of Membrane (cm2) 169474900 164733100 159991200 155249400 150507400 145765400 141023400 136281300 131539300 126797140 122164690 122033270 117312971

Product Stream Purity 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95

Molar Flow rate of Product Stream (mol/s) 490.048 490.564 491.08 491.597 492.113 492.63 493.146 493.663 494.18 494.697 495.202 495.214 495.731

Waste Stream purity

0.0941 0.0864 0.0785 0.0705 0.0623 0.0540 0.0455 0.0368 0.0280 0.0190 0.0100 0.0016 0.0004

Waste Stream Flow Rate (mol/s) 57.587 57.071 56.555 56.038 55.522 55.006 54.489 53.972 53.455 52.938 52.433 51.968 51.904

Table B31: Table of operational variables with respect to changing reflux ratio of the second recycle stream, for the three stage gas separation membrane model.

Reflux Ratio for The Second Recycle Stream 0.001 0.002 0.003 0.004 0.005 0.006 0.007 0.008 0.009 0.010 0.011 0.011 0.012

Waste Stream Value ($/year) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 2932176.70 2906144.89 2902588.24

Compression Cost ($/year) 861073.41 861677.25 862279.64 862880.96 863481.88 864081.01 864678.27 865275.20 865871.40 866465.41 867045.81 867059.41 867651.22

Membrane Cost ($/year) 547250.48 531938.76 516626.72 501315.00 486002.63 470690.26 455377.90 440065.21 424752.84 409439.96 394481.34 394056.97 378814.68

Product Stream Value ($/year) 39398155.05 39439639.65 39481124.26 39522689.26 39564173.86 39605738.87 39647223.47 39688788.47 39730353.48 39771918.48 39812518.72 39813483.48 39855048.48

Profit $/year 37989831 38046024 38102218 38158493 38214689 38270967 38327167 38383448 38439729 38496013 41483168 41458512 41511171

Table B32: Table of operational costs and product stream revenues with respect to changing reflux ratio for the second recycle stream, for the three stage gas separation membrane model.

48

Appendix B4: Four Stage Gas Separation Model:

Reflux Ratio for The Third Recycle Stream 0.0100 0.0178 0.0200 0.0300 0.0400 0.0500 0.0600 0.0700 0.0800 0.0900 0.1000 Area of each of the First Three Membranes (cm2) 48466000 50181800 50717800 53127100 55474600 57739700 59923800 62032500 64071900 66047700 67965100 Area of the Fourth Membrane (cm2) 16253600 10191900 9498520 7925100 7269770 6912390 6687050 6531540 6417420 6329870 6260400 Total Area of Membrane (cm2) 161651600 160737300 161651920 167306400 173693570 180131490 186458450 192629040 198633120 204472970 210155700 Product Stream Purity 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95 Molar Flow rate of Product Stream (mol/s) 494.484 495.202 495.284 495.470 495.548 495.590 495.617 495.635 495.649 495.659 495.667 Waste Stream Purity 0.0227 0.0100 0.0085 0.0052 0.0038 0.0030 0.0025 0.0022 0.0019 0.0017 0.0016 Waste Stream Flow Rate (mol/s) 53.151 52.433 52.351 52.165 52.087 52.045 52.018 52.000 51.986 51.976 51.968

Table B41: Table of operational variables with respect to changing reflux ratio of the third recycle stream, for the four stage gas separation membrane model.

Reflux Ratio for The Third Recycle Stream 0.0100 0.0178 0.0200 0.0300 0.0400 0.0500 0.0600 0.0700 0.0800 0.0900 0.1000

Waste Stream Value ($/year) 0.00 2932176.70 2927585.48 2917167.17 2912827.60 2910462.09 2908968.97 2907940.00 2907185.05 2906603.46 2906144.89

Compression Cost ($/year) 1155984.67 1205166.89 1220839.67 1292772.25 1365180.26 1437194.04 1508635.40 1579481.17 1649750.16 1719471.66 1788680.12

Membrane Cost ($/year) 521988.31 519035.95 521989.34 540248.19 560872.97 581661.62 602091.97 622017.39 641405.13 660262.56 678612.63

Product Stream Value ($/year) 39754794.02 39812518.72 39819111.24 39834064.99 39840335.92 39843712.57 39845883.28 39847330.42 39848455.97 39849259.93 39849903.10

Profit ($/year) 38076821 41020493 41003868 40918212 40827110 40735319 40644125 40553772 40464486 40376129 40288755

Table B42: Table of operational costs and product stream revenues with respect to changing reflux ratio of the third recycle stream, for the three stage gas separation membrane model.

49

Appendix C: Absorption using Water Additional Information

Appendix C1: Henrys Law constant values at top and bottom of column for various operating
conditions T (K) 298 298 298 298 273 P (psi) 480 520 590 660 480 Htop 1.87334 1.72923 1.52407 1.36243 0.40398 Hbottom 1.85521 1.71250 1.50932 1.34924 0.40488

Appendix C2:Consistency of profit values over different operating conditions and flow rates
T=298 K P=480 psi Liquid Flow Rate (mol/s) 655 675 700 725 750 775 800 825 850 875 900 925 950 975 1000 1025 1050 1075 1100 1150 Annual Profit ($/year) 52120750 52120391 52119941 52119492 52119043 52118593 52118144 52117695 52117245 52116796 52116347 52115897 52115448 52114999 52114549 52114100 52113651 52113201 52112752 52111853 T=298 K P =520 psi Liquid Flow Rate (mol/s) 456 475 500 525 550 575 600 625 650 675 700 725 750 775 800 825 850 875 900 950 Annual Profit ($/year) 52087512 52086169 52084402 52082635 52080868 52079100 52077333 52075566 52073799 52072032 52070264 52068497 52066730 52064963 52063196 52061428 52059661 52057894 52056127 52052592 T=298 K P=590 psi Liquid Flow Rate (mol/s) 404 425 450 475 500 525 550 575 600 625 650 675 700 725 750 775 800 900 1000 1200 Annual Profit ($/year) 52051729 52050113 52048189 52046266 52044342 52042418 52040495 52038571 52036647 52034724 52032800 52030876 52028953 52027029 52025105 52023182 52021258 52013563 52005868 51990479

50

T=298 K P =698 psi Liquid Flow Rate (mol/s) 359 375 400 425 450 475 500 525 550 575 600 625 650 675 700 725 750 775 800 850 Annual Profit ($/year) 52040194 52038766 52036535 52034303 52032072 52029841 52027609 52025378 52023146 52020915 52018683 52016452 52014221 52011989 52009758 52007526 52005295 52003063 52000832 51996369

T=273 K P=480 psi Liquid Flow Rate (mol/s) 236 250 275 300 325 350 375 400 425 450 475 500 525 550 575 600 625 650 675 700 Annual Profit ($/year) 52138611 52137680 52136017 52134354 52132691 52131028 52129365 52127702 52126039 52124377 52122714 52121051 52119388 52117725 52116062 52114399 52112736 52111074 52109411 52107748

51

Appendix C3: Comparison of liquid flow rate and capital cost between 298 K and 273 K
T=298 K Liquid Flow Rate (mol/s) (Lmin)236 250 275 300 325 350 375 400 425 450 475 500 525 550 575 600 625 650 675 700 750 800 850 Capital Cost ($) 1719271 1453857 1172164 1006213 896662 818877 760771 715709 679730 650344 625890 605218 587514 572182 558775 546951 536446 527051 518597 510952 497661 486502 477000 T=273 K Liquid Flow Rate (mol/s) (Lmin)655 675 700 725 750 775 800 825 850 875 900 925 950 975 1000 1025 1050 1075 1100 1150 1200 1250 1300 Capital Cost ($) 3317951 2725738 2253525 1939419 1715381 1547516 1417046 1312734 1227422 1156356 1096235 1044721 1000085 961029.8 926583.3 895963.6 868566.6 843915.7 821616.7 806507 750263.8 722523.6 698610

52

References
1. Combustion Values Fuel Gases. The Engineering ToolBox. Web. 18 April 2014. www.engineeringtoolbox.com/fuel-gases-combustion-values-d_510.html. 2. Hestermans, P. White, D. The Vapor Pressure, Heat of Vaporization and Heat Capacity of Methane from the Boiling Point to the Critical Temperature. J. Chem. Phys. 1961, 65, 362-365. Retrieved from webbook.nist.gov. 3. Giauque, W.F.; Egan, C.J., Carbon Dioxide. The Heat Capacity and Vapor Pressure of the Solid.The Heat of Sublimation. Thermodynamic and Spectroscopic Values of the Entropy, J. Chem .Phys. 1937, 5, 45-54. Retrieved from webbook.nist.gov. 4. Vrachnos, A. Kontogeorgis, G. Voutsas, E. Thermodynamic Modeling of Acidic Gas Solubility in Aqueous Solutions in MEA, MDEA and MEA-MDEA Blends. Ind. Eng. Chem. Res. 2006, 45, 51485154. 5. Subramanian, R.S. Thermal Analysis of a Steady State Heat Exchanger. Clarkson University. Web. 24 April 2014. http://web2.clarkson.edu/projects/subramanian/ch330/notes/Thermal%20Analysis%20of%20a %20Steady%20State%20Heat%20Exchanger.pdf. 6. Chiu, Li-Feng. Li, Meng-Hui. Heat Capacity of Alkanolamine Aqueous Solutions. Chem. Eng. Data, 1999, 44 (6), 1396-1401. //pubs.acs.org on November 19, 2008. 7. Methyl Diethanolamine. Wikipedia, the Free Encyclopedia. Wikimedia Foundation, Inc. 28 February 2013. Web. 24 April 2014. http://en.wikipedia.org/wiki/Methyl_diethanolamine. 8. Henrys Law. Wikispaces: ChemEngineering. Wikimedia Foundation, Inc. Web. 24 April 2014. http://chemengineering.wikispaces.com/Henry's+law. 9. Carroll, J. J., Slupsky, J. D., and Mather, A. E., J. Phys. Chem. Ref. Data, 20, 1201, 1991 10. Fernandez-Prini, R. and Crovetto, R., J. Phys. Chem. Ref. Data, 18, 1231, 1989 11. Lide and Frederikse, 1995 CRC Handbook of Chemistry and Physics, 76th Edition, D. R. Lide and H. P. R. Frederikse, ed(s)., CRC Press, Inc., Boca Raton, FL, 1995. 12. Specific heat of Methane Gas. The Engineering Toolbox, Web. 24 April 2014. http://www.engineeringtoolbox.com/methane-d_980.html. 13. Specific heat of Carbon Dioxide Gas. The Engineering Toolbox, Web. 24 April 2014. http://www.engineeringtoolbox.com/carbon-dioxide-d_974.html.

53