Anda di halaman 1dari 27

Separation of Carbon Dioxide from

Landfill Gas
Pennsylvania State University - Department of Chemical Engineering

CH E 410 - Project

Bader Alotaibi
Executive Summary

In our project we examined different separation methods to separate


carbon dioxide and methane. The four different techniques tested were
cryogenic distillation, absorption using water, absorption using methydiethanolamine, and
gas separation membranes. It was found that cryogenic distillation was losing over $400
million annually as its best scenario. Both absorption methods turned out making profit
annually whereas in the gas separation method only the low energy gas was profitable.

Introduction

As the demand for economically available fuel sources increases the use of natural
gas has become more prevalent over the last number of years. The ability to obtain and
utilize this flexible energy source for heating, electricity generation, transportation and even
chemical synthesis creates an increased profit potential based on these demands.
Traditionally natural gas is understood to be retrieved through gas wells or even enhanced
oil recovery methods; however, there exists a potential source that traditionally has gone
unharnessed and left to vent into the atmosphere. With increasing concerns about global
warming and the release of a potentially valuable source of low purity natural gas there
exists the possibility to capture and refine this gas into a usable energy source.

Landfill gas typically contains high concentrations of carbon dioxide and lower levels
of methane based on the fermentation stage and stability of the landfill decomposition. The
specific landfill gas conditions we address in the four separation methods that follow has
the following characteristics: 63 mole % carbon dioxide, a feed pressure of 45 psig, a feed
flow of 60 MMSCFD, with an operating time of 6000 hours per year. At its current state this
landfill gas is classified a low energy gas to be sold at $2.7/MMBtu for a total profit of just
over 15.1 million dollars per year. While this appears to be a reasonable profit we will
explore four different methods of separation to separate and purify the binary methane and
carbon dioxide mixture to be more economically desirable based on the table of methane
product stream values below.

Additionally, there is a market for carbon dioxide but only at purity concentrations of
99 percent or greater. This product could be usable and sold for the production of dry ice or
use in the chemical or food industries as a coolant source. It is valued at a price of $0.005
per SCF.
The separation techniques to improve the inherent value of this landfill gas feed
stream include: Cryogenic Distillation, Absorption with water, absorption with
methyldiethanolamine, membrane gas separation. The economic costs associated with each
technique utilizing the given utility and process costs below allow us to determine if any are
profitable. If this is the case we will make a recommendation for installation of such a
system at the facility producing the described feed gas to potentially increase their revenues
instead of venting this stream to the atmosphere.
Cryogenic Distillation Approach –

Distillation is the process of separating one or more components of a


multicomponent mixture by exploiting the differences in their boiling points. Cryogenic
distillation is this very same process performed at very low temperatures due to the
properties of the components that are being separated. In this approach specifically we
attempt to utilize the difference in the boiling points of methane (-258 ° F)[1] and carbon
dioxide (-109.3 °F)[2] to achieve mole fraction separation as a function of thermal
equilibrium in liquid and vapor phases.
Distillation makes use of the varying mole fractional compositions determined by the
binary phase diagram which dictates the fractional compositions of the components in the
vapor and liquid phases that are in equilibrium at a given temperature. Considering the
liquid and vapor equilibrium makes the selection of an equation of state (EOS) that fits the
appropriate operating conditions is essential. IN this analysis I chose to utilize the Peng-
Robinson EOS. Primarily because of its accurate representation of both liquid and vapor at
the cold operating temperatures and relatively low pressures required in cryogenic
distillation. This EOS combined with the temperature based phase equilibrium data included
in the simulation environment Aspen Plus V10 was utilized to generate the results discussed
below.
Based on the potential market data for specific mole fraction energy dense streams
that can be sold for combustions purposes and the market for high purity carbon dioxide
presented in the introduction allows for natural boundaries to consider for the separation.
Because the landfill gas feed being considered is 63 mole percent carbon dioxide it is logical
to make use of this as the primary separation goal to achieve 99 mole percent in the
bottoms product stream. The data below illustrates this necessity and focuses on the
relative cost breakdown based on the mole percent of methane in the distillate product
stream. Another operating assumption made was that the distillation column would operate
at a pressure 25 atmospheres which for normal separation purposes is much higher than
desired however this was used to bring the operating refrigeration and cooling
temperatures of the distillation column into a relatable range for cost analysis.

Figure 1:
Aspen
simulation
unit flow

In figure 1 above the Aspen diagram illustrates the units included in this evaluation
simulation. The feed stream at the left flows into a pre column heat exchanger to cool and
pressurize the feed to more favorable column separation conditions. This pre cooling unit
allows for a decreased duty of the condenser portion of the column. This is essential for cost
minimization because the cooling expenses increase exponentially at lower operating
temperatures. This is illustrated in the refrigeration cost basis figure 2.

Figure 2:

Through manipulating the feed to a precooled temperature this decreases the duty
of the condenser which recycles a portion of its liquid distillate product to the column as the
reflux ratio. The precooled feed enters the column and proceeds through the established
number of equilibrium stages that perform the separations as the vapor and liquid pass
through each other in each stage to facilitate the purification of the lower boiling point
methane rich vapor and higher boiling point carbon dioxide rich liquid. As the liquid passes
downwards through the trays more CO2 is stripped from the vapor to ultimately achieve a
desired higher concentration. When this liquid reaches the bottom it is converted back to
vapor and some is taken as a product stream called the bottoms while the rest is recycled
back into the column to begin the cycle again as vapor rising through the column.
The reverse is true for the methane which primarily travels in the vapor stream and
is enriched by the exchanges in the top portion of the tower until it is converted to liquid in
the condenser and some is taken off in higher mole fraction methane distillate product
stream and some is refluxed back in to the top of the column to begin the downward path
as liquid again. Finally beyond the distillate product stream a compressor has been added to
satisfy the 600 psi pressure requirement for pipeline quality and liquefied natural gas when
a methane concentration greater than 95 percent in this product stream can be achieved.
In each simulation below a specific goal of product stream mole fractions was set to
evaluate the economic product boundaries and provide a clear determination of most

Figure 3: Aspen design


specifications for product
streams to meet economic
boundaries.
profitable scenario. Utilizing these constraints Aspen allows for the user to vary specific
design components and it calculates the optimum values for others. In the data and
simulations below the product stream concentrations were specified the number of
equilibrium trays which Aspen calls stages were varied manually.

Once the product stream compositions have been specified as illustrated in figure 3 the
simulations were run allowing the monetary value of the product streams to be generated
with ease utilizing Aspen outputs of molar flow rates and the energy of combustion for
methane at 890.2 kJ/mol[1]. Additionally see table 5 located at the end of this section with
the necessary conversion factors and operating conditions. These stream values are

displayed below in table 1 below showing both the sale of the methane rich distillate and
carbon dioxide rich bottoms product.
Noticeably the spikes in value for each stream occur at the economic boundaries
established by the market values of the gas distillate products. The higher the purity in the
methane gas stream the higher the potential product stream value. The carbon dioxide
increases drastically in the .71 to .95 range due to our initial feed being already at 63
percent carbon dioxide this allows for the majority of it to be recovered as a sellable
product where the molal recovery of the methane peaks early at the .39 low boundary due
to its initial feed composition of 37 percent.
The primary cost tradeoffs occur between the utility costs (cooling, condensing, boiling,
pressurizing) and the cost associated with the number of equilibrium stages (trays). These
are related through the reflux ratio which determines the amount of liquid from the
condenser is sent back to the column versus what is sent out as the product stream. The
higher the reflux ratio the fewer the trays necessary to achieve the desired concentrations
but this also increases the duty required of both the condenser and reboiler. Multiple
iterations were completed at the same product stream compositions to illustrate the affect
that the number of trays has on the reflux ratio and costs associated with the high reflux

value. These can be seen in table 2 which illustrates the Reflux Dependent costs. The ideal
here is to find a cost that is minimized when the tray cost is added to the utility costs.
In order to completely grasp the utility cost however the pre cooler and compression
costs must be added which are included below in table 3. Noticeably these costs are much
lower than the actual costs associated with the column due to their higher operating
temperatures as described with the relationship to figure 2.
Finally adding up the costs associated with utilities and equilibrium tray costs and the
values of the product streams at varying methane concentrations in the distillate the full
economic analysis arises in table 4 where it is visible that the most economically favorable
option, set apart with a box around it, utilizing cryogenic distillation occurs utilizing 16 trays
with a distillate mol fraction of methane of .71 while selling a 99% pure carbon dioxide
bottoms product. This situation results in a net loss of approximatly 413.3 million dollars.
The primary factor to the lack of economic validity are the costs associated with
refrigeration being so high for products that are simply not valued at the costs of seperation
for this method. As a comparison the feed stream has been highlighted and tracked
throughtout the process and if sold unadaultered as low energy gas would result in a profit

of roughly 15.1 million dollars per year.


Absorption with Water –

Theoretical background

Absorption is a separation method that uses both liquid and gas. Using
liquid solvents, solutes in the gas phase are separated. The Absorption process
takes place in an absorption column shown in Fig 1. The column is a vertical
tower where the liquid solvent enters the column from the top and leave from
the bottom. However, on the other hand the gas solutes enter from the
bottom and leave at the top. The separation method works since one of the
solutes in the gas phase is soluble with the liquid solvent that flows through
the column. In our project landfill gas contains similar amounts of CO2 and CH4
and since water is very cheap and is obtained easily. Since CO2 is soluble in
water whereas CH4 is not.

Figure 1 - Absorption column


Assumptions

For our calculations and analysis, we made certain assumptions in order to


make the calculations simpler.

• The process was assumed to operate under ambient temperature (298


K) and this temperature was constant throughout the process
• Water entering the column was assumed to be pure
• The gas was assumed to be ideal
• The relationship between the gas and liquid phases are in equilibrium

Variables

In order to carry out the calculations and prior to designing the absorption
tower we needed certain variables:
Table 1 - Feed stock specifications
Carbon Dioxide Feed Pressure Feed Flow Operating time
Concentration
63% 45 Psig 60 MMSCFD 6000 hr/yr

• Minimum liquid flow (Lmin) is the least amount of water needed


to perform the absorption process. Lmin helps in giving a rough
estimate of the amount required even though the actual amount
is about 1.5 times larger. Using the following equation, we can
solve for the value of Lmin.

𝑦1 𝐿′ 𝑚𝑖𝑛
𝑦1 𝑉1 = 𝑦2 𝑉2 + ′
𝐻 1 − 𝑦1′
𝐻

Table 2- values of L'min for the different products


Product L’min (mol/s) Actual L’min (mol/s)
High Energy gas 284593.87 426890
Pipeline quality 32359.62 484889.426
gas
Liquefied natural 333472.48 500208.7235
gas
• H’ is needed for calculations and in order to find that we will need
to find Henry’s Constant. Using Table A.3-18 from the book H is
calculated using linear interpolation. Using the following equition
we were able to find H’:

𝐹𝑒𝑒𝑑 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒
𝐻′ =
𝐻

H’ 402

• The Mass Transfer Coefficient (K’y) is an essential variable in order


to find out the height of the tower. Using the below equation to
get K’y:

1 1 𝑀′
= +
𝐾′𝑦 𝑘′𝑦 𝑘′𝑥

Calculations and costs

The packing tower has a packing material (1” Rashing rings), which have
been estimated to cost $1800/ft3 of column volume which will last for 30 years.
Therefore, in order to find out the cost of the packing we need to first solve for
the volume, in consequence we will need to first solve for the height of the
tower. Using the variables that have been given and what we have calculated
we can solve for the height using the equations below.
Most towers have a height that range between 20m to 150m, where the
taller tower have a better separation since it results in purer product. That’s
mainly because the liquid flow has more height and so to have more
interaction with the gas, but this can cost much more and is more expensive
than a shorter tower.

𝑦1
1 𝑉 ∙ 𝑑𝑦
𝑧= ∫
𝐾𝑦 ∙ 𝑎 ∙ 𝑆 (1 − 𝑦) ∙ (𝑦 − 𝑦 ∗ )
𝑦2
(1 − 𝑦)∗𝑚
Table 3- Heights and volumes

Product Height (m) Volume (ft3)


High Energy gas 11.355 401.008
Pipeline quality 22.309 787.8679
gas
Liquefied natural 120.3986 4251.8404
gas

Liquid pressurized cost:


Since the water entering the absorption is not at the same pressure of
the column, therefore the water has to be pressurized to the absorption
pressure. Where in this case is 45 psig. Using the equation below we can
calculate the power required.

𝑃𝑜𝑤𝑒𝑟 = 𝑉𝐿 ∙ (𝑃2 − 𝑃1 )

Gas pressurized cost:


Pipeline quality and liquefied natural gas would require the gas feed to
be compressed from the specific pressure (59.7 psia to 600 psia). High energy
gas does not require to be compressed since pressure specifications would not
affect the price. Using the equation below we could work out the power
required and then multiply it by $0.1/kWhr.

𝐸𝑛𝑒𝑟𝑔𝑦 𝑃2
= 𝑅𝑇𝑙𝑛( )
𝑚𝑜𝑙𝑒 𝑃1
Economy Analysis –

Revenues

Revenues were calculated for the products; each product is priced in


$/MMBtu. First we had to convert the gas flow rate to units of mol/s by
multiplying it with the mol fraction. Next multiply it with the operating time,
heat of combustion and ideal gas constant to get the product in the units of
MMBtu/yr.

Table 4- revunues of products

Product Revenues ($) Price ($/MMBtu)


High energy gas 24,990,929.89 3.8
Pipeline quality gas 23,814,071.69 4.3
Liquefied Natural gas 28,951,341.86 5.5

Profits
As we can see in Fig 2 next page that high energy gas reflects higher
profits over 30 years than both pipeline quality and liquefied natural gas.
Although the difference between high energy gas and liquefied natural gas is
small, yet these small changes may be the reason in choosing a different
product.

Product Annual Profit ($)


High energy gas 14,789,655.00
Pipeline quality gas 9,729,997.38
Liquefied Natural gas 14,624,841.76
Figure 2 – graph of the total annual profit over 30 years
Absorption using methydiethanolamine –

Another potential technique that we could use to separate carbon dioxide (CO 2) and

natural gas (CH4) is absorption by methyl

diethanolamine (MDEA). Our group decided

to use the 23.3% MDEA solution with water as

the solvent. The operational condition for the

absorption was the feed condition at room

temperature, which was at 3 bar and 298

kelvins. The feed that we were dealing with

was Landfill gas with 63% CO2. The feed flow

Figure 3 Absorption Tower Diagram rate was fixed at 60 MMSCFD, which can be

converted to SI unit (moles per second) as 800 mol/s. The cross-sectional area was initially

set to 0.456 m2 and can be manipulated if needed.

The equilibrium data was obtained and listed in table #1.

Table 5 Equilibrium Data

pA xA yA

0 0 0

0.0025 0.00279 2.47E-06

0.0033 0.00398 3.26E-06

0.004 0.00478 3.95E-06

0.016 0.0109 1.58E-05

0.19 0.0575 0.000188

2.2 0.174 0.002171

10 0.296 0.009869
82 0.444 0.080928

240 0.476 0.236862

510 0.545 0.503331

X-Y graphs for diluted and full range of concentrations, figure #2, was generated from the

equilibrium data.

Figure 4: equilibrium data for dilute (on the left) and full range (on the right)

In the case of treating landfill gas, the assumption of diluted system would be no longer

valid because of the high concentration of CO2 in the feed stream. Thus, concentrated X-Y

graph was selected for further calculation. By fitting the data points within exponential

function, we were able to obtain a relation between hypothetical vapor fraction of CO 2 and

liquid fraction of CO2 when in equilibrium. The relation can be expressed in

Equation: 𝑦 ∗ = 0.0000089953 × 𝑒 21.4243671052𝑥 (1)

where y* is the hypothetical vapor fraction of CO 2 and x is the liquid fraction of CO2.

Since our objective was to find the condition that maximize the profit, we would need to

calculate the cost. The landfill gas could be readily obtained. Therefore, the cost of feed was

negligible. The total cost was only composed by the capital cost for constructing the tower

and the inert liquid flow cost. We were able to manipulate the inert liquid flow rate for the

absorption tower and adjust the cross-sectional area of the tower to maintain a safe and

efficient height. The height of the tower can be expressed in


𝑦2 𝑉′
Equation:𝑍𝑇 = ∫𝑦1 𝐾′𝑦 𝑎𝑠
𝑑𝑦 (2)
(1−𝑦)∗𝑀
(𝑦−𝑦 ∗ )(1−𝑦 2 )

where v’ is the inert vapor flow (CH4 flow in this scenario); s is the cross-sectional area for

the tower; a is the interface area per column volume; and y is vapor fraction of CO 2. The

value of ‘a’ can be maximized while designing the absorption tower, but it was treated as

constant for now while investigating the optimal operation condition for absorption tower.

The K’y value for calculating height of tower can be obtained by using

1 1 𝑀′
Equation:
𝐾𝑦′
= 𝑘′ + 𝑘′ (3)
𝑦 𝑥

where M’ is the average value of henry’s constant calculated based on the equilibrium data.

The values of M’, k’x, k’y are determined to be 0.55, 0.86 mol m-2 s-1 and 0.56 mol m-2 s-1

accordingly. Therefore, K’y is calculated to be 0.412 mol m-2 s-1.

In an effort to find the best way of treating the landfill gas, we used an excel calculator

produced by professor Zhang to perform numerical calculations. We set goals for different

product stream purities that have different prices. The costs and profits can be calculated as

follows:

Equation: 𝐶𝑜𝑠𝑡 = 𝑆 × 𝑍𝑇 × $1 + 𝐿′ × $2 × 𝑡0 + 𝑉1 × (𝑃2 − 𝑃1 ) × 𝑡1 × 𝑡𝑦 + 𝑖 × 𝑅 × 𝑇 × 𝐿𝑛 (𝑃𝑃3) × 𝑡𝑦 (4)


4

where S is the cross-sectional area; ZT is the height of the tower; $1 is the cost for 1 ft3

volume of the column, which is 1800 $; L’ is the inert liquid flow rate; t 0 is the one day in

seconds; t1 is the time of operation per year; ty is the number of years; V1 is the volumetric

flow rate of inert liquid; P1 is the top absolute pressure; P2 is the bottom absolute pressure; i

is a factor that is affected by the product pressure ( If pressurization is required, like in

pipeline quantity gas and liquefied natural gas, i is 1. Otherwise it’s 0); R is ideal gas

constant; T is the absolute temperature of operation condition; P 3 is the desired pressure;

and P4 is the feed pressure.


The Net profit can be calculated by the difference between overall profit and costs as

follows:

Equation: Net profit = 𝑉2 × 𝑡1 × 𝑡𝑦 × $3 − 𝐶𝑜𝑠𝑡

where V2 is the product flow rate; $3 is the selling price for product.

The example calculation for desired CH4 fraction of 95% and unit conversion are listed in

figure #3. The result can be summarized in table #2.

Figure 5 Unit Conversion and Sample Calculation

Table 6 summarized economic analysis


Desired CO2 concentration

feed 0.6 0.3 0.05

Optimized Inert Liquid Flow Rate (mol/s) NA 56 350 460

Optimized Tower Height (m) NA 2.08 19.72 36.12

Total Cost for one year ($) NA 91161 772881 2529768

Total Cost for thirty years ($) NA 981740 6612861 10540044

Net Profit for one year ($) 14632255 16542577 10112278 6546224

Net Profit for thirty years ($) 438967642 495295566 319941903 2.62E+08

Comparing the net profit for different desired CH4 concentration, it can be concluded that

the medium energy gas is the optimal option that would make the most profit in short term

and long term. The corresponding optimized inert liquid flow rate is 56 moles per second.

The optimized tower height is 2.08 meters.

Although the cross-sectional area is negatively related to the cost, the effect is negligible.

However, it can be used to control the tower height in the cases where tower height

exceeds the safety maximum. In this scenario, the cross-sectional area of 0.456 m2 is

appropriate.
Gas Membrane Separation
Theoretical Background
The progress of using membranes in gas separation has been growing very fast. It
started from early diffusion experiments and basic concepts of permeation, to commercially
accepted products. Since the membrane used is the most crucial part of this separation
method, it has attracted maximum attention for improvements research and development. Gas
separation in membranes is driven by a pressure gradient on either side of the membrane. The
inlet feed is entered at the high-pressure side and permeates through the membrane into the
low-pressure side. Membranes have different permeabilities for different components and the
rate of transfer of each component through the membrane varies between a completely mixed
model and plug flow.

Figure 6. Single Stage Gas Separation Membrane

Equations
1. Overall mass balance.
Feed flow rate (Lf )= Permeate flow rate (Vp )+ Retentate flow rate (L0)
2. Mass balance on Co2.
Lf Xf=Vp yp + L0 X0
3. Mole fraction.
y (CO2) + y (CH4) = 1
−𝑏+𝑠𝑞𝑟𝑡(𝑏2 −4∗𝑎𝑐)
4. yp = 2𝑎
𝑥𝑓 [1+(𝛼 ∗−1) 𝑟 (1−𝑥𝑓 )]
5. 𝑥𝑜𝑀 = 𝛼 ∗ (1−𝑥𝑓 )+𝑥𝑓
𝜃𝐿𝑓 𝑦𝑝
6. 𝐴𝑚 = 𝑃′𝐶𝑂
( 2 )(𝑝 𝑥 −𝑝 𝑦 )
ℎ ℎ 𝑜 𝑙 𝑝

7. Total Profit.
Profit = CH4 value (in retentate and permeate) + CO2 value (in retentate and
permeate) – Membrane cost (4$/ft2) – compression cost - Feed Value
8. Compression cost: The feed stream is at 45 psig. Pressurizing this feed would require
an energy that can be calculated using the following equation.
𝐸𝑛𝑒𝑟𝑔𝑦 𝑃2
= RT ln (𝑃1)
𝑇𝑖𝑚𝑒

Feed conversion and Equations:


• Feed pressure: 45 psig = 308.7 cm Hg
• Operation time= 6000 hours per year.
• Feed Temperature= 298 K
• kCO = 2.9 x 10 mol/(cm sec mm Hg) = 5.56*10^-7(cm) STP/(cm s cm Hg)
2
-11 2. . 3 2

• kCH = 3.2 x 10 mol/(cm sec mm Hg)


4
-13 2. .

• Heat of combustion of methane= 0.8445 MMBTU/kg*mol


• Feed= 60 *10^6 SCFD= 804 mol/s = 18.00*10^6 cm^3 STP/s

Simulation Conditions and Assumptions


To simplify the calculations, the complete mixing model was assumed to purify the
enhanced oil feed into medium gas oil. The ambient temperature of the system it was
assumed to be around 298 K. The temperature has an effect only in calculating the
compression cost and doesn’t substantially contribute to the purity of the streams or in the
balance equations. The pressure drop when the gas travels between multiple stages was
assumed to be 10%. Since α* and x f are given, yp,x0,Am are determined through
relationships. x0 is determined by the quality we are trying to achieve. There’s a minimum
reject composition for the final product quality which can be calculated by equation 5. This
minimum rejection composition refers to the minimum mole fraction that can be obtained
from the retentate when using a very large membrane area.

Case Study
For this project, a mixture of methane/carbon dioxide is to be separated by the technique
GMS. For this particular membrane, carbon dioxide has a higher permeability than methane,
making carbon dioxide pass through easier to the permeate side. Feed composition, pressure,
concentrations, flow rates along with product prices are given. The objective goal here is to
make as much profit as possible under the given conditions. The feed flow rate was 60
MMSCFD, carbon dioxide concentration 63% mole percent, methane was 37% mole percent,
and operating time of 6000 hours per year.
A few separation methods were studied to look for the best method to give the highest
profits. One of them is changing the pressure of the retentate, and the other is to use more than
a single stage. To simplify the process, several assumptions were made due to the nature of the
process. The ambient temperature was assumed to be at 298 K. Although the temperature will
change as the pressure varies, it will not be significant when calculating the cost of the system
because temperature variable is not present in both the mass transfer and balance equation.
Also, it was assumed complete mixing to purify the landfill gas stream.
The profitability of upgrading the landfill gas using a one stage GMS was studied for the
following qualities: medium energy gas, high energy gas, and low quality gas. The highest
quality level (liquefied natural gas) was not studied since to achieve a purity of 99.995%
required an extremely high pressure difference that will rupture the membrane and liquefy
CO2 immediately.
A GMS unit costs is defined by the capital cost, a function of membrane area, and operating
costs in gas pressurization, as shown in equations 7 and 8.

The goal here is to run the membrane at very high pressure and keeping the cut to a
lower number. And figure 2 shows the compression costs with varying p h.
Figure 7. compression costs with varying ph

Case 1. Low energy gas:


Table 1- A profit of $569,450.2 is made at low energy gas feed

objective Product Methane Energy Revenue($/yr) Cost($/yr) Profit


goal (kmol) conc.(mol%) (MMBT ($/yr)
U)
Low 964944 37% methane 569,450. $569,450.2 0 $569,4
energy (366678. 2 50.2
7
methane)
Case 2. Medium energy gas:

Table 2. The cut= 0.06, ph=1310 cm Hg, pl= 76 cm hg, Am=4.52*10^8 cm^2

Upgrading our landfill gas feed into a medium energy gas has yielded a loss of $306,207. After
trying to push the concentration of methane above 40%, the maximum mole fraction it can get
in a single stage was 40.4% methane purity under the highest pressure and decreasing the cut
to minimize the cost of the membrane area. A maximum pressure was used at 1310 cm Hg
because after 1310cm Hg, the compression cost will increase and this method will yield more
costs. CO2 was collected from the permeate stream, but it was almost impossible to reach %99
purity and still making a profit.
Case 3: High Energy Gas
A high-energy gas was obtained by setting x0 to 30%, and the membrane area
required for this specified retentate was very high, which also resulted in high membrane cost
($205,310.82 at a pressure of 50,000 cmHg). This is why the high-energy gas product does
not yield great profits compared to the low energy discussed above. In fact, producing high-
energy gas with high pressure in a single stage produced negative returns of 5.6 million.
Which also resulted in low CO2 purity in the permeate which has gone to waste due to a
large fractional cut of 50%, but the profits are still negative even by running the separation at
very HIGH pressures (low r value) that can be unrealistic and also rupture the membrane.
(Figure 3).

Profits Vs r -High Energy Gas


-$5,250,000.00
0.009212286 0.0128972 0.032243
-$5,300,000.00

-$5,350,000.00

-$5,400,000.00
Profits ($/yr)

-$5,450,000.00
single stage
-$5,500,000.00

-$5,550,000.00

-$5,600,000.00

-$5,650,000.00
r (pl/ph)

Figure 3: Profits obtained to produce High-energy gas

by running the separation at different values of r (pressure ratio) and multiple stages. The low
CO2 purity recovered, that is not sellable, caused this expected dip in both profit curves.
However, Figure 4 below demonstrates how the total costs decreases as we increase the
pressure. That happens because as we increase the pressure, the area of the membrane required
decreases. Since the membrane area costs much more than the compression, the membrane
costs dominate.

Figure 4. costs and pressure


CO2 Analysis
Upgrading the feed into a low energy gas provided CO2 revenue. In a single stage
membrane with high Ph pressure. But for most cases, it does not meet the specified purity.
Also, upgrading the feed into high quality gas reduced economic potential although the
permeate can be rich in CO2, but the fractional cut is increased to about 0.5, which means
half of the feed that end up in the permeate side goes to waste. For a medium quality gas, a
very low CO2 purity is collected in the permeate and this is due to the very large fractional
cut required to run this separation which was 83%. This is why a medium quality production
costs a lot and makes no profit.

Sources of error and optimization


The calculations made were based on the assumption of a 10% drop in pressure,
which may have overestimated the revenue. In a multiple stage system, the stream could have
gone through a higher pressure drop and entered the next stage at a lower pressure than what
was recorded. Therefore, the separation may not have been as good as what was analyzed.
The temperature assumed could have been higher, which will require higher energy for
compression, and therefore, higher costs. A reverse osmosis phenomena may have occurred
during the operation, which allows the stream to permeate back into the retentate effecting
the final methane composition and therefore, the final profits. The complete mixing model
may not be an accurate assumption in this analysis, which may have inaccurately presumed
the composition of the retentate and permeate leaving the unit is the same of what is inside.
Also, another source of error could be the presumed assumption that the membrane can
handle a 50,000 cmHg pressure or more, we are not really sure about the maximum pressure
the membrane used can handle, so the profits may have been lower if the pressure is way too
high. For optimization, a reflux of the permeate could be sent back with the original feed for
further purifications of CO2 (figure 5). This would save on membrane costs and additional
profits will be gained.

Summary
Upgrading the landfill feed to a low energy gas with a one-stage system at a high
yielded the maximum profit of 0.5 million. Adding three or more stages to this system
doesn’t provide a higher return because of non-profitable permeate stream. The production of
high & medium energy gas gives a net negative return even with the addition of multiple
stages, this is a result of having a large fractional cut of 50% that ends up in the non-sellable
permeate stream. For the pipeline quality gas, the net profits are negative even at very high
pressure ratio, that when exceeded, might break the membrane unit. So it would not be
feasible to produce pipeline quality gas under realistic conditions.
Recommendations

One of the reasons that performing under the given conditions has led to no profits was
the low methane concentration in the feed (63% carbon dioxide), but the high flow rate and the
operating time of (6000 hour/yr) should balance the feasibility of further taking advantage of
these constraints.
For absorption, a higher entrance pressure and higher operating time is recommended.
The incoming inlet stream. Absorption with MDEA is feasible and further calculation will
prove to be give out Future calculations will also involve pumping costs needed to overcome
pressure drop over the tower which was assumed to be negligible in this evaluation.
For gas membrane separation, these conditions make it difficult to make profit since
most of the processes required large membrane and higher pressure. Also, there was a
maximum pressure that a membrane cannot hold when exceeding this pressure. This value
depends on the thickness of the membrane and the membrane materials.
For cryogenic distillation, a higher entrance pressure, a longer operating time, and a
larger feed flow rate are needed for a better profit. The operational costs and the capital cost
can be further lowered if the constraints of the feed are different. To obtain a better profit from
distillation it is prudent to lower the operation costs especially that of the condenser. Cryogenic
distillation could prove to be a useful method, if the feed was purer either in methane or carbon
dioxide and if the operation time was longer.
Appendix

Physical Properties

Feedstock specifications
Composition: 63% CO2, 34% CH4
Pressure: 45 psig
Feed Flow: 60 MMSCFD
Operating time: 6000 hr/yr
Gas constant R: 8.314 kJ/kg-mol K
Temperature: 298 K

Cost of Utilities
Electric $0.1/kWh
Heating $3.2/MMBtu
Cooling/Process Water $0.2/1000 gal
Steam $3.9/1000 lb

Cryogenic Distillation
Column: $405,000/plate-yr

Adsorption
1”Rashig rings: $1,800/ft3 with life expectancy of 30 years

Membrane
Membrane cost: $4/ft2
Permeance of CO2: 2.9 x 10-11 mol/(cm2 s mmHg)
Permeance of CH4: 3.2 x 10-13 mol/(cm2 s mmHg)
References

1. National Center for Biotechnology Information. PubChem Database. Methane,


CID=297, https://pubchem.ncbi.nlm.nih.gov/compound/297 (accessed on Apr. 26,
2019)
2. National Center for Biotechnology Information. PubChem Database. Carbon dioxide,
CID=280, https://pubchem.ncbi.nlm.nih.gov/compound/280 (accessed on Apr. 26,
2019)