Separation and Purification Technology xxx (xxxx) xxx

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Separation and Purification Technology

journal homepage: www.elsevier.com/locate/seppur

Methane separation and capture from nitrogen rich gases by selective

adsorption in microporous Materials: A review
Qi Wang a, 1, Yixuan Yu a, 1, Yunhe Li a, Xiubo Min a, Jin Zhang b, Tianjun Sun a, *
a
Marine Engineering College, Dalian Maritime University, Dalian 116026, China
b
Environmental Science and Engineering College, Dalian Maritime University, Dalian 116026, China

A R T I C L E I N F O A B S T R A C T

Keywords: The rapid increase of natural gas consumption has induced imbalance between supply and demand of natural
Methane gas, and the continuous growth of methane emissions has severely exacerbated greenhouse effects and destroyed
Adsorbent the atmospheric methane cycle. High-efficiency CH4 capture and separation from N2 rich gases has become a
Nitrogen
significant challenge for the recovery and utilization of low-grade natural gas and also industrial tail gas, which
Separation
Progress
was important for sustainable energy and environment and attracted much attention from both researchers and
engineers in recent years. This review provides an overview of selective separation techniques for N2 removal
from natural gas including the benefits and drawbacks of these typical methods. Most notably, the review pri­
marily outlines the progress of metal–organic frameworks, zeolites and activated carbons as superior adsorbents
for separating CH4-N2 mixtures in worldwide laboratories, respectively, with an emphasis on the relationship of
the pore size, surface chemistry and composition of adsorbents with the CH4/N2 selectivity and methane ca­
pacity. We also highlight the potential for the development of the new adsorbents with the best possible
matching between aperture control and atomic-scale tuning of the composition for CH4 capture and separation
from N2 rich gases, and indicate that the MOFs possess both the advantages of activated carbons and zeolites and
will become one of the most promising candidates for high-efficiency CH4 separation from N2 rich gases in the
future.

1. Introduction consumption of resources. Obviously, the unconventional natural gas

Methane (CH4), a typical non-polar molecule [1], has the highest
hydrocarbon ratio and good chemical inertness. As the main component
of natural gas (greater than85 vol%), it has a high burning heat value, up
to 9510 kcal/Nm3. Given that the products after burning are only H2O,
CO2 and a little NOx, methane has been regarded as a relatively clean
fossil fuel and the most important modern industrial raw materials. With
the acceleration of the energy transformation to low-carbonization, the
global natural gas consumption has been increased continuously, espe­
cially if Chinese natural gas demand maintains a growth rate of more
than 10% in the next ten years, the world will enter a new era of natural
gas completely [2].
As we all know, the conventional natural gas resources will be unable
to meet the demand because of the switch away from carbon-intensive
fossils to cleaner energy around the world. Meanwhile the difficulty of
conventional natural gas mining will increase greatly with the rapid
resources may become the most powerful support for the sustainable
development of the natural gas industry owing to their abundant re­
serves and extensive distributions. However, the separation of a large
amount of impurities in unconventional natural gas has become a key
technical obstacle in large-scale utilization, especially the high-efficient
separation of nitrogen contaminants [3]. It should be noted that
methane is also a potent powerful greenhouse gas and the second-largest
contributor to global warming with much higher global warming po­
tential than that of the equivalent amount of CO2. As shown in Fig. 1,
methane can be released from a variety of sources, such as wetlands, rice
cultivation, enteric fermentation, wastewater treatment, landfills, coal
mining, natural gas systems, oil industry and combustion process, in
which more than 25% methane emissions are from coal, oil and gas
production that ought to be avoided. According to the study of Lawrence
Berkeley National Laboratory in the United States, the atmospheric
methane concentration has risen from 722 ± 25 ppbv in 1750 to 1803 ±

* Corresponding author.
E-mail address: suntianjun@dlmu.edu.cn (T. Sun).
1
These authors contributed equally to this study and share first authorship

https://doi.org/10.1016/j.seppur.2021.120206
Received 8 October 2021; Received in revised form 15 November 2021; Accepted 23 November 2021
Available online 26 November 2021
1383-5866/© 2021 Elsevier B.V. All rights reserved.

Please cite this article as: Qi Wang, Separation and Purification Technology, https://doi.org/10.1016/j.seppur.2021.120206
Q. Wang et al.
2 ppbv in 2011[4]. Worryingly, atmospheric methane mixing ratios
have started to grow much more rapidly since 2007, the current glob­
al atmospheric concentrations of methane have reached 1870 ppbv, and
its contribution to the greenhouse effect has exceeded 30%, as shown in
Fig. 1 [5].
Manifestly, methane is not only an important low-carbon clean en­
ergy that bridges fossil resources with future sustainable energy, but also
a worrisome heat-trapping and climate change pollutant. Therefore,
finding a high-efficient methane enrichment technology is of vital
importance for the utilization of unconventional natural gas and the
recovery of methane-containing tail gases in the industry to overcome
the nature gas shortage. What’s more, finding a cost-effective method
for methane emission reduction is of great significance for rebalancing
the atmospheric methane cycle to slow down the rise of global average
temperature. Among the purifications of the above-mentioned methane
resources, the high-efficient separation of CH4-N2 mixture is one of the
critical issues to achieve the low-quality methane enrichment and
methane recovery from industrial tail gases [3,6]. This paper gives an
overview of the advancement in porous adsorbents for methane sepa­
ration from nitrogen, and emphasis will be given on the critical
parameter of adsorbents for the capacity and selectivity of methane as
well as the structure–property relationships and adsorbent-adsorbate
interactions. Based on the discussion of the similarities and differences
of methane adsorption on the metal organic frameworks (MOFs), zeo­
lites, and activated carbons, the challenges and opportunities for the
typical adsorbents were proposed. We wish to meet the ever-increasing
demand for the methane and nitrogen separation, and help the re­
searchers to learn the state of the art in adsorbents for CH4-N2 separation
and understand the innovative conceptual ideas of new adsorbent
design.
2. Nitrogen removal methods from low-grade methane
Compared with other fossil fuels, methane is a more clean and eco-
friendly energy. However, the raw gas of methane obtains several
accompanying substances, removing them is necessary to meet the
specific requirements of storage and transportation systems, including
moisture, acid gases, inerts, and heavier hydrocarbons. So that, the
typical purification process of raw nature gas includes the sour gas
removal and sulfur recovery, dehydration (dewpoint control), C2+ hy­
drocarbon recovery, cryogenic nitrogen rejection, helium recovery, and
Fig. 1. Schematic representation of methane emissions and rapidly increase of atmospheric methane mixing ratios.
2
Separation and Purification Technology xxx (xxxx) xxx
mercury removal units [6–9], among which the cryogenic nitrogen
rejection is the most energy-consuming step in the methane purification
processes, limiting the large-scale application of low-quality methane
resources, as shown in Fig. 2 [9]. In other words, these above-mentioned
impurities, except nitrogen, can now be removed from raw nature gas
efficiently and economically by different process technologies based on
absorption, distillation, adsorption, membrane separation or hydrates.
Efficient nitrogen separation has become the urgent problem needing
to be solved for the purification of high concentrated methane, the
enrichment of low concentrated methane and methane recovery from
the exhaust gas, as CH4 and N2 have very similar physical and chemical
properties [6,10,11]. At first glance in Table 1, it can be found that CH4
and N2 are typical non-polar molecules without the dipole moments,
except for the critical temperature, CH4 and N2 have the similar kinetic
diameter, polarizability and quadrupole moment [7–9,11–15]. At pre­
sent, there are some available technologies that have been tried to
separate the CH4-N2 mixtures efficiently, including not just cryogenic
distillation, but also adsorption, absorption, hydrate separation and
membrane separations. Concurrently, the gas separation is going in the
direction of process diversification, the lower overall costs and the
higher environmental sustainability, both featuring low energy con­
sumption, high yield, high purity, and high recovery. The economically
viable alternatives cannot be used in the large-scale gas processing of
methane with different concentrations from various sources, until more
energy efficient methods for the CH4 and N2 separation are found and
developed to replace the commercial technologies.
Cryogenic separation is also known as cryogenic distillation process,
in which the effective separation is carried out through a distillation
column coupled with a refrigeration system. As for the cryogenic sepa­
ration of CH4-N2 mixture, it is primarily according to the boiling point
difference of ca. 34 ◦ C between methane and nitrogen at atmospheric
pressure (− 196 ◦ C vs − 161.4 ◦ C), taking the advantage of cry­
ogenic gas compression system to cool the gas mixtures for inducing a
phase change for effective separation[9]. Now, cryogenic distillation is a
mature and reliable method used to reject N2 from CH4, and it can
produce CH4 in high purity (up to 99.9 vol%) and high recovery (greater
than98 %) while the N2 is removed in the distillate at the top of the
column owing to the lower boiling point of N2. However, in order to
obtain the relative volatility αCH4/N2 value of 5–8 for the guarantee of
product purity, the distillation column is generally operated at tem­
peratures below − 100 ◦ C and pressures of about 13–28 atm, resulting in
Q. Wang et al. Separation and Purification Technology xxx (xxxx) xxx

Fig. 2. Conventional gas processing operations in a typical natural gas plant, and the process flow arrangements finally depending on the feed gas properties and
product specifications.

[20]. For polymeric membranes, the small differences of kinetic diam­

Table 1
eter, polarity, and quadrupole moment between CH4 and N2 not only
Physico-chemical properties of some molecules present in natural gas* [6]
limit the efficiency separation by diffusion separation, but induce the
Molecule σ [Å] α [Å3] μ [D] Θ [D Å] Tc [K] counterproductive effects between diffusion and solubility, making N2
CH4 3.80 2.448 0.000 0.02 190 hard to be removed effectively. As for inorganic membranes, silica
N2 3.64 1.710 0.000 1.54 126 membranes have shown superior performances in the selectivity of CH4/
CO2 3.30 2.507 0.000 4.30 304
N2 up to 10, but it is still difficult to separate N2 because the permeance
H2O 2.65 1.501 1.850 2.30 647
H2S 3.60 3.630 0.970 3.74 373
will drop by 4.5 orders of magnitude for every order of magnitude in­
He 2.60 0.208 0.000 0.00 5 crease in selectivity [8]. Notably, the NitroSepTM commercial system has
H2 2.89 0.787 0.000 0.43 33 employed multi-stage process and excessive recycling to offset the poor
*
σ: kinetic diameter, α: polarizability, μ: dipole moment, Θ: quadrupole performance of membranes, but the running cost of this system will
moment, Tc: critical temperature. Quadrupole moment indicative values have quickly rise with the increase of N2 concentration in feed and product
been calculated by Density Functional Theory (DFT) method. purity. In a word, there is a rare case of membrane systems for N2
removal, especially for handling large volumes of CH4-N2 mixtures
the very high capital investment of compressor and high operating costs (greater than50 MMscfd), because the high-efficiency CH4-N2 separa­
[16]. Like air cryogenic separation process, the cryogenic nitrogen tion by membranes is still limited by low selectivity, poor permeability,
rejection unit will bring out the economic benefits as the gas processing membrane materials and fabrication techniques [8,9].
capacity more than 100 million cubic feet per day, which has been Methane separation by clathrate hydrates is based on the fact that
designed and validated by many companies such as Linde, Praxair, and there is a significant difference in phase equilibrium pressure of hydrate
Air Products & Chemicals [17]. Consequently, how to further reduce the formation between CH4 and N2 (2.56 MPa vs 14.3 MPa at 273.13 K)
energy consumption in gas compression by the optimization of system [21]. Clathrate hydrate is kind of inclusion compound like zeolite, and it
integration and energy efficiency, is the biggest challenge facing cryo­ can trap small molecules (<10 Å) in the cage of hydrogen-bonded water
genic system for the selective N2 separation from the low-quality molecules. Generally, the clathrate hydrates have three different struc­
methane resource, especially for the nitrogen rejection of medium and tures (sI, sII, and sH) that consist of some small (512 cages with 12
small-scale resources with high nitrogen content. pentagonal faces) and large (51262, 51264, 51268, etc.) cages [8]. For the
Membrane separation process is to employ the semi-permeable se­ separation of CH4-N2 mixtures by hydrates, CH4 is encaged preferen­
lective barrier to separate the gas mixtures into two streams, in which a tially in the frameworks of hydrates from the feed gases owing to its
sufficient driving force in the form of a partial pressure gradient must be good stability in the hydrate phase at a relatively low pressure, and then
applied between the feed and the permeate stream [8,9]. Compared with the richer CH4 stream will be produced after the dissociation of the
cryogenic separation, membrane separation has many unique advan­ formed hydrates. As mentioned above, the biggest obstacle of hydrate
tages, such as no phase change, low thermal energy consumption, formations is the high pressure, inducing a very high running cost and
continuous operations, simple processes and types of equipment, equipment investments in the nitrogen separation from methane like
compact plant footprints and convenient procedures. Membrane sepa­ cryogenic separation process. So that, many researchers have tried to
ration process has been used for the removal of CO2, N2, H2S and He overcome this limitation by adding some promoters in the hydrate for­
recovery from raw nature gas resources in the past forty years, but only mation process. With this idea, tetra-n-butylammonium bromide (TBAB)
membrane separation for CO2 capture has good market competitiveness and tetrahydrofuran (THF) have been found firstly that they can effi­
and is widely used in the natural gas industry [9]. For the separation of ciently reduce the pressure of the hydrate formation [22,23]. Until now,
CH4-N2 mixtures, polymeric, inorganic, and mixed matrix membranes many processes of hydrate formations have been proposed for methane
have been studied, such as glassy and perfluoro polymers, rubbery separation, including the stirred tank reactor, bubble-column reactor,
polymers, CMS, zeolite membranes and polybenzimidazole (PBI)-based fluidised-bed reactor, and the use of promoters. Based on the fluidised-
mixed matrix membranes (MMMs) [18,19]. The polymeric membranes bed reactor, Marathon oil company has developed a pilot-scale contin­
usually achieved nitrogen rejection by the differences in the solubility uous flow gas hydrate reactor with a rate of 4750 kg hydrate slurry (10
and mobility behaviors, while the inorganic membranes separated the wt%) per day. Based on the use of promoters, researchers examined the
N2 from CH4 by a molecular sieving or activated transport mechanism effects of amino acids L-tryptophan and L-leucine on hydrate formation,

3
Q. Wang et al.
which enriched CH4 from 30.0 mol% in the feed gas to 56.8 mol% in the
hydrates [24]. In short, CH4 and N2 can be separated through the
pressure control of hydrate formations with the advantages of no pre­
treatment and environment friendly, but there are many challenges
facing commercial-scale process for methane purification due to the
slow hydration rate and harsh conditions of hydrate formation [22].
Adsorption separation is a well-known and widely used method to
separate gas mixtures in the natural gas industry, such as the removal of
water, CO2, sulphur, mercury, heavy hydrocarbons, and N2. In fact, the
adsorptive separation is a selective adsorption–desorption process of the
components from the gas mixture on the surfaces of porous solid ad­
sorbents, in which the adsorbent selection and process are designed
seriously depend on the nature of feed and products. That is to say, the
integration and optimization between superior adsorbents and advanced
adsorption processes are the central parts for the development and
implementation of adsorption-based nitrogen rejection unit. First of all,
an adsorbent that prefers to adsorb the desired component is the most
immediate demand of the high-performance separation of CH4-N2 mix­
tures, and there are three categories of adsorbents that can be employed
such as zeolite, metal–organic frameworks (MOFs), and porous carbon
materials. In general, adsorption is based on attraction forces between
the porous adsorbent and gas molecules, including Van der Waals forces
and electrostatic forces. For this reason, the strength of adsorption forces
is not only directly related to the size, polarizability, dipole and quad­
rupole moments of adsorbate molecular, but also determined by the
surface chemistry and pore structure of adsorbents, which should be
considered during adsorbent choice and tailoring. Secondly, pressure-
swing adsorption (PSA) process is typical adsorption-based process for
gas separation, in which the adsorbent regeneration can be achieved by
the difference in adsorption capacities at different pressures. In the PSA
cycle, adsorption usually occurs in the range of 400–2000 kPa and
desorption occurs at near-ambient pressure, which can be achieved
rapidly. Commercial PSA N2 rejection processes include NitrexTM pro­
cess of UOP, NitrotecTM process of CMS Energy, micro-scale NRU of AEP
and Molecular GateTM process of BASF. Among of them, they all adsorb
preferably CH4 over N2, except that Molecular GateTM process presents
the selective adsorption of N2 over CH4 on proprietary adsorbents of the
titanosilicate ETS-4 zeolite. In order to increase productivity, typical
PSA process always employs three or more beds, multi-layered adsor­
bent beds to remove different impurities, multiple pressurization steps,
cocurrent and counter-current depressurization steps, and several purge
steps. Interestingly, structured adsorbents and new valve technologies
have been used to develop the rapid cycle PSA system with very short
cycle time, and the Xebec M− 3100 Rotary-valve fast cycle PSA system
can finish 50 cycles per minute at least, overcoming the rate limit at
conventional PSA process and enhancing the productivity greatly. In a
word, adsorption-based processes are potential for energy and capital
investment savings over the cryogenic separation nitrogen rejection
units, but the performance of existing commercial adsorbents and the set
of operational values still need to be improved continuously for high-
efficient separation of CH4-N2 mixtures with high processing rates
(greater than15 MMscfd) [9,25–27,28].
Absorption is also an available method for N2 separation from
methane, in which one component is dissolved selectively by liquid or
solid solvents. To achieve the energy-efficient process of N2 rejection
from nature gas, the choice of solvent with different solubility for
methane and nitrogen is an important thing, which can effectively avoid
the prohibitively high cost resulting from the large solvent rates and gas
recompression [8]. Until now, there are hardly any commercial N2
rejection units based on the absorption process of CH4 in a hydrocarbon
oil. In the typical CH4 selective adsorption process, the cooled CH4-N2
mixtures (ca. –32 ◦ C) is absorbed firstly in the tower with a lean oil
solvent, and then absorption solution enters the regeneration vessels to
recover the high purity methane and the unabsorbed N2 is vented at the
top of absorber [29]. For the N2 selective adsorption process, some
multidentate transition metal complexes have used to absorb the
4
Separation and Purification Technology xxx (xxxx) xxx
nitrogen, such as the toluene solution of (bis)tricyclohexylphosphine
molybdenum tricarbonyl, but the degradation of the phosphine complex
and regeneration of the N2-bound complex are still the very tricky
questions, resulting in no commercial process has been developed suc­
cessfully [30]. In brief, absorption process is difficult to meet the re­
quirements of nitrogen rejection in nature gas industry, because the low
solubility of methane and nitrogen, poor regeneration, stability, and
safety of solvents lead to the large requirement of absorbent and much
higher solvent circulation rates.
In conclusion, there are many conventional and developing gas
separation techniques that can be used to remove nitrogen from
methane, such as distillation, absorption, hydrates, membrane, and
adsorption. Among of them, the cryogenic distillation remains the pri­
mary technology of N2 rejection in natural gas industry, especially for
the larger-scale units with the feed rates greater than 15 MMscfd, while
it still has a high energy consumption. The solvent absorption is unlikely
to be applied widely for N2 separation from natural gas owing to the
unacceptable absorption efficiency and safety, and the separation per­
formance of clathrate hydrates is also limited seriously by the unsatis­
factory reaction rate and hash hydration conditions. Although
membrane separation of CH4-N2 mixtures is promising owing to its
lowest cost treatment option, it is still not to be an effective process of
nitrogen rejection before reaching the prospective selectivity in the
future. It should be noted that PSA technologies based on CH4 selective
adsorption, as well as N2 selective adsorption, are commercially avail­
able for medium and small-scale gas processing facilities because of their
natural advantages of compact module, simple process, high stability,
and low operating cost [31]. In particular, the rapid cycle PSA process,
such as Xebec M− 3100 Rotary-valve system, has exhibited outstanding
performance in the PSA process intensification, revealing that it is a
promising alternative to conventional PSA for more efficient N2 removal
in the nature gas industry. However, there are still many problems need
to be solved for the use of adsorption technology for bulk separation of
N2 from CH4, especially the medium and dilute-concentration sources
with the feed rate more than 100 MMscfd.
Hereinto, the preparation of adsorbents for the high-efficient sepa­
ration of CH4-N2 mixtures is still a prominent problem, in which to
design novel adsorbents coupling multiple separation mechanisms/
functions, and to tailor the pore structure and surface chemistry of
porous materials at the nanoscale will be one of the most effective so­
lutions to enhance the adsorption separation efficiency of CH4-N2 mix­
tures continuously.
3. Advanced adsorbents for nitrogen separation from methane
The separation of CH4-N2 mixtures is based on the preferential
adsorption of the solid porous adsorbents, in which the selectivity
mainly follows as one or combination of the following mechanisms:
thermodynamic equilibrium effect, steric effect and kinetic effect
[6,32–34]. The separation essence of adsorptive separation is to prepare
the desired adsorbent for the selective adsorption–desorption of gas
mixtures, and to design a high-performance process matched with the
corresponding adsorbents. Obviously, the choice of excellent adsorbent
is the basic work in the adsorptive separation of CH4-N2 mixtures,
because it plays a dominant role for the improvement of mass transfer
and system efficiency. As mentioned above, an excellent adsorbent
should have high adsorption selectivity and high adsorption capacity in
the first place, and it also needs to possess good physical and chemical
stability, nice regenerability, fast adsorption and desorption kinetics,
reasonable packing density, and low cost. So that, it has been one of the
most challenging cases to find a superior adsorbent for the N2 removal
from CH4, because there is a serious conflict between the interactions of
CH4 and N2 with porous materials that the high polarization always
leads to the selective adsorption of methane, and the small molecular
size and high quadrupole moment of nitrogen also dramatically promote
its preferential adsorption. Currently, the microporous adsorbents used
Q. Wang et al. Separation and Purification Technology xxx (xxxx) xxx

for the separation of CH4-N2 mixtures can be divided into three main Table 2
categories, including metal–organic frameworks, zeolites, and porous Summary of selective adsorption of methane and nitrogen in rigid MOFs.
carbon materials [34]. MOF CH4/N2 adsorptive CH4 adsorption Ref.
selectivity capacity (mmolg− 1)
[Co3(HCOO)6] 5.50a 0.79a [10]
3.1. Metal organic frameworks [Mg3(HCOO)6] 4.90a 0.77a [10,41]
[Mn3(HCOO)6] 4.80a 0.58a [10]
Metal organic frameworks, as the largest category of porous crys­ [Ni3(HCOO)6] 6.3a 0.8a [13]
[Cu(Me-4py-trz-ia)] 4.0–5.0b 1.12b [36]
talline materials with various controllable structures, are composed of
MIL-53(Al) (Basolite® 3.70b ~0.71b [3]
multidentate organic ligands and transition metal cations, possessing A100)
many advantages such as exceptional specific surface area, large pore MIL-101 (Cr) 2.65c ~0.25c [38]
volume, high modularity, and variable functionality of the channels. USTA-30a 3.0–5.0a 0.616a [39]
MOFs have currently exhibited great application potentials in many [Cu(INA)2] 8.14a 0.82a [13]
[Cu(hfipbb) 6.9a 0.47a [43]
fields such as storage, catalysis, biological imaging and sensing, drug
(H2hfipbb)0.5]
delivery, separation, magnetic devices, nonlinear optics, water vapor ROD-8 6-9a 0.77a [44]
capture, etc. [35]. In particular, the experimental and simulation studies Ni-L 7.0a 1.15a [45]
of MOFs on gas adsorption revealed that MOFs with ultramicropores (<7 MOF-5 1.13d 0.125d [46]
MOF-177 4.0d 0.59d [46]
Å) have promising properties for separating methane from other similar
Cu-BTC — 0.91d [47]
gas molecules that are similar in size [3,6,7,10,13,14]. In recent years, MOF-5 — 0.62 d [47]
MOFs also have shown the high adsorption capacity and selectivity for Cu-BTC 3.69d 0.79d [48]
the separation of nitrogen-containing methane mixtures, such as MIL-53 ZIF-8 2.80c 0.2c [4]
(Al) [36], [Cu (Me-4py-trz-ia)] [36], MIL-101 [37,38], USTA-30a [39], Mg-MOF-74 1.5a 1.62a [51]
Ni-MOF-74 3.82a 1.89a [51]
[M3(HCOO)6] [40], [Cu(hfipbb) (H2hfipbb)0.5] [43], Rod-8 [4 4 ], Ni-L
Co-MOF-74 3.18a 1.90a [51]
[45], MOF-5 [46], HKUST-1 [47,48], ZIF series [49], M− DOBDC [51], MIL-100(Cr) 2.81a 0.74a [51]
Zn2(5-aip)2(bpy) [52], ATC-Cu [60], [Cu(dhbc)2(bpy)] [55] and Zn2(5- aip)2(bpy) 7.1a 0.36a [52]
[Co3(C4O4)2(OH)2] [59], etc., as shown in Fig. 3 and Table 2. ATC-Cu 9.80a 2.90a [60]
[Co3(C4O4)2(OH)2] 8.5–12.5a 0.88a [59]
In 2012, J Möllmer and coworkers found that the novel [Cu(Me-4py-
Uio-66-Br2 5.06a 0.72a [62]
trz-ia)] framework and Basolite® A100 all have good CH4/N2 selectiv­ Uio-6 2.73a 0.57a [62]
ities in the range of 4.0–5.0 and 3.4–4.5, respectively, which have been CAU-21-BPDC 11.9a 0.99a [63]
measured by the gravimetric method and volumetric–chromatographic CAU-8-BPDC 4.9a 0.85a [63]
method. It was the first time that the separation performances of CH4-N2 [Co(ma)(bpy)0.5 7.2a 0.92a [74]
[Ni(ma)(bpy)0.5 7.4a 1.01a [74]
mixtures on microporous MOFs were determined by adsorption exper­
SBMOF-1 11.5 0.92 [64]
iments of pure gas and binary mixtures [36]. But almost immediately, Al-CDC 13.1–16.7 1.42 [65]
MIL-101(Cr) has been confirmed that it is not satisfied to separate ni­
a 298 K, 1 bar；b 273, 298, 323 K, 1 bar；c 303 K, 1 bar；d 298 K, 1 bar (CH4:
trogen from methane because of its CH4 uptakes and CH4/N2
N2 = 1:1 breakthrough curve)；e 298 K, 35 bar. The adsorptive separation of
selectivity<0.5 mmol/g and 3.3 respectively, although MIL101 has a
CH4/N2 mixtures for each adsorbent is mainly driven by the thermodynamic
high specific surface area, large pore volume, easy regeneration, and equilibrium.
good stability [37,38]. Subsequently, USTA-30a, a lanthanide organic
framework with three-dimensional pore channels, was designed to pu­
surface area, and narrow pore-size distribution at 5–6 Å, but also has the
rify the methane from an 8-component gas mixture, and the results
alternative arrays of C-H and O at the inner surface of pore channels,
showed that this as-synthesized MOF with the surface area of over 600
which makes this ultramicropore materials present the fantastic surface
m2/g has a methane capacity of 0.6 mmol/g and a CH4/N2 selectivity of
polarizability and the enhanced affinity of methane [41,42]. Further­
5 at room temperature and atmospheric pressure [39]. In 2013, XY Ren
more, the separation performances of CH4-N2 mixtures on [Ni3(H­
and TJ Sun revealed that the [Ni3(HCOO)6] framework constructed by
COO)6], [Cu(INA)2], MIL-53(Al) and Ni-MOF-74, were studied
the smallest and shortest monodentate ligand, HCOO–, exhibited pref­
systematically, and the corresponding results showed that the CH4/N2
erential adsorption of CH4 over N2 with methane capacity of 0.75 mmol/
adsorptive selectivity of [Ni3(HCOO)6] and [Cu(INA)2] could reach up
g and CH4/N2 selectivity up to 6.5, which measured by adsorption iso­
to 6.5 and 7.6, respectively, indicating that the apolar MOFs with 1D
therms of pure gas and breakthrough experiments of binary mixtures at
micropores (<6 Å) are suitable for the CH4 separation from CH4-N2
298 K in the pressure range of 0.1–1.0 MPa [40]. [Ni3(HCOO)6]
mixtures [42]. During these times, SG Deng also synthesized a micro­
framework not only has the highest metal proportion, the relatively low
porous [Cu(hfipbb)(H2hfipbb)0.5] framework with the pore size of 4.6 Å
and BET-specific surface area of 105 m2/g through a microwave-assisted
method, and displaying good CH4/N2 selectivity up to 6.9 at 298 K [43];
XP Zhou reported a 3D framework of [Cd2(TBAPy)(H2O)2]⋅
DMF⋅0.5dioxane (Rod-8) that has two kinds of 1D micropores of 6.5 ×
11.8 Å2 and 8.5 × 9.5 Å2, and the structure of two nearest parallel
pyrene core planes with distance of 4.35 Å, which show that the
methane uptake amount is 0.77 mmol/g and the CH4/N2 selectivity can
be up to 9.0 at normal temperature and pressure [44]. From that ti­
me forth, MOFs with ultramicropores, especially when its pore size is
close to the molecular sizes of CH4 and N2 (3.8 and 3.64 Å), are often
considered as the promising adsorbents for separating CH4 and N2
mixtures. Soon afterwards, a 3D Ni-L framework (L:1,10-methylenebis
(3,5-dimethyl-1H-pyrazole-4-carboxylic acid) with alternating large and
small channels along the a and b directions, has obtained the methane
Fig. 3. Selectivities of CH4/N2 and the CH4 sorption capacity of the state-of- capacity of 1.15 mmol/g and the CH4/N2 selectivity of 7.0 at 298 K and
the-art adsorbents at ambient temperature and pressure. atmospheric pressure, attributing to the shortest contact distance

5
Q. Wang et al.
between methane and the pyrazole ring of 4 Å that is similar to the
carbon-arene distances reported for C-H… arene interactions, as shown
in Fig. 4 [45]. Last year, a zinc-based pillar-layer MOF, Zn2(5-aip)2(bpy),
was first made by solvent-free mechanochemical synthesis and preferred
to adsorb CH4 over N2 with high CH4/N2 selectivity of 7.0, because the
same pore can hold two spheroidal CH4 molecules while adsorb only one
linear N2 molecule owing to the stronger binding energies of CH4 with
the pore walls [52]. Moreover, JP Li and coworkers have found that ZIF-
94, a very stable MOF with a pore size of 8.4 Å, exhibits the prefer­
ential adsorption of methane over nitrogen with methane capacity of
1.5 mmol/g and CH4/N2 selectivity of 6.0–7.0, but it is very difficult to
achieve the large-scale synthesis as other ZIFs because of the harsh
synthesis conditions [53]. In addition, the separation performance of the
CH4-N2 mixtures in MOFs can be enhanced at the low-temperature. For
instance, the framework of [Ni8(5-bbdc)6(μ3-OH)4 has been demon­
strated that it can be used to take up a moderate amount of N2 from low-
grade CH4 owing to the gate opening of about 3.75 Å at 113 K [54], and
the flexible layer MOFs [Cu(dhbc)2(bpy)] showed high CH4 capacity of
3.58 mmol/g and high CH4/N2 adsorption ratio of 42 because the gate-
opening pressures of methane and nitrogen are about 0.2 bar and 6 bar
at 195 K, respectively [55].
In order to obtain better performance of CH4-N2 separation, the
creation of special adsorption sites has been considered. Firstly, the
improvement of effective contact areas and the formation of multiple
interactions are the essential methods to enhance the selectivity and
capacity of methane or nitrogen in MOFs. W Zhou et al. found that the
Ni2(DHTP) MOF (DHTP: 2,5-dihydroxyterephthalate) with exception­
ally large densities of open metal sites can adsorb ~ 200 cm3(STP)/cm3
methane at 298 K and 35 bar, because the electrostatic forces of coor­
dinatively unsaturated metal sites could greatly enhance the binding
strength of methane which was confirmed by neutron diffraction ex­
periments and initial first-principles calculations. As the M2(DHTP) MOF
structures have relatively large ( ~ 13.6 Å) one-dimensional channel
pores, in which the open metal sites can be easily accessed and touched
by methane molecules [56]. After that, H Lee proposed the idea of using
water adsorption to occupy the hydrophilic sites of MOF channels to
enhance selective adsorption of methane over nitrogen, which was
clearly demonstrated that the extraordinary selectivity for the separa­
tion of CH4-N2 mixtures can be 24.7 on the HKUST saturated with water
by vaporization at 80 bar and 243 K, owing to the blockage of
6
Separation and Purification Technology xxx (xxxx) xxx
hydrophilic pore by water and the empty hydrophobic pores acting as
selective sites of methane [57]. Meanwhile, DH Liu prepared a 3D Cu-
BTC (BTC: 1,3,5-benzentricarboxylate) MOF in methanol that contains
two kinds of micropores with the size of 7 Å and 5 Å, respectively, and
discovered that C-H atoms in the ester groups in the hydrophobic
channels and μ2-coordinated carboxylate O atoms in hydrophilic chan­
nels prefer to enhance the interactions with CH4 by strong multiple Van
der Waals forces while weakening the interaction with N2, leading to a
high CH4/N2 adsorption selectivity of 10–12.6 [58]. Subsequently, an
ultra-microporous [Co3(C4O4)2(OH)2] (C4O42-: squarate) MOF, with
enhanced negative oxygen binding sites, exhibited a high CH4/N2
selectivity of 8.5–12.5 as well as a methane capacity of 0.89 mol/g under
ambient condition due to the strong affinity of CH4 with the exposed
negative O atoms derived from hydroxide groups [59]. And then, a
Cu2(ATC) MOF (ATC: 1,3,5,7-adamantane tetracarboxylic acid) with
rectangular channels (4.43 × 5.39 Å) that constructed by oppositely
adjacent open metal sites and dense alkyl groups, exhibited a record-
high methane capacity of 2.90 mmol/g and CH4/N2 selectivity of 9.7
at 298 K and 1 bar. The corresponding single-crystal X-ray diffraction
experiments and molecular simulation studies indicated that the low
polarity aliphatic hydrocarbon cavities and the unsaturated metal sites
in Cu2(ATC) all could generate the preferential absorption site for
methane, thereby providing a new perspective of adsorbent develop­
ment for the separation of CH4-N2 mixtures, as shown in Fig. 6 [60].
Moreover, heterometal doping and grafting functional groups in MOFs
have become important ways to regulate the adsorption potential of gas
in the micropores and to improve the separation performances of MOFs.
For instance, Mg2+ doped MIL101(Cr) has been prepared by hydro­
thermal method to enhance the separation of the CH4/N2 mixtures, and
the result showed that doped Mg2+ can inhibit the formation of
hydrogen bonds in MIL101, which greatly improve the methane ca­
pacity and CH4–N2 selectivity of MIL-101 [61]. Similarly, YS Bae and
coworkers have systematically investigated the influence of the incor­
porated -H, –NH2, –NO2, -Br, and -Br2 for adsorption properties of UiO-
66, and found that the adsorption capacity and selectivity of CH4-N2
mixtures on UiO-66-Br2 increase obviously, probably due to the high
polarizability of Br2 induced a strong interaction with methane [62].
Furthermore, with the deep-going of the research, to endow MOFs with
various advantages by the fine-tuning of multiple adsorption in­
teractions, such as achieving the tradeoff between high CH4 capacity
Fig. 4. (A) The structure of H2L; (B) The X-ray
structure of a NiL unit in the asymmetric unit of 1
with heteroatoms labelled; (C) The structure of a
square assembly of four adjacent Ni centres; (D)
The side view of a zigzag chain along the a axis
with edge-sharing squares, and the Ni centres
shown as large green spheres; (E) The lattice of
NiL viewing down the a axis, the individual chains
are colour coded in alternating red and green; (F)
CH4 and N2 gas adsorption isotherms from a 1: 1
mixture of CH4/N2 at 298 K; Reproduced from ref.
[45]. Copyright 2018, The Royal Society of
Chemistry.
Q. Wang et al.
and high CH4/N2 selectivity, has become one of the pioneering trends.
QB Xia and coworkers have prepared an Al-based MOF with four highly
symmetric polar sites in the pore walls, CAU-21-BPDC, that exhibits
higher CH4 uptake of 0.99 mmol/g, greater CH4/N2 adsorption selec­
tivity of 11.9, and better moisture stability at 298 K and 1 bar, and
revealed that four symmetrical μ2-O atoms from four different metal
clusters located at the neck of the pores could selectively combine with
four H atoms of methane via multiple C–H⋯O interactions despite the
pore size of MOF is more than 7 Å, which greatly improves the methane
adsorption capacity and separation selectivity concurrently [63]. Taking
the above-mentioned facts that the low-polarity aromatic rings in the
surface of micropores prefer to strongly interact with the saturated hy­
drocarbons over unsaturated ones (such as with quadrupole moment),
DH Liu and coworkers synthesized a robust Ca-based MOF, SBMOF-1
(ligand: 4,4′ -dicarboxylic diphenyl sulfone) with a pore size of 7.3 Å,
that exhibits a high CH4/N2 selectivity of 11.5 and relatively high CH4
adsorption capacity of ca. 0.93 mmol/g at normal temperature and
pressure, owing to the organic ligand in micropores containing low
polarity multiple-aromatic rings, as-shown in Fig. 5 [64]. Likewise,
with the guidance of the results that low polarity channel liner can
induce a strong affinity with methane, CL Zhong and coworkers pre­
pared Al-CDC MOF with a pore size of 5.4 Å, which shows the high
methane capacity of 1.42 mmol/g and high CH4/N2 selectivity up to
16.7, achieving a good tradeoff between adsorptive capacity and
selectivity because 1D ultra-micropores, saturated C-H as well as the
corresponding trans corner in the ligand endow Al-CDC MOF with great
adsorption potential to preferentially adsorb CH4 molecules as shown in
Fig. 6 [65]. From the opposite point of view, the selective nitrogen
adsorption is another effective way for the separation of CH4-N2 mix­
tures, which is more economical for the methane separation from the
mixture with low nitrogen concentration. Inspired by selective dini­
trogen binding to transition metal ions for biomimetic nitrogen fixation
to produce ammonia, a 3D mesoporous MIL-100 with unsaturated Cr(III)
site has been designed to capture N2 from CH4 for the first time, and the
corresponding experimental and computational results showed that the
N2 adsorption capacity and CH4/N2 selectivity are up to 1.6 mmol/g and
8 at normal temperature and pressure, owing to the selective back-
bonding interaction between N2 and Cr(III) combined with the rela­
tively strong Lewis acid strength of these metal sites, as shown in Fig. 7
[66]. Similarly, TYUT-96(Cr) also exhibited a good performance in N2
Fig. 5. The crystal structure of SBMOF-1 viewed along different crystallographic axes: (A) b axis and (B) a axis. Blue polyhedra are Ca atoms; C, gray; O, red; S,
yellow. (C) N2 adsorption–desorption isotherms at 77 K with an embedded pore size distribution; (D) Experimental adsorption–desorption isotherms of pure CH4 and
N2 in SBMOF-1 at 298 K; The DFT-optimized adsorption configurations of adsorbate molecules in SBMOF-1: (E) CH4; (F) N2. Reproduced from ref. [64]. Copyright
2020, Elsevier.
7
Separation and Purification Technology xxx (xxxx) xxx
selective adsorption due to the strong interactions from Lewis acid sites
[67]. And, the DFT simulation showed that MIL-101(Cr) with the Cr(III)
unsaturated site is also a selective N2 adsorption material, which was
verified by adsorption experiments after activation at 523 K [68]. In
2020, JR Long also reported a new metal–organic framework,
V2Cl2.8(btdd) (H2btdd: bis(1H-1,2,3-triazolo[4,5-b],[4′ ,5′ -i])dibenzo
[1,4]dioxin) with exposed vanadium(ii) sites that can donate electron
density into an adsorbate π* orbital like nitrogenases and their bio­
mimetic analogs, that exhibits the record N2 capacity of 1.9 mmol/g and
CH4/N2 selectivity more than 20 at 298 K and 1 bar, as shown in Fig. 8
[69]. In addition, the separation performance of CH4–N2 mixture can be
enhanced by adopting multi-material compounds, in which some new
pores or interactions can be created for selective adsorption of methane
or nitrogen. ZG Qu prepared Cu-BTC/CuO/CFP (0.30:0.13:0.57) com­
posites with a microporous copper benzene-1,3,5-tricarboxylate/CuO
coating on a macroporous carbon fiber paper (CFP) by an atomic layer
deposition technique, in which the new micropore volume is more than
20% created by the interlayer CuO with CuBTC and CFP, respectively.
This multi-level porous composites showed a higher CH4/N2 selectivity
of 8.0, which is 2.5 times higher than that of pure Cu-BTC at 100 kPa and
273 K [70]. ZM Liu and coworkers proposed a strategy that subunits of
MOFs are introduced into zeolite to obtain a new adsorbent with ad­
vantages of both zeolites and MOFs for the separation of CH4–N2
mixtures, and the CH4/N2 selectivity of as-synthesized ZnY-pIM and
ZnZSM-5-pIM composites were validated to be as high as 7.5 and 8.4
respectively at 1 bar and 298 K which were significantly higher than that
of Y, ZSM-5 and Zn-pIMs [71].
By the way, in order to avoid the tedious trial and error, a high-
throughput computational screening method has been employed to
predict the promising candidates for separating CH4-N2 mixtures, and
the selectivities of many MOFs have exceeded [Co3(C4O4)2(OH)2],
which was assumed to have the highest CH4/N2 selectivity currently. For
example, the CH4/N2 selectivities of KAXQOR01 and ADIQEL are 20.88
and 13.71, respectively, and the CH4 adsorption capacity can reach as
high as 4.07 mmol/g, which is about 2.7 times higher than that of Mg-
MOF-74 (1.5 mmol/g) [72]. Interestingly, S Ordóňez have thought­
fully studied the adsorption behavior of CH4 and N2 in three commercial
MOFs, basolite C300, F300 and A100, in order to obtain a practical data
model. It was found that C300 had a significant interaction with
methane, and A100 had a good adsorption and desorption rate, but they
Q. Wang et al. Separation and Purification Technology xxx (xxxx) xxx

Fig. 6. Illustration of the crystal structure of Al-CDC: along an axis (A) and c axis (B); Reproduced from ref. [65]. Copyright 2020, The Royal Society of Chemistry.
(C)The channel of ATC-Cu. Reproduced from ref. [60]. Copyright 2019, Wiley-VCH.

Fig. 7. (A) Illustration of the crystal structure of the mesoporous Cr(III) trimesate MIL-100(Cr); (B) IAST-predicted CH4/N2 selectivities of MIL-100(Cr) for a molar
CH4/N2 (20/80) mixture at two temperatures (283 K and 293 K); (C) In situ IR spectra of the self-supported MIL-100(Cr) wafer recorded following CO adsorption at
100 K with increasing adsorbed amounts of CO by 0.49, 1.82, 2.56 and 3.53 mmol g− 1; (D) Experimental (filled symbols) and simulated (open symbols) breakthrough
curves of a CH4/N2 mixture (molar composition 20/80) for MIL-100(Cr) at 283 K. Reproduced from ref. [66]. Copyright 2016, Springer Nature.

all could not meet the commercial demand [73]. Briefly, many apolar continuously search for novel MOF adsorbents with excellent compre­
MOFs with 1D micropores (<7 Å) have been demonstrated to be suitable hensive performance in CH4/N2 separation [74]. Further studies should
for separating methane from nitrogen followed the thermodynamic continue to focus on the unique advantages of the MOFs such as
equilibrium mechanism, especially when its pore size is close to the exceptional specific surface area, large pore volume, high modularity,
molecular sizes of CH4 and N2 (3.8 and 3.64 Å). Most importantly, the especially the variable functionality of the channels in the future.
creation of special adsorption sites has become an effective method to Additionally, except for the selectivity, CH4 (or N2) capacity, the thermal
enhance the selectivity and capacity of methane or nitrogen in MOFs by stability, and hydrophobicity suitable are also needed to be improved
additional potential between them, such as [Co3(C4O4)2(OH)2], greatly.
Cu2(ATC), CAU-21-BPDC, SBMOF-1 and Al-CDC. Interestingly, the se­
lective nitrogen adsorption of MOFs from CH4-N2 mixtures will be a
3.2. Zeolites
good idea for the removal of a small amount of nitrogen as the case of
V2Cl2.8(btdd) and MIL-101(Cr), and the multi-material compounds/
Zeolites are generally defined as the coordination of alumina (AlO4)
composites will also be an economical way to create some new pores or
and silicon oxide (SiO4) tetrahedral atoms, which are composed of a
interactions for improving the selective adsorption of methane or ni­
silicon or aluminum cation coordinated with four oxygen atoms and
trogen. In other words, positive progress in MOFs has been achieved for
connect to adjacent tetrahedra by sharing oxygen atom [75]. Zeolites
the adsorptive separation of CH4-N2 mixtures in recent years, however,
possess a specific spatial network, abundant micropores, high specific
most of them still have the problems like poor selectivity, low capacity,
surface area, adjustable hydrophilicity-hydrophobicity, superior ion-
poor stability and high cost, etc. For example, structures of MOF-5, Cu-
exchange property, good thermal stability, and chemical stability,
BTC, M− DOBDC and MFF-MOF are unstable after exposure to water
which make them naturally become high-quality adsorbents [76,77]. As
vapor, which greatly deteriorates their adsorption performances and
above-mentioned, the studies revealed that ultramicroporous adsor­
limits their practical applications. Therefore, it is of great significance to
bents had better ability to separate the gas mixtures with similar

8
Q. Wang et al. Separation and Purification Technology xxx (xxxx) xxx

Fig. 8. (A) Portion of the V2Cl2.8 (btdd) structure; (B) a single five-coordinate vanadium center within the framework determined from powder X-ray diffraction data,
Cyan, green, blue, red and grey spheres represent V, Cl, N, O and C, atoms respectively; (C) Structure of the organic linker H2btdd. (D) Adsorption isotherms for N2
(blue) and CH4 (black) collected at 25 ◦ C in V2Cl2.8(btdd); (E) IAST selectivity values calculated at 25, 35 and 45 ◦ C for varying N2:CH4 ratios at a total pressure of 1
bar; (F) Cycling data for successive N2 adsorption and desorption: Adsorption (blue circles) was collected at 25 ◦ C and 1 bar, desorption (red circles) occurred by
applying dynamic vacuum at 50 ◦ C for 10 min. Reproduced from ref. [69]. Copyright 2020, Springer Nature.

polarizability and size, so that most of the followed researches on CH4- which was 20% higher than that of zeolite-5A grains with binders [84];
N2 separation were focused on the zeolites with 8-ring and/or 10-ring The CH4 selectivity of alkaline earth metal ion-exchanged zeolite-X
pores (<7 Å) [3,6,7,10] (Table 3). increased with the augment of the size of cations, especially the CH4/N2
The separation of CH4-N2 mixtures in conventional zeolites, such as selectivity of Cs-NaX was greatly improved and could reach 3.84
4A, 5A, mordenite, 13X, etc., were researched systematically for the first [86,87]. And then, JP Li and coworkers found that Li+, Na+, K+, Ca2+,
time, as shown in Fig. 3. It was found that the equilibrium adsorption and CS + ions had a great influence on the separation of CH4-N2 mixtures
capacity of methane and nitrogen is relatively small, making it difficult in CHA-zeolites, in which the CH4/N2 adsorption selectivity of K+
to achieve efficient separation [78–83]. Subsequently, the separation exchanged SSZ-13 zeolite increased to 4.5 while adsorption capacity of
performance of conventional zeolites for CH4-N2 mixtures has been methane and nitrogen was significantly reduced, and Li+ exchanged
improved by optimization of shaping method, ion exchange, adjustment SSZ-13 zeolite almost had no CH4 selectivity [87]. Additionally, the
of Si-Al ratio, or composite modified zeolites. For example, the methane composites X-zeolite/AC (activated carbon) have been prepared and
capacity of zeolite-5A grains without binders was up to 0.7 mmol/g, treated by dilute NH4Cl solution, and found that CH4 capacity of com­
posites was determined by the loading of activated carbon, the polar
Table 3 functional groups and micropore volumes, while N2 capacity of com­
Summary of selective adsorption of methane and nitrogen in rigid zeolites. posite mainly depended on X-zeolite content and surface basic proper­
ties. Interestingly, the modified composites showed higher CH4/N2
Zeolite CH4/N2 adsorptive CH4 adsorption capacity Ref.
selectivity (mmolg− 1)
adsorption selectivity of 3.4 while CH4 capacity decreased slightly to
0.77 mmol/g, which can be attributed to the reduction of the micropores
K-Chabazite 5.5c 0.70c [76,87,118]
and the increase of acidic oxygen-containing groups in composites
SSZ-13 2.7c 1.38c [76]
SAPO-34 3.1c 0.73c [76] [88,89].
Linde 4A 2.4a 0.46 a [78] In order to enhance the separation selectivity of CH4-N2 mixtures by
H+mordenite 2.8a 0.45 a [78] reducing the strong interaction between nitrogen and zeolites, the high
Na-X 1.84d 0.83 [82,85]
silicon zeolites such as DDR, Beta, ZSM-5, silicalite-1, and SAPO zeolites
Ca-X 1.36d 1.58 [82,85]
Sr-X 1.45d 1.27 [82,85]
have been investigated in detail, as shown in Fig. 3 [77,78,90,91]. JP
Ba-X 1.78d 1.02 [83,85] Li’s group found that high-silica zeolite, silicalite-1, had the CH4-N2
β-zeolite 2.63d 0.38 [77] selectivity of 3.6–3.8, which is not only attributed to the most suitable
SAPO-18 2.29c 0.16 [95] pore size of 4.6–5.4 Å and the high proportion of micropores, but also
SAPO-34 2.00c 0.60 [95]
ascribed to the fewer balance ions by comparison with DDR and Beta
NaETS-4 2.65d 0.44 [101,102]
ZSM-5 3.28e 0.69 [90] zeolites, as shown in Fig. 9 [92,93]. They also synthesized nano-flake
MEA(40)-β 3.33d 0.10 [77] SAPO-34 zeolites by concentrated gel conversion method, possessing
Silicalite-1 3.52f 0.652c [92,93] better pore structure (the specific surface area is 818.68 m2/g, pore
DD3R 3.13f 0.442c [91,92]
volume is 0.57 cm3/g) than that of micron SAPO-34 crystals, and they
Beta 2.58f 0.558c [92]
5A 2.5f 0.71c [92]
exhibit a high methane capacity of 1.15 mmol/g and the CH4/N2
13X 1.23f 0.50c [92] selectivity of 3.1 [94]. MJ Maple has found that the CH4/N2 selectivity
Clinoptilolites 3.2 0.86 g [98,99] of SAPO-34 and SAPO-18 zeolites exceeded 3 at 303 K and atmospheric
a 273 K,1atm; b 308 K,1atm; c 298 K,1atm; d 303 K,1atm; e 313 K,1atm; f 298 pressure, and their methane adsorption capacities are 0.36 mol/g and
K,1atm (CH4:N2 = 1:1 breakthrough curve); g 300 K,1atm. 0.51 mmol/g, respectively [95]. Recently, AE Rodrigues also

9
Q. Wang et al.
Fig. 9. The main channels of zeolite (A) DDR, (B) silicalite-1, and (C) beta; (D) Adsorption selectivity of mixtures CH4/N2 on DDR, silicalite-1, beta；(E) Break­
through data of silicalite-1 at 298 K and 1 bar for an equimolar CH4/N2 mixture (C, the content of outlet gas; C0, the content of raw gas). Reproduced from ref. [92].
Copyright 2013, The American Chemical Society.
systematically investigated the adsorption equilibrium and kinetic
behavior of CH4 and N2 on H-Beta-25, H-Beta-150 and Na-Beta-25, and
found that there are no significant improvements in the adsorptive
separation of CH4/N2 mixtures [96].
The pore size control of the molecular sieve is an effective method to
achieve the kinetic separation of CH4-N2 mixtures on zeolites. In 1958,
Habgood has found that 4A molecular sieve shows a certain degree of
molecular sieve action, in which methane will be selectively adsorbed at
equilibrium because of a higher affinity with 4A zeolite while nitrogen
preferentially moves into the channels in the early stage of adsorption
owing to its faster diffusion rate [79]. Later, RJ Mohr also found the
same phenomenon when they used the isotope exchange technique (IET)
to measure the equilibria and kinetics of pure and binary gas adsorption
in methane and nitrogen simultaneously on 4A zeolite pellets, demon­
strating that the diffusivity of N2 is an order of magnitude quicker than
that of CH4 [80]. After that, TC Frankiewicz and RG Donnelly discovered
that clinoptilolite with 10-member and 8-member ring channels shows
selective nitrogen adsorption, and the diffusion rate of nitrogen in cli­
noptilolite is 103-104 times faster than that of methane, making it very
suitable for the rapid cycle PSA process for nitrogen removal [97]. RT
Yang confirmed the excellent performance for kinetic separation of CH4-
N2 mixtures that the diffusion rate of nitrogen in clinoptilolite is 55
times faster than that of methane while the adsorption capacities of
methane and nitrogen are equal at equilibrium [98,99]. In 1999, Kuz­
nicki and coworkers invented a new method to tune the pore size of the
titanium silicate ETS-4 zeolite (4 Å) by dehydration at elevated tem­
peratures for providing a ‘molecular gate’ effect. And the as-synthesized
NaSr/Sr-ETS-4 showed the excellent selective adsorption of nitrogen
from methane after dehydration at 270 ◦ C, which is attributed to the
NaSr/Sr-ETS-4 with a pore size between the molecular kinetic diameters
of nitrogen and methane suitable for the nitrogen passing through
[100–102]. In the following two decades, clinoptilolite (<6 Å) and ETS-
4 molecular sieves have attracted much interests in the nitrogen sepa­
ration from methane by steric effect and kinetic effect. RT Yang firstly
studied the effects of the cation exchange treatments of purified
10
Separation and Purification Technology xxx (xxxx) xxx
clinoptilolite with Na+, Mg2+, Ca2+, K+, H+, Li+, Sr2+, and Ce3+ on the
separation of CH4-N2 mixtures, and found that partially exchanged cli­
noptilolites with Ce3+, Mg2+, Ca2+ and Li+ not only show a good se­
lective adsorption of nitrogen over methane at equilibrium, but also
have a much higher diffusion rate of nitrogen than that of CH4.
Compared with the purified clinoptilolites, these mixed ion-exchanged
clinoptilolites showed 50% improvement in product throughput while
a slight decrease in recovery for similar product purity, revealing that
the tailored clinoptilolites are potential adsorbents on nitrogen separa­
tion from methane by PSA process [103,104]. Other corresponding re­
searches have also indicated that sodium has a negative effect for the
separation of CH4-N2 mixtures on the ion-exchanged clinoptilolites
[105], Li+ and Na+ exchanged clinoptilolites promotes the adsorption of
nitrogen and methane at high-pressure [106], and Cu2+ exchanged cli­
noptilolite shows the lowest selectivity in the separation of N2 from CH4
[107]. Moreover, JA Delgado synthesized Sr-ETS-4 zeolite by hydro­
thermal method and liquid-phase ion exchange with the microwave
heating at 473 K, and the kinetic selectivity of nitrogen over methane on
the Sr-ETS-4 is up to 26 at 298 K when the pore size of as-synthesized Sr-
ETS-4 zeolites were shrunk by dehydration at 473 K [108]. S Farooq and
coworkers found that the dehydration temperature of Ba-ETS-4 signifi­
cantly effects on the adsorption equilibrium and kinetics of methane and
nitrogen, in which the ideal kinetic selectivities of Ba-ETS-4 zeolites are
as high as 18.7 and 205 after dehydration at 543 K and 673 K, respec­
tively [109].
Recently, there has been great progress in zeolites for separating
CH4-N2 mixtures based on the thermodynamic equilibrium. For
instance, Z Li found that NH4+, Cs+, and Cu2+ exchanged clinoptilolites
have good equilibrium selectivities for methane against nitrogen of 2.56,
2.31, and 1.95 respectively, while the Na+ and Ag+ exchanged cli­
noptilolites show excellent equilibrium selectivities for nitrogen over
methane of 7.25 and 6.53 respectively [110,111]. XW Liu firstly has
achieved the adjustment of the methane and nitrogen adsorption ca­
pacity on natural clinoptilolite by heat treatment, and found that the
adsorption capacity of methane and nitrogen are all increased by raising
Q. Wang et al.
the calcination temperature, and the influence of calcination tempera­
ture on nitrogen is particularly remarkable. The natural clinoptilolites
show the selective methane adsorption and the ratio of the methane and
nitrogen adsorption capacities is about 5.73 at heat-treatment temper­
ature of 100 ◦ C, but the clinoptilolite exhibits selective nitrogen
adsorption after the calcination temperature more than 150 ◦ C and the
ratio of nitrogen and methane adsorption capacities is up to 1.52 after
treatment at 190 ◦ C [112]. FT Tezel’s group have deeply investigated the
effects of ion exchange on the absorption of methane and nitrogen in
natural clinoptilolite, including alkali metal cations (Li+, Na+, K+, Rb+,
CS+), alkali earth metal cations (Be2+, Mg2+, Ca2+, Sr2+, Ba2+), transi­
tion metal cations (Fe3+, Ni2+, Cu2+, Zn2+, Ce3+) and H+. And they
found that Cs+-exchanged clinoptilolite has high adsorptive selectivity
of CH4 over N2 at equilibrium, Li+ and Ni2+-exchange clinoptilolites
show better kinetic selectivity of N2 over CH4, and Ca2+-exchanged
clinoptilolite improves the CH4/N2 kinetic selectivity at the cost of the
micropore blockages and the diffusion resistance increase [113]. After
that, it also has been found that there is a slight decrease in the micro­
pore distribution of Ag+-exchanged clinoptilolite, which slows down the
adsorption rate of CH4 and N2, but has little effect on the adsorption
capacity of nitrogen. As a result, the equilibrium selectivity of nitrogen
against methane was in the range of 2.8–7.6, which was higher than that
of most clinoptilolites, showing its favorable promising future for the
separation of CH4-N2 mixtures [114]. Moreover, they also noticed that
the CH4/N2 adsorption selectivity of Fe3+-exchanged clinoptilolite
ranges from 3.9 to 7.3 between 288 K and 303 K, much higher than that
of most activated carbons, indicating that clinoptilolite is a promising
adsorbent for the separation of CH4-N2 mixtures [115,116]. In addition,
PA Webley discovered a molecular trapdoor adsorbent, K-CHA zeolite,
that can achieve the conversion of adsorption mechanism between
Fig. 10. (A) CH4 and (B) N2 adsorption isotherms of NaY, TMAY, ChY and TEAY at 25 ℃, up to 103 kPa; (C) IAST-predicted selectivities for equimolar CH4/ N2
mixtures on NaY, TMAY, ChY and TEAY at 25 ℃; (D) Breakthrough curves of equimolar CH4/ N2 (50/50) on NaY, TMAY and ChY at 100 kPa and 25 ℃(solid
symbols: N2, open symbols: CH4). Reproduced from ref. [118]. Copyright 2021, Elsevier.
11
Separation and Purification Technology xxx (xxxx) xxx
thermodynamic equilibrium and molecular sieving separation of CH4/
N2 mixtures with the operating temperature changes. The K-CHA zeolite
exhibited the selective adsorption of methane over nitrogen above 293
K, and could convert to the selective nitrogen adsorption over methane
with the decrease of temperature and become more selective for N2 at
253 K, which shed light on the development of adsorbents with a
controlled invertible selectivity for the separation of CH4/N2 mixtures
[117]. Very recently, YP Xu and ZM Liu found that the Y zeolites
exchanged with tetramethylammonium cation (TMA+) and choline
cation (Ch+) had relatively high CH4/N2 selectivities of 6.32 and 6.50 at
25 ◦ C and 100 kPa respectively, while their specific surface areas
decreased obviously, which can attribute to the greater CH4 affinity of
zeolite framework after TMA+ and Ch+ loading, as shown in Fig. 10
[118].
In a word, great progress has been made in the development of
zeolite-based adsorbents with high adsorption selectivity and high ca­
pacity for the separation of CH4-N2 mixtures, especially the molecular
sieving of methane and nitrogen have paved the way for designing
valuable alternative process for nitrogen rejection from nature gas
[119,120]. Significantly, great progresses have been achieved on zeo­
lites for separating CH4-N2 mixtures based on the thermodynamic
equilibrium, such as the clinoptilolites and Y zeolites exchanged with
different cations. However, there are still many difficulties and chal­
lenges to develop the energy efficient zeolites for separating CH4-N2
mixtures there are still many difficulties and challenges. For example,
how to solve the conflict between the preferential adsorption of methane
with high polarizability and high kinetic selectivity of nitrogen with
small kinetic diameter, how to solve the conflict between the difference
of methane and nitrogen in quadrupole moment and polarizability, and
how to achieve the regulation of adsorption potential of different
Q. Wang et al. Separation and Purification Technology xxx (xxxx) xxx

zeolites by ion exchange and Si/Al ratio modulation. are the most representative materials, and with the CH4/N2 adsorption
selectivity of more than 3 for RB3 and up to 4.5 for BPL [126–129].
3.3. Carbon-based adsorbents Another thing should be noticed is that coal has been widely used to
prepare activated carbons for the selective methane adsorption from
Carbon-based materials are the traditional porous materials with nitrogen because it is one of the cheapest raw materials with the high­
excellent performance in the adsorptive separation of CH4-N2 mixtures. est content of carbon. M Gu has employed the bituminous coal as the
These materials also have many other advantages such as simple prep­ raw material to prepare the shaped active carbons by carbonization-
aration, abundant raw materials, low cost, and wide applications in activation-chemical vapor deposition process for concentrating
various adsorption processes. Among carbon-based materials, activated methane from CH4-N2 mixtures, and as-prepared adsorbents with a CH4/
carbon (AC) and carbon molecular sieves (CMS) are the two most N2 selectivity of 3.1 indicates that it is a cost-effective alternative to
commonly used carbon-based adsorbents. The activated carbons with obtain high-performance ACs [130]. And then, TE Rufford and ZH Zhu
well-developed pore structure and large specific surface areas, have have produced the activated carbon monoliths by low-pressure foaming
been attracted much attention in a wide range of industrial processes process, in which the mixtures of petroleum tar pitch and powdered coal
due to the advantages of the high adsorption capacity, good chemical were made into raw materials and potassium hydroxide was used as
stability, good hydrophobic, and easy regeneration [121]. As for carbon activation. This carbon monolith featured a specific area of 1044 m2/g
molecular sieves, it is the typical carbonaceous adsorbents with the and well-developed hierarchical pore structures containing high vol­
narrow pore size distribution in the range of 3 Å to 10 Å. Importantly, umes of micro-, meso- and micropores, which leads to a good separation
these micropores in CMS are mainly slit-like pores, which allows performance not only with high CH4/N2 selectivity of 3–4 but also with
some small-size molecules to cross it more easily than other big ones by large methane adsorption capacity of 1.1 mmol/g [131]. Afterward, the
the molecular sieving effect [122] (Table 4). super activated carbon with a high specific surface area and pore volume
The activated carbon is a typical carbon material composed of up to 3068 m2/g and 1.779 cm3/g, respectively, has been made from the
graphite-like microcrystals arranged in a “spiral layer structure”. The low-rank bituminous coal with KOH as an activating agent, in which the
well-developed pore structure was constructed through a high degree of coal-based activated carbons (CACs) with different pore structures can
crosslinking of these graphite-like microcrystals, in which the pore size be controlled by the activation temperature. These CACs all exhibited
distribution is always disordered, including macropores, mesopores, selective methane adsorption with CH4/N2 selectivity of 3–4, and it has
micropores and ultra-micropores. The separation of CH4-N2 mixtures been discovered that the pore size in the range of 5.5–8.5 Å has a sig­
usually achieved by the difference of adsorption capacities between nificant effect on the separation of CH4-N2 mixtures while the mesopores
methane and nitrogen on AC at equilibrium. It is well known that there and macropores have no effects on the selectivity [132]. Subsequently, it
are many significant differences in properties for different activated has been noticed that the CH4/N2 adsorption selectivity and the
carbons such as the specific area, surface properties, pore size distri­ methane adsorption capacity of the asphaltene-based carbon pellets are
bution and adsorption performances, which should normally attribute to up to 5.5 and 1 mmol/g at 303 K and 100 kPa, making it a good choice
the differences of the raw materials and preparation methods of acti­ for methane capture from coalbed methane gas [133]. Furthermore,
vated carbon materials. Therefore, many researches have long been AE Rodrigues’s group systematically investigated the structure control
concerned with the surface modification, pore size optimization, and and structure–activity relationship of ACs from coconut shells (typical
performance simulation and analysis of gas adsorption on the new acti­ biomass derived porous carbon materials) with potassium hydroxide as
vated carbon materials to improve the relative adsorption capacity of activation agents, including the effect of raw material for AC structures,
methane against nitrogen. And now, it has been confirmed that the the effect of activators on the methane adsorption capacity, the rela­
adsorption selectivity of methane against nitrogen in the commercial tionship between the specific surface area of porous carbon materials
carbon-based adsorbents is usually in the range of 2.1 to 5.5, which is and methane capacity, and the relationship between micropore size
higher than that of zeolites, although there are some variations in the distribution of ACs and the mechanism of CH4/N2 adsorption separa­
adsorption capacity and selectivity of methane due to the difference of tion. They revealed that the specific surface area of ACs is not a key
carbon sources [123–125]. Among them, Maxsorb, Norit RB3, and BPL parameter for the adsorption capacity when the specific surface area
reaches above 1000 m2/g, and the separation of CH4/N2 mixtures on
ACs with relative bigger micropore size follows the thermodynamic
Table 4
Summary of selective adsorption of methane and nitrogen in rigid ACs. equilibrium mechanism, whereas the CMS with smaller micropore size is
controlled by kinetic factors. Under the same experimental conditions
AC CH4/N2 adsorptive CH4 adsorption capacity Ref.
with KOH as activation agent, the as-synthesized porous carbon mate­
selectivity (mmolg− 1)
Takeda CMS 3 k 1.9a 0.97a [122] rials had different micropore structures due to the difference of raw
MAC 3.33a ~0.98a [124] materials, and the order of CH4/N2 separation selectivity of activated
Norit RB 3 3.0–7.0c ~0.48c [125] carbons from different raw materials was as follows: coconut charcoal >
ACMs 3.27b 1.4b [131]
pitch-based activated carbon > coal-based activated carbon > wood-
CACs 2.8–3.1a 5.8a [132]
Activated carbon 5.5c 1.1c [133]
derived activated carbon [134]. In addition, the novel rice-derived
beads activated carbon has been prepared by carbonization, and activated
PRCs 5.7a 1.12a [125] by CO2. These rice-based particles exhibited a specific BET surface area
GACs 1.88–3.17a 1.5–2.5a [139] of 776 m2/g, the methane adsorption capacity of 1.12 mmol/g and the
ACs 5.33a 0.35a [141]
selectivity of CH4/N2 separation up to 5.7 at 298 K and 100 kPa. The
SAC-ben 4.87a 2.25a [144]
SAC-ben-P-N2 5.08a 1.5a [144] computational simulation revealed that the hydroxyl/carboxyl/alde­
SAC 3.16a 2.1a [144] hyde groups on the surface of rice-derived activated carbon play an
N-doped porous 7.62a 1.01a [148] important role in the enhancement of the selective methane adsorption
carbon from nitrogen, as shown in Fig. 11 [135].
OTSS-1–550 5.22a 1.7a [149]
PS-2–450 7.6a 1.2a [150]
The adsorption capacity and selectivity of activated carbons are
PS-1–550 6.6a 1.6a [150] mainly determined by the micropore size distribution and surface
CMS-P-N 3.32a 6.67a [150] properties. Non-local density functional theory (DFT) has been used to
CMS-3 2.71a 0.6a [158] simulate the CH4 and N2 adsorption behaviors of the activated carbons
a 298 K, 1 bar；b 273, 298, 323 K, 1 bar；c 303 K, 1 bar；d 298 k, 1 bar (CH4: with the pore size in the range of 5–50 Å, and predicted that the CH4/N2
N2 = 1:1 breakthrough curve)；e 298 K, 35 bar. separation selectivity of activated carbon with a pore size of 8 Å should

12
Q. Wang et al.
Fig. 11. The photograph of PRCs: (A) glutinous rice, (B) after carbonization, (C) after CO2 activation; (D) pore-size distribution of PRCs; (E) CH4 and N2 isotherms of
PRCs adsorbents at 298 K; (F) Breakthrough curves of CH4/N2 mixture. Reproduced from ref. [135]. Copyright 2019, Elsevier.
be between 7.8 and 9.7 at room temperature and atmospheric pressure
[136]. L Zhou also confirmed that the pore size of ACs in the range of
7–13 Å is the best size for separating the CH4-N2 mixtures and there is no
linear correlation between pore volume and the separation coefficient,
but the separation coefficient is linearly related with the pore volume
when it reduces to unit surface area of ACs [137]. SP Xu investigated the
influence of microporous structure for the adsorption separation of CH4-
N2 mixtures on ACs, and found that the CH4/N2 separation selectivity of
as-synthesized sample is up to 5.29 owing to the pore size smaller than
4.8 Å [138]. The effect of the pore size distribution of anthracite-based
ACs for the separation of CH4-N2 mixtures was also discussed, and re­
sults revealed that the activated carbons can be used to enrich methane
from nitrogen when the pore size is in the range of 5.0–13 Å, and the
optimal CH4/N2 selectivity can be obtained when the pore size is be­
tween 5.0 and 8.0 Å [139]. On the other hand, it is noteworthy that the
separation performance of CH4-N2 mixtures on ACs can be enhanced by
surface modification with other species or hetero-elements. In 1989, RT
Yang began to modify the BPL activated carbons by Br2 vapor deposi­
tion, and the methane adsorption capacity of the modified activated
carbons had no significant improvement while the adsorption of nitro­
gen was effectively suppressed, resulting that the selectivity of CH4 over
N2 was improved by nearly 40% [140]. And then, the microporous
activated carbons were modified via impregnation with NH3, HCl and
KOH for enhancing the adsorption of methane, and found that the
modified sample with HCl and KOH possessed the dynamic methane
adsorption capacity of 0.35 mmol/g and the CH4/N2 selectivity of 5.33,
which were increased about 38.9% and 38.4%, respectively [141]. The
synergistically modified activated carbon that was activated by phos­
phoric acid first, and then treated with steam at 800 ◦ C, exhibited a
dynamic CH4 adsorption capacity of 0.29 mmol/g, which is two times
higher than that of original sample. The pronounced increment of
methane adsorption capacity on these modified ACs was proven to be
resulted from the increase of micropores with the diameter of 4.5–6.5 Å,
but the surface oxygen-containing groups on the surface of ACs pro­
hibited the adsorption of methane slightly [142]. Moreover, molybde­
num dioxide (MoO2) has been loaded into the activated carbon to
improve the separation performance of CH4-N2 mixtures many years
ago, and the modified activated carbon with MoO2 loading of 18.3 wt%
could significantly increase the CH4/N2 selectivity to 4.25 at ambient
temperature and pressure [143]. Synergistically, modified activated
13
Separation and Purification Technology xxx (xxxx) xxx
carbons impregnated with organic reagents firstly and treated with low-
temperature plasma showed a high adsorption selectivity of methane
over nitrogen of 5.08, which is 1.6 times higher than the original sample.
It was found that the loaded organic solvents played an important role in
the mesoporous regulation of this activated carbon, and some ester
groups were grafted into the surface of the SACs [144]. In addition, the
doping of hetero-element such as N, has been turned out to be a very
effective method to change the structure of activated carbons and
enhance their adsorption selectivity of methane over nitrogen, as-shown
in Fig. 3. The coconut shell charcoal was firstly modified with ammonia,
and results showed that the loading of ammonia increased the dynamic
and static selectivity of methane over nitrogen by 11.7% and 14.9%
respectively. It was proved that amine and amino groups were helpful to
enhance the adsorption affinity of methane, and the reduction of amine
and hydroxyl weakened the interaction between methane and AC
adsorbent, indicating that nitrogen doping could improve the adsorption
performance of CH4-N2 mixtures on activated carbon [145]. Afterward,
nitrogen-doped carbon foam which was synthesized from banana peel
via a soft-template method with zinc nitrate, furfural, and 2-aminophe­
nol, contained up to 6.0 wt% nitrogen and had high specific surface
areas up to 1426 m2 g− 1. These monolithic carbon foams exhibited the
high CH4 adsorption capacity of 1 mmol/g and the CH4/N2 equilibrium
selectivity between 3 and 4 [146]. Soon afterward, ultramicroporous
activated carbon with nitrogen doping content of more than 10 wt% was
synthesized by the pyrolysis of a perchloro-substituted porous covalent
triazine-based framework (ClCTF). This highly N-doped activated car­
bon showed a high methane adsorption capacity of 1.4 mmol/g and the
CH4/N2 selectivity greater than 9, indicating that introducing high
amounts of N-dopant into microporous activated carbon is an effective
means to improve the selective adsorption of methane against nitrogen
[147]. Interestingly, novel porous carbon with high N content of 14.48
wt% that was synthesized from waste wool with potassium hydroxide
(KOH) as activation agent and urea as N dopant, featured micropore size
in the range of 5.2–1.2 Å and the specific surface area of 862 m2/g. The
CH4/N2 selectivity and methane adsorption capacity of the wool-derived
ACs are as high as 7.6 and 1.01 mmol/g at room temperature and or­
dinary pressure, respectively [148]. Recently, nitrogen-doped porous
carbons with a large surface area of 2965.7 m2/g and high N-doping
level of 6.6 wt% were fabricated via a low-temperature and one-pot N-
doping method from oil-tea seed shell with NaNH2 as activation agent
Q. Wang et al.
and N dopant, which showed the CH4/N2 adsorption selectivity is up to
5.6 at 298 K and 1 bar [149]. And then, N- and O-rich porous carbons
with the surface area up to 2181 m2/g were prepared by the same
method at 350–550 ℃ with the palm sheath as the precursor, in which
the surface area, pore size distribution, and polar functional groups (O/
N) ratio can be regulated by the control of activation temperature or
NaNH2/biomass ratio. The as-prepared activated carbons showed
excellent CH4/N2 selectivity of 7.6 and CH4 uptake of 1.5 mmol/g at
298 K and 1.0 bar, respectively, indicating that both ultra-micropores
and heteroatoms (O/N) dominated the CH4 adsorption capacity as
well as the selectivity [150]. In addition, AH Lu and coworkers reported
a new self-pillared 2D polymer and ultramicroporous carbon with in­
tegrated surface protrusions that were prepared via a one-pot multi-
component sequential assembly method with P-PDA to trigger the
condensation reaction of Pol, TPA, and P-PDA, as shown in Fig. 12.
These pillared 2D carbons featured the proportion of 4.8 Å micropores,
more than 65%, and exhibited a very high CH4/N2 selectivity up to 24,
which is 3–10 times higher than that of 5A and 13X molecular sieves,
and 2–3 times higher than that of other nitrogen doped activated car­
bons, indicating that this liquid phase synthesis method is a very
effective and controllable strategy to fabricate activated carbon adsor­
bents for CH4/N2 separation [151].
Carbon molecular sieves are essentially ultra-microporous activated
carbons, exhibit a good adsorption affinity for non-polar small mole­
cules with kinetic diameter of<5 Å. The adsorption separation of CH4-N2
mixtures in the carbon molecular sieves usually employs two different
mechanisms of kinetic effect or/and thermodynamics equilibrium effect
[152,153]. Especially, the kinetics effect will dominate the gas separa­
tion when the pore size of CMS is between kinetics diameters of the two
different gas molecules, and the separation efficiency will be enhanced
greatly by the big difference between the adsorption and desorption
rates of gas molecules in these ultramicropores [154]. In 1991, HY Ma
has measured the diffusion time constants of N2 and CH4 on the Takeda
3A carbon molecular sieve at 303 K, revealing the good kinetic selec­
tivity of CH4/N2 owing to the adsorption rate of nitrogen (2.64 × 10-4
s− 1) much higher than that of methane (2.86 × 10-5 s− 1) [155]. And
immediately thereafter, HJ Schröter found that narrow-pore CMS had
Fig. 12. (A) The synthesis scheme based on p-PDA triggered condensation of POL, TPA and p-PDA; (B) The corresponding polymerization reactions for the formation
of the pillared 2D structures; (C) SEM image of polymer nanoplates with nanopillars; (D) CH4 and N2 adsorption isotherms at 298 K. Reproduced from ref. [151].
Copyright 2020, Wiley-VCH.
14
Separation and Purification Technology xxx (xxxx) xxx
better CH4/N2 separation performance than broad-pore CMS, and the
ratio of the diffusion rate of them could be more than 102 [156]. CH Lee
also investigated the adsorption behavior of methane and nitrogen on
CMS by volumetric method, and confirmed the feasibility of the sepa­
ration of CH4-N2 mixtures on CMS by the kinetic effect [157]. Recently,
X Yang systematically studied the adsorption performance of several
carbon molecular sieves in coalbed methane enrichment, and results
showed that the equilibrium adsorption capacity of methane is higher
than that of the oxygen and nitrogen, the CH4/N2 selectivity will in­
crease with the increasing of the proportion of micropores. But the
diffusion time constant of oxygen and nitrogen was higher than that of
methane, and the critical role of its excellent molecular sieving effect in
CH4 enrichment from nitrogen has been verified dynamic adsorption
process [158]. Furthermore, coal-based and biomass-derived carbon
molecular sieves have also continued to be investigated for the separa­
tion of CH4-N2 mixtures. For instance, JP Lukaszewicz has fabricated the
CMS from pines and willows with zinc chloride as activation agents. This
biomass-derived CMS featured the average pore size of 8 Å and the
specific surface area of 1263 m2/g, and exhibited the highest CH4/N2
separation selectivity up to 7.36–10.2 [159]. JH Zhang prepared the
carbon molecular sieves by chemical vapor deposition method with
benzene as depositing agent based on coal-based ACs, and the obtained
coal-based CMS showed the average pore size of 4.7 Å, resulting that the
maximum methane adsorption capacity is up to 1.41 mmol/g at equi­
librium, the CH4/N2 separation selectivity is 4.74 at equilibrium and the
kinetic CH4/N2 separation selectivity is up to 35.26 [160]. GN Okolo
also has investigated the adsorption performance of methane and ni­
trogen in CMS prepared from South African bituminous coal, and found
that the critical properties of gases and the characteristics of coal also
had an impact on the adsorptive separation of CH4-N2 mixtures [161].
Moreover, coal-based CMS have been modified synergistically by
impregnated with organic reagents firstly and treated with low-
temperature plasma for CH4-N2 mixture separation, and it was found
that the methane capacities of all modified samples were improved
obviously, and the CH4/N2 separation selectivity was about 3.32 [162].
Notably, the dynamic separation performance of CH4-N2 mixtures in
CMS also had more in-depth researches. Many years ago, RT Yang has
Q. Wang et al.
researched the PSA separation performance of BF company’s CMS, and
demonstrated that it was difficult to obtain 90 vol% methane products
from CH4-N2 mixtures of 50:50 v/v in a two-bed setup by simple four-
step PSA process, where the separation efficiency was directly affected
by adsorption pressure, feed gas concentration and gas flow rate of
product [163]. AI Fatehi also studied that the CH4/N2 separation per­
formance of BF company’s CMS using a two-column PSA experimental
unit, and confirmed that the CH4 concentration can be enriched to 75%
from 60% easily, but it is difficult to reach 90% [164]. Computer sim­
ulations have been employed to predict the separation performance of
CH4-N2 mixtures in a two-bed PSA system with the CMS as adsorbents. K
Warmuziński found that the adsorption equilibrium of CH4 and N2
mixtures on CMS is nonlinear, and there is an optimum point of the
adsorption pressure that can shift with the change of feed gas concen­
tration, cycle length, and other factors [165]. Furthermore, the vacuum
pressure swing adsorption process (VPSA) has been carried out to verify
the separation performance of CH4-N2 mixtures in CMS. B Yang and
coworkers researched the separation performance of CH4-N2 mixtures in
CMS by VPSA experiment and computer simulation, and reported that
the CMS-VPSA cycle could concentrate 10% CH4 to 79% with a recovery
of 93% and a yield of 0.072 mL g− 1 min− 1, which is of important
reference for the enrichment of low-quality methane [50]. In the near
past, it has been verified that the CH4 concentration could be increased
nearly 2.5 times with a recovery of 80% at the adsorption pressure of
120 kPa in the VPSA process with CMS adsorbents, revealing it is
feasible for the coal mine gas purification [166].
In one word, the separation performance of CH4-N2 mixtures in the
carbon-based adsorbents has already been improved greatly by the
control of micropore size distribution and surface properties. It is worth
emphasizing, specially the doping of hetero-element such as N, which is
becoming a very effective method to regulate the surface properties of
activated carbons and enhance their adsorptive selectivity of methane
over nitrogen by the thermodynamic equilibrium mechanism. The dis­
advantages like disordered distribution of the pores, and the complex
and uncertain functional groups in the surface of the carbon-based ad­
sorbents still lead to the difficulty in the further improvement of the
separation efficiency. Therefore, there are some important cases that
need to be dealt in the carbon-based adsorbents implement during the
large-scale industrial process for the separation of CH4-N2 mixtures
[167], like finding physicochemical methods for effective control of
micropores, improving the structural stability, overcoming the deacti­
vation of CMS with ‘molecular gate’ effect, increasing the adsorption
capacity of specific volume and mechanical stability, and reducing the
manufacturing cost.
4. Conclusions and prospects
Methane is the cleanest and cheapest fossil energy; however, it is also
the second-largest contributor to global warming after carbon dioxide.
The development of new nitrogen rejection from methane for achieving
the enrichment and utilization of unconventional natural gas and in­
dustrial tail gas, not only can alleviate the shortage of natural gas, but
also have important significance for rebalancing the global methane
cycle. Adsorption separation has becoming an alternative of the con­
ventional cryogenic distillation for more energy efficient N2 removal
from the low-quality methane due to the advantages of compact module,
simple process, and low operating cost. Undoubtedly, the development
of high-efficient adsorbents is the key procedure of adsorptive separa­
tion to improve the nitrogen removal efficiency from nature gas
continuously.
Theoretically, the difference between the polarizability, kinetic
diameter, and the quadrupole moment can be directly used as the design
basis of adsorbents for separating CH4 and N2 mixtures, but the differ­
ence is relatively small: the polarizability of CH4 is only 1.4 times higher
than that of N2, and the kinetic diameter of CH4 is only 0.16 Å larger
than that of N2. Based on these two differences between CH4 and N2,
15
Separation and Purification Technology xxx (xxxx) xxx
many different adsorbents such as porous carbon, zeolites, and MOFs,
have been considered in the study of adsorptive separation of CH4-N2
mixtures, and great progress has been made in recent years. From the
point of view of selective methane adsorption, MOFs have exhibited the
superiority, for example, the methane adsorption capacity and CH4/N2
selectivity of [Ni3(HCOO)6], [Cu(INA)2], ROD-8, Ni-L, ATC-Cu,
[CO3(C4O4)2(OH)2], Cau-21-BPDC and [Co/Ni(ma)(bpy)0.5] have
exceeded 0.75 mmol/g and 6 respectively. The CH4/N2 selectivities of
porous carbons and silica-alumina zeolites are usually<5.0 and 3.0
respectively, but it has been confirmed that the selectivity of nitrogen-
doped carbon materials can exceed 7.0 recently. From the point of
view of selective nitrogen adsorption, Ce3+, Ca2+, Ni2+, Ag+, and Cs+
exchanged clinoptilolites all have exhibited good CH4/N2 kinetic
selectivity, and the CH4/N2 selectivity of Ag+ exchanged clinoptilolite
have reached 6.53 at equilibrium. Significantly, the Ba-ETS-4 zeolite
presented that the highest equilibrium N2/CH4 selectivity is more than
18 and can be up to 205, and V2Cl2.8(btdd) MOF exhibited the kinetic
N2/CH4 selectivity is also more than 20 and even close to that of Ba-ETS-
4.
In conclusion, the research on the adsorbents for separating CH4-N2
mixtures has been very in-depth, and the adsorption behaviors of many
adsorbents with different structures have been mastered, as well as the
principle of performance optimization. From the viewpoint of materials
design and construction, however, there are still many problems that
need to be improved for continuously exploring new strategies to
enlarge the difference in attraction forces with adsorbents between
methane and nitrogen. For example, the present control and optimiza­
tion strategy of surface properties and pore size of zeolites and porous
carbons cannot meet the requirements, especially difficult for the fine-
tuning of aperture and surface properties of ultramicropores (<8 Å) at
the molecular scale. It was virtually impossible to achieve the control or
conversion of selective methane or nitrogen adsorption in zeolite, MOFs,
and carbon-based adsorbents. The controllability and reproducibility of
heteroatom doped carbon-based adsorbents should be concerned and
taken further research, particularly the fabrication cost need to be
greatly reduced. Interestingly, MOFs show their own strengths in the
adsorption separation of CH4-N2 mixtures, and their effective and
controllable optimization strategy of pore structure and surface prop­
erties provides a new idea for the properties tailoring of adsorbents for
CH4-N2 separation. However, the adsorption selectivity and capacity of
MOFs still have a great potential for further optimization and
improvement in the future, the stability and cost control of MOF-based
adsorbents in particular, need deeper and further research.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work was supported by the National Natural Science Foundation
of China (22078037, 21776266, and 21476231) and the Fundamental
Research Funds for the Central Universities (3132021221).
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