Article

pubs.acs.org/IECR

Upgrading Biogas at Low Pressure by Vacuum Swing Adsorption

Aarti Arya, Swapnil Divekar, Ruchika Rawat, Pushpa Gupta, Madhukar O. Garg, Soumen Dasgupta,
and Anshu Nanoti*,
CSIR-Indian Institute of Petroleum, Dehradun 248005, India

Ranjeet Singh, Penny Xiao, and Paul A. Webley

Department of Chemical and Biomolecular Engineering, The University of Melbourne, Melbourne, Victoria 3010, Australia
S Supporting Information
*

ABSTRACT: Performance of four adsorbents (three zeolites and one molecular sieve carbon) for CO2CH4 separation from
simulated biogas feed containing 42% CO2 (balance methane) is compared in a simple four step dual bed vacuum swing
adsorption (VSA) cycle. The VSA cycle consisted of four sequential steps in each column namely adsorption, cocurrent
depressurization, evacuation and pressure equalization. Among the adsorbents tested, zeolite NaUSY appears to give the best
results for producing pipeline grade methane (>98%) at recoveries exceeding 85%. The methane productivity obtained by the
present process is in the range of 1116 mol/h/kg, which is considerably higher than the literature reported values with zeolite
and carbon based adsorbents. The high methane productivity of the present process is due to the absence of purge step during
regeneration with methane rich adsorption product as well as due to absence of any blow down step in the VSA cycle. Another
advantage of the present process is that operation for biogas up-gradation is at near atmosphere pressure, which is typically the
pressure available for biogas generated from an anaerobic digester.

1. INTRODUCTION
Biogas produced by anaerobic fermentation of biomass contains
about 4060% CH4 the balance being CO2 along with trace
amounts of H2S (ppm level). As such, the caloric value of
biogas is low (21.5 MJ/m3) due to the presence of a
considerable amount of inert CO2. Such raw biogas, however, is
commonly used as a low quality fuel for domestic cooking in
rural areas of many developing countries. If biogas is to be
considered as a renewable source of methane for power
generation and vehicular fuel, then it has to be upgraded to
methane with specications matching that of pipeline quality
natural gas (CH4 purity >98%, caloric value 35.8 MJ/m3).1
The up-gradation of biogas has also potential implications in
improving the rural energy economy of a developing country
such as India where the penetrations of conventional energy
sources are still abysmally low.2,3 Community level biogas
digesters along with suitable up-gradation and bottling facilities
could be the key to improving the economic conditions of these
communities.
Biogas up-gradation would mainly involve integration of
suitable low cost CO2CH4 separation facilities with the
anaerobic digester. Many separation techniques such as water
scrubbing, absorption, membranes and adsorption could be
considered.4 High pressure water scrubbing is eective in
removing CO2 and H2S simultaneously. Though a relatively
mature technology, its implementation is dicult in areas
where there is water scarcity. Organic solvents such as
polyglycol ether and alkanolamines based absorptive separation
have also been used. Although the yield of high purity methane
is good, the process investment cost is higher in comparison to
membranes and pressure swing adsorption at a given scale.5,6
XXXX American Chemical Society

Energy requirement for solvent regeneration is high. Membrane

based separation processes can also be used for CO2/CH4
separation from a biogas stream; however, their long-term
performance has to be established before any commercial
application.7 Pressure swing adsorption (PSA) based processes
are also emerging as an alternative technology for ecient
CO2/CH4 separation.8 However, existing PSA processes for
this particular separation requires considerable compression of
biogas feed coupled with complex sequences of adsorption and
regeneration steps in order to have an acceptable separation
performance. In this context, the vacuum swing adsorption
(VSA) process,9which is a subset of PSA, has high potential
because here the adsorption step is carried out at near
atmospheric pressure, at which the biogas is generally available,
thus negating the high compression cost of PSA. The
regeneration of CO2 loaded adsorbent is carried out by
applying a vacuum in such processes. It has been reported that,
for a blast furnace feed containing around 22% CO2, the typical
energy requirement of vacuum regeneration is 186 kWh/t CO2.
The power consumption, however, decreased as the CO2
concentration increased in the feed. Thus, when the CO2
concentration in feed was 33%, the power consumption fell
to 120 kWh/t CO 2. 10 With biogas where the CO 2
concentration is generally in the range of 4060% the energy
requirement is expected to fall further. The eciency of a VSA
process will depend on CO2 capacity and selectivity of the
Received: August 14, 2014
Revised: December 9, 2014
Accepted: December 10, 2014

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Figure 1. Schematic diagram of the two column VSA unit.

relevant to natural gas purication at high pressure up to 60

bar.18
It may be mentioned here that typically biogas is available at
near atmospheric pressure from a biogas digester, and for an
economical process, it will be desirable to operate VSA at low
adsorption pressure. A single and four bed VSA process at near
atmospheric pressure has also been reported.19,20 Although the
methane purity reported is very high, the methane recovery
reported is only 30% to 50%. The regeneration pressure in
Delgados study was in the range 0.0130.1 bar.
In the present work, we demonstrate a simple VSA process
for more ecient CO2CH4 separation from a simulated
biogas feed at an adsorption pressure of 1.5 bar(a) with
regeneration at 0.1 bar(a). The biogas separation performance of
three zeolite based equilibrium selective adsorbents and one
kinetic selective carbon molecular sieve adsorbent has been
compared using this VSA process.

adsorbent in the moderate adsorption pressure range of 12

bar while simultaneously having good desorption characteristics
under a moderate evacuation level. A cost based comparison of
chemical absorption, membrane, pressure swing adsorption and
vacuum swing adsorption has also been made for CO2 recovery
in the context of postcombustion ue gases over a range of feed
composition and feed ow rates.11,12 In this case the simulation
modeling results indicate that CO2 can be captured with the
least cost using a MEA-based chemical absorption when the
feed CO2 composition is less than 1520%. For higher CO2
compositions, VSA is the preferred process.
Few reports are available in the open and patent literature on
CH4CO2 separation using zeolite adsorbents. Both kinetic
and equilibrium selective adsorbents have been reported. Most
of the literature is based on high pressure adsorption typically
in the range of 2.5 to 13 bar and regeneration under vacuum.
Thus, Sircar et al. have reported a four bed VSA process using
13X zeolite at moderate adsorption pressure of 5.76 bar and
regeneration pressure 0.125 bar with simulated gas mixture
representing biogas composition as feed.13 A single column
VSA has also been reported using 5A and 13X zeolite at 4 and 5
bar adsorption pressure, respectively.14,15 The corresponding
evacuation pressures were 0.34 and 0.1 bar, respectively. With
kinetic selective adsorbents such as CMS 3K, a single column
four step VSA process has also been reported which gave
methane purity in the range of 9799 mol % and recovery in
the range of 6080% at adsorption pressure (37 bar) and
regeneration pressure (0.1 bar).16 Beside using a single
adsorbent, attempts were also made to simulate layered bed
congurations with 13X zeolite and CMS 3K adsorbent layers
for a two bed and ve steps VSA process. The simulation study
was carried out for the process at an adsorption pressure of 8
bar and regeneration pressure of 0.1 bar.17
A computational screening approach was also recently
proposed to select cost-eective zeolite based adsorbents and
adsorption process conditions for CH4/CO2 separation

2. EXPERIMENTAL SECTION
2.1. Adsorbent Preparation. A commercial 13X zeolite
(Z10-04, M/s ZEOCHEM, spherical beads of 1.5 mm dia) was
modied by room temperature ion exchange with potassium.
The ion exchange procedure is reported elsewhere.21 The
adsorbent is designated as KZ10-04. Total potassium content
was 12.5% as per ICP-AES analysis. The extent of potassium
exchange was estimated to be 73.53%.
A commercial NaUSY powder was obtained from M/s
Zeolyst. This powder adsorbent was formulated into extrudate
form using 30% -alumina as a binder. Extrudates were
prepared using a hand extruder. A detailed extrudate formation
procedure is reported elsewhere.22 Adsorbents were characterized by surface area and X-ray diraction measurements.
A carbon molecular sieve adsorbent CMS 3K obtained from
M/s Japan EnviroChemicals Ltd. was also tested.
2.2. CO2 and CH4 Equilibrium Isotherm Measurements. Single component equilibrium adsorption isotherms
B

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for CO2 and CH4 adsorption on zeolite based adsorbents were
measured in an automated gravimetric micro balance (IGA-001
from HIDEN Isochema, U.K.) at three dierent temperatures,
i.e., 0, 30 and 60 C. Around 100 mg of the adsorbent sample
was loaded into the adsorption cell of the microbalance. The
sample was then activated in situ at 375 C under evacuation
for 6 h. Next the adsorbent was cooled down to the
measurement temperature under evacuation and CO2 or CH4
was dosed into the adsorption chamber at dierent pressure
values. Weight gain due to adsorption was recorded at each
equilibrium pressure.
2.3. Column Breakthrough Studies and VSA Setup.
Breakthrough and VSA experiments were performed in a
custom designed PC-PLC based automated dual bed VSA unit.
A schematic of the unit is shown in Figure 1. The unit is
equipped with solenoid valves, a pressure controller, a recycle
compressor, a vacuum pump and a heavy product storage
vessel. The metallic (SS 316 steel) adsorber columns have a
diameter of 22 mm i.d. and 3 mm wall thickness with an
eective bed length of 1000 mm. Each column is surrounded by
a three zone tubular furnace with temperature ramp
programming facility up to 500 C. The feed section is
composed of mass ow controllers for delivering CO2 and CH4
feed mixtures of desired composition. A separate mass ow
controller was used for countercurrent light product purge of
the column.
The columns were loaded with adsorbent in the middle
portion. The top and bottom dead volumes of the column were
lled by inert ceramic beads. After loading of each column with
75 g of adsorbent, in situ adsorbent activation was carried out
by purging the column with dry nitrogen at 350 C for 6 h.
To decide on the VSA cycle timings, breakthrough
experiments were carried out in the same unit with a feed gas
mixture representing a biogas.
For VSA experiments, the valve opening and closing
sequences were programmed and inputs for feed ow rate,
purge ow rate, column pressure, etc. were made through a
SCADA based software system. The concentration of CO2 and
CH4 in the process streams coming out of column during
dierent steps such as adsorption, evacuation, adsorption
product purge etc. were measured with the help of a owthrough IR based analyzer. Gas ows of dierent streams were
measured by a gas meter. From these measurements, the
recovery and purity of CH4 in the adsorption stream and CO2
in the regeneration (evacuation) stream were calculated.
2.4. VSA Process Description. A simple dual bed VSA
cycle comprising four sequential steps viz. (1) adsorption, (2)
cocurrent depressurization, (3) evacuation and (4) pressure
equalization was tested. The coupling of these four steps in two
columns during the VSA cycle operation is shown in Table 1. A
binary gas mixture consisting of 42% CO2 and balance CH4 was
used as a representative dry biogas feed during all VSA
experiments. Each VSA experiment was studied for over 40
cycles and ow and CO2 and CH4 concentration in dierent
product streams were measured at dierent cycles in order to
determine the establishment of column steady state. The
adsorption temperature during all the VSA experiments was
xed at 30 C. Adsorption/evacuation step times were
systematically varied in order to understand its eect on CH4
purity and recovery in the adsorption product stream and CO2
purity and recovery in the evacuation product stream.

Table 1. VSA Cycle Description

step
no.

column 1

column 2

adsorption

evacuation

pressure
equalization
evacuation
pressure
equalization

pressure
equalization
adsorption
pressure
equalization

3
4

step duration
xed at 50 and 60% with respect to
the column breakthrough time
(BT) of CO2 for a xed operating
conditions
10 s

5060% of CO2 BT
10 s

For instance, if for a xed set of operating conditions such as feed

composition, feed ow rate, temperature and pressure, the adsorber
column breakthrough time (BT) of CO2 for a particular adsorbent is
600 s., then the adsorption/evacuation step time in the VSA cycle
corresponding to 50% of CO2 BT will be 300 s.
a

2.5. Breakthrough Model and Simulation. A mathematical model was used to simulate the experimental
breakthrough data.
The model has the following assumptions:
1. axial dispersed plug ow model is used to describe ow
behavior;
2. the total pressure remains constant;
3. adsorption equilibrium is presented by the Langmuir
model;
4. mass transfer rate is governed by the linear driving force
(LDF) model;
5. gas and solid phase are at thermal equilibrium at a given
location along the length of the column;
6. heat loss from the column is negligible.
The partial dierential equations describing the mass and
heat balance in the column are described below along with
initial and boundary conditions:
uid phase mass balance for component i
Ci
2C
C
1 qi
v

= DL 2i v i Ci

t
t
x
x
x

(1)

solid phase mass balance for component i

qi
t

= ki(qi* qi)

(2)

adsorption isotherm
qi =

qsibiCi
n

1 + i = 1 biCi

(3)

The above equation for binary gas feed adsorption isotherm

assumes that the monolayer amount for component i in the
mixed adsorbed phase remains the same as that in pure
component adsorption.
temperature dependence of isotherm parameter b
H 1
bi
1
i
= exp

bi0
T0
R T
C

(4)
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Table 2. Parameters Used for Experimental Breakthrough Simulations
mass transfer coecient, ki
(s1)
adsorbent

packed height
(m)

weight of adsorbent per

column (kg)

diameter of the
column (m)

ow rate
(NLPM)

Z10-04
KZ10-04
NaUSY
CMS 3K

0.160
0.180
0.250
0.245

0.075
0.075
0.063
0.075

0.022
0.022
0.022
0.022

2.0
2.0
2.0
1.5

(5)

qi
t

102
102
103
102

3.78
3.36
2.42
1.85

104
104
104
104

void
fraction

overall
selectivity

0.56
0.55
0.57
0.47

352.0
342.9
451.0
311.9

3. RESULTS AND DISCUSSION

The surface area of NaUSY, Z10-04 and KZ10-04 were
measured by BrunauerEmmettTeller (BET) method and
found to be 559.3, 576.0 and 301.7 m2/g, respectively. Powder
X-ray diraction (PXRD) patterns of these materials are shown
in Figure 2. The PXRD pattern showed a loss in crystallinity

velocity variation
v
1 1
= n
i Ci
x

2.26
1.67
8.46
3.05

CH4

in these simulations and the best t values of these are also

given in Table 2.

heat balance

T
1
C
+
Cps
g pg
s t
T
2T
v
1 qi
= KL 2 g Cpg v
+ T + (Hi)
x
t
x
x

CO2

(6)

boundary conditions
C
= v(Cx = 0 Cx = 0 +)
DL
x x = 0

(7)

=0
x x = L

(8)

T
KL
= vg Cpg(Tx = 0 Tx = 0 +)
x x = 0

(9)

=0
x x = L

(10)

vx = 0 = v0

=0
x z = L

(11)
Figure 2. XRD pattern of zeolite based adsorbents NaUSY, Z10-04
and KZ10-04.

initial conditions
at t = 0

Ci(x , t = 0) = 0

(12)

T(x) = T _init

(13)

qCO2(x , t = 0) = 0

(14)

qi(x , t = 0) = 0

(15)

after potassium exchange of commercial 13X adsorbent Z10-04

(sample KZ10-04). However, the crystalline structure upon K
ion exchange was retained as the characteristic peaks are
present. The loss in peak intensity could be attributed to the
partial blocking of the pores due to the incorporation of
potassium ion. A similar phenomenon was observed by Dangi
et al. in the case of L and KL zeolite.23
CO2 and CH4 equilibrium isotherms at 30 C with the three
zeolite adsorbents Z10-04, KZ10-04 and NaUSY are shown in
Figure 3. Isotherms were also measured at 0 and 60 C (see
Figures S1, S2 and S3 of Supporting Information). These
isotherms are correlated using the Langmuir model. The
equilibrium isotherm data for CMS 3K was not determined
experimentally; however, the equilibrium parameters for CMS
3K were calculated from equilibrium data reported by Cavenati
et al.16
The graphs shown in Figure 3 indicate a reasonably close
correlation of experimental data by the Langmuir model for the
zeolite adsorbents. Single component equilibrium loading ratios
at 0.63 and 0.87 bar for CO2 and CH4, respectively, were
calculated from CO2 and CH4 isotherm data considering the

The above equations in the mathematical model were

nondimensionalized and solved numerically by nite element
orthogonal collocation method (OCFEM) using the gPROMS
software. The axial dimension was discretized into 50 segments
with three internal collocation points in each element.
The column dimensions and various input parameters
required in the model simulations along with the overall
selectivity of dierent adsorbents tested are given in Table 2.
The overall selectivity is dened as the product of equilibrium
loading ratio (ratio of equilibrium capacities of qCO2:qCH4 at the
respective partial pressure) and kinetic selectivity (ratio of mass
transfer coecients kCO2:kCH4).The LDF mass transfer
coecient, ki and void fraction were used as a tting parameter
D

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Figure 3. Experimental and simulated CH4 and CO2 isotherms at 30 C with Z10-04, KZ10-04 and NaUSY (experimental data tted with the
Langmuir model).

Table 3. Compilation of Heat of Adsorption and Pure Component Equilibrium loading data
CO2
adsorbent
KZ10-04
Z10-04
NaUSY
b
CMS
3K
a

CH4

qs
[mmol/g]

bo
[bar1]

H
[J/mol]

loading at 0.63 bar

[mmol/g]

qs
[mmol/g]

bo
[bar1]

H
[J/mol]

loading at 0.87 bar

[mmol/g]

ratio of pure component

loadinga

2.58
5.34
5.30
2.68

18.54
35.08
12.24
11.69

22042
32591
31105
39974

2.00
4.33
3.38
1.55

2.40
6.00
1.50
2.898

0.33
0.25
0.47
1.99

13374
14509
15500
33674

0.34
0.62
0.26
0.82

5.88
6.98
13.00
1.89

At 0.63 and 0.87 bar for CO2 and CH4, respectively. bPredicted from literature (Cavenati et al.16).

Figure 4. Experimental and Simulated CO2 Breakthrough curve with (a) Z10-04, (b) KZ10-04, (c) NaUSY and (d) CMS 3K.

adsorbents. For CMS the ratio obtained is lowest among the

four adsorbents studied (Table 3). The equilibrium data for
CMS 3K for 30 C were predicted with parameters derived
from isotherm data15 reported for 25, 35 and 50 C.

biogas composition of 42% CO2 balance methane used in the

VSA experiments at 1.5 bar(a). Among the zeolite based
adsorbents studied, NaUSY shows almost two times higher
CO2/CH4 loading ratio compared to Z10-04 and KZ-10-04
E

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The Heat of adsorption was calculated from the single
component isotherm data at three dierent temperatures using
the ClausiusClapeyron equation and is reported in Table 3
along with the equilibrium loading ratio data.
Column breakthrough experiments were performed with a
simulated biogas feed comprising of 42 mol % CO2 and balance
CH4 at 30 C with all the adsorbents under identical operating
conditions of 1.5 bar (a) pressure and 2.0 NLPM feed ow rate.
The unit of feed ow rate NLPM stands as the abbreviated
form of Normal Liter Per Minute. The breakthrough curves
are reported in Figure 4.
A comparison of experimental and simulated breakthrough
curves for all the adsorbents is also reported in Figure 4. The
experimental and predicted breakthrough curves show a good
match. This indicates that the LDF approximation, implying the
major resistance to mass transfer to be in the adsorbent phase,
captures the essence of the mass transfer process in this system.
The slight discrepancy in the predicted breakthrough curves
when compared with experimental curves noticed at longer
times where equilibrium pertains to conditions of high CO2
partial pressure may be due to the fact that the Langmuir
equilibrium isotherm model used in the simulations also shows
slight deviation from experimental isotherm data at high CO2
pressures.
VSA experiments using the four step cycle given in Table 1
were carried out at dierent adsorption times with three classes
of adsorbents namely X and Y zeolites and kinetic adsorbent
(carbon molecular sieve). The adsorption time in the VSA cycle
was xed at 40%, 50% and 60% with respect to CO2 column
breakthrough time. The VSA performance was evaluated based
on purity, recovery of both CH4 and CO2 in the adsorption and
evacuation product streams at dierent adsorption timings. The
adsorption step timings in a VSA cycle were xed as a certain
fraction (0.4, 0.5 and 0.6) of the CO2 breakthrough time of
respective adsorbents. This approach was used for comparing
performance of dierent adsorbents on a uniform basis as the
breakthrough time for the dierent adsorbents is governed by
the equilibrium and dynamic capacity of the adsorbents. The
adsorption pressure in all the reported experiments was xed at
1.5 bar(a) and regeneration pressure was 0.1 bar(a). The VSA
performance of dierent adsorbents tested at a feed ow rate of
1.72 NLPM are compared in Figures 57. The results indicate
(Figure 5) that at adsorption time set at 40% of CO2
breakthrough, the CH4 purity in the adsorption product was
highest (99.5 mol %) in the case of NaUSY followed by CMS
(97 mol %). The corresponding purities obtained with Z10-04

Figure 6. Comparison of CH4 recoveries obtained in adsorption

product at dierent adsorption times and with dierent adsorbents.

Figure 7. Comparison of CO2 purities obtained in evacuation product

at dierent evacuation times and with dierent adsorbents.

and KZ10-04 were around 95 and 97 mol %, respectively. The

highest CH4 purity obtained with the NaUSY adsorbent could
be attributed to its highest CO2/CH4 equilibrium loading ratio
among the zeolite based adsorbents, as reported in Table 3. A
slight decrease in CH4 purity was observed when adsorption
time was increased to 50% of CO2 BT time. Thus, the CH4
purity level dropped down to 98.5% with NaUSY adsorbent
while for Z10-04 and KZ10-04 it was in the range of 90%. With
further increase in adsorption time corresponding to 60% of the
CO2 breakthrough time the methane purity obtained with
NaUSY adsorbent was further decreased to 95% level while for
Z10-04 and KZ10-04 the purity level dropped down
signicantly to 85% level. The results are in the expected
line as with increasing adsorption step time, the CO2 mass
transfer front progresses further into the column, which may
lead to decreased methane purity due to partial leakage of CO2
from the column during VSA cycle operation. With CMS
adsorbent the pore size exclusion mechanism is believed to be
responsible for selective separation of CO2 from methane. In
this, the CO2 molecules having smaller kinetic diameter (3.3 )
compared to CH4 molecules (3.8 ) are able to preferentially
enter the small pores (3.8 ) of CMS) and get selectively
adsorbed. This leads to high degree of accumulation of
methane molecules in the column outlet during adsorption
product withdrawal and there is negligible drop in methane
purity on increase in adsorption cycle time and >96% methane
purity is achieved with this adsorbent. Breakthrough curve
simulation results also indicate that mass transfer coecient for
CO2 is highest while mass transfer coecient for CH4 is lowest
in CMS so that the kinetic selectivity will be the highest in this
adsorbent.

Figure 5. Comparison of CH4 purities obtained in adsorption product

at dierent adsorption time and with dierent adsorbents (adsorption
pressure, 1.5 bar(a); regeneration pressure, 0.1 bar(a)).
F

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An inverse relationship between methane recovery and purity
can be seen with all the adsorbents with increasing adsorption
time (Figure 6). Thus, for a particular adsorbent, the methane
recovery values tend to improve while the purity values drop
down with increasing adsorption step time. This trend can be
explained due to displacement of more methane from the void
space of the adsorbent bed as the CO2 front progresses toward
the exit side of the column with increasing adsorption time.
Thus, for example at adsorption time 40% of CO 2
breakthrough the methane recovery value for Z10-04 is 88%
while at 50 and 60% of CO2 BT, the corresponding values are
93 and 95%, respectively. Also, the CO2 purity improved with
increased penetration of CO2 mass transfer front, corresponding to increased adsorption time. The CO2 purity level in the
range 8590 mol % could be achieved with Z10-04 and NaUSY
and CMS 3K adsorbents when the VSA was operated at
adsorption time equivalent to 60% of CO2 BT. The higher CO2
purity in the evacuation product is desirable as it signies lower
methane loss from the regeneration stream.
The eect of feed ow rate variation on VSA performance
was also studied with NaUSY adsorbent. The results are shown
in Figure 8, which shows a slight drop in CH4 purity when the

Figure 9. Cycle-to-cycle variation in methane purity and recovery

values obtained with NaUSY adsorbent at feed ow rate 2.48 NLPM.

P 1/

B
high

1
power =

R gTfeed
Plow
100
1
productivity =

(16)

amount of CH4 recovered

3600
cycle time(s) adsorbent wt
(17)

Table 4. Experimental Results for Dierent Adsorbents

Studied
adsorbent
Z10-04
KZ10-04
NaUSY
CMS 3K

Figure 8. Eect of feed ow rates on VSA performance using NaUSY

adsorbent.

cycle
time
(s)

methane
purity
(mol %)

methane
recovery
(mol %)

power
(kW/mol CH4)

productivity
(mol/h/kg)

362
430
182
214
336
400
290
342

90.21
83.51
91.19
84.80
99.28
96.96
98.17
96.91

92.73
94.83
83.72
87.70
85.94
87.42
82.00
86.94

0.089
0.066
0.248
0.170
0.123
0.097
0.150
0.117

14.05
14.50
11.90
12.69
15.58
15.54
10.64
11.28

We have used a (ratio of specic heats of biogas) value of 1.3,

as calculated by Aspen. The methane productivity increases
with the increase in adsorption step time with all the four
adsorbents reported in Table 4. This behavior can be explained
on the basis of a larger amount of methane displacement from
the column outlet as the CO2 mass transfer front progresses
with increasing adsorption time. It is also observed that the
methane productivities with zeolite based adsorbents are higher
than that of the carbon based adsorbent. The productivity and
power consumption values obtained in the present study were
also compared with literature reports with single and two
column VSA only. The productivity values with zeolite based
adsorbents in the present study are in the range of 1115 mol
methane/h/kg adsorbent, which is higher than the reported
value26 with 13X zeolite, as summarized in Table 5. The higher
productivity values obtained in the present study may be
attributed to employing a simple VSA cycle without blow down
and light product purge step, as such steps may lead to methane
loss. Thus, for example, the productivity value reported by
Cavenati et al.15 for Zeolite 13X at 78.6% methane purity level
is 9.66, whereas for the Zeolite 13X Z10-04, the methane
productivity obtained in our work is 14.05 and 14.50 for cycle
times of 362 and 430 s, respectively, when the level of methane

feed ow rate was increased from 1.72 to 2.48 NLPM. This

behavior could be explained due to the fact that an increase in
CO2 input in the adsorber at higher ow rate leads to CO2
breakage to a greater extent from the adsorber thus aecting
methane purity in the adsorption product. An opposite trend is
observed in the case of CO2 rich evacuation product which
shows a slight improvement in CO2 purity with increasing feed
ow rate. With increasing ow rate more and more methane
gets displaced from the void space of the adsorber due to better
progression of the CO2 front during the adsorption step. This
leads to both improvements in CH4 recovery in the adsorption
product as well as CO2 purity in the product obtained during
the subsequent countercurrent evacuation step. A typical cycle
to cycle variation in CH4 purity and recovery has been shown in
Figure 9 with respect to NaUSY adsorbent at 2.48 NLPM. This
shows almost stable VSA separation performance over dierent
cycles.
The performance of these adsorbents were further evaluated
based on methane productivity and energy requirements of the
VPSA unit. The power consumption24 and productivity25 have
been calculated using the following equations. Values are
reported in Table 4.
G

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Table 5. Experimental PSA/VSA Results from Literature Reports
reference

adsorbent

16

CMS 3K

15

Zeolite
13X

feed
(mol
%)
CO2:
45
CH4:
55

CO2:
20

feed
ow
SLPM
1.5

3.5

pressure (high)/
pressure (low)
(bar)
3.2/0.1

5.0/0.1

step description

step
duration
(s)

purity
(mol
%)

recovery
(mol %)

power
kW/mol
CH4

productivity
calculated using eq
17 (mol/kg/h)

reported in
Spoorthi et al.26
(mol/kg/h)

70

97.1

79.4

0.578

4.27

2.52a

78.6

80.33

0.160

9.66

11.04b

93.33

93.4

0.407

3.04

3.02

95.8

71.2

0.276

2.89

2.87

pressurization with
feed
adsorption

100

countercurrent
blow down
countercurrent
purge with
product
countercurrent
pressurization
with methane

100

adsorption (feed)
countercurrent
blow down
purge
pressurization with
Feed
cocurrent
depressurization
counter current
blow down
countercurrent
evacuation
pressurization with
feed gas
high-pressure
adsorption
depressurizing
pressure
equalization
countercurrent
depressurization
purge with light
product
pressurizing
pressure
equalization

300
230

70

65

CH4:
60
N2: 20

14

27

CMS 3K

CMS 3A

CO2:
50
CH4:
50

CO2:
50
CH4:
50

5.4

3.79/0.34

4.05/1.01

50
30
30
30
30
20
200
20

20
200
20

Spoorthi et al.26 have calculated the productivity based on adsorption time only (100 s) whereas the productivity values we report here take into
account total methane input during both pressurization with feed and the adsorption step (170 s). bThe productivity value reported by Spoorthi et
al.26 is based on the feed ow rate of 4.0 SLPM whereas the feed ow rate in the experiments reported by Cavenati et al.15 is 3.5 SLPM, which has
been used to recalculate the productivity value by us for this paper; SLPM = standard liter per minute.

product. The lower productivity values in these studies are due

to substantial amount of methane loss during purge.
The VSA cycle studied can also produce a highly enriched
CO2 stream with purity levels in the range of 8590 mol %.
Kapoor and Yang14 have also reported a high purity and
recovery of methane with CMS 3K, but the adsorption pressure
is higher (3.8 bar) than the present study (1.5 bar). An overall
selectivity calculated as product of kinetic selectivity (ratio of
mass transfer coecient of CO2 and CH4) and equilibrium
selectivity is also included in Table 2 and the values indicate
that NaUSY is the preferred adsorbent among those tested. Our
experimental VSA results also indicate this and pipeline quality
methane (>98%) at decent recoveries are only possible using
CMS 3K or NaUSY. From point of view of productivity and
power requirements, among these two adsorbents, NaUSY
appears to be the better one for biogas up-gradation.

purity achieved was 90 and 83.5%, respectively. It may be noted

that the cycle studied by Cavenati et al. employs countercurrent
pressurization and purge step with a methane rich adsorption
product. As the methane product fed to the column during the
purge step is not recovered, the methane recovery value is
lower than our results. Similarly, with carbon molecular sieve
adsorbent, the productivity value (1011 mol methane/h/kg
adsorbent) obtained in the present study is also higher than the
values (34 mol methane/h/kg adsorbent) reported in the
literature.14,16,27 Thus, for example, in the case of adsorbent
CMS-3K, the productivity values obtained by Kapoor et al.,14
Cavenati et al.16 and Kim et.al.27 are 3.04, 4.27 and 2.89 mol/
kg/h, respectively. The CH4 productivity values in case of CMS
3K adsorbent obtained in the present study are 10.64 and 11.28
for cycle times of 290 and 342 s, respectively. The PSA cycle
studied by Kapoor et al. has a countercurrent blow down step,
which could lead to some methane loss while the PSA cycle
studied by Cavenati et al.16 and Kim et al.27 consists of a
countercurrent purge step with a methane rich adsorption

4. CONCLUSION
A simple four step dual bed VSA cycle was tested with four
dierent adsorbents for biogas up-gradation at low adsorption
H

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= Adsorbent density
= Mechanical eciency
= Ratio of specic heats

pressure using a simulated biogas feed. Among the adsorbents

tested, NaUSY appears to give the best results for producing
pipeline grade methane (>98%) at recoveries exceeding 85%. A
comparison of results with literature reports indicates that CH4
productivity of the present process is higher than literature
reported processes for CH4/CO2 separation with zeolite and
carbon molecular sieve adsorbents. This is mainly due to the
operation of a simple VSA cycle in the present study without
any blow down and column purge step with a methane rich
adsorption product. Another advantage of the present process
is that operation for biogas up-gradation is at near atmosphere
pressure.

ASSOCIATED CONTENT

AUTHOR INFORMATION

Subscript

g = Gas phase
i = Component
s = Solid phase
Superscript

* = Equilibrium

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S Supporting Information
*

CO2 and CH4 equilibrium isotherm data at 0, 30 and 60 C for

Z10-04 (Figure S1), KZ10-04 (Figure S2) and NaUSY (Figure
S3). This material is available free of charge via the Internet at
http://pubs.acs.org.
Corresponding Author

*Dr. Anshu Nanoti. E-mail: anshu@iip.res.in. Ph.: +91-1352525727 (O).

Author Contributions

These authors have contributed equally.

Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
We acknowledge Dr. A. N. Goswami, Ex. Chief Scientist, Indian
Institute of Petroleum, Dehradun, India for helpful discussion
and suggestion in simulation and modeling of breakthrough
curves. We are grateful for nancial support from DST, India
under the Indo-Australia Strategic Research Fund (AISRF) in
the form of a project grant (DST/INT/AUS/P-35/2010).

NOTATION
B = Molar ow rate of the stream
b = Langmuir adsorption constant
b0 = Langmuir adsorption constant at T0
C = Gas phase concentration
Cp = Specic heat at constant pressure
DL = Axial dispersion coecient
H = Isosteric heat of adsorption
k = Eective mass transfer coecient
KL = Thermal diusivuty
L = Length of adsorption bed
n = Number of components
Phigh = Discharge pressure
Plow = Suction pressure
q = Adsorbed phase concentration
qsi = Langmuir monolayer adsorption constant
R = Universal gas constant
T = Temperature of bed
T_init = Initial temperature of adsorber (303 K)
T0 = Reference temperature (273 K)
v = Linear velocity of uid
v0 = Linear velocity of uid at x = 0
x = Axial distance coordinate

Greek Letters

= Bed void
I

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DOI: 10.1021/ie503243f
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