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





2
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)
Methane
Concentration
(mol%)
Carbon Dioxide
Concentration
(mol%)
Feed Flow (MMSCFD)
494.7 77 86 14 35


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 Methane
Concentration (mol%)
Price ($/MMBtu) Specifications
Waste Gas <10% - -
Low Energy Gas 10-40% 2.50 -
Medium Energy Gas 40-70% 3.00 -
Table A. Properties of the feedstock from the natural gas well.
3
High Energy Gas 70-95% 3.50 -
Pipeline Quality Gas 95% 4.00 600 psia
Liquefied Natural Gas 99.995% 5.20 600 psia
High Purity Carbon
Dioxide
1% 0.003/SCF -


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.
(

)
(

)
(

( (

Table B. Product stream market prices based on purity.
4
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.














5
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 with
8
T:

* (

)+
-

- : constant
8
(=2400 Kelvin for CO
2
)
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. H
top
and H
bottom
were calculated for
all operating conditions tested. Since H
top
/H
bottom
is approximately one for all operating conditions(Table
6), it is valid to assume H is constant throughout the column.




6
Table 6 :Comparison of Henrys Law Constant Values at Top and Bottom of Column
9,10

T (K) P (psi) H
top
/H
bottom

298 480 .9903
298 520 .9903
298 590 .9903
298 660 .9903
273 480 1.0022
Note: See Appendix C1 for H values

Table 7: Solubility of Carbon Dioxide in Water at Various Temperatures and Pressures
9,10


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.


7
Table 8: Henrys Law Constants at Various Operating Conditions
T (K) P (psi) H
298 480 1.20236
298 520 0.831172
298 590 0.73256
298 698 0.554863
273 480 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 dioxide
11
(H
methane
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 x
out

2. Use CO
2
species balance to calculate approximate L
min

3. Generate table of L
in
and column volume over range of L
min
2.5L
min

4. Calculate annual profit and capital cost for each value of L
-

-
- (

- (

- (

*
-
-

- **
* See introduction for revenue calculations. Revenue values are constant due to 100% recovery.
**4 C
pw
= 4.183 Jg
-1
k
-1

Cp
CO2
= .846 Jg
-1
k
-1
Cp
CH4
=2.203 Jg
-1
k
-1
Cp
Feed
=0.86(Cp
CO2
) +0 .14(Cp
CH4
)= 2.0328 Jg
-1
k
-1 12,13


8
Discussion
The inlet feed of 86% methane leaves only three product options: sell the feed as high energy gas (70-
95%), 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.

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.
Figure 23
9
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.
10
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. T
w
= T
feed
.
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.)

L
w
=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
11
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.





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

Figure 27
12





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, L
in
= 375 mol/s, and L
cooling
= 250 mol/s. Relaxation of
cooling assumptions will likely require a higher cooling liquid flow rate.
Figure 28
13
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.



32.1
41.5
52 52.1
11.23
1.246
0.4335 0.3955
Distillation Gas Separation MDEA Absorption Water Absorption
Maximum Profit and Total Costs for Different Operations
Maximum Profit ($M/yr) Operational Costs ($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.
14

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%.








15
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) P (psi) H
top
H
bottom

298 480 1.87334 1.85521
298 520 1.72923 1.71250
298 590 1.52407 1.50932
298 660 1.36243 1.34924
273 480 0.40398 0.40488

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



16

T=298 K P =698 psi T=273 K P=480 psi
Liquid Flow
Rate (mol/s)
Annual Profit
($/year)
Liquid Flow
Rate (mol/s)
Annual Profit
($/year)
359
375
400
425
450
475
500
525
550
575
600
625
650
675
700
725
750
775
800
850
52040194
52038766
52036535
52034303
52032072
52029841
52027609
52025378
52023146
52020915
52018683
52016452
52014221
52011989
52009758
52007526
52005295
52003063
52000832
51996369
236
250
275
300
325
350
375
400
425
450
475
500
525
550
575
600
625
650
675
700
52138611
52137680
52136017
52134354
52132691
52131028
52129365
52127702
52126039
52124377
52122714
52121051
52119388
52117725
52116062
52114399
52112736
52111074
52109411
52107748











17

Appendix C3: Comparison of liquid flow rate and capital cost between 298 K and 273 K
T=298 K T=273 K
Liquid Flow Rate (mol/s) Capital Cost ($) Liquid Flow Rate (mol/s) Capital Cost ($)
(L
min
)236
250
275
300
325
350
375
400
425
450
475
500
525
550
575
600
625
650
675
700
750
800
850

1719271
1453857
1172164
1006213
896662
818877
760771
715709
679730
650344
625890
605218
587514
572182
558775
546951
536446
527051
518597
510952
497661
486502
477000

(L
min
)655
675
700
725
750
775
800
825
850
875
900
925
950
975
1000
1025
1050
1075
1100
1150
1200
1250
1300

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






18
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