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TRANSCRIPT
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
Tokyo Metropolitan University
Carbon dioxide Capture and Storage (CCS)
Carbon dioxide Capture and Utilization (CCU)
etc.
CO2
/
etc.
etc.
Tokyo Metropolitan University
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
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
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)
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.
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.
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
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)
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)
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
(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
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
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
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
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
-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
Tokyo Metropolitan University
