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5 CO2
27 10 2
* Phone 042-677-1111 (ext.4972) Fax 042-677-2821 E-mail [email protected]
CO2
CO2
Ref. IPCC
2
Tokyo Metropolitan University
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Tokyo Metropolitan University
Carbon dioxide Capture and Storage (CCS)
Carbon dioxide Capture and Utilization (CCU)
etc.
CO2
/
etc.
etc.
Tokyo Metropolitan University
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Post-combustion CO2/N2
Pre-combustion CO2/H2
Oxy-combustion O2/N2
Ref.1-4: D.F. Sanders et al. , Polymer, 54, 4729-4761 (2013)
Post-combustion
Pre-combustion
Oxy-combustion
CO2
CO2
O2
CO2
CO2
CO2
N2
O2 ,N2
O2H2
N2
CCS
*Ref. Robeson, L. M. J. Membr. Sci., 320, 390–400 (2008). *Barrer = 1×10-10 [cm3 (STP) cm / (cm2 ·sec ·cmHg)].
104102110-210-4
10
102
103
CO2 permeability (Barrer)
CO
2/N2 s
elec
tivity
1
O
O
CN
CN
O
O
n
Si
CH3
CH3
O
n(PDMS)
PIM-1PCO2 = 2300 DCO2 = 26, SCO2 = 88
PCO2 = 2800 DCO2 = 625, SCO2 = 4.4
Tokyo Metropolitan University
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10
15
20
25
30
35
40
0 20 40 60 80 100
CO2 permeance
1000GPU
1500GPU
3000GPU
CO2/N2 selectivity
Cos
t of c
aptu
re ($
/ to
n-C
O2)
CO2
*Ref.(DOE)
104102110-210-4
10
102
103
CO2 permeability (GPU)
CO
2/N2 s
elec
tivity
1
* 1μm
*Ref. ( ) (RITE)
*GPU = 1×10-6 [cm3 (STP) / (cm2 ·sec ·cmHg)].
Tokyo Metropolitan University
0 5
10 15 20 25 30 35 40 45 50
0 10000 20000 30000
μ
Cos
t of c
aptu
re ($
/ to
n-C
O2)
CO2 permeance (GPU)
*CO2/N2 selectivity = 20
1 : T.C. Merkel et al., Journal of Membrane Science, 359, 126 (2010) 2 : (ARPA-E)
CO2 Capture Cost
Tokyo Metropolitan University
$20-25/t-CO21,500 /t-CO2
$5/t-CO2
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MMM
Polyimide
O
O
O
F3C CF3
O
O
O
NH2H2NN
O
O
F3C CF3
N
O
On
N
O
O
F3C CF3
N
O
On
6FDA 3MPA 6FDA-3MPA Polyimide
P=1×10-10 [cm3(STP)cm/(cm2 sec cmHg)] (Barrer)
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Thermally Rearranged (TR) Polymer
N CF3
CF3
N
OHO
O
O
OF3C CF3
N
OF3C CF3
F3C CF3N
O450
F3C CF3H2N
HO
NH2
OH
O
F3C CF3
O
O
O
O
O
DBZbisAPAF
(1) Naiying Du et al., Energy Environ. Sci., 5 (2012) 7306. (2) Ho Bum Park et al., Science, 318 (2007) 254. (3) Jung IK Choi et al., J. Membr. Sci., 349 (2010) 358.
Polyimides containing ortho-positioned functional group (PIOFG) Thermally Rearranged (TR)
Ⅱ
Ⅰ Ⅰ
Ⅱ
Ⅰ= meta (m)-position; Ⅱ= para (p)-position
N
OF3C CF3
F3C CF3N
O
6FDA
TR-1-450
H2N
H2N
NH2
NH2
Polymer of Intrinsic Microporosity (PIM)
HO
HO OH
OH
CNF
FCN
F
F
O
O O
O
H3CCH3
H3CCH3
CN
CN n
O
O O
O
H3CCH3
H3CCH3
CN
CN n
O
O O
O n
NNN
N
NN N
N
H
H
N
N
n
PIM-1
(4) Peter M. Budd et al., J. Membr. Sci., 325 (2008) 851. (5) Naiying Du et al., Nature Materials, 10 (2011) 372. (6) Mariolino Cate et al., Science, 339 (2013) 303.
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Silica nanopartticles
Fumed Silica (FS) (7
CH3
CH3
O O SO
O n
O
O O
O
H3CCH3
H3CCH3
CN
CN n
Si
O
O
OOO O
OO
Octyl
OctylOctyl
Octyl
OctylOctyl
Octyl
Octyl
Modified Si nanoparticles (9
F3C CF3
N Nn
(7) Juhyeon Ahn et al,. J. Membr. Sci., 314 (2008) 123. (8) Juhyeon Ahn et al,. J. Membr. Sci., 346 (2010) 280.(9) Vajiheh Nafisi et al,. ACS Appl. Mater. Interfaces, 6 (2014) 15643.
O Si O SiOSiCH3
H3C CH3
Si
Zeolite
ZIF-7 (10 ZIF-8 (12
NNH
N
HN
n
N
OO
O
N
O
O n
O
O O
O
H3CCH3
H3CCH3
CN
CN n
(10) Tingxu Yang et al,. Energy Environ. Sci., 4 (2011) 4171. (11) Ma. Josephine C. Ordonez et al,. J. Membr. Sci., 361 (2010) 2(12) Alexanda F. Bushell et al,. J. Membr. Sci., 427 (2013) 48.
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Mixed Matrix Membranes (MMM)Br
Br
BrBr
Ni(COD2)
PAF-1 (14
(13) Lujie Cao et al., Chem. Commun., 49 (2013) 8513. (14) Cher Hon Lau et al., Angew. Chem. Int. Ed., 53 (2014) 5322.
CAU-1-NH2 (MOF) (13
CC
OCH3
H2CCH3
On
O
O O
O
H3CCH3
H3CCH3
CN
CN n
•
•
CO2
CO2-
O
H2N NH
O
NH2NH3
HCOO
In wet state
ex.) CO2
CCS(CO2 )
CO2
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MMM
( )
( )
(5 wt%)
THF (95 wt%) ( 5, 10, 15, 20, 25wt%)
(600rpm)
/(5, 10, 15, 20, 25wt%)
(1h) (1200rpm)
N N
CF3F3C O
O
O
O
CH3
CH3H3C n6FDA-3MPA
PCO2 = 5.7×10-8
PCO2/PN2 = 19
150 , 15
P : cm3(STP) cm / (cm2 sec cmHg)
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10
15
20
25
5
7
9
11
0 5 10 15 20 25
G0 (control)
P CO
2 (×1
0-2 B
arre
r)
Nanoparticle content (wt%)
CO
2/N2 s
elec
tivity
*Barrer = 1×10-10 [cm3 (STP) cm / (cm2 ·sec ·cmHg)].
Tokyo Metropolitan University
10
15
20
25
5
10
15
20
0 5 10 15 20 25
P CO
2 (×1
0-2 B
arre
r)
Nanoparticle content (wt%)
CO
2/N2 s
elec
tivity
G2 /
10
15
20
25
5
7
9
11
0 5 10 15 20 25
P CO
2 (×1
0-2 B
arre
r)
Nanoparticle content (wt%)
CO
2/N2 s
elec
tivity
G1 /
)
*Barrer = 1×10-10 [cm3 (STP) cm / (cm2 ·sec ·cmHg)].
Tokyo Metropolitan University
DABA-NP (R2)
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0
100
200
300
400
0 5 10 15 20 25 0
20
40
60
80
100
0 5 10 15 20 25
5
10
15
20
0 5 10 15 20 25 5
7
9
11
0 5 10 15 20 25
P CO
2 (×1
0-2 B
arre
r)
P CO
2 (×1
0-2 B
arre
r)
Nanoparticle content (wt%) Nanoparticle content (wt%)
Clu
ster
size
(nm
)
Clu
ster
size
(nm
)
0 1 1G1 (DLS )
G1 ( )
G2 ( )
G2 (DLS )
(Pd , φd)
(Pc , φc)
P , φ (φc + φd = 1)
(Pc , φc)
(Pd , φd)
*Ref. W. J. Koros et al. : Journal of Membrane Science 137 (1997) 145–154
5
7
9
11
0 5 10 15 20 25
P CO
2 (×1
0-2 B
arre
r)
Nanoparticle content (wt%)
G1
9
11
e
P , Pc , Pd , φ
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(1) (ex. )
(2) (Pn)
( , Pc)
( , Pd)
(Ps , φs) ( )
Ps = 0 ( )
(Pn , φn) ( )
P , Pc , Pd , φ
Pd
*Ref. W. J. Koros, Polymer Engineering and Science 42 (2002) 1420–1431. G. C. Sarti et al, Current Opinion in Chemical Engineering 1 (2012) 148-155.
PCO2 PCO2/PN2 DCO2 DCO2/DN2 SCO2 SCO2/SN2
PI 600 19 16 1.4 38 15
PIM 1300 22 39 1.3 34 18
Table Gas permeability properties of polymer
P=1 10-10 [cm3(STP)cm/(cm2 sec cmHg)], D=1 10-8(cm2/sec), S=1 10-2[cm3(STP)/cm3cmHg]
N N
CF3F3C O
O
O
O
CH3
CH3H3C n
O
O
CN
CN
O
O
n
No methanol treatment
Tokyo Metropolitan University
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HO
HO OH
OH
CNF
FCN
F
F+ O
O
CN
CN
O
O
n
PIM-1
Tokyo Metropolitan University
PIM(1) (1300[Barrer] 7300[Barrer])(2)
HOOC COOH
HOOC
NH2
NH2
HOOC
CH3
CH3
R1 RRRRRRRRRRRRRRRRRRRRRRRRRRR11111111111111111111111
R2 RRRRRRRRRRRRRRRRRRRRRRRRRRRRRRRRRRRRRR22222222222222222222222222222222
R3 RRRRRRRRRRRRRRRRRRRRRRRRRRRRRRRRR3333333333333333333333333333333
=
=
=
O SiOH
OHCH2 3
HN R
OSi
HO
OH
CH 2 3
HNR
OSi
OH
HO CH2
3
NHR
Tokyo Metropolitan University
R1 : TAP-NP, R2 : DABA-NP, R3 : DMBA-NP
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0 10 20 30 40 50
5 20 35 50 65 80
0 5 10 15 20 25
0 10 20 30 40 50
5 20 35 50 65 80
0 5 10 15 20 25
P CO
2 (×1
02 B
arre
r)
CO
2/N2 s
elec
tivity
Nanoparticle content (wt%)
(a)DMBA (R3)
(b)DABA (R2)
0 10 20 30 40 50
5 20 35 50 65 80
0 5 10 15 20 25
P CO
2 (×1
02 B
arre
r)
CO
2/N2 s
elec
tivity
Nanoparticle content (wt%)Nanoparticle content (wt%)
(c)TPA (R1)
P CO
2 (×1
02 B
arre
r)
Tokyo Metropolitan University
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P CO
2/PN
2
PCO2 (Barrer)
102
10103 104
Upper bound (2008)
PIM-1
4
1 2
3
TPA TTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTPPPPPPPPPPPPPPPPPPPPPPPPPPPPPPAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAA COOH NH2
NH2DABA DDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAABBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAA CH3
CH3DMBA DDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMMBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBBAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAA
1 PIM-EA-TB,
2 PIM-SBI-TB
Neil B. McKeown, Science, 339, 303 (2013) 3 TZ-PIM-1
Michael D. Guiver, Nature Materials, 10, 372 (2011)4 PIM-1/MOF
Peter M. Budd, J. Membr. Sci., 427, 48 (2013)
n
N
N
n
N
N
O
O
O
O
n
NNN
HN
NN N
NH
PIM-1
Tokyo Metropolitan University
0
20
40
60
80
0 30 60
PIM-1
DMBA
PIM-1 ( )
P CO
2 (×1
02 B
arre
r)
Time (day)
Neil B. McKeown et al. , Science, 339, 303 (2013)
N
N
PIM-EA-TB
0
20
40
60
80
PIM-EA-TB
Neil B. McKeown et al. , Science, 339, 303 (2013)
Tokyo Metropolitan University
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0 50 100 150 Chemical shift (ppm)
PIM-1PIM-1 (
)PIM-1/20wt%DMBA-NP
PIM-1 Methanol
8900 20 115 1.0 77
P=1 10-10 [cm3(STP)cm/(cm2 sec cmHg)] , D=1 10-8(cm2/sec), S=1 10-2[cm3(STP)/cm3cmHg]
Fig. Structure of PIM-1, showing peak assignments.
O
O
CN
CN
O
O
n
12
3 4
56
7
89 10 11
12
4, 5
7, 8, 10
6, 9, 12 11
2, 3
1
CH3
T1 )13C_torchiaT1_cpmas_toss Delay: 0.01, 0.1, 0.5, 1, 5, 10, 20, 40 [s]
Fig. Structure of PIM-1, showing peak assignments.
O
O
CN
CN
O
O
n
12
3 4
56
7
89 10 11
12
T1 )13C_torchiaT1_cpmas_toss Delay: 0.01, 0.1, 0.5, 1, 5, 10, 20, 40 [s]
Tokyo Metropolitan University
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-20.0
-10.0
0.0
10.0
20.0
30.0
40.0
50.0 PIM-1 (methanol treatment) 20wt%DMBA-NP
PIM-1
Methanol
8900 20
P=1 10-10 [cm3(STP)cm/(cm2 sec cmHg)]
Fig. Structure of PIM-1, showing peak assignments.
O
O
CN
CN
O
O
n
12
3 4
56
7
89 10 11
12
Rel
ativ
e ch
ange
in T
1 (%
)
Peak positions
PIM-1
CH3 (1)
(2, 3)
(11)
(6, 9, 12)
(7, 8, 10)
(4, 5)
Table Gas permeability and selectivity of PIM-1 and nanoparticle composite membranes.
Tokyo Metropolitan University
CO2
CO2
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