Separation and Purification Technology 230 (2020) 115858

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Separation and Purification Technology

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

High-pressure CO2/CH4 separation of Zr-MOFs based mixed matrix T

membranes
Mohd Zamidi Ahmada,b,c,1, Thijs A. Petersd, Nora M. Konnertze, Tymen Vissere, Carlos Téllezc,
Joaquín Coronasc, Vlastimil Filaa, Wiebe M. de Vosb, Nieck E. Benesb,
⁎

a
Department of Inorganic Technology, University of Chemistry and Technology Prague, Technicka 5, Dejvice – Praha 6, 16628 Prague, Czech Republic
b
Membrane Science and Technology, Faculty of Science and Technology, MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217, AE Enschede,
Netherlands
c
Chemical and Environmental Engineering Department and Instituto de Nanociencia de Aragón (INA) and Instituto de Ciencia de Materiales de Aragón (ICMA),
Universidad de Zaragoza-CSIC, 50018 Zaragoza, Spain
d
SINTEF Industry, P.O. Box 124, Blindern, N-0314 Oslo, Norway
e
European Membrane Institute Twente (EMI), Faculty of Science and Technology, University of Twente, P.O. Box 217, AE Enschede, Netherlands

ARTICLE INFO ABSTRACT

Keywords: The gas separation properties of 6FDA-DAM mixed matrix membranes (MMMs) with three types of zirconium-
Zr-based MOF based metal organic framework nanoparticles (MOF NPs, ca. 40 nm) have been investigated up to 20 bar. Both
Mixed matrix membrane NPs preparation and MMMs development were presented in an earlier publication that reported outstanding
High-pressure separation CO2/CH4 separation performances (50:50 vol% CO2/CH4 feed at 2 bar pressure difference, 35 °C) and this
CO2 capture
subsequent study is to demonstrate its usefulness to the natural gas separation application. In the current work,
H2S separation
CO2/CH4 separation has been investigated at high pressure (2–20 bar feed pressure) with different CO2 content
in the feed (10–50 vol%) in the temperature range 35–55 °C. Moreover, the plasticization, competitive sorption
effects, and separation of the acid gas hydrogen sulfide (H2S) have been investigated in a ternary feed mixture of
CO2:H2S:CH4 (vol% ratio of 30:5:65) at 20 bar and 35 °C. The incorporation of the Zr-MOFs in 6FDA-DAM
enhances both CO2 permeability and CO2/CH4 selectivity of this polymer. These MMMs exhibit high stability
under separation conditions relevant to an actual natural gas sweetening process. The presence of H2S does not
induce plasticization but increases the total acid gas permeability, acid gas/CH4 selectivity and only causes
reversible competitive sorption. The overall study suggests a large potential for 6FDA-DAM Zr-MOF MMMs to be
applied in natural gas sweetening, with good performance and stability under the relevant process conditions.

1. Introduction membranes have allowed the technology to increase its share of the
total membrane market, comprising over 1000–1500 million US dollar
The acid gas content (carbon dioxide, CO2; hydrogen sulfide, H2S) per year [8] and appear to be the most viable alternative to substitute
in raw natural gas varies accordingly to the hydrocarbon geo-origins the conventional highly energy consuming processes, including the
[1,2] and is commonly in the range of 25–55 mol.% for CO2 and below solvent-based adsorption processes [5]. However, due to challenges
2 mol.% for H2S (≥5 mol.% in several regions) [3,4]. CO2, the most such as plasticization especially at high-pressure operation and de-
undesirable diluent aside from H2S, is essential to be discarded from the gradation, membrane processes only represents < 5% of the natural gas
gas stream as it corrodes transmission pipelines in the presence of water sweetening market [9,10].
[5,6]. Additionally, CO2 lowers the natural gas caloric value and causes Both plasticization and degradation effects can be suppressed by
atmospheric pollution [2,3,5]. Consequently, the content of these im- polymer blending and cross-linking [11–15], but a more promising
purities must be reduced to meet the industrial processing and pipeline method is the combination of polymeric and inorganic materials as
distribution requirements, e.g., maximum allowable contents of mixed matrix membranes (MMMs) [16–20]. Yong et al. [16] reported
2–3 mol.% CO2 and 0.0004–0.0005 mol.% (4.3–5.0 ppm) H2S (see the effectiveness of 2 wt% POSS (polyhedral oligomeric silsesquioxane)
Table S1) [7]. In the last decades, the advances in gas separation nanoparticles into the highly permeable PIM-1 to suppress the neat

⁎
Corresponding author.
E-mail address: n.e.benes@utwente.nl (N.E. Benes).
1
Current address: Organic Materials Innovation Center (OMIC), School of Chemistry, University of Manchester, Oxford Rd, M13 9PL Manchester, United Kingdom.

https://doi.org/10.1016/j.seppur.2019.115858
Received 25 June 2019; Received in revised form 24 July 2019; Accepted 24 July 2019
Available online 25 July 2019
1383-5866/ © 2019 Elsevier B.V. All rights reserved.
M.Z. Ahmad, et al. Separation and Purification Technology 230 (2020) 115858

polymer CO2-induced plasticization pressure of 15 bar in the range of solution was centrifuged, rinsed with fresh CHCl3 (15 mL, 3x) and dried
tested pressure (30 bar) with 50:50 vol% CO2:CH4 feed mixture, at overnight at 150 °C before characterization and use. The conversion
35 °C. Additionally, the MMM presented 40.8% CO2 permeability and yield was determined by the percentage of amide groups present in the
11.4% CO2/CH4 selectivity improvements. Adams et al. [17] reported a modified NPs using proton nuclear magnetic resonance (1H NMR), and
more than five times increase of CO2 partial pressure needed to plas- the digestion method was presented elsewhere [38,39]. All reactants
ticize PVAc-50 wt% zeolite 4A at 30 bar, also measured with 50:50 vol applied in the NP synthesis were supplied by Sigma-Aldrich.
% CO2:CH4 feed mixture, at 35 °C. Both Shahid and Nijmeijer [18] and 6FDA-DAM (Mw = 418 kDa) was purchased from Akron Polymer
Samadi and Navarchian [19] reported higher CO2-plasticization pres- Systems, Inc. and dried overnight at 100 °C before use. Pure polymer
sures of Matrimid® 5218 (neat Pplasticization. of ~10 bar) by in- membranes (“neat”) and MMMs were fabricated by dissolving the
corporating 30 wt% mesoporous Fe-BTC [18], 5 wt% MgO [19] and corresponding amount of 6FDA-DAM in chloroform, making a dope
10 wt% modified clay mineral with polyaniline [19], up to 21, 15 and solution of 10 wt%. In the case of MMM, a priming step was conducted
30 bar, respectively. with 10–15 wt% of the total polymer weight that proves to improve the
Permeation of a mixture of gases through a membrane can depend inorganic filler dispersion in the continuous polymer phase [40–42].
strongly on the operating parameters, for example, the feed pressure The final dope solutions were casted in a Petri dish and covered for
and temperature, amongst others due to the gases’ non-ideal behavior controlled solvent evaporation overnight before being treated at 110 °C
[21–23] and their competitive sorption [21,23–25]. Moreover, in a before subsequent characterization and permeation measurements. The
MMM system, the presence of a porous filler and the new filler-polymer flat sheet membranes were in the thickness range of 100–150 μm.
interfacial phase created need to be understood as they further influ-
ence the gas mobility and sorption through the membrane. Metal or- 2.2. Standard permeation measurement
ganic frameworks (MOFs), formed with metal-based clusters linked by
organic ligands [26] in three-dimensional crystalline frameworks with To assess the gas separation performance of the membranes, a 25/
permanent porosity, are an emerging class of porous fillers [27]. They 25 cm3(STP)·min−1 CO2/CH4 binary feed mixture was used at a pres-
have gained substantial attention due to their high CO2 uptake (i.e., sure difference of 2 bar at 35 °C applying He as sweep gas at 1 cm3
HKUST-1 of 7.2 mmol·g−1 [28], MOF-74 of 4.9 mmol·g−1 [29], at 1 bar, (STP)·min−1. The permeate composition was analyzed online by an
273–298 K), large surface areas up to 7000 m2·g−1 [30], well-defined Agilent 3000A micro-GC equipped with a thermal conductivity detector
selective pores due to their crystallinity, amongst other features. Many (TCD) at the Institute Nanoscience of Aragon (INA), University of
researchers observed that the incorporation of a MOF into the polymer Zaragoza. The membrane module is as described elsewhere [43]. The
continuous phase improved not only its separation properties but also permeability was calculated as the penetrated gas flux, normalized for
its physical properties [16,31–33], due to interfacial interactions be- the membrane thickness and the partial pressure drop across the
tween the polymer and the MOFs. The polymer, in some cases, pene- membrane, and presented in Barrer (1 Barrer = 10−10
trates the MOF open pores or rigidifies and forms microvoids at the cm3(STP)·cm·cm−2·s−1·cmHg−1 (Eq. (1)).
interface [34,35], thereby affecting the membrane’s physical properties
Flux gas (cm3 (STP ). cm 2 . s 1) × Thickness (cm)
and gas separation performance. Permeability, Pgas =
Zr-based MOF UiO-66 is a highly stable new material and has re- pgas (cm . Hg )
cently been applied as part of a MMM [31,36,37]. The synthesis of three (1)
types of Zr-MOFs, namely UiO-66 and its functionalized derivatives,
The separation factor (α) of two competing gases was calculated
UiO-66-NH2 and UiO-66-NH-COCH3, as well as MMM fabrication with
using Eq. (2), considering the mole fraction (x) of gas i and j in both
6FDA-DAM have been presented earlier [31,34]. In the current paper,
feed and permeate streams. The mixed gas separation performance was
we present the gas separation performance of the neat 6FDA-DAM
previously discussed [34], and the best performing MMMs are with
membranes and their derived Zr-MOF MMMs as a function of feed
14–16 wt% Zr-MOF particle loadings.
pressure between 2 and 20 bar. At the highest pressure, the effects of
CO2 content in the feed mixture on membrane performance have been xi perm ./ xjperm .
=
investigated, at various temperatures (35–55 °C). Finally, the presence i/j
x i feed / x jfeed (6-2)
of H2S to the separation performances has been studied.

2. Experimental 2.3. High-pressure performance evaluation

2.1. Materials and membrane fabrications The membranes were placed in a proprietary high-pressure per-
meation module obtained from the European Membrane Institute (EMI,
The UiO-66 and UiO-66-NH2 NPs (ca. 40 nm in size) were synthe- The Netherlands). The membrane was supported with an S&S 589/1
sized accordingly to Hou et al. [38], at 1 to 1 M ratio of zirconium (IV) black ribbon ash-less filter paper on a perforated plate to avoid mem-
chloride (ZrCl4, ≥99.5% trace metal basis) to 1,4-benzenedicarboxylic brane deformation during the high-pressure testing. The sample was
acid (BDC, 98%) or 2-amino-1,4-benxenedicarboxylic acid (NH2-BDC, sealed with an o-ring system providing for an effective membrane area
99%), in N,N-dimethylformamide (DMF, ≥99.9%), through a sol- of 0.78 cm2. Both feed and retentate sides were connected by high-
vothermal process in a pre-heated oven at 120 °C/24 h for UiO-66 and pressure Swagelok quick-connects whereas the permeate gas was col-
at 80 °C/14 h for UiO-66-NH2. A second heating step was conducted for lected using a 1/8 in. Swagelok connector.
UiO-66-NH2 at 100 °C for 24 h. UiO-66 was activated by thermal The permeation module was placed inside a Memmert UF450 forced
treatment in a furnace at 300 °C for 3 h, with a heating rate of air circulation oven, connected to a proprietary high-pressure per-
15 °C·min−1, whereas chemical activation was conducted for UiO-66- meation set-up at SINTEF Materials and Chemistry, Oslo for gas se-
NH2, where the precipitated NPs were washed in an absolute ethanol paration measurement (Fig. 1). The permeation set-up is designed to
bath at 60 °C, three times in three days (ethanol was changed daily). withstand pressures up to 92 bar with a forced air temperature control
After the complete cycle, the NPs were dried at room temperature. A up to 300 °C. The feed (150 cm3(STP)·min−1) and permeate
covalent post-synthetic modification (PSM) was conducted onto UiO- (10 cm3(STP)·min−1) flow rates were controlled by automated Bron-
66-NH2 to produce UiO-66-NH-COCH3 in chloroform (CHCl3, anhy- khorst High-Tech mass controllers (MFC), equipped with a back pres-
drous ≥99%) and acetic anhydride (AcO2, ACS Reagent, ≥98.0%) sure controller (Bronkhorst High-Tech, P-512C equipped with an F-
solution, under reflux at 55 °C/24 h. Once completed, the colloidal 033C control valve, max of 92 bars) on the feed side for pressure

2
M.Z. Ahmad, et al. Separation and Purification Technology 230 (2020) 115858

Fig. 1. Schematic representation of the high-pressure experimental set-up. The mass flows are calibrated at standard temperature and pressure condition.

Table 1 It is important to note that the samples were allowed to reach

CO2, CH4 permeability and CO2/CH4 selectivity of neat 6FDA-DAM and its Zr- permeation steady-state overnight, after each pressure or feed compo-
MOF MMMs, measured 35 °C, at a pressure difference of 2 bar with an equi- sition change. Specific attention was given to Health, Safety and
molar binary mixture of CO2 and CH4. Environmental (HSE) matters, and the lab was equipped with pre-
Membrane Gas permeability (Barrer) CO2/CH4 Selectivity ventive safety measures which include H2, CO, and H2S detection sys-
tems, personal portable gas detectors, and separate floor level ventila-
CO2 CH4 tion suction.
Neat 335 17.7 19.3
MMM UiO-66 14 wt% 888 35.9 25.1 3. Results and discussions
MMM UiO-66-NH2 16 wt% 521 21.9 23.8
MMM UiO-66-NH-COCH3 459 18.1 25.4 In the previous publication [34], we found very promising perfor-
16 wt%
mance indicators for several 6FDA-DAM MMMs with Zr-MOFs when
tested at low pressure (2 bar), with the best performance observed for
membranes that contain 14–16 wt% Zr-MOF. An increase in the Zr-MOF
regulation. The atmospheric-pressure permeate gas analyzed by a two-
loading shows a clear permeability-selectivity trade-off, and selectivity
channel column (MolSieve 5A, MS5 and PoraPLOT U, PPU) Agilent 490
reductions have been observed [34,44]. Table 1 shows the re-measured
micro-GC, coupled with thermal conductivity detectors (TCD). The
gas separation performance of the duplicate membranes, at 35 °C, with
micro-GC was calibrated for low CO2 (0–12 vol%), CH4 (0–5 vol%) and
a pressure difference of 2 bar with an equimolar binary mixture of CO2
H2S (0–0.5 vol%) concentrations in argon. Good correlation coefficients
and CH4 in SINTEF facility. The permeability values are lower than the
of R2 = ≥0.999 were obtained for the µ-GC response as a function of
published data [34], possibly due to the aging phenomenon which may
CO2, CH4, and H2S concentration. The fluxes were calculated from the
have occurred during shelf-storage at room temperature for over
measured permeate concentrations and the calibrated flow of Ar sweep
250 days. However, the similar improvement trends upon Zr-MOF in-
gas.
corporation were observed. The presence of 14 wt% UiO-66, 16 wt%
High-pressure gas permeation measurements were conducted ac-
UiO-66-NH2 and 16 wt% UiO-66-NH-COCH3 improves the CO2 perme-
cordingly to the following experimental sequence, and the separation
ability of 6FDA-DAM (PCO2 = 335 Barrer) by 165%, 56% and 37%,
performances were calculated correspondingly to Eqs. (1) and (2).
respectively. These enhancements are well-related to the CO2-philic
nature of the Zr-MOFs where a stronger energetic interaction between
1. Pressure variation with 50:50 vol% CO2: CH4 feed mixture:
CO2 (higher quadrupole moment than CH4) and the nanoparticle sur-
Preliminary measurement at 2 bar and 35 °C was conducted to va-
faces at zero coverage, and to the increments in fractional free volume
lidate the initial membrane performances, and the pressure was
(FFV) in the MMMs (Neat 6FDA-DAM, FFV = 0.238). 14 wt% UiO-66
subsequently increased to 5 and 10 bar. Before proceeding to 20 bar,
MMM presents the highest increment value of 39%, followed by 16 wt%
the CO2 feed content was decreased to 10 vol% for the second step
UiO-66-NH2 and 16 wt% UiO-66-NH-COCH3 with 16% and 22%, re-
measurements.
spectively. The CO2/CH4 selectivity of the samples also increased by
2. CO2 feed content variation at the feed pressure of 20 bar: At 20 bar,
23–32%.
the 10 vol% CO2 feed content was subsequently increased to 20 vol
At these observed optimum loadings, the Zr-MOFs addition en-
%, 30 vol%, and 50 vol% with CH4.
hances both CO2 permeability and CO2/CH4 selectivity tremendously.
3. The effect of temperature variation on the separation performance,
Besides a higher gas diffusion in the Zr-MOFs, the NPs addition im-
with 30:70 vol% CO2:CH4 feed mixture at 20 bar: The temperature
proved the MMM gas diffusivity by inducing an ancillary selective in-
increase was conducted by stepwise increments from 35 °C to 45 °C
terface phase [45] with additional free volume [46,47]. Agglomeration
and 55 °C, and followed by a reduction back to 35 °C prior to the H2S
of the NPs was more prominent at the highest loadings, and the con-
introduction (step no. 4).
current reduction of the selectivity reduction is likely due to the for-
4. Investigation of separation performance in the presence of H2S with
mation of non-selective by-pass channels in the filler agglomerates [46]
30:5:65 vol% CO2:H2S:CH4 feed mixture was conducted at 20 bar
and possibly micro-voids in the filler-polymer interface region [41],
and 35 °C.
although such morphological features are not observed by SEM ana-
5. Finally, the H2S in feed was removed and the system was allowed to
lyses. All the MMMs also presented excellent distribution and inorganic
purge before the separation efficiency was re-evaluated with
filler-polymer interface interaction (please refer to SEM images, Fig. S5
30:70 vol% CO2:CH4 feed mixture, at 20 bar and 35 °C.
in the previous publication [34]).

3
M.Z. Ahmad, et al. Separation and Purification Technology 230 (2020) 115858

Fig. 2. (a) CO2 and (b) CH4 permeabilities of 6FDA-DAM and its Zr-MOFs as a function of feed pressure, measured with 50:50 vol% CO2: CH4 feed mixture at 35 °C.
Their corresponding CO2/CH4 selectivity values are presented in (c), against the 2008 Robeson upper bound [58].

3.1. Effect of feed pressure variation to mixed gas separation 6FDA-DAM membrane between ~10–20 bar, at 35 °C [51,52]. The
plasticization pressure differences may be attributed to different phy-
Most of the fundamental studies on Zr-MOF polyimide MMMs re- sical properties, i.e., molecular weight, density, and polymer free vo-
lated to Matrimid® and 6FDA-copolyimides have been conducted at low lume, as previously discussed [31,34].
pressures where CO2-induced plasticization is expected to be of minor The pressure dependence of the CH4 permeability (Fig. 2(b)) over
importance [31,48,49]. Here, we have investigated the gas separation the measured pressure range, however, suggests that the neat 6FDA-
performance of 6FDA-DAM and its Zr-MOF MMMs at a pressure ranging DAM starts to swell immediately after the first pressure increment. It
from 2 to 20 bar in a 50:50 vol% CO2:CH4 feed mixture at 35 °C. The can be explained by dynamic swelling of the polymer matrices upon
obtained mixed gas permeability and CO2/CH4 selectivity behavior as a exposure to the CO2 at high pressure [53], where the penetrating CO2
function of pressure are shown in Fig. 2. causes the material dilation and subsequently increases its macro-
The CO2-induced plasticization pressure is defined to occur at the molecular mobility. Several researchers have reported the thermo-
minimum observed in the CO2-permeability as a function of CO2-partial dynamics of swollen glassy polymers by a penetrant [54,55], and a
feed pressure. In the case of mixed gases, the permeation rate of all thorough discussion was recently presented by Ogieglo et al. [53] when
gases is affected due to swelling of the polymer matrix and the in- studying the glassy polymer relaxation in this films. The phenomenon,
creased chain mobility caused by the high CO2 concentration. The to the function of pressure, causes extensive dilation of the matrices,
permeation enhancement is more pronounced for the least permeable influencing the penetrants’ permeation. Here, the effect is more ap-
gases, resulting in a decrease of the selectivity as a function of pressure. parent in CH4 permeability increase compared to the readily high-
In contrast, for all samples in the present study, a monotone decrease in permeability CO2. In the case of UiO-66-NH2 MMM, the high CO2-af-
CO2 permeability with increasing pressure is observed (Fig. 2), which finity amino functional group increases the CO2 adsorption in the
does not indicate substantial plasticization [21]. The decrease in CO2 polymer matrixes and directly further influences the molecular dynamic
permeability reduction is a result of competitive sorption and the dilation. Even though it is not the membranes’ plasticization pressure,
concave shape of the sorption isotherm [25,50]. This constitutes a re- their CO2/CH4 selectivity reduced by 55% and 58% respectively. This
duction in driving force for transport with increasing pressure and also behavior also defined as swelling-induced perm-selectivity losses [34],
gradual saturation of the material may result in lower mobility. Overall, which was observed in several other co-polyimides, such as 6FDA-APAF
this results is further supported by the clear decrease in permeation and TPDA-APAF, when measured with CO2/CH4 binary mixture up to
coefficient in the polymer matrices (see Fig. S1). The CO2 permeability 25 bar feed pressure, at 35 °C [56]. Heck et al. [57] also observed si-
continuously decreases with increasing pressure indicating there is no milar behavior in (6FDA-mPDA)-(6FDA-durene) block co-polyimide,
apparent CO2-induced plasticization in the thick membrane [21], op- for which they reported an increase in CH4 permeability with pressure
posite to the reported single-gas CO2-plasticization pressure of neat (up to 20 bar feed pressure), causing CO2/CH4 and He/CH4 selectivity

4
M.Z. Ahmad, et al. Separation and Purification Technology 230 (2020) 115858

reductions. permeability for the neat membrane (9%) and UiO-66-NH2 MMM
The continuous decrease of CH4 permeability in both UiO-66 and (21%) is observed, indicating the possibility of CO2-induced plastici-
UiO-66-NH-COCH3 MMMs demonstrated the competitive sorption ef- zation that started to take effect [61,62]. These samples exhibited the
fect [59], where CO2 penetrated the membranes’ sorption sites which highest CO2/CH4 selectivity reductions of between 28 and 33% in all
associated to the non-equilibrium free volume in glassy polymer and the samples (shown in Fig. S2(c), relative to 2008 Robeson’s upper
hindered CH4 to permeate. Polymer plasticization was not observed in bound [58]). Despite this CH4 permeability increment, the behavior can
these membrane samples. be explained as swelling-induced perm-selectivity losses, an early stage
in polymer plasticization [56].
With regard to the initial separation performance (with 10 vol%
3.2. Effect of CO2 feed composition in high-pressure separation CO2), similarly to the previous discussion, neat 6FDA-DAM showed a
lower CO2/CH4 selectivity than that of MMMs (UiO-66-NH2 < UiO-
Fig. S2(a-b) show the CO2 and CH4 permeability of the neat 6FDA- 66 < UiO-66-COCH3). The proportional selectivity increase in MMMs
DAM and Zr-MOF MMMs, measured at 20 bar feed pressure and 35 °C, to the increasing CO2 partial pressure [63–65], which only observed in
with a different CO2 feed content between 10 and 50 vol%. The sig- UiO-66 MMM at the tested feed pressure of 20 bar (3% selectivity in-
nificant differences in the initial CO2 permeabilities between the crement) represents the membrane’s extended CO2 sorption capability
membranes were discussed in the previous publication [34]; higher CO2 due to the CO2-induced plasticization or swelling at constant pressure
permeability in the UiO-66 MMM is attributed to the easiness of CO2 to [63]. Its reduction conversely was explained based on CO2 self-inhibi-
diffuse into its frameworks, compared to the higher steric hindrance tion as a consequence of saturation of the filler active sites at a high CO2
functionalized-MOFs, and also its higher FFV. concentration in a feed mixture [60,66]. Referring to that hypothesis, a
The CO2 permeability in the neat 6FDA-DAM and its Zr-MOFs lower reduction exhibited by UiO-66-NH-COCH3 MMM (13%) com-
MMMs decreases between 9 and 22%, with the increase of CO2 partial pared to UiO-66-NH2 MMM (28%), represented by its lesser concave
pressure when tested at 20 bar. The lowest reduction of 8.7% was ob- shape in the permeability isotherm, may be due to a higher CO2 affinity
served for the UiO-66 MMM. The observation, however, is opposite to towards acetamide functional groups, with a higher number of ad-
the previously reported CO2 permeability relationship with CO2 partial sorption sites compared to UiO-66-NH2 NPs. Moreover, constant se-
pressure at low-pressure measurements, i.e., 6FDA-DAM Zr-MOF lectivity values demonstrate no dependency of an MMM system towards
MMMs (at 2 bar) [34] and PES/SAPO-34/2-hydroxyl 5-methyl aniline the increasing CO2 partial pressure, as also revealed in the PES/SAPO-
MMMs (at 3 bar) [60]. At the low pressure, a higher CO2 partial pres- 34/HMA MMM system, measured at 3 bar [60]. This hypothesis implies
sure produced a more prominent competitive sorption effect, where an that only a minor amount of the active sites is occupied at low pressure.
increase in CO2 solubility and transport through the membrane medium
was observed and inversely decreased the second component’s ability to
permeate, in this case, CH4. 3.3. Effect of operating temperature in the high-pressure separation
Evidently, the continuous CO2 permeability reduction with in-
creasing pressure suggests that the competitive sorption effect at high Fig. S3(a–c) shows the CO2 and CH4 permeability and the CO2/CH4
pressure is less influenced by the CO2 partial pressure (see Fig. 3). In- selectivity as a function of the operating temperature applying a
stead, it is related to the gradual saturation of permeating gases inside 30:70 vol% CO2:CH4 feed mixture at 20 bar. A minor increase in CO2
the polymer micro-voids [18]. Nevertheless, a slight increase in the CH4 permeability of < 6% was recorded for all samples, whereas for CH4

Fig. 3. CO2 and CH4 permeabilities, and CO2/CH4 selectivity of 6FDA-DAM and its Zr-MOF MMMs against CO2 partial pressure, at 20 bar and 35 °C.

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M.Z. Ahmad, et al. Separation and Purification Technology 230 (2020) 115858

Table 2
Activation energy of permeation for CO2 and CH4 in neat 6FDA-DAM and its Zr-
MOF MMMs, calculated for the temperature operating range of 35–55 °C, with
30:70 vol% CO2/CH4 at 20 bar.
Gas Membrane Permeability activation energy,
kJ·mol−1

Ea, (35–55 °C)

CO2 Neat 0.16

MMM UiO-66 14 wt% 0.05
MMM UiO-66-NH2 16 wt% 0.07
MMM UiO-66-NH-COCH3 16 wt −0.03
%

CH4 Neat 0.85

MMM UiO-66 14 wt% 0.86
MMM UiO-66-NH2 16 wt% 0.76
MMM UiO-66-NH-COCH3 16 wt 0.68
%

Ea
P = P0 e RT (3)

where P0 is a pre-exponential factor of permeation, Ea is activation

energy for permeability (kJ·mol−1), R is the universal gas constant
(8.314 J·mol−1), and T is the temperature in K. Using CO2/CH4 se-
lectivity expression of the permeability coefficient ratio of CO2 over
CH4, the gas selectivity is defined as the following:
PCO2
(CO2 /CH4 ) = PCH 4

=
P0 (CO2)
P0 (CH4)
exp ( Ep (CO2)
RT
Ep (CH4 )
) (4)

Fig. 4 indicates that CH4 permeability in the 6FDA-DAM neat

membrane and its Zr-MOF MMMs followed Arrhenius rule in the tem-
perature range of 35–55 °C, while the CO2 permeability was less in-
fluenced by the temperature. Their permeability coefficients are sum-
marized in Table 2. The permeability dependency is a combination of
the diffusion and solubility coefficients temperature dependencies, and
the lower CO2 and CH4 activation energies in MMMs as compared to the
neat polymer indicate the gas transport through filler porosity [49], and
in the interfacial voids on polymer-MOF and MOF-MOF regions which
may also reduce the overall permeability Ea of MMMs. Regarding 6FDA-
DAM, in addition to polymer matrix compression at the high pressure,
the overall CO2 activation energy trend does not show a clear correla-
tion to the membrane FFVs (MMMs (UiO-66; 0.331 > UiO-66-COCH3,
0.292 > UiO-66-NH2; 0.277) > neat 6FDA-DAM, 0.238). Instead, the
activation energy seems profoundly influenced by the presence of Zr-
MOF nanoparticles in MMMs, in the order of their group functionalities
(UiO-66-NH-COCH3 > UiO-66-NH2 > UiO-66 > neat 6FDA-DAM).
It also concludes that the CO2 permeation is predominately influenced
by its solubility (sorption) in the membrane systems, and less depen-
dent on temperature. The higher activation energies presented by the
non-polar CH4 also indicated that its diffusion or transport was more
influenced compared to CO2 molecules, giving higher CH4 permeability
increments and consequently reduced the CO2/CH4 selectivity by
22–26%. This observation is also consistent with activated diffusion of
non-polar molecules in glassy polymers (related to chain mobility and
polymer free volumes) [68], where the least permeable gas often pos-
Fig. 4. (a) CO2 and (b) CH4 permeability and its (c) perm-selectivity to tem- sesses higher activation energy and realizes a more substantial perme-
perature dependence, for neat 6FDA-DAM and its Zr-MOFs membranes at the ability increase with increasing temperature. In any event, the activa-
measurement temperature of 35–55 °C. tion energies (temperature-dependent) are low for both the neat
polymer membrane and the MMMs, compared to the other 6FDA-based
permeability, the increments were higher in between 28 and 37%, as polyimides in the literature (see Table S2). This suggests a low pene-
the operating temperature increased from 35 to 55 °C. The effect of trant-membrane interaction perhaps because there is a relatively large
temperature on the gas permeability can be quantitatively observed in difference between the CO2 and CH4 kinetic diameter and the mem-
their activation energy for permeability, following Arrhenius rule using brane controlling pore size.
Eq. (3) [67]: Lower CO2 temperature-dependency at this high-pressure separa-
tion also indicated by its fugacity coefficient values, closing to 1.0 (ideal

6
M.Z. Ahmad, et al. Separation and Purification Technology 230 (2020) 115858

Table 3
The compressibility Z factors for CO2 and CH4, calculated using Dranchuk and Abou-Kassem equation of state (DAK – EOS) [69], presented at 35 °C, 45 °C and 55 °C,
at 20 bar.
Temperature, °C Compressibility Z factor Fugacity coefficients, ϕ Fugacity (bar)

CO2 CH4 CO2 CH4 CO2 CH4

35 0.9049 0.9699 0.9953 1.0293 19.9051 20.5858

45 0.9953 0.9735 0.9998 1.0258 19.9953 20.5153
55 0.9998 0.9767 1.0000 1.0227 19.9998 20.4539

Calculated from the following constant values and critical state variables:
CO2: gas constant, R = 188.92 J·kg−1·K−1; isentropic exponent = 1.301; pcrit = 73.77 bar; Tcrit = 30.98 °C.
CH4: gas constant, R = 518.27 J·kg−1·K−1; isentropic exponent = 1.304; pcrit = 45.92 bar; Tcrit = −82.59 °C.

gas) when temperature is increased (see Fig. S4(a) and S4(b)), proves Table 4
that the molecule’s non-ideal behavior is less influenced by the in- Gas separation performances of 6FDA-DAM and its 14–16 wt% Zr-MOFs MMMs,
creasing temperature but predominantly by pressure. It is supported by tested with binary (30:70 vol%; CO2:CH4) and tertiary (30:5:65 vol%;
the fact that CO2 possesses lower fugacity coefficients at the tested CO2:H2S:CH4) feed mixture at 20 bar, 35 °C.
separation conditions Table 3 (overall compressibility factor and fu- Feed mixture Separation 6FDA-DAM membranes
gacity coefficient calculated values are presented in Fig. S4). The performances
compressibility factors were determined by an eleven-constant Dran- Neat MMM MMM MMM
UiO-66 UiO-66- UiO-66-
chuk and Abou-Kassem equation of state (DAK-EOS) [69]. The detail is
NH2 NH-
presented in the supporting information document. COCH3
Besides that, the CH4 permeability increase was also influenced by
the increase of polymer free volume (as a function of polymer chain CO2:CH4 PCO2 231 541 359 291
(30:70 vol%) PCH4 21.7 33.0 33.1 14.8
packing and intersegmental motion) by the effect of elevated tem-
Before exposure αCO2/CH4 10.6 16.4 10.8 19.7
perature. The activated diffusion often proves to be a significant ad-
CO2:H2S:CH4 PCO2 167 385 243 193
vantage in the separation of non-polar H2 from CO2, giving enhanced
(30:5:65 vol%) PH2S 137 352 224 172
H2/CO2 selectivity at higher temperatures as demonstrated in 6FDA- P(CO2+H2S)* 304 737 466 365
mPBI [68] and PBI-ZIF8 MMMs [70]. PCH4 18.5 25.4 25.7 10.6
αCO2/CH4 9.1 15.2 9.5 18.2
Ep 3 αH2S/CH4 7.4 13.6 8.7 16.2
logP0 = × 10 +Z
R (5) α(CO2+H2S)/CH4* 16.4 29.0 18.1 34.4

Regardless of common polymer chemical structures, Van Krevelen CO2:CH4 PCO2 227 543 347 284
(30:70 vol%) PCH4 20.4 33.7 29.8 14.3
[71] presented a positive slope of 1 × 10−3 for log P0 and Ep/R plot After exposure αCO2/CH4 11.1 16.1 11.7 19.8
(Eq. (5)), with Z values of −7.0 and −8.2 for rubbery and glassy
polymers respectively, for permeability measurement below their glass Permeability is in Barrer.
transition temperatures. Fig. S5 indicates that the addition of Zr-MOFs * Acid gas, CO2 + H2S.
into 6FDA-DAM altered CO2 permeability-temperature dependency
significantly, giving a negative Ep/R slope of −0.15 × 10−3, while only CH4 of 16.4 for the neat 6FDA-DAM and in the range of 18.1–34.4 for
reduced CH4 permeability-temperature dependency by roughly 70% its MMMs. Besides the competitive sorption of a two-component gas
(CH4 permeability Ep/R slope = 0.32 × 10−3). mixture, the presence of a third component intensifies the gas mixtures
non-ideal behavior and influences each penetrant permeation rate,
3.4. Effect of the presence of H2S on membrane separation especially at elevated pressures [21]. Based on gas permeability values,
the observed adsorption preference trend is in the order of
The concentration of H2S in the natural gas mixture varies de- CO2 > H2S > CH4, well-agreed to the gasses’ isosteric adsorption heat
pending on the geo-origin and can be more than 5 vol% [4,72]. As in UiO-66 (CO2; 25.7 kJ·mol−1 > H2S; 23.8 kJ·mol−1 > CH4;
aforementioned, besides investigating the 6FDA-DAM and its Zr-MOF 18.8 kJ·mol−1, reported at 30 °C [36]). Functionalized UiO-66 deriva-
MMMs performances for H2S separation, it is important to understand tives presented higher values, in the same order. The gas physical
the H2S effect on membrane performance. We studied the gas separa- properties; dipole moment (Debye), quadrupole moment (au) and po-
tion performance of 6FDA-DAM and its Zr-MOF MMMs with 30:70 vol% larizability (a03), also greatly contributed to the competitive sorption
CO2:CH4 feed mixture at 20 bar and 35 °C, before adding 5 vol% of H2S, outcomes and H2S high polarizability explained its higher permeability
making the feed composition to 30:5:65 vol% CO2:H2S:CH4. The se- despite its relatively low content in the feed mixture compared to CO2;
paration performance after H2S exposure was also investigated and CH4: 5.4 × 10−6 Debye, 0 au, 17.3 a03; CO2: 0 Debye, 3.2 au, 18 a03;
summarized in Table 4. H2S: 0.978 Debye, 0 au, 25 a03 [73]. Hence, the observed αCO2/CH4
Upon the addition of 5 vol% H2S in the mixed gas, PCO2 in all reduction can be explained by a larger competitive sorption effect in-
samples decreased by an average of 28–34%, accordingly to their duced by H2S (its solubility is larger than that of CH4) in the membrane
functionality order: MMMs (UiO-66-NH-COCH3 > UiO-66- systems. In addition to H2S competitive sorption effect, the reduced
NH2 > UiO-66) > neat 6FDA-DAM. 6FDA-DAM MMMs showed a CO2/CH4 selectivity may also be contributed by the fact that CH4 par-
higher CO2 permeability reduction in the presence of H2S, compared to tial pressure in binary mixed gas (70 vol% in feed) is higher than that in
the neat membrane. The observation exhibited the influence of Zr- ternary system (65 vol% in feed). As a higher CH4 partial pressure will
MOFs in the MMMs, of which their active metal sites also preferentially result in its higher permeability, subsequently lowers the CO2/CH4 se-
adsorb H2S and thus reduce their CO2 adsorption capacity. PH2S values lectivity and its competitive sorption effect towards H2S and CO2 per-
are in the range of 137–352 Barrer, slightly lower than those of PCO2, meability may also not be the same.
contributing to the total acid gas permeability of between 304 and 737 In the presence of H2S, all MMMs presented higher CO2, H2S and
Barrer. The increments directly presented the acid gas selectivity over acid gas selectivities compared to the neat 6FDA-DAM (αCO2/CH4 = 9.1;

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M.Z. Ahmad, et al. Separation and Purification Technology 230 (2020) 115858

Table 5
Separation comparison of 6FDA-DAM and its Zr-MOF MMMs with several other dense membranes, when tested with ternary mixed gas feeds containing ≤ 15 mol.%
of H2S at 35 °C.
Polymer Pressure (bar) Feed compositions mol.% (CO2:H2S:CH4) Permeability (Barrer) Selectivity Refs.

CO2 CO2 + H2S CO2/CH4 (CO2 + H2S)/CH4

6FDA-DAM 20 30:5:65 167 304 9.1 16.4 This study

MMM UiO-66 20 30:5:65 385 737 15.2 29.0
MMM UiO-66-NH2 20 30:5:65 243 466 9.5 18.1
MMM UiO-66-NH-COCH3 20 30:5:65 193 365 18.2 34.4

Cellulose acetate 10 29:6:65 2.4 4.6 22.0 41.5 [77]

Pebax 1074 10 18.1:12.5:69.4 155 850 11.0 61.6 [77]
PU2 10 18.1:12.5:69.4 195 813 5.6 23.4 [77]
PIM-6FDA-OH 34.5 15:15:70 54.7 90.7 27.8 46.1 [81]
6FDA-DAM:DABA (3:2)
Annealed at 180 °C 48 20:10:70 55.6 81.0 32.1 46.7 [82]
Annealed at 230 °C 48 20:10:70 50.8 74.4 31.1 45.5 [82]
6FDA-DAM 6.9 20:20:60 414 672 24.4 39.7 [79]

Abbreviation: 6FDA: 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane diandydride; DAM: 2,4,6-trimethyl-1,3-diaminobenzene; PEBAX: polyether block amide; PU:
polyurethane; PIM: polymers of intrinsic microporosity; DABA: 3,5-diaminobenzoic acid.

Fig. 5. XRD patterns of UiO-66 (simulated [80]), 6FDA-DAM and its Zr-MOF derived MMMs after H2S-exposure in the tertiary mixture (30:5:65 vol%; CO2:H2S:CH4)
separation, at 20 bar, 35 °C.

αH2S/CH4 = 7.4; α(CO2+H2S)/CH4 = 16.4) with the highest values pre- PCO2 and αCO2/CH4 of all membranes were regained to pre-H2S exposure
sented in UiO-66-NH-COCH3 MMM (αCO2/CH4 = 18.2; αH2S/CH4 = 16.2; values, indicating H2S presence only causes reversible competitive
α(CO2+H2S)/CH4 = 34.4). The UiO-66-NH-COCH3 MMM presented si- sorption between the permeating molecules, no H2S-induced plastici-
milar or higher αH2S/CH4 selectivity than several reported membranes, zation and no other permanent effect. Referring to the XRD patterns
such as in 6FDA-PAI-3/TmPDA (ideal αH2S/CH4 = 10.9), Torlon® 4000 T (Fig. 5), based on their characteristic diffraction peaks of Zr-MOF [80],
(ideal αH2S/CH4 = 14.8), both tested at 4.5 bar, 35 °C [74], and in a rigid we found that the MOF maintained their crystallinity phase in the
(6FDA-mPDA)-(6FDA-durene) block co-polyimide, (αH2S/CH4 = ca. 15), polymer matrix, after H2S-exposure (average H2S-exposure time of
tested with 1 vol% H2S in a CO2:H2S:N2:CH4 quaternary mixture at 20–30 h). These remarkable results confirmed 6FDA-DAM and its Zr-
3.8 bar, 22 °C [75]. The performance is also comparable to the com- MOF MMMs capability, effectiveness and stability for simultaneous acid
mercial poly(ester urethane) urea, PEUU, αH2S/CH4 = 16 [76] gases separation from CH4.
(CO2:H2S:CH4 feed ratio of 5.4:3:remaining, at 55 °C, 20 bar) and cel-
lulose acetate, CA, α(CO2+H2S)/CH4 = 41.5 [77] (CO2:H2S:CH4 feed ratio
4. Conclusion
of 29:6:65, at 35 °C, 10 bar). In the separation of an actual natural gas
sample containing 5008 ppm H2S, water vapor, C1-nC5, and mercaptan,
6FDA-DAM polyimide offers an attractive opportunity in gas se-
commercial polyphenylene oxide hollow fibers presented αH2S/
paration application, and the incorporation of the highly stable zirco-
CH4 = 2.9, while a commercial poly (ester urethane) urea (PEUU) flat
nium-based UiO-66 and its functionalized derivatives as MMM further
sheet membrane gave αH2S/CH4 = 3.4, measured at 40 °C and 23 °C,
enhanced the separation properties. The membranes possessed ex-
respectively [78]. The separation performances of several other dense
cellent CO2/CH4 separation performance and presented high-perfor-
membranes to the ternary gas mixture with H2S at 35 °C are presented
mance stability at conditions relevant to actual gas processing (pres-
in Table 5 for comparison. Most interestingly, Liu et al. [79] also de-
sure, CO2 content, temperature). The Zr-MOFs improved not only
monstrated acid gas permeability and selectivity over CH4 improve-
6FDA-DAM gas separation properties but also deterred CO2-induced
ment of 6FDA-DAM (PCO2+H2S = 671.8 Barrer, α(CO2+H2S)/CH4 = 39.7)
plasticization and swelling. Additionally, in the presence of high H2S
by incorporating 30 wt% Y-fum-fcu-MOF (PCO2+H2S = 1057.7 Barrer,
content (50,000 ppm in feed mixture) at high total pressure, both CO2-
α(CO2+H2S)/CH4 = 52.8) and 19 wt% Eu-naph-fcu-MOF
and H2S-induced plasticization were suppressed, and only reversible
(PCO2+H2S = 747.8 Barrer, α(CO2+H2S)/CH4 = 49.2).
competitive sorption effect was observed. This successful high-pressure
Interestingly, after the H2S exposure for a period of 20–40 h, both
testing of 6FDA-DAM MMMs with Zr-MOFs is encouraging and

8
M.Z. Ahmad, et al. Separation and Purification Technology 230 (2020) 115858

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