Mixed Matrix Membranes of NH

2
-MIL-53 and Hydroxyl-containing Co-
polyimide for CO
2
/CH
4
separation

N. Tien-Binh, H. Vinh-Thang, Denis Rodrigue and Serge Kaliaguine
Department of Chemical Engineering, Universit Laval, Qubec, Canada
Tien-binh.nguyen.1@ulaval.ca, Vinh-thang.hoang.1@ulaval.ca , Denis.rodrigue@gch.ulaval.ca,
Serge.Kaliaguine@gch.ulaval.ca

Mixed matrix membranes (MMMs) based on NH
2
-functionalized metal-organic frameworks (MOFs),
NH
2
-MIL-53(Al), and MIL-53(Al) dispersed in co-polyimides containing hydroxyl group, 6FDA/DAM-
HAB (1:1 and 2:1) were fabricated. The MOF loadings were varied over the range of 5-30 wt. % for NH
2
-
MIL-53 and 5-15 wt. % for MIL-53. The incorporation of the functional group into the backbone of
polyimide is expected to improve the interaction between polymer matrix and inorganic fillers, hence,
enhancing performance of MMMs. Gas separation of synthesized MMMs was tested with pure gases and
equimolar CO
2
/CH
4
mixture (T = 35 C, P = 150
psi). The introduction of MIL-53(Al) in MMMs
resulted in a moderate enhancement in the
separation performance involving a steady
increase in CO
2
permeability with MOF loading.
Furthermore, the ideal selectivity was
unchanged. On the contrary, the incorporation of
NH
2
-MIL-53(Al) gave a great improvement in
ideal selectivity while CO
2
permeability was
stable. Permeation data of pure gases showed
that performance of MMM with 6FDA/DAM-
HAB (1:1) at 10 wt. % is excellent for CO
2
/CH
4

separation, situating above the 2008 Robersons upper bound. The results confirmed that there is an
interaction between polymer matrix and NH
2
-MIL-53(Al) which could not be observed in MMMs with
MIL-53(Al).
Abbreviation: 6FDA: 4,4-(hexafluoroisopropylidene)diphthalic anhydride; HAB: 3,3-dihyroxyl-4,4-diamino-biphenyl; DAM:
1,3,5-trimethyl-2,6-phenylenediamine
1 10 100 1000
1
10
100
1 10 100 1000
1
10
100
Robeson upper bound-1991
Robeson upper bound-2008

C
O
2
/
C
H
4

s
e
l
e
c
t
i
v
i
t
y
CO
2
Permeability (Barrer)


Pure 6FDA/DAM-HAB (1:1)
5% NH2-MIL 53
10% NH2-MIL 53
15% NH2-MIL 53
20% NH2-MIL 53
5% MIL-53
10% MIL-53
15% MIL 53