Separating methane and carbon dioxide

from enhanced oil recovery

An Economic Evaluation of Four Common Separation Methods
Authors:

Date:

Chandler Stiles

Water Absorption

James Gamble Jr.

MDEA Absorption

Quoc Tran

Membrane Separation

Logan Renninger

Cryogenic Distillation

April 25, 2016

1 TABLE OF CONTENTS
2

Executive Summary.....................................................................................................................3

Introduction ...............................................................................................................................4

3.1

Natural Gas ................................................................................................................................... 4

3.2

Carbon Dioxide .............................................................................................................................. 4

3.3

Enhanced Oil Recovery ................................................................................................................. 4

Water Absorption .......................................................................................................................6

4.1
4.1.1

Column Cost .............................................................................................................................. 6

4.1.2

Water Cost ................................................................................................................................ 6

4.1.3

Pressurization Cost.................................................................................................................... 6

4.2

Choosing L ................................................................................................................................. 7

4.2.2

Choosing Temperature ............................................................................................................. 8

4.2.3

Choosing Pressure ..................................................................................................................... 8

4.2.4

Column Height .......................................................................................................................... 9

Summary ....................................................................................................................................... 9

MDEA Absoprtion ..................................................................................................................... 10

5.1

Initial Design and Assumptions ................................................................................................... 11

5.2

Cost Guidelines ........................................................................................................................... 13

5.3

Relevant Variable Analysis .......................................................................................................... 14

5.3.1

Optimization 1......................................................................................................................... 14

5.3.2

Optimization 2......................................................................................................................... 14

5.4
6

Design Analysis.............................................................................................................................. 6

4.2.1

4.3
5

Cost Considerations ...................................................................................................................... 6

Conclusion ................................................................................................................................... 15

Membrane Separation .............................................................................................................. 16

6.1

Cost Considerations .................................................................................................................... 16

6.1.1

Capital Costs ............................................................................................................................ 16

6.1.2

Operating Costs ....................................................................................................................... 16

6.2

Design Analysis............................................................................................................................ 17

6.2.1

Single Stage Membrane System .............................................................................................. 17

6.2.2

Single Stage Membrane System with Compressor .................................................................. 20

6.2.3

Two Stage Counter-Current Membrane System with Compressors ........................................ 22

Page | 1

6.2.4
6.3
7

Cost Considerations .................................................................................................................... 27

7.1.1

Capital Costs ............................................................................................................................ 27

7.1.2

Refrigeration Costs.................................................................................................................. 27

7.2

HYSIS Model ................................................................................................................................ 28

7.2.1

Assumptions of the Model ...................................................................................................... 29

7.2.2

Choosing the Condenser ......................................................................................................... 29

7.2.3

Condenser Inlet Phase ............................................................................................................ 29

7.3

Optimization ............................................................................................................................... 29

7.3.1

Purity Determination .............................................................................................................. 30

7.3.2

Effect of Number of Stages ..................................................................................................... 30

7.3.3

Effect of Entrance Pressure..................................................................................................... 31

7.3.4

Revenue Analysis .................................................................................................................... 32

7.4

Summary ..................................................................................................................................... 33

Recommendations .................................................................................................................... 34
8.1

Summary ..................................................................................................................................... 26

Cryogenic Distillation ................................................................................................................ 27

7.1

Three Stage Counter-Current Membrane System with Compressors ..................................... 24

Physical Considerations .............................................................................................................. 35

Appendix .................................................................................................................................. 36

Page | 2

2 EXECUTIVE SUMMARY
This report conducts a technical and economic analysis to determine the most profitable course
of action for a natural gas stream from an enhanced oil recovery process. Composing of 18%
methane and 82% percent carbon dioxide, the raw feed can be sold for $ 8.3 million per year.
By separating the stream into a methane-rich stream and a carbon dioxide-rich stream, higher
profits may be achieved. This report evaluates four common gas separation methods: water
absorption, MDEA absorption, membrane separation, and cryogenic distillation. Using
membrane separation to produce high energy natural gas was found to be the most profitable
option generating a net $ 44.5 million per year. Before initiating plans for construction, we
recommend further research to ensure the accuracy of our evaluation and the sustainability of
such a venture.

Page | 3

3 INTRODUCTION
3.1 NATURAL GAS
Natural gas serves as a source for safe, clean, and efficient energy apart from traditional fossil
fuels and coal. This alternative clean-burning fuel can take different qualities of energy. Its
versatility heats homes, fuels industries, and serves as raw material for products while emitting
a low amount greenhouse gases.1 In the United States, the total natural gas consumption was
estimated to be 27,473,081 MMcf in 2015.2 Energy consumption and natural gas demand is
expected to rapidly grow in the future. In order to meet growing demands of energy
worldwide, exploration and extraction of this abundant resource will help supply countries with
natural gas.

3.2 CARBON DIOXIDE

When emitted to the atmosphere from human activities, carbon dioxide is considered a
greenhouse gas. Sources of carbon dioxide emissions include electricity, transportation, and
industry.3 To reduce the emissions of carbon dioxide, capturing and purifying this gas may be
beneficial for the food and beverage industry. Additionally, plants such as algae may use
carbon dioxide to produce bio-fuel.4

3.3 ENHANCED OIL RECOVERY

Oil recovery can occur up to three phases: primary, secondary, and tertiary. The primary phase
of oil recovery occurs when the natural pressure of the reservoir produces oil. Only 10% of the
original amount of oil in a reservoir is recovered of the primary phase. When the reservoir is no
longer pressurized to produce on its own, secondary recovery is utilized to repressurize the
reservoir through the use of water flooding techniques or gas injection. These methods can
recover 20% to 40% of the original reservoir. Efforts to extend the effective life of a reservoir
after secondary recovery is known as tertiary or enhanced oil recovery (EOR). EOR can recover
30% to 60% of the oil in the reservoir through various techniques includes practices such as
thermal recovery, gas injection, and chemical injection.5
One type of EOR includes the gas injection of carbon dioxide (CO2) into the reservoir from an
injection well. The CO2 expands throughout the reservoir and encounters pushes trapped oil
1

Natural Gas. Chevron Corporation. May 2015

Natural Gas. U.S. Energy Information Administration. April 21, 2016.
3
Carbon Dioxide Emissions. U.S. Environmental Protection Agency. April 15, 2016.
4
Carbon Dioxide. The Linde Group. 2016
5
Enhanced Oil Recovery. U.S. Department of Energy. April 21, 2016.
2

Page | 4

toward the producing well. Not only does this injection push crude oil, but it can also drive
residual natural gas up for production as well. Consequently, the natural gas from this method
of EOR can contain varying concentrations of CO2 and CH4 over time.
Depending on the composition, separation of the production containing both CO 2 and CH4 can
yield various products. Natural gas can be sold as low energy gas (10-40% CH4), medium energy
gas (40-70% CH4), high energy gas (70-95% CH4), pipeline quality (95% CH4), and liquefied
natural gas (99.995 %). Figure 1.1 shows the price decks are used to sell different qualities of
natural gas product.
Product Grade
Waste Gas
Low Energy Gas
Medium Energy Gas
High Energy Gas
Pipline Quality Gas
Liquefied Natural Gas (LNG)

Purity
< 10%
10 - 40 %
40 - 70 %
70 - 95 %
95%
< 50 ppm CO2

$
$
$
$

Price
2.50
3.00
3.50
4.00

$ 5.20

Figure 1.1. Price estimates by methane concentration in natural gas

Despite a limited, market, CO2 product (>99.5% CO2) can be sold and used in the beverage
industry to make soft drinks. Additionally, pure CO2 can be used in chemical processes such as
EOR as described above.
From the production of EOR, a feed of 60 MSCFD or with a composition of 82% CO2 and 18%
CH4 will be analyzed with different unit operations to determine economic degrees of
separation. These unit operations include methyl diethanolamine (MDEA) absorption, water
absorption, cryogenic distillation, and gas membrane purification. For the separation to be
economically feasible, the overall value of the products must be greater than the value of the
feed and cost to separate with the given unit operations. The following equation gives the
value of the feed sold as low energy gas at a price deck of $2.5/MMBTU6:
Feed Value
mol
890.7 0.947817 BTU 1 MMBTU
$2.5
6900 hr
(0.18 mol CH4 ) (
=
)(
)( 6
)(
)(
)
hr
mol
1 kJ
10 BTU
MMBTU
year
= $8,284,318.39 per year
This equation uses the heat of combustion, CH4 composition, and operating time to calculate
the value of the feed stream as low energy gas. Since the feed is below 82% CO2, it cannot be
sold as CO2 product. Moreover, if the profit from separation is greater than the feeds original
value of $8,284,318.39 per year, then the unit operation will be determined as economical.
6

Pittam, D. A.; Pilcjer, G. J. Chem. Soc. Faraday Trans. 1972

Page | 5

4 WATER ABSORPTION
Absorption is a process by which a substance in a gas state is transferred into another
substance in a liquid state. Water can be used in absorption of carbon dioxide from a gas
mixture containing carbon dioxide and methane. The reason for this is because the carbon
dioxide is water-soluble while the methane is water-insoluble. The amount of carbon dioxide
absorbed is related to the amount of contact between the gas and liquid phases. For this
reason, many absorption columns contain packing material to increase the contact area. In this
analysis, 1 Rashig rings will be used as packing material in the column.

4.1 COST CONSIDERATIONS

When it comes to the cost and efficiency of an absorption column, the success of absorption
itself is the greatest factor. Things that affect the success of absorption are the size of the
column, life span of the packing material, amount of water used, pressure, and temperature. All
of which contribute their own cost to the process.
4.1.1 Column Cost
The column cost with packing material can be estimated to be $1800/ft3. The packing material
needs to be replaced every 30 years which gives a yearly cost of $60/ft3-yr.
4.1.2 Water Cost
The cost of water is one of the dominating costs in this process. Since water is not the best at
absorbing carbon dioxide like MDEA is, it requires a much larger volumetric flow rate. The
water cost is roughly $0.15/1000 gal.
4.1.3 Pressurization Cost
Depending on the pressure that is optimal to run the feed at, it may be beneficial to change the
pressure of the feed stream. To calculate how much power this requires the equation is
Power=VV(R*T*ln(P2/P1) for the gas stream. Also the pressure of the water stream needs to be
accounted for and adjusted to the same pressure of the gas feed to make sure both streams
flow through the column properly. The equation for this is Power=V L(P2-P1). The price for the
electricity to power the pumps is around $0.08/kW-hr.

4.2 DESIGN ANALYSIS

The design of the absorption column was based off of a few assumptions:
1. The water feed into the column contains no carbon dioxide.
2. The absorption column runs at room temperature.
3. The Henrys law constant is valid because carbon dioxide would be dilute in water
and could be considered constant throughout the column for carbon dioxide at 25 oC
which is .8317.
Page | 6

4. Ideal gas law was used whenever needed.

5. Pressure drop in column is negligible.
With these assumptions the absorption column shown in figure 4.1 can help to solve the
equations 4.1 to 4.5.
Equations

L
XL,CO2=0

Vout
YV,CH4

4.1

CA=

4.2

Vout=

4.3

Lmin =

,,4
,,4
1
,,2

( ,,2

,,2 )
1

CL,out,CO2 = ( ,,2

4.4

,,2 )
4.5 A=
L
XL,CO2

Vin=60
MMSCFD
YV,CO2=.82

0 (1 )

,,2 ,,2

,,2

(1
),,2 +(
),,2

Figure 4.1. Absorption Column Design

4.2.1 Choosing L
Figure 4.2 shows that the optimal flow rate for the water stream happens between a multiple
of 1 and 1.2 of Lmin. This figure also shows that a product feed containing 99.995% methane will
maximize profit. When obtaining a product stream of this concentration you want to use
L=1.3*Lmin for max profit.7

Appendix: Table 9.4.1

Page | 7

$16,000,000.00
$14,000,000.00
$12,000,000.00

Profit

$10,000,000.00
$8,000,000.00
$6,000,000.00

CH4=.4
CH4=.5
CH4=.7
CH4=.95
CH4=.99995

$4,000,000.00

$2,000,000.00
$0.00
1.0

1.2

1.4

1.6

1.8

2.0

2.2

Multiple of Lmin
Figure 4.2 Optimization of Liquid Flow Rate

4.2.2 Choosing Temperature

Changing the temperature requires energy which comes at a cost. To increase the profit the
temperature would need to decrease but to decrease the temperature the gas needs to be
cooled. To cool the gas stream it would require more energy and more water which would
increase the cost way more than it helps the profit. So for this absorption process the
temperature is left at room temperature since it creates the smallest cost.
4.2.3 Choosing Pressure
In the absorption process increasing the pressure increases the amount of carbon dioxide that
can dissolve into the water. Since a product feed of 99.995% methane is the most profitable it is
worth looking at pressure change to this process to find the most profitable pressure to operate
at. Figure 4.3 graphs the pressure versus profit to find the maximum profit. This shows that the
most profitable pressure is at 1500 psi.

Page | 8

$14,200,000.00
$14,100,000.00
$14,000,000.00

Profit

$13,900,000.00
$13,800,000.00
$13,700,000.00
$13,600,000.00
$13,500,000.00

$13,400,000.00

CH4=.99995

$13,300,000.00
0

500

1000

1500

2000

Pressure (psi)
Figure 4.3 Pressure that Maximizes Profit

4.2.4 Column Height

The optimal column height is when the height/diameter is equal to 6. For this process the
optimal conditions give a column height of 18m and a diameter of 3m. This is a little tall but at
the industrial level this column height would be fine.

4.3 SUMMARY
All of the revenue in this absorption process is from the sale of methane and no profit comes
from carbon dioxide because it is not pure enough.
Optimal Conditions:
Pressure-1500 psi
Water Flow Rate-1122 m3/hr
Temperatue-298 K
Height-18 M
With the feed we were given and the optimal conditions listed above, we get a profit of $13.8
million per year which is not bad for absorption but other processes would be able to generate
more profit and are discussed later in this report.

Page | 9

5 MDEA ABSOPRTION
Separation of CO2 from Natural Gas is facilitated by using an aqueous solution of MDEA as the
solvent due to its reactivity with the acid gasses. When considering enhanced oil recovery the
acid gas is CO2 and the term acid gas is used because it is attracted to the basicity of the MDEA.
The basic nature of MDEA is as a result of its amine functional group. This acid-base interaction
between MDEA and CO2 allows for a better separation than in a neutral solvent like water. The
hydroxyl groups on the MDEA allow it to be soluble in water forming an aqueous solution.8 This
aqueous solution formation is pertinent to the separation because the MDEA cant react
directly with CO2, but they can react with each other in-situ.1 Other attributes that make CO2 a
great solvent are that it has a very slow degradation rate and a rather high loading capacity.9
The direct effect on the profit of the slow degradation be seen in the cost analysis portion of
this operation.

Partial pressure CO2 kPa

The specific MDEA used was 2M and 23.3 wt% MDEA in solution at 313K. This type of MDEA
was employed due to its high loading capacity over a range of partial pressures of CO2. Figure 1
below shows the loading capacity ranges of MDEA at different temperatures.

Loading (mol CO2/mol MDEA)

Figure 5.1. Plot of Partial Pressure CO2 vs Loading1

This plot exhibits the large capacity of MDEA at 313k hence why the separation proceeded at
313K. The principal disadvantage of using MDEA is the large cost associated, but detrimental
financial impact is thwarted due to the long life of MDEA.
8

Vrachnos A., Kontogeorgis G., Voutsas E, Ind. Eng. Chem. Res. 2006, 45, 5148-5154
STEPHEN T. DONNELLY Bryan Research & Engineering, Inc., Bryan, Texas, Propak Systems, Inc.,
Lakewood, Colorado
9

Page | 10

5.1 INITIAL DESIGN AND ASSUMPTIONS

When designing the MDEA separation principal objective was to yield a product significantly
more pure than our feed stream. The MDEA separation design was governed by a few major
simplifying assumptions. The first being that the methane and MDEA are completely immiscible
at the pressures and flow rates investigated which means that all of the CH4 in the feed is also
in the purified natural gas product. The application of this assumption allows for the easy
computation of the outgoing vapor molar flow rates. The calculation for a 40% mole percent
methane product can be seen below.

(4 , ) = (4 , )
877.87

<1>

(. 18) = (. 40) = 395.04

The second assumption is that the liquid flow rate is constant throughout the column and that
the MDEA feed is supplied at 313k. The last two design restrictions are the temperature and
MDEA used. As has been previously stated the 23.3 wt% MDEA has the best loading at 313 so
the design parameters will abide by these conditions. The counter-flow absorption column can
be seen in figure 5.2 below.

Liquid In

Vapor Out

Liquid Out

Vapor In

Figure 5.2. Design of counter-flow absorbance column

As can be seen in the diagram above the vapor inlet and liquid outlet are at the same end of the
absorption column which allows the developing of an equilibrium relationship through the
Henrys Law constant. The same happens at the top of the absorption column at the vapor
Page | 11

outlet/liquid inlet. The Henrys law constant provides an avenue for relating the concentrations
in the vapor and liquid phases respectfully. The Henrys Law constants can be seen in equations
2 and 3 below.
=

,
,

,
,

<2>
<3>

These equations hold true, but when H is not constant H = can be used, but for
this design another key assumption was that when calculating volume and monetary values
only the inlet figures were used. This helped simplify the design calculations because varying H
values, flowrates, etc. did not have to be considered. The necessary volume of the column
increases exponentially with the purity of CH4 in the product stream. The height is a function of
area as can be seen in equation 4 below.
=

, ,
1
(
)

(1 )
(1 ),+( ), ,

<4>

Since the height is a function of the area, every time the height is varied at the keeping
everything else the same, the area would just compensate the change in height to keep the
volume constant. As a result of the area being a component of the height formula, the volume
was just calculated by multiplying both sides by the area. This produces hA which equals
volume, on the left side of the equation while cancelling out the area term on the right side of
the equation. Since computation of volume is possible without the height or area, the volumes
of the absorption column and its effect on price were investigated instead of the height effect
on profit. A plot of volume vs CH4 product stream concentration at qL = 1.5 qL,min can be seen in
figure 5.4 below.

Page | 12

16000

Colum Volume (m3)

14000
12000
10000
8000
6000
4000
2000
0
0

0.2

0.4

0.6

0.8

1.2

XCH4
Figure 5.3: Plot of Column Volume vs CH4 purity

The large jump at the in volume when concentration approaches 1 is the principle reason why
the LNG product was not economically feasible. The cost of separation due to the volume is an
analyzed in the next section of this report. For sizing purposes, the smallest volume possible
should be used and the ratio of h/d should be as close to 6 as possible assuming a cylinder
shaped absorbance column.

5.2 COST GUIDELINES

Numerous costs had to be taken into consideration when determining the profit that a certain
stream could produce. The first cost considered was the capital cost for the volume of the
column due to the Raschig Rings used for separation. The price of Raschig Rings is $1800/ft3 of
column volume. This value changed dramatically over the different desired methane gas
product streams. The cost of Raschig Rings per year is relatively large, but since their lifetime is
approximately thirty years and assuming not much maintenance is needed, they will eventually
pay for themselves. The second and largest cost considered for any profitable product stream is
MDEA. The price of the MDEA is approximately 15749104 x qL, but again, as was previously
stated, the large cost is compensated for by the regeneration and long life of the MDEA. The
two costs involved with this separation are pressurization costs. The MDEA has to be
condensed to the same pressure as feed in order for them to mix. This pressurization cost is a
not a recursive cost and ranges from .2*677008 - .4*667008, where .2 and .4 are molar flow
rates in units of m3/s based on the intended methane product stream.

Page | 13

5.3 RELEVANT VARIABLE ANALYSIS

With the given conditions of our design the two variables that can be analyzed for their direct
impact on the profit are pressure and flowrate. There is a flowrate at which the profit is
maximized and will be reviewed in the optimization portion of this operation. The profit is
maximized when the costs are minimized. Since there are two variables being analyzed there is
an optimal situation for flowrate at constant pressure and there is an optimal pressure trend
we will investigate at constant flowrate.
5.3.1 Optimization 1
The first variable optimized was the flowrate of MDEA. The pressure of the system was held at
a constant value of 420 psig which is the feed pressure. The flowrate term is involved in the
MDEA cost as well as the Raschig Ring cost for the separation. Since increasing the flowrate
doesnt vary the MDEA cost in a linear fashion like it does for Raschig Ring cost, but rather in a
polynomial fashion, the profit vs flowrate plot, didnt have a simple linear trend. The two
streams that created the largest revenue were the lowest purity option of medium energy gas
(40% CH4) and the lowest purity form of medium energy gas (70% CH4). The optimization of
profit plot for 40% and 70% methane product streams can be seen below in figure 5.3 below.
5.50E+06
5.00E+06

Profit($)

4.50E+06
4.00E+06
40% Opt

3.50E+06

70% Opt
3.00E+06
2.50E+06
2.00E+06
0.9

1.1

1.2

qL

1.3

1.4

1.5

1.6

(m3/s)

Figure 5.4: Plot of profit vs flowrate for 40% and 70% methane product streams

Plotting profit vs flowrate allowed for the discovery of the optimum flowrates for 40% methane
product stream and 70% product stream which are q l=1.18qL,min and qL=1.34qL,min respectively.
5.3.2 Optimization 2
The second optimization is varying pressure while keeping the flowrate constant. Since there is
no cap on pressure a general trend was developed based on a flowrate of 1.18q L at three
different pressures. 1.8qL,min is being employed because it produces the optimum profit when
selling a 40% CH4 product stream. The plot and table of profit vs pressure are below in table 5.1
and figure 5.5.
Page | 14

Table 5.1: Profit of 40% CH4 product at various pressures

Pressure(psig) qL(m3/S)
150
0.223
300
0.223
420
0.223
600
0.223
750
0.223

Profit
3.01E+06
4.69E+06
5.09E+06
5.34E+06
5.42E+06

6.00E+06

Profit ($/yr)

5.00E+06
4.00E+06
3.00E+06
2.00E+06
1.00E+06
0.00E+00
0

200

400

Pressure(psig)

600

800

Figure 5.5: Plot of Profit vs Pressure at qL = 1.18 qL,min

This chart and plot demonstrates the general trend that as pressure increases with everything
else held constant the profit increases. The pressure data was calculated up to 750psig for
simplicity sake because at higher pressures other complications occur and there is a need for
other safeguarding equipment just to be able to run properly. These complications and extra
equipment obviously incur other cost so pressures above 750 psig were not considered.

5.4 CONCLUSION
The optimization allows for the increase of profit by finding the most efficient flowrates at
specific purities of CH4 product streams. The pressure trend also shows that the profit increases
with pressure. With the optimal flowrate a profit of $5.089 million/yr can be made using MDEA
separation. This figure can be increased with pressure and amount of separations, but only one
separation was considered for simplicity. Due to costs only medium and high energy gas could
be produced. The recommendation for an engineer with the given conditions using MDEA
separation is to produce and sell 40% CH4 rich gas.

Page | 15

6 MEMBRANE SEPARATION
Membrane plants have been installed to treat natural gas production through the removal of
carbon dioxide. Historically, membranes that have been used in this process include selective
cellulose acetate membranes with CO2/CH4 selectivities of 12-15 in small scale operations (5-40
MMSCFD). Large membrane systems (>40 MMSFD), however, have also been employed on
offshore platforms and enhanced oil recovery operations. Since the overall composition of
production from carbon dioxide flooding projects may change over time, polyimide and
polyaramide membranes with CO2/CH4 selectivities of 20-25 are being used to replace cellulose
acetate membranes for better carbon dioxide removal. Performance of this particular
separation process is largely dictated by the membranes permeability and selectivity of gas
components.10 Since economic advantages associated with gas membrane separation include
operating flexibility and low capital investment, a 60 MMSCFD natural gas feed of 82% CO2 and
18% CH4 will be analyzed with models using polysulfone membranes to determine the optimal
separation design.11

6.1 COST CONSIDERATIONS

Gas separation membrane includes capital investment of membranes and operating costs of
pressurization of the feed/or permeate streams. Operating costs will also include the cost to
heat the feed to carbon dioxides critical temperature of 304.14 K.12
6.1.1 Capital Costs
Capital costs with gas separation membrane is the investment of the membrane. The costs are
$4/ft2 with an expected life-time of one year. The permeances of the membranes are given as
follows:
K(CH4) = 1.04 x 10-4 mol/psia ft2 hr
K(CO2) = 0.00778 mol/psia ft2 hr
Since the permeance of carbon dioxide is greater than the permeance of methane, carbon
dioxide will be removed through the polysulfone membrane.
6.1.2 Operating Costs
The energy costs associated with pressurizing the feed/or permeate streams with a gas
compressor are given as:
P2

Cost to compress/year = RTln (P1)

10

$0.08
kwh

Abedini, R.; Bezhadmogadam, A., S. Petroleum and Coal. 2010

Baker, R. Ind. Eng. Chem. Res. 2002
12
Suehiro, N.; J. Chem. Thermodyn., 1996
11

Page | 16

kwh

3,600,000 J

6900 hrs
year

(Eq. 6.1)

where is molar flow rate in units of mol/hr and 6900 hours per year is the operating time of
the plant. Operating temperature in units of K and the gas constant R in units of J/mol K were
also used in calculating compression costs.
To prevent the gas mixture from condensing at high operating pressures, heat exchanger costs
will be factored in to heat the appropriate streams above the critical temperature of the carbon
dioxide to ensure that the carbon dioxide remains in the vapor phase. Heating requirements
are determined by the following equation:
1 kJ

/ = 1000J

0.947817 BTU
1 kJ

1 MMBTU
106 BTU

6900 hrs
year

$3.0

MMBTU
(Eq. 6.2)

where the following assumptions are made:

1. Cp of mixture is approximately 36 J/mol K13

(Heat capacities of methane and carbon dioxide are very similar to one another to so
this approximation is used)
2. Tinitial = 298 K
3. Tfinal = 304.18 K (critical temperature of carbon dioxide)

6.2 DESIGN ANALYSIS

The following cases will be designed and evaluated to determine the most economical gas separation
membrane design: single stage system without compression, single stage system with compression, two
stage countercurrent system with compression, and three stage counter current system with
compression.
Additionally, the following assumptions were made during the overall calculations and analysis of the
four main cases:
1. Feed exhibits ideal gas behavior
2. Constant Temperature in the overall membrane system unless a heat exchanger is
specifically used to heat streams
3. No pressure drop occurs between entrance and exit of membrane system
4. The permeate pressure of the membrane is 15 psia (approximate atmospheric pressure)

6.2.1 Single Stage Membrane System

A preliminary single stage depicted in Figure 6.1 case was analyzed without any compression of
the feed gas to determine the profitable products from the retentate and/or permeate streams.
The only operating cost to heat this feed stream to 304.18 K was calculated to be $13,795.11.
Moreover, the capital cost will depend on the size of the membrane. The following parameters
were defined to determine that quality of the retentate and permeate streams that yielded the
most profit:
1. Pr = 434.4 psia (absolute feed pressure)
13

Chase, N.; J. Phys. Chem. Ref. Data, Monograph 9., 1998

Page | 17

2.
3.
4.
5.
6.

Pp = 15 psia (approximate atmospheric pressure)

yCO2f = 0.82
yCH4f = 0.18
Vf = 3,160,379.494 mol/h
yCH4r varies from 0.2 to 0.95

Figure 6.1 Base Case-Single Stage Membrane

Furthermore, the parameters were used to solve the following system of six equations to
determine area of the membrane (A), retentate molar flow rate (Vr), permeate molar flow rate
(Vp), carbon dioxide mole fraction in retentate (yCO2r), methane mole fraction in permeate
(yCH4p), and carbon dioxide mole fraction in permeate (yCO2p).
= +

(Eq. 6.3)

k4 (4 4 ) = 4

(Eq. 6.4)

k2 (2 2 ) = 2

(Eq. 6.5)

2 = 2 + 2

(Eq. 6.6)

2 + 4 = 1

(Eq. 6.7)

2 + 4 = 1

(Eq. 6.8)

By varying the final methane retentate composition, it was found that the mole fraction of carbon
dioxide in the permeate (yCO2p) was greater than 0.995 from yCH4r = 0.2 to 0.26. Between these

mole fraction ranges, the methane retentate can be sold as low energy gas at $2.5/MMBTU and
the permeate can be sold as carbon dioxide product at $0.003/SCF. Figure 6.2 depicts the
maximum profit of approximately $22.6 M/year from the low energy gas and carbon dioxide
products in the range of yCH4r = 0.2 to 0.26.14

14

Appendix: Figure 9.6.1-9.6.2

Page | 18

$25,000,000.00

$/year

$20,000,000.00

$15,000,000.00

$10,000,000.00

$5,000,000.00

Low energy gas and

Carbon Dioxide
$-

0.2

0.22

0.24

0.26

0.28

yCH4r
Figure 6.2 Base-Case Permeate and Retentate Profit vs ych4r from yCH4r = 0.2 to 0.26

After yCH4r = 0.26, the carbon dioxide mole fraction in the permeate feed drops below 0.995

and can no longer be sold along with methane products. Figure 6.3 illustrates the behavior of
profits after yCH4r = 0.26 to 0.6.

$7,000,000.00
$6,000,000.00

$/year

$5,000,000.00
$4,000,000.00
$3,000,000.00
$2,000,000.00
Low Energy Gas
Medium Energy Gas

$1,000,000.00
$0.2

0.3

0.4

yCH4r

0.5

0.6

0.7

Figure 6.3 Base-Case Retentate Profit vs ych4r from yCH4r = 0.26 to 0.6

Page | 19

Profits after yCH4r = 0.6 are negative due to the high capital cost of the membrane and are not
included. It is important to note that only the methane retentate stream can only be sold as
low energy gas and medium energy gas. As a result, the maximum profit is only $5.7 M/year
after yCH4r = 0.26. Consequently, the preliminary design analysis of a single stage membrane
separation indicates that maximum profitability will occur when both low energy gas and
carbon dioxide products can be sold from the retentate and permeate streams respectively.
6.2.2 Single Stage Membrane System with Compressor
A compressor was now utilized to pressurize the feed to drive mass transfer of carbon dioxide
from the retentate side to the permeate side of the membrane as shown in Figure 6.3. To
achieve maximum profit, the parameter of yCO2p was fixed at 0.995 and feed pressure was
increased. The maximum pressure that the membrane can experience before rupturing was
assumed to be 1000 psia in this analysis.15 The pressure of the feed was increased from 434.4
psia to 984.4 psia. This pressure range yielded retentate products with mole fractions of
yCH4r=0.264 to 0.269 which can only be sold as low energy gas. Additionally, the permeate
molar flow rate also increases as compression of the feed occurs.16

Vf
E-1

Vr
Vp

Figure 6.4 Single Stage System with Compressor

As pressure was increased, the total capital cost for the membrane decreased while the
operation cost to compress increased. This trend is captured in Figure 6.5 with total costs
ranging from $1.74 M per year to $1.79 M per year.

15
16

Appendix: Figure 9.6.3

Appendix: Figure 9.6.4-9.6.5

Page | 20

$2,000,000.00
$1,800,000.00
$1,600,000.00
$1,400,000.00

$ per year

$1,200,000.00
$1,000,000.00
$800,000.00
$600,000.00
$400,000.00

Capital Cost
Operation Costs
Total Cost

$200,000.00
$300

500

700

900

1100

Pressure (psia)
Figure 6.5 Single Stage System with Compressor Separation Costs

Although the minimum total cost occurs at 584.4 psia, the maximum profit of $23.8 M occurs at
984.4 psia. The maximum revenue from the carbon dioxide product and low energy gas
outweigh the total separation cost at this pressure. The total revenue, total cost of separation,
and overall profit is shown in Figure 6.6.

$30,000,000.00

$25,000,000.00

$ per year

$20,000,000.00

Total Cost (Operation

and Capital)
Revenue from CO2 and
CH4 Product
Profit

$15,000,000.00

$10,000,000.00

$5,000,000.00

$-

300

500

700

Pressure (psia)

900

1100

Figure 6.6 Single Stage System with Compressor Costs, Revenue, and Profit

In this particular case, the total cost of separation does not increase significantly as pressure
increases whereas there is noticeable increase in revenue from low energy gas and carbon
Page | 21

dioxide product. Total revenue from carbon dioxide and low energy gas is substantially greater
than separation costs over points of increased feed pressure. Accordingly, profit is dominated
by the increasing revenue from increasing feed pressure.
6.2.3 Two Stage Counter-Current Membrane System with Compressors
Further optimization from the base case in this design analysis considered a two stage countercurrent membrane system with two compressors as shown in Figure 6.7. The second permeate
stream was recycled back into the first stages retentate side. Recycling the carbon dioxide rich
permeate stream causes a higher concentration gradient for carbon dioxide transport across
the membrane. Two compressors were needed for this operation to occur where one
compressor pressurized the feed pressure from its initial pressure of 434.4 psia up to 984.4
psia. To obtain consistent pressures throughout the system, the second compressor was
employed to pressurize the second permeate stream from its estimated atmospheric pressure
of 15 psia to matching feed pressure for proper recycle. 17 Consequently, the second retentate
increases in methane concentration from yCH4r=0.576 to 0.597. The quality of the second
retentate stream would be sold as medium energy gas at a price deck of $3 per MMBTU. 18

Vf

Vr1

Vr2

E-3

Vp1

Vp2

Figure 6.7 Two Stage Counter-Current System with Compressors

Since there two membranes and two compressors were considered in this design optimization,
both the total capital and operating costs increased significantly as captured in Figure 6.8. In
this two stage separation system, the minimum total separation costs occurs when the feed
and permeate stream 2 are pressurized to 984.4 psia. Total separation costs ranged from $4.66
M per year to $5.43 M per year depending on the pressurization of the permeate and feed
streams.

17
18

Appendix: Figure 9.6.6

Appendix: Figure 9.6.7- Figure 9.6.8

Page | 22

$6,000,000.00

Total Capital Cost

Total Operating Cost
Total Cost

$5,500,000.00
$5,000,000.00
$4,500,000.00

$/year

$4,000,000.00
$3,500,000.00
$3,000,000.00
$2,500,000.00
$2,000,000.00
$1,500,000.00
$1,000,000.00
400

500

600

700

800

900

1000

Pressure (psia)

Figure 6.8 Two Stage Counter-Current System with Compressors Separation Costs

In this particular case, the maximum profit of $41.3 M per year occurs when the total
separating costs are at a minimum depicted in Figure 6.9.

$51,000,000.00
$46,000,000.00
$41,000,000.00
$36,000,000.00

$/year

$31,000,000.00
$26,000,000.00

Profit
Total Cost
Total Revenue

$21,000,000.00
$16,000,000.00
$11,000,000.00
$6,000,000.00
$1,000,000.00
400

500

600

700

800

900

1000

Pressure (psia)

Figure 6.9 Two Stage Counter-Current System with Compressor Costs, Revenue, and Profit

Page | 23

In the two stage counter-current design, the total revenue does not increase significantly in
comparison to the observable decrease in total separating costs. As result, profit is dominated
by the decreasing cost to separate with increasing feed pressure.
6.2.4 Three Stage Counter-Current Membrane System with Compressors
A three stage counter-current membrane design system with compressors was assessed to
determine any significant increase in profits from previous designs as depicted in Figure 6.10.
The second and third carbon dioxide rich permeate streams were fed back into the retentate
side of the membrane in stages one and two respectively. In addition, there were a total of
three compressors used in this design to pressurize the feed from its initial pressure of 434.4
psia to 984.4 psia.19 The second permeate stream and third permeate streams were
pressurized from atmospheric pressure of 15 psia to matching feed pressure for proper recycle.
This arrangement also drives carbon dioxide mass transport by increasing the concentration
gradient on stages 1 and 2. It was calculated that the methane mole fraction in the third
retentate stream ranged from yCH4r =0.818 to 0.843.20 This stream can then be sold as high
energy gas at a price deck of $4 per MMBTU.

Vr1

Vf

Vr3

Vr2

E-4

Vp1
Vp3

Vp2

Figure 6.10 Three Stage Counter-Current System with Compressors

Three stages include three membranes and three compressors which result in an increase in
capital and operating costs as reflected in Figure 6.11. Depending on the pressurization of the
feed and permeate streams, total costs ranged from $7.76 M per year to $11.8 M per year.

19
20

Appendix: Figure 9.6.9

Appendix: Figure 9.6.10- Figure 9.6.11

Page | 24

$13,000,000.00

Total Capital Cost

Total Operating Cost
Total Cost

$11,000,000.00

$/year

$9,000,000.00
$7,000,000.00
$5,000,000.00
$3,000,000.00
$1,000,000.00

400

600

800

1000

Pressure (psia)

Figure 6.11 Three Stage Counter-Current System with Compressors Separation Costs

As compressors were used to pressurize the streams, the overall capital cost for area decreases
rapidly while the total operating costs slowly increased. In a three stage counter-current
system, the maximum profit $44.5 M per year also occurs when the total separating costs are at
a minimum shown in Figure 6.12.
$60,000,000.00
$50,000,000.00

$/year

$40,000,000.00

Profit
$30,000,000.00

Total Cost
Total Revenue

$20,000,000.00
$10,000,000.00
$400

500

600

700

800

900

1000

Pressure (psia)
Figure 6.12 Three Stage Counter-Current with Compressor Costs, Revenue, and Profit

In the three stage counter-current design, the total revenue does not increase significantly in
comparison to the observable decrease in total separating costs. Similar to the two stage
Page | 25

counter-current system, profit is dominated by the separation costs associated with increasing
feed pressure.

6.3 SUMMARY
Based on the maximum yearly profits of the different designs, it was found that the three stage
counter-current membrane system was the most economical as shown in Figure 6.13.
$50
$45
$40

$ M / year

$35
$30
$25
$20
$15
$10
$5
$-

Figure 6.13 Maximum Profit of Designs compared to Value of Feed

The three stage system was found to have the maximum yearly profit of $44.5 M which is much
higher than the feeds value of $8.2 per year. This analysis reflects that multiple stage
membrane systems are effective and profitable in separating natural gas streams with high cut
carbon dioxide. Operating flexibility allows for an economical separation as both methane and
carbon dioxide products can be sold. It should be noted that selling carbon dioxide product
with low-high energy gas dominated revenue while pressurizing feeds substantially decreased
capital costs. Moving forward, suggestions to continue optimizing these systems include placing
compressors between stages to reduce membrane area and thus decrease capital cost.

Page | 26

7 CRYOGENIC DISTILLATION
Conventionally, carbon dioxide is removed from natural gas streams via absorption or
membrane permeation. However, if the feed concentration of carbon dioxide is high enough,
these conventional methods can become less economically viable.21 Alternatively, cryogenic
distillation can be used to separate gases. Distillation is a process that separates liquids based
on their boiling points. Because methane and carbon dioxide are both gases at standard
conditions, they must be brought cryogenic (very low) temperatures. Naturally, operating at
such conditions can be quite energy intensive, and therefore quite expensive.

7.1 COST CONSIDERATIONS

The utility of cryogenic distillation faces two major cost constraints: capital costs, which include
the column and operating costs, which are dominated by the cost of refrigeration.
7.1.1 Capital Costs
Capital costs for the distillation column are estimated as $420,000 per distillation plate per
year. These costs include maintenance and depreciation on the column.
7.1.2 Refrigeration Costs
Refrigeration costs dominate the operating cost of the column. Both the heat exchanger used
to cool the feed before it enters the column and the reflux condenser require high amounts of
electricity. The cost of refrigeration depends on the temperature and the mass flowrate of the
fluid being cooled. The costs of refrigeration can be approximated graphically from Figure 7.1.

21

Maqsood, K.; Mullick, A.; Ali, A.; Kargupta, K.; Ganguly, S. Rev Chem Eng. 2014

Page | 27

Figure 7.1. Cost of Refrigeration versus temperature

7.2 HYSIS MODEL

The separation process was modeled using Aspen HYSIS. The setup consisted of a heat
exchanger to cool the feed gas and a distillation column with a condenser and a reboiler as
shown in Figure 7.2. (NOTE: Blue lines represent material streams and purple lines represent
energy streams.)

Figure 7.2. Aspen HYSIS simulation setup for cryogenic distillation

Page | 28

7.2.1 Assumptions of the Model

The model created in Aspen HYSIS comprised of a four primary assumptions.
1. The reboiler requires zero energy. Liquid at the bottom of the column can simply be revaporized with an ambient air vaporizer.
2. The column exhibits minimal pressure drop. The pressure drop through the column and
condenser was taken as 2.00 psi and the pressure drop through the reboiler was
assumed to be zero.
3. The feed is pre-compressed. For consistency, in cases where the feed was compressed
above the feed original pressure, the cost of compression was calculated in the same
manner as in the separation methods above (rather than modeled with a compressor in
HYSIS).
4. The Lee-Kesler Method accurately describes the state of the system. Generally this is a
valid assumption. The SRK Method was also tested and it yielded similar results. For
more a more extensive analysis, other equations of state should be also be considered.
7.2.2 Choosing the Condenser
The separation was first simulated to achieve the minimum purity for low energy gas (40%
methane) in the distillate (stream exiting the top of the column) while also obtaining sellable
CO2 (99.5%) in the bottoms (stream exiting the bottom of the column). The simulation was
evaluated using both a total condenser and a full reflux condenser. In all cases, using a full
reflux condenser was more profitable. While a total condenser produces a liquid distillate
stream, a full reflux condenser produces a vapor distillate. Therefore, not having to liquefy the
distillate products, the full reflux condenser enjoys the advantage of considerably lower
refrigeration costs.
7.2.3 Condenser Inlet Phase
The feed was isobarically cooled at its original pressure (420 psig) to saturated vapor (7.372 F)
and saturated liquid (-96.50 F).22 In both cases the feed was distilled to the minimum purity of
each gas grade (40%, 70%, 95%, 99.995%). Because cooling the feed to saturated vapor
required significantly less refrigeration, it proved to be more profitable.

7.3 OPTIMIZATION
Profit is optimized when the margin between revenue and costs is at a maximum. The revenue
and costs for this model depend on the following parameters:

22

Inlet temperature
Inlet pressure
Reflux Rate
Purity

Appendix: Figure 9.7.1

Page | 29

Number of stages

By manipulating these variables to understand their trends, we can arrive at optimum

operating conditions.
7.3.1 Purity Determination
The distillation column was evaluated by taking saturated vapor to the minimum purity for each
gas grade respectively. Evaluating the profitability of compositions between the purity grade
minimums is futile because as the distillate purity increases, the distillate flowrate decreases.
Because the value of the gas remains the same until it reaches the next purity threshold, the
revenue simply decreases. In other words, maximum revenue for each gas grade is achieved at
the minimum purity.
This process was repeated while increasing the number of distillation trays (N) so that a local
maximum could be observed for each gas grade. Through this process, high energy grade
methane (70%) proved to be the most profitable option for cryogenic distillation.23
7.3.2 Effect of Number of Stages
Increasing the number of distillation trays N in the distillation column decreases the load on the
condenser thereby reducing refrigeration costs. However, increasing N also increases capital
costs ($420,000/tray/year). We can therefore assume that there is some value Nopt that
optimizes these two constraints. Figure 7.3 shows the effect of the number of trays on profit. In
this case, Nopt corresponds to four trays.24
45
40

$39.3

$39.4

$39.0

$38.8

$35.4

Profit (MM $/yr)

35
30

$26.6

25
20
15
10
5
0
1

N
Figure 7.3. Profit in million dollars per year verses N for high energy gas at 434.7 psia
23
24

Appendix. Table 9.7.1

Appendix. Table 9.7.2

Page | 30

7.3.3 Effect of Entrance Pressure

Another important parameter to be optimized is the pressure of the stream entering the
distillation column. At higher pressures, the lower temperatures for distillation are no longer
required. Consequently, as the entrance pressure is increased, the cost of refrigeration
decreases. However, the increasing pressure requires work from a compressor and therefore
higher pressures mean higher costs. The effect of entrance pressure P is illustrated in Figure 7.4
below.
(NOTE: Because in our case, the stream is entering at saturated vapor, the temperature (T sat)
determined by the pressure and therefore not an independent parameter.)
10.0
9.0
8.0

Costs (MM $/yr)

7.0
6.0
5.0
4.0
3.0

Compression

2.0

Refrigeration

1.0
0.0
400

450

500

550

600

650

700

P (psia)
Figure 7.4. Refrigeration and compression costs versus entrance pressure

In this case, with all other parameters constant, revenue is independent of P. Consequently,
profit is maximized where total cost is minimized. Here the total cost is only a function of
refrigeration and compression costs as capital costs are constant at constant N. Figure 7.5
illustrates the effect of P on profits. In this case, costs are minimized by operating at 550 psia.

Page | 31

41.0
40.8
40.6

Profit (MM $/yr)

40.4
40.2
40.0
39.8
39.6

39.4
39.2
39.0
400

450

500

550

600

650

700

P (psia)
Figure 7.5. Profit in million dollars per year versus column entrance pressure

7.3.4 Revenue Analysis

It is important to note that the majority of the revenue generated from this separation is not
from methane, but in fact from carbon dioxide as seen in Figure 7.6. Considering the fact that
the feed stream contained 82% carbon dioxide, these results are less surprising.

Methane
23%
Carbon
dioxide
77%

Figure 7.6. Revenue composition for optimized product

Page | 32

7.4 SUMMARY
We have shown that cryogenic distillation holds promise as a profitable means of separation.
High energy methane proved to be the most profitable grade of natural gas to produce with
this method.
The optimal operating conditions were determined to be:

P = 550 psia
T = 96.50 F
N = 4 trays
Reflux Ratio = 3.518

At these conditions, it is possible to generate an annual profit of $40.1 million from our feed
stream using cryogenic distillation.

Page | 33

8 RECOMMENDATIONS
Of the four separation methods evaluated in this report, membrane separation was proven to
be the most profitable venture as shown in Table 8.1.
Table 8.1 Summary comparison of separation methods
Separation
Method

Optimal
Grade

High Purity
CO2

Annual Profit

Absorption
(Water)

High
Energy

No

$ 13.8 million

Absorption
(MDEA)

High
Energy

No

$ 5.1 million

Membrane
Separation

High
Energy

Yes

$ 44.5 million

Cryogenic
Distillation

High
Energy

Yes

$ 40.1 million

Figure 8.1 depicts the comparison between the maximum profits of each unit operation with
the original feed value.
$50.0

Feed Value

$45.0

Max Profit of Unit Operation

$44.5

$40.1

$40.0

$ M/year

$35.0
$30.0
$25.0
$20.0
$13.8

$15.0
$10.0

$8.3

$8.3

$8.3

$8.3

$5.1

$5.0
$MDEA Absorption Water Absoprtion

Cryogenic
Distillation

Gas Membrane
Separation

Figure 8.1 Comparison between Feed Value and Maximum Profits of Unit Operations

Page | 34

For each separation process, high energy gas was deemed the most profitable. An important
distinction between cryogenic distillation and membrane separation from absorption, is the
ability to sell purified carbon dioxide from the feed stream. This is a significant advantage
considering the feed gas is 82% CO2 by composition.
We therefore recommend that membrane separation be pursued as the most viable option.
However, there are physical constraints that are not addressed in this evaluation.

8.1 PHYSICAL CONSIDERATIONS

There are several physical constraints that may increase or decrease the feasibility of any given
method. For example, membrane separation is an inherently voluminous process; therefore,
the space for such a facility would have to be taken into consideration. The additional capital
costs of construction and real estate may in fact render it less economically viable than other
methods.
Some physical constraints that may justify consideration include:

Real estate costs. Lease rates, interest rates, and the condition of the market can
complicate the costs of each separation method.
Availability of resources. Geographic location and political climate can effect availability
of resources like MDEA, water, and electricity. It can also change the price of these
resources.
Fluctuations in market value. Oil and gas industries suffer from volatility. Prices for fossil
fuels tend to oscillate in a cyclical manner in response to new advancements in
technology and changes in the economy.

Before plans for construction begin, these factors need to be considered. Further research is
critical to ensuring the long-term profitability of these proposed separation methods.

Page | 35

9 APPENDIX
Table 9.4.1. Initial economic evaluation of absorption

Page | 36

Table 9.6.1 Single Stage System Calculated Values

ych4r
0.2
0.21
0.22
0.23
0.24
0.25
0.26
0.3
0.35
0.4
0.4
0.45
0.5
0.55
0.6
0.65
0.7
0.7
0.75
0.8
0.85
0.9
0.95

Page | 37

VR
VP
Area
mol/hr
mol/hr
ft^2
yco2p
0.99653 2,838,763.14
321,616.35
123,784.00
0.99631
2700822.171
459,557.32
179,174.18
0.99608
2575350.633
585,028.86
231,097.78
0.99585
2460719.327
699,660.17
280,068.06
0.99561
2355570.44
804,809.05
326,516.01
0.99537 2,258,763.26
901,616.23
370,807.00
0.99511
2169332.428
991,047.07
413,253.47
0.99403 1,870,564.94
1,289,814.55
569,502.83
0.99248 1,591,648.33
1,568,731.17
747,676.05
0.99067 1,380,655.11
1,779,724.39
921,416.81
0.99067 1,380,655.11
1,779,724.39
921,416.81
0.98851 1,214,478.83
1,945,900.66
1,102,547.31
0.98591 1,079,076.78
2,081,302.71
1,302,140.55
0.98270
965,253.15
2,195,126.34
1,533,020.13
0.97865
866,478.65
2,293,900.84
1,812,615.26
0.97337
777,577.68
2,382,801.82
2,167,594.22
0.96623
693,683.74
2,466,695.76
2,643,086.37
0.96623
693,683.74
2,466,695.76
2,643,086.37
0.95603
608,907.46
2,551,472.03
3323978.992
0.94029
513,519.88
2,646,859.61
4392644.66
0.91297
385,114.23
2,775,265.26
6323661.632
0.85518
147,244.43
3,013,135.06
10,811,966.53
0.67947
(705,584.33) 3,865,963.82
29,267,942.06

Value of Retentate
CH4 per year
$
8,077,405.06
$
8,069,153.81
$
8,060,681.40
$
8,051,978.84
$
8,043,036.63
$
8,033,844.72
$
8,024,392.53
$
7,983,746.79
$
7,925,521.90
$
7,857,020.81
$
9,428,424.98
$
9,330,317.40
$
9,211,202.03
$
9,063,540.36
$
8,875,709.33
$
8,628,813.78
$
8,289,980.49
$
9,671,643.90
$
9,096,059.70
$
8,182,537.31
$
6,520,024.62
$
2,639,502.81
$
(11,443,700.60)

Value of Permeate
CO2 per year
$
5,266,344.29
$
7,525,074.68
$
9,579,622.92
$
11,456,666.54
$
13,178,439.17
$
14,763,619.50
$
16,228,015.10
$
$
$
$
$
$
$
$
$
$
$
$
$
$
$
$
Total Revenue
$
13,343,749.35
$
15,594,228.48
$
17,640,304.32
$
19,508,645.38
$
21,221,475.79
$
22,797,464.22
$
24,252,407.63
$
7,983,746.79
$
7,925,521.90
$
7,857,020.81
$
9,428,424.98
$
9,330,317.40
$
9,211,202.03
$
9,063,540.36
$
8,875,709.33
$
8,628,813.78
$
8,289,980.49
$
9,671,643.90
$
9,096,059.70
$
8,182,537.31
$
6,520,024.62
$
2,639,502.81
$
(11,443,700.60)

Cost of Membrane
per year
$
495,136.00
$
716,696.72
$
924,391.10
$
1,120,272.24
$
1,306,064.06
$
1,483,228.00
$
1,653,013.87
$
2,278,011.32
$
2,990,704.19
$
3,685,667.24
$
3,685,667.24
$
4,410,189.26
$
5,208,562.20
$
6,132,080.52
$
7,250,461.05
$
8,670,376.87
$
10,572,345.50
$
10,572,345.50
$
13,295,915.97
$
17,570,578.64
$
25,294,646.53
$
43,247,866.11
$
117,071,768.25

Cost of Heat
Exchanger per
year
$
13,795.11
$
13,795.11
$
13,795.11
$
13,795.11
$
13,795.11
$
13,795.11
$
13,795.11
$
13,795.11
$
13,795.11
$
13,795.11
$
13,795.11
$
13,795.11
$
13,795.11
$
13,795.11
$
13,795.11
$
13,795.11
$
13,795.11
$
13,795.11
$
13,795.11
$
13,795.11
$
13,795.11
$
13,795.11
$
13,795.11

Profit
$
12,834,818.24
$
14,863,736.65
$
16,702,118.12
$
18,374,578.03
$
19,901,616.63
$
21,300,441.12
$
22,585,598.66
$
5,691,940.36
$
4,921,022.60
$
4,157,558.47
$
5,728,962.64
$
4,906,333.04
$
3,988,844.72
$
2,917,664.74
$
1,611,453.18
$
(55,358.20)
$
(2,296,160.12)
$
(914,496.70)
$
(4,213,651.37)
$
(9,401,836.44)
$ (18,788,417.01)
$ (40,622,158.41)
$ (128,529,263.96)

Table 9.6.2 Single Stage System Revenue, Costs, and Profits

Page | 38

(Eq. 9.6.1)
(Eq. 9.6.2)
(Eq. 9.6.3)
(Eq. 9.6.4)
(Eq. 9.6.5)
(Eq. 9.6.6)

Table 9.6.3 Single Stage System with Compressor Calculated Values

Pr
psia
434.4
484.4
534.4
584.4
634.4
684.4
734.4
784.4
834.4
884.4
934.4
984.4

Page | 39

Vr
Vp
A
mol/h
mol/h
ft^2
yCH4
yCO2p
2,131,735.48
1,028,644.01
431,597.43
0.264126061
2,123,894.66
1,036,484.84
388,563.54
0.265147047
2,117,563.43
1,042,816.07
353,303.51
0.265971688
2,112,344.11
1,048,035.39
323,892.33
0.266651656
2,107,967.43
1,052,412.06
298,990.09
0.267221952
2,104,244.57
1,056,134.92
277,636.06
0.267707129
2,101,039.21
1,059,340.28
259,123.76
0.26812492
2,098,250.46
1,062,129.04
242,922.24
0.268488453
2,095,802.04
1,064,577.45
228,624.88
0.268807652
2,093,635.25
1,066,744.25
215,915.02
0.269090162
2,091,704.13
1,068,675.37
204,542.46
0.269341964
2,089,972.22
1,070,407.28
194,306.90
0.269567807

0.995
0.995
0.995
0.995
0.995
0.995
0.995
0.995
0.995
0.995
0.995
0.995

Page | 40

Cost to
compress
per year

$
$ 133,513.37
$ 253,899.54
$ 363,510.35
$ 464,117.27
$ 557,087.90
$ 643,500.12
$ 724,218.58
$ 799,947.45
$ 871,267.84
$ 938,664.90
$ 1,002,547.87

Total Captial
Cost

$ 1,726,389.74
$ 1,554,254.15
$ 1,413,214.02
$ 1,295,569.31
$ 1,195,960.36
$ 1,110,544.24
$ 1,036,495.03
$ 971,688.96
$ 914,499.50
$ 863,660.07
$ 818,169.84
$ 777,227.59

$
$
$
$
$
$
$
$
$
$
$
$

13,795.11
13,795.11
13,795.11
13,795.11
13,795.11
13,795.11
13,795.11
13,795.11
13,795.11
13,795.11
13,795.11
13,795.11

Cost to heat
feed per year
13,795.11
$
147,308.48
$
267,694.64
$
377,305.46
$
477,912.38
$
570,883.01
$
657,295.23
$
738,013.69
$
813,742.56
$
885,062.94
$
952,460.01
$
$ 1,016,342.98

$
$
$
$
$
$
$
$
$
$
$
$

1,740,184.84
1,701,562.63
1,680,908.67
1,672,874.77
1,673,872.74
1,681,427.24
1,693,790.26
1,709,702.65
1,728,242.06
1,748,723.01
1,770,629.85
1,793,570.56

Total operation Total Cost per

year
Cost per year
$ 16,843,650.69
$ 16,972,041.16
$ 17,075,712.64
$ 17,161,176.97
$ 17,232,843.38
$ 17,293,803.72
$ 17,346,290.29
$ 17,391,955.10
$ 17,432,046.96
$ 17,467,527.38
$ 17,499,148.71
$ 17,527,508.09

Value of CO2
$
$
$
$
$
$
$
$
$
$
$
$

8,010,456.70
8,011,843.82
8,012,804.49
8,013,489.31
8,013,988.91
8,014,360.27
8,014,640.50
8,014,854.58
8,015,019.72
8,015,148.07
8,015,248.38
8,015,327.05

Value of CH4

Profit
$ 23,113,922.55
$ 23,282,322.36
$ 23,407,608.46
$ 23,501,791.51
$ 23,572,959.55
$ 23,626,736.74
$ 23,667,140.54
$ 23,697,107.03
$ 23,718,824.63
$ 23,733,952.44
$ 23,743,767.24
$ 23,749,264.58

Revenue
$ 24,854,107.39
$ 24,983,884.99
$ 25,088,517.13
$ 25,174,666.28
$ 25,246,832.29
$ 25,308,163.99
$ 25,360,930.79
$ 25,406,809.69
$ 25,447,066.68
$ 25,482,675.45
$ 25,514,397.09
$ 25,542,835.15

Table 9.6.4 Single Stage System with Compressor Revenue, Costs, and Profits

(Eq. 9.6.7)
(Eq. 9.6.8)
(Eq. 9.6.9)
(Eq. 9.6.10)
(Eq. 9.6.11)
(Eq. 9.6.12)
(Eq. 9.6.13)
(Eq. 9.6.14)
(Eq. 9.6.15)
(Eq. 9.6.16)
(Eq. 9.6.17)
(Eq. 9.6.18)

Table 9.6.5 Two Stage Counter-Current System with Compressor Calculated Values
Pressure Vp1
psi
mol/hr
Vr2
ych4r2
Vp2
Area
434.4
2,192,194
968,185.70
0.5762400
1,234,661.99
952,502.43
484.4
2,198,752
961,627.05
0.5801361
1,233,141.96
850,368.39
534.4
2,203,981
956,398.45
0.5832803
1,231,888.46
767,995.45
584.4
2,208,247
952,132.51
0.5858713
1,230,838.15
700,159.25
634.4
2,211,794
948,585.76
0.5880431
1,229,945.91
643,326.47
684.4
2,214,789
945,590.45
0.5898900
1,229,178.91
595,022.29
734.4
2,217,352
943,027.24
0.5914798
1,228,512.71
553,461.92
784.4
2,219,571
940,808.92
0.5928626
1,227,928.80
517,325.85
834.4
2221509.21
938870.2545
0.594076503
1,227,412.90
485617.5961
884.4
2223217.961
937161.5029
0.595150582
1,226,953.83
457570.5922
934.4
2224735.413
935644.0508
0.596107704
1,226,542.74
432585.5078
984.4
2226091.989
934287.475
0.596965986
1,226,172.50
410187.019

Page | 41

Page | 42

434.4
484.4
534.4
584.4
634.4
684.4
734.4
784.4
834.4
884.4
934.4
984.4

$
$
$
$
$
$
$
$
$
$
$
$

3,810,009.72
3,401,473.57
3,071,981.80
2,800,637.02
2,573,305.87
2,380,089.18
2,213,847.68
2,069,303.39
1,942,470.38
1,830,282.37
1,730,342.03
1,640,748.08

Pressure Total Capital

psi
Cost per year
$
$
$
$
$
$
$
$
$
$
$
$

13,795.11
13,795.11
13,795.11
13,795.11
13,795.11
13,795.11
13,795.11
13,795.11
13,795.11
13,795.11
13,795.11
13,795.11

Cost to
heat per year
$
$
$
$
$
$
$
$
$
$
$
$

1,625,288.58
1,810,961.47
1,978,378.77
2,130,811.12
2,270,722.04
2,400,013.40
2,520,184.19
2,632,436.84
2,737,750.62
2,836,933.67
2,930,660.67
3,019,500.73

Total
Operational
Cost per year
$
$
$
$
$
$
$
$
$
$
$
$

5,435,298.30
5,212,435.04
5,050,360.57
4,931,448.14
4,844,027.91
4,780,102.57
4,734,031.88
4,701,740.24
4,680,221.01
4,667,216.04
4,661,002.70
4,660,248.80

$ 35,896,331.00
$ 36,003,726.30
$ 36,089,342.63
$ 36,159,195.75
$ 36,217,272.47
$ 36,266,319.56
$ 36,308,291.11
$ 36,344,615.31
$ 36,376,360.15
$ 36,404,340.30
$ 36,429,187.99
$ 36,451,401.40

Revenue
Total Cost per from
year
CO2 (VP1)
$
$
$
$
$
$
$
$
$
$
$
$

9,524,803.52
9,524,243.67
9,523,797.34
9,523,433.19
9,523,130.44
9,522,874.75
9,522,655.95
9,522,466.59
9,522,301.10
9,522,155.24
9,522,025.71
9,521,909.91

Revenue from
CH4 (VR2)

$ 45,421,134.53
$ 45,527,969.97
$ 45,613,139.97
$ 45,682,628.95
$ 45,740,402.91
$ 45,789,194.31
$ 45,830,947.07
$ 45,867,081.90
$ 45,898,661.25
$ 45,926,495.54
$ 45,951,213.70
$ 45,973,311.31

Total Revenue

Profit
$ 39,985,836.23
$ 40,315,534.93
$ 40,562,779.40
$ 40,751,180.81
$ 40,896,375.00
$ 41,009,091.73
$ 41,096,915.19
$ 41,165,341.66
$ 41,218,440.24
$ 41,259,279.50
$ 41,290,211.00
$ 41,313,062.50

Table 9.6.6 Two Stage System with Compressor Revenue, Costs, and Profits

(Eq. 9.6.19)
(Eq. 9.6.20)
(Eq. 9.6.21)
(Eq. 9.6.22)
(Eq. 9.6.23)
(Eq. 9.6.24)

(Eq. 9.6.25)
(Eq. 9.6.26)
(Eq. 9.6.27)
(Eq. 9.6.28)
(Eq. 9.6.29)
(Eq. 9.6.30)
(Eq. 9.6.31)
(Eq. 9.6.32)
(Eq. 9.6.33)
(Eq. 9.6.34)
(Eq. 9.6.35)
(Eq. 9.6.36)

Page | 43

Pressure Vp1
mol/hr
psig
Area
Vp3
Vp2
ych4r3
Vr3
ych4r2
Vr2
824927.7233
447595.0721
1007391.948
0.818390995
1,192,888.75
0.5762400
968,185.70
1,967,491
434.4
740872.7664
445035.4195
1009872.631
0.822940921
1,182,854.32
0.5801361
961,627.05
1,977,525
484.7
672325.6341
442945.4071
1011837.332
0.826627825
1,174,786.57
0.5832803
956,398.45
1,985,593
534.7
615365.7207
441207.1227
1013431.004
0.829675972
1,168,159.25
0.5858713
952,132.51
1,992,220
584.7
567288.8204
439738.9387
1014749.17
0.83223812
1,162,618.40
0.5880431
948,585.76
1,997,761
634.7
526170.1618
438482.5992
1015857.274
0.834421913
1,157,917.21
0.5898900
945,590.45
2,002,462
684.7
490602.869
437395.4375
1016801.624
0.836305395
1,153,878.33
0.5914798
943,027.24
2,006,501
734.7
459534.9677
436445.5002
1017615.89
0.837946525
1,150,371.06
0.5928626
940,808.92
2,010,008
784.7
432164.2309
435608.3902
1018325.129
0.83938925
1,147,296.95
0.594076503
938870.2545
2013082.514
834.7
407868.2847
434865.1613
1018948.369
0.840667498
1,144,580.45
0.595150582
937161.5029
2015799.018
884.7
386156.9209
434200.8788
1019500.314
0.841807877
1,142,162.59
0.596107704
935644.0508
2018216.871
934.4
366638.8081
433603.6122
1019992.505
0.842831551
1,139,996.72
0.596965986
934287.475
2020382.745
984.4

Table 9.6.7 Three Stage Counter-Current System with Compressor Calculated Values

Figure 9.6.10

Page | 44

Pressure
psi
434.4
484.7
534.7
584.7
634.7
684.7
734.7
784.7
834.7
884.7
934.4
984.4

Total Capital
Cost per year
$ 9,899,132.68
$ 8,890,473.20
$ 8,067,907.61
$ 7,384,388.65
$ 6,807,465.85
$ 6,314,041.94
$ 5,887,234.43
$ 5,514,419.61
$ 5,185,970.77
$ 4,894,419.42
$ 4,633,883.05
$ 4,399,665.70

Total
Operational
Cost
$ 1,912,859.06
$ 2,047,131.18
$ 2,229,156.63
$ 2,393,923.11
$ 2,544,703.92
$ 2,683,698.23
$ 2,812,622.27
$ 2,932,841.58
$ 3,045,460.79
$ 3,151,386.22
$ 3,250,977.45
$ 3,345,492.72
Total Cost
$ 11,811,991.74
$ 10,937,604.37
$ 10,297,064.24
$ 9,778,311.76
$ 9,352,169.77
$ 8,997,740.17
$ 8,699,856.69
$ 8,447,261.19
$ 8,231,431.56
$ 8,045,805.64
$ 7,884,860.50
$ 7,745,158.41

Revenue
from
CO2 (VP1)
$ 32,216,904.83
$ 32,381,214.76
$ 32,513,321.07
$ 32,621,840.89
$ 32,712,570.15
$ 32,789,550.35
$ 32,855,685.46
$ 32,913,115.69
$ 32,963,453.06
$ 33,007,934.77
$ 33,047,526.17
$ 33,082,991.54
Revenue from
CH4 (VR2)
$ 19,444,712.64
$ 19,388,341.63
$ 19,342,372.28
$ 19,304,177.84
$ 19,271,944.74
$ 19,244,381.37
$ 19,220,543.36
$ 19,199,724.46
$ 19,181,386.06
$ 19,165,110.32
$ 19,150,568.12
$ 19,137,496.79

Total Revenue
$ 51,661,617.47
$ 51,769,556.39
$ 51,855,693.35
$ 51,926,018.74
$ 51,984,514.89
$ 52,033,931.72
$ 52,076,228.81
$ 52,112,840.15
$ 52,144,839.12
$ 52,173,045.08
$ 52,198,094.30
$ 52,220,488.33

Profit
$ 39,849,625.74
$ 40,831,952.01
$ 41,558,629.11
$ 42,147,706.98
$ 42,632,345.13
$ 43,036,191.55
$ 43,376,372.12
$ 43,665,578.96
$ 43,913,407.56
$ 44,127,239.44
$ 44,313,233.79
$ 44,475,329.91

Table 9.6.8 Three Stage Counter-Current System with Compressor Revenue, Costs, and Profits

Page | 45

40
20
0

P(bub)

Temperature (F)

-20

P(dew)

-40
-60
-80
-100
-120
-140

-160
0

0.2

0.4

0.6

0.8

x Methane
Figure 9.7.1. Txy diagram for methane-carbon dioxide system at 434.7 psia
1
0.9
0.8

y Methane

0.7
0.6

0.5
0.4
0.3
0.2
0.1
0
0

0.2

0.4

0.6

0.8

x Methane
Figure 9.7.2. xy diagram for methane-carbon dioxide system at 434.7 psi

Page | 46

Table 9.7.1. Initial economic evaluation of cryogenic distillation

Table 9.7.2. Optimization for high energy gas using cryogenic distillation

Page | 47