Fuel Processing Technology 143 (2016) 185194

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Fuel Processing Technology

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Research article

Carbon dioxide removal for methane upgrade by a VSA process using an

improved 13X zeolite
Marta C. Campo a,1, Ana M. Ribeiro a,, Alexandre F.P. Ferreira a, Joo C. Santos a,1, Cecile Lutz b,
Jos M. Loureiro a, Alrio E. Rodrigues a
a
Laboratory of Separation and Reaction Engineering, Associate Laboratory LSRE/LCM, Department of Chemical Engineering, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias,
4200-465 Porto, Portugal
b
Service Adsorption, Groupement de Recherches de Lacq, ARKEMA FRANCE, BP 34, F-64170 Lacq, France

a r t i c l e i n f o a b s t r a c t

Article history: The main polluting compound in natural gas is CO2. Therefore, the removal of CO2 from that fuel is a major pro-
Received 15 June 2015 cess in the industry for upgrading its energy content. The separation by Pressure Swing Adsorption can be ef-
Received in revised form 26 November 2015 cient energy wise and many microporous zeolites have been mentioned in the literature as promising
Accepted 30 November 2015
adsorbents to carry out this separation. In this work, adsorption equilibrium isotherms of methane, nitrogen
Available online 10 December 2015
and carbon dioxide on an improved 13X zeolite were measured at three temperatures (308, 323 and 348 K)
Keywords:
up to 5 bar. The adsorption capacity of carbon dioxide at 323 K and 5 bar was approximately 50% higher than
13X zeolite values reported in literature. The experimental adsorption equilibrium isotherms of nitrogen and methane
CO2 separation were well described by the Langmuir equation, while carbon dioxide isotherms were tted with Toth equation.
Natural gas upgrade Single and ternary breakthrough curves were measured and simulated with a mathematical model for xed bed
Adsorption adsorbers. A pilot scale 4-step Vacuum Swing Adsorption cycle was suggested and validated experimentally to
VSA remove carbon dioxide down to 3.7% in the methane stream. An industrial scale process was designed in order
Simulation to produce an upgraded methane stream with less than 2% carbon dioxide. A methane recovery of 96% and a
power consumption of 4.27 Wh/molCH4 were obtained.
2015 Elsevier B.V. All rights reserved.

1. Introduction Within conventional (natural gas, biogas) and unconventional

The energy and chemical sectors are undergoing remarkable chang-
es. This is mainly due to the difference between the use and availability
of oil, affecting chemical and petrochemical industry. Indeed, more
and more attention has been given to natural gas, biogas, shale gas,
and tight gas; i.e. methane, not only as a fuel, but as a feedstock for
other chemicals. Methane is a cleaner form of energy, producing less
carbon dioxide than coal and oil (respectively 45% and 30%), when
burned [1], and is also economically attractive. Indeed, the recent indus-
trial recovery in the USA is due to the lower energy prices when com-
pared to Western Europe and Japan, due to their large shale and tight
gas reservoirs. Upgraded methane is utilized as a source of energy for
commercial as well as domestic purposes: heating of buildings, fuel
for cooking, fuel in vehicles, feedstock and/or energy source in power
plants and industries [2]. Its market has risen in the last 10 years but
variations in its consumption have been observed due to oil price
uctuations.
Corresponding author.
E-mail address: apeixoto@fe.up.pt (A.M. Ribeiro).
1
Present Address: Jacobs Engineering Group Inc., Haven 190, Noorderlaan 127,
Antwerp 2030, Belgium.
(shale gas, tight gas, coalbed methane) methane sources, natural gas is
still the most important. Natural gas is composed of essentially methane
(normally, 8095%), C2+ hydrocarbons in a variable composition, and
also minor amounts of nitrogen and carbon dioxide. However, depend-
ing on its source, the composition of natural gas may differ [3], some
being richer in contaminants like CO2 [2].
Natural gas is transported from suppliers to consumers through
pipelines. Therefore, it should meet the pipeline-quality methane
specications. These specications accept an upper limit for nitrogen
and carbon dioxide of 4 and 2%, respectively [3,4]. It is important to
keep carbon dioxide values low to prevent corrosion in equipments
and/or pipelines.
In order to upgrade natural gas by removing carbon dioxide, dif-
ferent technologies are available [5], some of them placed locally
at the natural gas elds. Among them are a) chemical absorption,
b) physical absorption, c) cryogenic distillation, d) membrane processes
and e) adsorption processes [58]. Chemical absorption normally
uses monoethanolamine or other amines as absorbents to remove CO2
from the gas stream. However, the amine regeneration step is energy
intensive and there are problems of corrosion. In physical absorption,
the interaction between CO2 and the absorbent (glycols or other organic
solvents) is weak relative to chemical solvents, reducing the energy

http://dx.doi.org/10.1016/j.fuproc.2015.11.024
0378-3820/ 2015 Elsevier B.V. All rights reserved.
186 M.C. Campo et al. / Fuel Processing Technology 143 (2016) 185194

Table 1 been reported that zeolites behave more efciently than activated car-
Bed dimensions and adsorbent properties. bon concerning the removal of CO2 [15]. Zeolite 13X has indeed been
Bed length (m) 0.83 employed in a VSA/PSA system to separate CO2 for natural gas upgrade.
Bed diameter (m) 0.0215 Cavenati et al. [2,4,10,16] have done substantial work on this topic using
Bed porosity 0.5 a commercial 13X zeolite. These authors were successful in achieving
Adsorbent 13X
CO2 levels lower than 2%, as required, with methane recovery higher
Adsorbent shape Spheres
Particle radius (m) 3.5 104 than 80%, without recycle [10]. More recently, the use of metal organic
Particle density (kg/m3) 1300 frameworks to separate CO2 from natural gas has been reported [17
Particle porosity 0.39 20]. This new category of microporous materials is currently under de-
Crystal diameter (m) 2.8 106
velopment by the scientic community.
In this study, an improved 13X zeolite is evaluated for the removal
of CO2 for natural gas upgrade. Adsorption equilibrium data was obtain-
requirement for the regeneration step. Finally, cryogenic distillation ed experimentally by a gravimetric method at different temperatures
is an appealing technology when natural gas needs to be transported and pressures. The dynamics of adsorption was also assessed by break-
as liqueed natural gas (LNG). Despite the high energy consump- through experiments. A pilot-scale VSA cycle was simulated and vali-
tion used to reduce temperatures down to liquefaction of methane, in dated experimentally. Finally, an industrial scale VSA process was
this form, its volume is reduced about 600 times [9]; LNG represents designed for carbon dioxide removal from a methane stream. The con-
nearly one quarter of the natural gas transported all over the world. sidered VSA process should be positioned in the natural gas processing
For economic reasons these three processes are preferably applied train after natural gas drying and H2S removal.
to treat large volumes of natural gas. Going to smaller scales of gas
to be processed, alternatives with lower operating costs are pursued. 2. Experimental
Comparatively, adsorption-based processes, particularly pressure/
vacuum swing adsorption (PSA/VSA) [10,11], arise as a reliable and 2.1. Materials
cost-effective alternative with an additional advantage of possessing
higher degree of automation. An improved 13X zeolite, provided by CECA (Arkema group) as
PSA is a well-known and reliable technology already established spheres with an average diameter of 0.7 mm (see Supporting informa-
in the market of gas separations. Recently, a lot of effort has been tion Fig. S1), was employed in this study. The improvements in the
done in the study of pressure swing adsorption technology to remove material arise mainly from reducing the binder amount in the particles
contaminants like carbon dioxide, water and nitrogen from natural to around 11% and from optimizing the dehydration process during the
gas [1214]. This technology involves the use of an adsorbent capable manufacturing of the adsorbent. The mechanical properties of the ad-
of selectively adsorbing CO2 by equilibrium or kinetic differences. The sorbent are not affected by the new manufacturing procedure. The
adsorbents used for this purpose are microporous materials. It has gases used in this study were research grade pure components, supplied

Fig. 1. Adsorption equilibrium isotherms of a) nitrogen, b) methane and c) carbon dioxide on 13X zeolite at 308, 323 and 348 K. The dots correspond to experimental points and the lines
correspond to the Langmuir (N2, CH4) or Toth (CO2) tting, respectively.
 M.C. Campo et al. / Fuel Processing Technology 143 (2016) 185194 187

Table 2 employed in the simulation of the breakthrough curves and of the vac-
Toth parameters obtained for nitrogen, methane and carbon dioxide adsorption equilibri- uum swing adsorption processes for removal of carbon dioxide from a
um isotherms over 13X zeolite at 308, 323 and 348 K.
methane stream. The model equations (mass, energy and momentum
qm(mol kg1) b(kPa1) k H (kJ mol1) balances) can be found in Table S1, and the required initial and bound-
Nitrogena 3.37 1.34 106 1 17.1 ary conditions are given respectively in Tables S2 and S3. A detailed de-
Methanea 5.30 1.41 106 1 17.2 scription of the mathematical model is presented elsewhere [2325].
Carbon dioxide 7.06 4.79 107 0.48 35.4 Several transport parameters are required within the model. These
a
The Langmuir model was regressed against the experimental data; therefore the pa- were calculated by correlations, such as: the Wakao and Funazkri corre-
rameter k was automatically set to 1 and not considered as tting parameter. lations [2628] for the axial (mass and heat) dispersion coefcients and
the mass transfer and heat convective coefcients; the Wasch and
by Air Liquide without further treatment. The purity of sorbate gases Froment correlation [29] for the convective heat transfer coefcient
was N50 for nitrogen (N 99.999%), N35 for methane (N 99.95%), and between the gas and the column wall; the Bosanquet equation for the
N48 for carbon dioxide (N99.998%). macropore diffusivity; the ChapmanEnskog equation [30] for the
molecular diffusivities. The crystal diffusivity values were taken from
2.2. Adsorption equilibrium measurements the literature [10,31]. The gas density, viscosity, and molar specic
heat were calculated as described by Bird et al. [30]. The molar specic
A gravimetric method was employed in the adsorption equilibrium heats of the components in the adsorbed and bulk gas phases were
measurements of pure components, for which a magnetic suspension assumed to be the equal [32]. The model was implemented in gProms
balance from Rubotherm (metal version with 2 10 5 g precision) interface [33] and solved using the numerical method of orthogonal
was used. The isotherms were determined at 308, 323 and 348 K, up collocation in nite elements with second order polynomials and 100
to 500 kPa (absolute). Before starting the adsorption measurements, intervals.
the adsorbent sample was activated under vacuum at 423 K until no
mass loss was observed. The buoyancy effects were taken into consider- 4. Results and discussion
ation and corrected in accordance with the methodology presented
elsewhere [21]. 4.1. Adsorption equilibrium

2.3. Fixed bed experiments Single component adsorption equilibrium isotherms were deter-
mined experimentally at 308, 323, 348 K, up to 5 bar (absolute) for
A xed bed unit described elsewhere [22] was used for the xed bed N2, CH4 and CO2 over the 13X zeolite. The experimental data was tted
experiments. A scheme of this unit is shown in Fig. S2. The unit can be by the Langmuir equation for N2 and CH4 as this model described well
used for the determination of pure component breakthrough curves or the experimental data (see Fig. 1). For the experimental data of CO2,
their mixtures (up to ternary) and also for cyclic operation, namely due to the higher CO2 afnity towards the zeolite and the adsorbent het-
PSA or VPSA. erogeneity, the Toth Eqs. ((1) and (2)) was necessary to describe ade-
In this study, a xed bed stainless steel column with an inner diam- quately the equilibrium data.
eter of 2.15 cm and height of 83 cm was used. Three K type thermocou-
ples, placed inside the bed at different bed heights, respectively, 16.2, bP
q qm
1 =k 1
41.2 and 66.2 cm from the bottom end, were used to follow the temper- k
1 bP
ature history. The bottom and middle thermocouples are located ap-
proximately at the radial center of the bed and the top one near the  
wall. A gas chromatograph (Chrompack CP9001 equipped with a H
b b exp 2
Poraplot U capillary column (J&W Scientic) and a Thermal Conductiv- RT
ity Detector) was used to analyze the composition of the outlet stream.
Ethane was used as internal standard. Table 1 shows the bed and adsor- The Langmuir equation can be represented by Eq. (1) when k = 1.
bent properties. The isotherms parameters were obtained using Excel Solver tool. The
sum of the absolute error between the experimental and the calculated
3. Model and simulation adsorbed amounts was minimized. The obtained values are presented
in Table 2.
A mathematical model that describes the dynamic behavior of a As expected, carbon dioxide is the most adsorbed species, presenting
non-diluted, non-isothermal, multicomponent adsorption bed was a much favorable isotherm, followed by methane and nitrogen.

Fig. 2. Comparison between the adsorption equilibrium values obtained on the improved 13X zeolite at 308 K, and the ones obtained at 308 K on a shaped commercial 13X zeolite [2] and
on 13X zeolite crystals obtained at 303 K [34] and the values of the improved 13X zeolite corrected by the binder content.
188 M.C. Campo et al. / Fuel Processing Technology 143 (2016) 185194

Fig. 3. Isosteric heat of adsorption of nitrogen, methane and carbon dioxide over improved 13X zeolite beads, as a function of loading.

The isotherms for the three components were fully reversible as can
be seen in Fig. 1 when comparing the closed symbols, corresponding to
equilibrium points measured during the adsorption branch, with the
open symbols, corresponding to equilibrium points assessed during
the desorption branch. By comparing the adsorption equilibrium curves
obtained in this work with those reported elsewhere for a classical 13X
zeolite [2], usually containing 20% binder; it is seen that this improved
13X zeolite presents a much higher adsorption capacity for CO2, around
50% at 5 bar and 323 K. Fig. 2 compares the data obtained in this study at
308 K with data obtained by Cavenati et al. [2] at 308 K and data obtain-
ed by Mani et al. [34] for 13X zeolite crystals at 303 K. It can be seen that
the adsorption capacity obtained for the improved material reported in

Fig. 4. Adsorption (top) of 20% nitrogen diluted in helium over 13X zeolite and desorption (bottom) in helium ow at 320 kPa and 323 K (feed owrate: 1 SLPM) (left); temperature pro-
les inside the bed (right). Points correspond to experimental data and lines to simulation results.
 M.C. Campo et al. / Fuel Processing Technology 143 (2016) 185194 189

Fig. 5. Adsorption (top) of 60% methane diluted in helium over 13X zeolite and desorption (bottom) in helium ow at 320 kPa and 323 K (feed owrate: 1 SLPM) (left); temperature pro-
les inside the bed (right). Points correspond to experimental data and lines to simulation results.

this study is signicantly higher than the values reported previously for in this study is corrected for the binder content (divide by 0.89), the two
a commercial sample, but it is still below the value determined for 13X isotherms (for the crystals and the improved material) are in very good
zeolite crystals at 303 K and 1 bar. However if the isotherm determined agreement.

Fig. 6. Adsorption (top) of 20% carbon dioxide diluted in helium over 13X zeolite and desorption (bottom) in helium ow at 320 kPa and 323 K (feed owrate: 2 SLPM) (left); temperature
proles inside the bed (right). Points correspond to experimental data and lines to simulation results.
190 M.C. Campo et al. / Fuel Processing Technology 143 (2016) 185194

4.2. Isosteric heat of adsorption

The isosteric heat of adsorption for a pure component can be calcu-

lated from the van't Hoff equation [35]:

ln P i 
H i RT 2 : 3
T qi

These were determined from the experimental adsorption data of N2,

CH4 and CO2 over zeolite 13X as a function of loading and are represented
in Fig. 3. The values obtained from the isotherm model's tting also rep-
resented in the same gure by dashed lines. It is seen that the values ob-
tained from the van't Hoff equation are in good agreement with the
values determined by the Toth model tting. These values are also in ac-
cordance with values previously reported in the literature, 16.7 kJ/mol,
13.8 kJ/mol and 34.3 kJ/mol respectively for N2, CH4 and CO2 [36].

4.3. Breakthrough curves

Figs. 47 show the breakthrough curves of nitrogen, methane and
carbon dioxide over 13X zeolite measured at 323 K. The points in
these gures represent the experimental data, while the lines describe
the simulation results obtained by the mathematical model presented
in Section 3. The multicomponent adsorption equilibrium was calculat-
ed in the model with the extended Toth isotherm (4) using the param-
eters given in Table 2. The transport parameters used in the simulations
are reported in Table S4.
bi P i
qi qmi 0 11 =k
X ki
i um. The temperature increase associated with the adsorption phenome-
@1 b j Pi A non is only of 2 K. In the case of methane, the breakthrough time is higher,
j
4.3.1. Single component breakthrough curves of N2, CH4 and CO2 at 323 K
The single component breakthrough curves of N2, CH4 and CO2 at
323 K and 320 kPa (absolute) are shown in Figs. 46, respectively. In
Fig. 8. Skarstrom cycle sequence and respective conditions used in the VSA experiment.
Co-c: co-current, Count-c: counter-current.
the case of N2 and CH4, a total owrate of 1 SLPM was used, by diluting
the species to 20% and 60% respectively, in He. As for CO2, a total
owrate of 2 SLPM was used with a dilution to 20% in He. The adsorp-
tion of each species is accompanied by a temperature increase, the so
called thermal wave, registered by the thermocouples placed at differ-
ent bed positions.
Nitrogen presents the lowest adsorption, as expected from equilibri-
4
as well as the temperature increase, which reaches almost 8 K. Carbon di-
oxide presents the greatest adsorption, but less steep curve, with a tem-
perature increase of 58 K. The adsorption capacities predicted from the
adsorption equilibrium isotherms at 323 K are in agreement with those
obtained by breakthrough curves (xed bed experiments). Additionally,

Fig. 7. Adsorption (top) of a mixture comprising methane 60%/nitrogen 20%/carbon dioxide 20% over 13X zeolite and desorption (bottom) in helium ow at 320 kPa and 323 K (feed
owrate: 2 SLPM) (left); temperature proles inside the bed (right). Points correspond to experimental data and lines to simulation results.
 M.C. Campo et al. / Fuel Processing Technology 143 (2016) 185194 191

the simulation curves describe well the dynamics of adsorption of the
above-mentioned species over this improved 13X zeolite beads.
4.3.2. Ternary breakthrough curve at 323 K
The ternary breakthrough curve was determined with the purpose
of studying the dynamics of adsorption when the three species are in
contact, as will be the case of natural gas upgrade by removing CO2
using VSA technology. This allows the determination of the accuracy
of the Extended Toth model to predict the multi-component adsorption
equilibrium of this system. The composition of the 2 SLPM feed stream
was: 60% methane, 20% nitrogen and 20% carbon dioxide. The results
are shown in Fig. 7 where it can be seen that the mathematical model

Fig. 9. VSA cycle experimental and simulation results (feed 20% CO2/20% N2/60% CH4 at 323 K and 3.2 bar): (a) molar ow rate, (b) temperature histories in the column, (c) molar ow rate
at CSS (cycles 5 and 6), and (d) temperature histories in the column at CSS (cycles 5 and 6). Points correspond to experimental data and lines to simulation results.
192 M.C. Campo et al. / Fuel Processing Technology 143 (2016) 185194
describes well the adsorption dynamics and equilibrium of the ternary
system over 13X zeolite.
4.4. Pilot scale experimental VSA
A pilot scale VSA scheme was designed to be performed experi-
mentally in the unit described above. Looking at the shape of the CO2
isotherm (Fig. 1c), it is possible to observe that it presents a sharp
increase at low pressure values. For this reason, and in order to have a
good working capacity between adsorption and regeneration in the
process, vacuum should be used for regeneration, and therefore a VSA
process is preferable. The process design took into consideration the
experimental limitations such as maximum pressure, available steps
(equalization steps are infeasible in the described unit), and owrates.
The experimental limitations have repercussion in results obtained
for the purity and mainly recovery. This shortcoming can be easily over-
come in the design of an industrial scale unit, where all steps are possi-
ble. The designed cycle consists of 4 elementary steps, the classical
Skarstrom steps, pressurization (Press.), feed, evacuation, and evacua-
tion with purge (see Fig. 8). The total cycle time was 1550 s: pressuriza-
tion step 70 s; feed step 930 s, evacuation step 150 s, and
evacuation with purge step 400 s. A high pressure of 3.2 bar and a
low pressure of 0.1 bar (average value with an experimentally mea-
sured range between 0.085 and 0.110 bar) were employed.
Fig. 9 represents the VSA experimental and simulation results of
the molar ow rate and temperature histories and in Fig. 10 the exper-
imental and simulated pressure histories are shown. In general a good
description of the experimental results is obtained by simulation, espe-
cially the partial molar ow of the three components. The transport pa-
rameter values required for the VSA cycle simulation are the same as the
ones used to simulate the ternary mixture breakthrough curve, and are
given in Table S4. Cyclic steady state (CSS) was rapidly attained and cy-
cles 5 and 6 are represented in detail as example of the CSS behavior (cf.
Fig. 9). The rst cycle differs most from the following due to the different
initial state (bed full of helium at 3.2 bar). At cyclic steady state the bed
temperature changes approximately 27 K between its maximum,
attained during the pressurization and feed steps, and its minimum dur-
ing evacuation. The purity and recovery obtained from the mathemati-
cal model for the designed pilot experimental VSA are 81.5% pure CO2
with 86.5% recovery, and 70.8% pure CH4 with 93.4% recovery. The CO2
content on the CH4 stream was 3.7%, which is slightly above the 2%
limit. The recovery of methane can be improved with the use of equali-
zation steps with the advantage of reducing the energy requirements.
However, as mentioned before, these steps are not possible experimen-
tally in the existing set-up. Furthermore, pure CH4 was used as feed
Fig. 10. VSA cycle experimental and simulation results (feed 20% CO2/20% N2/60% CH4 at
323 K and 3.2 bar): pressure history.
stream for the evacuation with purge step, instead of a stream with
the light product composition as is employed in industrial processes.
4.5. Design and simulation of an industrial scale VSA process
A 3-column VSA process for the removal of carbon dioxide from a
methane stream at industrial scale was designed. The cycle is composed
of six steps: feed, pressure equalization depressurization, evacuation,
evacuation with purge, pressure equalization pressurization and pres-
surization. During the feed step, a mixture of 20% CO2, 20% N2 and 60%
CH4 at 3.2 bar (absolute) and 323 K is fed to the column, and on the
other end of the column, a stream with a CO2 content below 2% (on a
nitrogen free basis) is obtained (light product). Then, the pressure of
the column is decreased to 1.1 bar (absolute) co-currently (pressure
equalization depressurization) by connecting it to another column.
The column pressure is further reduced countercurrently to 0.1 bar
(absolute) in the evacuation step. The regeneration of the column is
completed in the evacuation with purge step, in which a fraction of
the light product is fed to the column at 0.1 bar also countercurrently.
In these two steps (evacuation and evacuation with purge) a CO2
enriched stream is obtained (heavy product). Afterwards the pressure
of the column is increased, rstly by the pressure equalization pressur-
ization step, and then with part of the light product in the countercur-
rent pressurization step. The extension of the cycle to a 3-column
process imposes restrictions on the steps durations, that is, the sum of
the durations of the pressure equalization, evacuation and evacuation
with purge, and the sum of the durations of the pressure equalization
and pressurization must be equal to the duration of the feed step.
Also, the pressure equalization depressurization/pressurization steps
must coincide. Furthermore, when the feed step ends in one column,
it starts in another one, in order to have continuous consumption of
the feed stream. The dimensions of the columns were set to 2 m in
length and 0.4 m in diameter and it was assumed that each column is
packed with 200 kg of adsorbent which results in a bed porosity of
0.39. The feed stream ow rate was 1000 SLPM which corresponds to
a supercial velocity of 0.049 m/s. This value is below the minimum u-
idization velocity for the conditions employed (0.187 m/s). Fig. 11
shows the cycle scheme, the operating conditions and the cycle exten-
sion to the 3-column process.
In the simulations, cyclic steady state was assumed to be achieved
when the sum of the differences between the purities and recoveries
obtained in consecutive cycles is less that 105 (Eq. (5)).
jPur i1 Pur i j jReci1 Reci jb105 5
Fig. 12 shows the pressure, temperature (at the middle of the
column) and outlet molar ow rates histories obtained at cyclic steady
state. A temperature increase is observed in the feed step, while the
temperature decreases in the depressurization steps. During the feed
step the outlet stream is mainly composed by methane and nitrogen,
while during the evacuation and evacuation with purge steps, the outlet
stream is mainly carbon dioxide.
The performance parameters obtained for the designed VSA process
are given in Table 3. The composition of the CH4 product is 73.8% CH4;
1.4% CO2 and 24.8% N2. However the CO2 content, considering a nitrogen
free basis, is only 1.9%. This low value (b 2%) was a constraint used in the
design of the process, so that, after the separation of the nitrogen from
the product stream of this process, the CO2 content on the nal CH4
product would be within the required value (b2%). Therefore, a nitro-
gen rejection unit is required after this process in order to obtain
pipeline-quality methane. Possible alternatives are cryogenic processes
or adsorption based processes. Several aspects must be considered in
the process selection, such as feed ow rate and nitrogen content uctu-
ations. Cryogenic technologies are capital intensive and therefore eco-
nomically feasible for larger ow rates. For ow rates lower than 5
MMSCFC non-cryogenic processes such as PSA are preferable.
 M.C. Campo et al. / Fuel Processing Technology 143 (2016) 185194 193

Fig. 11. Three column VSA cycle designed for the industrial scale separation and respective conditions. Co-c: co-current, Count-c: counter-current, PEQ: pressure equalization, Evac: evac-
uation; Ev. Purge: evacuation with purge.

The methane recovery was high N 96% and the process productivity
was 2.54 molCH4/kgads/h.
Regarding the power consumption of the process, a value of
4.27 Wh/mol CH4 (0.17 kWh/m3CH4) was calculated, of which 62% is
for compression of the feed stream from 1 bar to 3.2 bar, 18% is for
the vacuum pump of the evacuation step and 20% is for the vacuum
pump of the evacuation with purge step. Efciencies of 85% and 60%
were considered respectively for the compressor and vacuum pumps.
Comparing this value with results previously described in the literature
it can be seen that the designed process is attractive. Khunpolgrang
et al. [37] reported a new PSA cycle, with a commercial 13X zeolite,
in which N2 is employed to purge the bed. They obtained a methane
stream with 99% purity and 93% recovery, and a power consumption
of 0.232 kWh/m3CH4. Ferreira et al. [19] presented the results of a PSA
process with a Mil-53(Al) MOF and obtained a power consumption of
5.1 Wh/molCH4. Both values are slightly higher than the value obtained
in this study.
5. Conclusions
Adsorption equilibrium isotherms of methane, nitrogen and carbon
dioxide on an improved 13X zeolite were measured at three tempera-
tures (308, 323 and 348 K) up to 5 bar. The experimental adsorption
equilibrium isotherms of nitrogen and methane were well described
by the Langmuir equation, while that of carbon dioxide was tted
with the Toth equation. The adsorption capacity of carbon dioxide at

Fig. 12. Industrial scale VSA cycle simulation results at CSS: (a) pressure history, (b) temperature history in the middle of the column, (c) molar ow rate.
194 M.C. Campo et al. / Fuel Processing Technology 143 (2016) 185194

Table 3
Performance parameters of the industrial scale VSA process.
Light product Heavy product
Composition
CO2 purity 87.1%
CH4: 0.738; CO2: 0.014; N2: 0.248
CH4 recovery CO2/(CH4 + CO2)
CO2 recovery 94.6%
96.2% 1.9%
Power consumption 4.27 Wh/molCH4 Productivity 2.54 molCH4/kgads/h
323 K and 5 bar was approximately 50% higher than values reported in
literature for binder containing 13X zeolites shaped adsorbents. Single
and ternary breakthrough curves were measured and simulated with
a mathematical model for xed bed adsorbers. A 4-step VSA cycle was
suggested to remove carbon dioxide down to 3.7% in order to produce
a methane stream. The proposed cycle was validated experimentally
at pilot scale. An industrial scale process with six steps was designed
and an upgraded methane stream with only 1.9% of CO2 on a nitrogen
free basis was obtained. The calculated methane recovery and power
consumption were respectively 96% and 4.27 Wh/molCH4 which indi-
cate that the use of the improved 13X zeolite in VSA processes for meth-
ane upgrade is very appealing.
Acknowledgments
This work is partially supported by projects UID/EQU/50020/2013,
QRENON2FEDER NORTE-07-0124-FEDER-0000006, and QREN
ON2FEDER NORTE-07-0162-FEDER-000050, nanced by FEDER
through COMPETE Programa Operacional Factores de Competitividade
and by FCT Fundao para a Cincia e a Tecnologia.
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.fuproc.2015.11.024.
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