Hybrid-type
membrane system

High purity H2H2H2CO2CO2

separation
separation
separation
separation
membranemembranemembranemembrane

Hydrogen
Production Unit

Outlet gas

H2 H2H 2O

Porous Supporter2

Hydrophobic membrane

COCO

2Fig.1 Image of hybrid-type membrane system.

H2OCO

2H2Ionic Liquid•CO2 Selective•Thermostable

COCO

22CO2CO

2

H2

Fig.2 Supported ionic liquid membrane for CO2/H2

N

R1 NO

R3

H2NO

R2R

Imidazolium

Amino carbonate

RRPO
RR

H2 NRSOO

Phosphonium

Amino sulfonate

Cations

AnionsFig.3 Examples of our synthesized “CO2-phillic” ionic

0

JXIL- 120

Weight loss，％10

JXILJXIL-106

JXILJXIL-79

2030

JXILJXIL-105
JXILJXIL-102

4050100

150200Temperature, ℃

250300

Fig.4 Thermostability of the ionic liquids consisting of the same kind of amino carbonate.

Weight loss，％020

JXIL-120
JXILJXIL-106
JXILJXIL-102
JXIL-

JXILJXIL-119
JXILJXIL-205
JXILJXIL-116

Amino acid F type

Amino sulfonicacid type

JXILJXIL-203
JXILJXIL-112

40Amino acid A type

JXILJXIL-202
JXILJXIL-11160 Amino acid D type
100

400

200300Temperature, ℃

Fig.5 Thermostability of the ionic liquids consisting of phosphonium cations.

160
CO2 /H2 selectivity

140120JXILM-105▲ JXILM-121(IL : JXIL-116)

JXILM-63

100
80
60
4020

ILM-A
(conventional）
ILM-B(conventional）

ILM-C(conventional＋basic compound）

0
1×10-14 1×10-13 1×10-12 1×10-11 1×10-10
CO2 permeability, m3(STP)m/(m2 ・s・kPa)

Fig.6 Gas Separation ability of our synthesized facilitated transport membranes.

4×10-11

5×10-14
4×10-14

3×10-11

○：25℃
△：80℃

2×10-11

3×10-14
2×10-14

1×10-11

1×10-140

H2 permeability，

6×10-14m3(STP)・m/(m2・s・kPa)

CO2 permeability，m3(STP)・m/(m2・s・kPa)

5×10-11

0
0.0

0.1

0.2

0.3

0.4

0.5

Partial pressure of each gas，MPa(A)Fig.7 Relationship between partial pressure of each gas and gas permeability measured inJXILM-105.

CO2/H2 selectivity

1200
1000
800

25℃
80℃

600
400
200
00.0

0.1
0.2
Partial pressure of CO2, MPa(A)0.3

Fig.8 Relationship between partial pressure of CO2 and CO2/H2 selectivity measured in JXILM-105.

1．

R2R2 P R2R2anionb)

2．

a)cationcationaniona)3．

cationanionppm

Fig.9 CO2 absorption experiments; 1)before CO2 treatment, 2) CO2 treatment, 3) after heating at 100∘C.

a) Chemical absorption （Carbamate – ammonium species）
O

CO2 + 2 H2N

RSOOOCOHNORSOOO+H3NRSOOb) Chemical absorption (HCO3- -ammonium, CO32--ammonium species）
O

CO2 + H2NRSO

HCO3O+ H2O

CO32-O+ H3N

RSOOc) Physical absorption (CO2）
CO2

Fig.10 Estimated CO2 permeation mechanism.

Hydrophobic membrane
Porous ceramic filter
filled with Ionic liquid
Hydrophobic membrane

Fig.11 Layer structure of the tubular type membrane.

100

CO280
4×10-1260
40

2×10-12

CO2/H2 selectivity

Gas permeability, m3(STP)・m/(m2・s・kPa）

6×10-1220
H20Plate typemembrane

Tubular typemembrane

0Fig.12 Modularization of the membrane.

18㎝
18㎝

1tube

18㎝

10㎝
11tubes

18㎝

10㎝
1tube

11tubes154
tubes

2.0×10-10100

1.5×10-10

80
CO260

1.0×10-10400.5×10-10

CO2/H2 selectivity

Gas permeance, mol/(m2・s・Pa）

Fig.13 Scale-up of the membrane modules.

200H2Monotubular
type module

Multitubular
Multitubular 0type module type modulewith 11 tubes with 154 tubes

Fig.14 Gas separation ability of membrane modules in different sizes.

100

1×10-680
60

1×10-740
1×10-820

1×10-9CO2/H2 selectivity

CO2 permeation rate, mol/s

1×10-50
1

10100

1000

10000

Surface area, cm2100

120

98

100
80

96

60
94

4092

2090

CO2/H2 selectivity

CO2 concentration rate
in permeate side, %Fig.15 Gas separation ability of membrane modules in different sizes.

002468101214Time , hFig.16 Stability of the CO2 selectivity.
80∘Cwet)100

100909080806060404020200051015

H2 recovery rate，％

CO２ concentration rate in permeate side，％(Feed gas: H2:CO2=30:70,0Time, hFig.17 Gas separation figure of H2 purification system with hybrid-type membranes.
(Feed gas; H2:CO:CH4:CO2=70:5:5:20, wet, 2MPa G)