Professional Documents
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Landfill Gas
Pennsylvania State University - Department of Chemical Engineering
CH E 410 - Project
Bader Alotaibi
Executive Summary
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 –
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
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
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.
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
𝑦1 𝐿′ 𝑚𝑖𝑛
𝑦1 𝑉1 = 𝑦2 𝑉2 + ′
𝐻 1 − 𝑦1′
𝐻
𝐹𝑒𝑒𝑑 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒
𝐻′ =
𝐻
H’ 402
1 1 𝑀′
= +
𝐾′𝑦 𝑘′𝑦 𝑘′𝑥
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
𝑃𝑜𝑤𝑒𝑟 = 𝑉𝐿 ∙ (𝑃2 − 𝑃1 )
𝐸𝑛𝑒𝑟𝑔𝑦 𝑃2
= 𝑅𝑇𝑙𝑛( )
𝑚𝑜𝑙𝑒 𝑃1
Economy Analysis –
Revenues
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.
Another potential technique that we could use to separate carbon dioxide (CO 2) and
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
pA xA yA
0 0 0
10 0.296 0.009869
82 0.444 0.080928
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
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
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
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:
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
pipeline quantity gas and liquefied natural gas, i is 1. Otherwise it’s 0); R is ideal gas
follows:
where V2 is the product flow rate; $3 is the selling price for product.
The example calculation for desired CH4 fraction of 95% and unit conversion are listed in
Net Profit for one year ($) 14632255 16542577 10112278 6546224
Net Profit for thirty years ($) 438967642 495295566 319941903 2.62E+08
Comparing the net profit for different desired CH4 concentration, it can be concluded that
the medium energy gas is the optimal option that would make the most profit in short term
and long term. The corresponding optimized inert liquid flow rate is 56 moles per second.
Although the cross-sectional area is negatively related to the cost, the effect is negligible.
However, it can be used to control the tower height in the cases where tower height
exceeds the safety maximum. In this scenario, the cross-sectional area of 0.456 m2 is
appropriate.
Gas Membrane Separation
Theoretical Background
The progress of using membranes in gas separation has been growing very fast. It
started from early diffusion experiments and basic concepts of permeation, to commercially
accepted products. Since the membrane used is the most crucial part of this separation
method, it has attracted maximum attention for improvements research and development. Gas
separation in membranes is driven by a pressure gradient on either side of the membrane. The
inlet feed is entered at the high-pressure side and permeates through the membrane into the
low-pressure side. Membranes have different permeabilities for different components and the
rate of transfer of each component through the membrane varies between a completely mixed
model and plug flow.
Equations
1. Overall mass balance.
Feed flow rate (Lf )= Permeate flow rate (Vp )+ Retentate flow rate (L0)
2. Mass balance on Co2.
Lf Xf=Vp yp + L0 X0
3. Mole fraction.
y (CO2) + y (CH4) = 1
−𝑏+𝑠𝑞𝑟𝑡(𝑏2 −4∗𝑎𝑐)
4. yp = 2𝑎
𝑥𝑓 [1+(𝛼 ∗−1) 𝑟 (1−𝑥𝑓 )]
5. 𝑥𝑜𝑀 = 𝛼 ∗ (1−𝑥𝑓 )+𝑥𝑓
𝜃𝐿𝑓 𝑦𝑝
6. 𝐴𝑚 = 𝑃′𝐶𝑂
( 2 )(𝑝 𝑥 −𝑝 𝑦 )
ℎ ℎ 𝑜 𝑙 𝑝
7. Total Profit.
Profit = CH4 value (in retentate and permeate) + CO2 value (in retentate and
permeate) – Membrane cost (4$/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
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
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).
-$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)
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.
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