3✓✓✓✓他の気体CO2他の気体

供給側分離前（処理前）分離前他の気体

他の気体他の気体CO2

再生塔

吸収塔(吸収液)

CO2

リボイラー

吸着塔(吸着剤)

CO2

分離前

高分子分離膜CO2吸収液

吸収法

吸収液膜分離法

透過側分離後（処理側）

分離前

吸着法

Gas Separation (GS)Pervaporation (PV)Reverse Osmosis (RO)Nanofiltration (NF)

Ultrafiltration (UF)Microfiltration (MF)NonporousmembranePorous membrane (Type I Porous–PorousVI)VI)(TypemembraneVI)I I–I––Porous(TypemembraneVI)(Typemembrane(Type VII)

lowccc c ccccc

KnudsenSurfaceCapillaryHagenHagenConvectiveConvectiveCapillarySurface SolutionCapillaryKnudsen MolecularSurfaceKnudsenHagenConvectiveCapillarySurfaceKnudsenflowdiffusionsievingflow condensationPoiseuilleflowPoiseuilleflowflowcondensatiodiffusionDiffusionflowcondensationdiffusionflowflowPoiseuilleflowcondensatiodiffusionflowVII)(Type(Type(TypeV)III)VI)IV)II)(TypeII)IV)(Type(TypeI)III)(TypeV)(TypeIV)(Type(Type(TypeV)V)III) (Type(Type(TypeIII)II)(TypeI)I)(Type(TypeIV)(Type(Type他の気体103

供給側分離前（処理前）分離前

Upper Bound (2008)HyperbranchedFiller

他の気体

CO2吸着塔(吸着剤)

CO2

高分子分離膜透過側分離後（処理側）

分離前✓

Selectivity (CO 2/N2)

他の気体10PEO-Copolymer

2PIM

101Crosslinked

100 -1210GeneralSiloxaneCopolymer

10-1110-10

10-910-810-7

P(CO2) (cm 3(STP)cm/(cm2 s cmHg))

膜分離法

吸着法

10-6

溶解（界面への溶け込み）ee I(Type– VI) I – VI)

拡散（内部の移動）

脱着（界面からの脱離）NonporousNonporousNonporous溶解脱着溶解 拡散溶解 拡散拡散脱着脱着membranemembranemembrane（界面への溶け込み）（内部の移動）（界面からの脱離）（界面への溶け込み）（界面への溶け込み）（内部の移動）（内部の移動）（界面からの脱離）（界面からの脱離）材料の断面(Type VII)(Type VII)(Type VII)cccccc材料の断面材料の断面 材料の断面cccc
c材料の断面ccccccc

✓✓✓✓✓✓
✓✓✓
✓
✓✓✓✓

✓✓•
••
•
•
•
•

•

•
•

225

Upperbound(2008)Upperbound(2008)

CO2/CH4 selectivityCO2/CH4 selectivity

CarbonB BCarbonCarbonC CCarbonCu-BTCCu-BTCPI PI

POP-2POP-2

CarbonA ACarbonOtherMMMsOtherMMMs

ZIF-8ZIF-8

Matrimid-basedMMMsMatrimid-basedMMMs11

10 100010 10110 101CO2COpermeability(barrer)2 permeability(barrer)✓

CO2 permeability enhancement ratio

10 10210 102

volume fraction: 0.21-0.22Cu-BTC

4ZIF-8POP-2Carbon C

3Carbon B2Carbon A2r = 0.957
1
1102

31010
2Surface area (m /g)

104

-5

4

1010

T = 35 oC

Permeability

101

10010-1

p = 10 atm-7

10

T = 35 oC-910-11

10310(cm (STP)cm/(cm s cmHg))

p = 10 atm

2Diffusivity (cm 2/s)(a) CO2(a) CO2

310-2-131010-15-310103456781FFV

910345761FFV✓8910

1250000

1040000

830000620000410000

2Benchmark

00.01

00.11Thickness （μm）

CO2/N2 Selectivity

CO2 Permeance (GPU)

60000

✓

Raw natural gasComponents

for water vapour removal

Composition

CH475 – 90%

CO2

3 – 40%H2S

4 – 10000 ppm

H2ODehydrationCoalescing Filter

for liquid and mist elimination

AdsorbentGuard Bedfor trace contaminant removal

Particle Filter

for dust removal

800 – 1200 ppm

Pre-treatmentBTEX*200 – 2000 ppm

Others(C2+, N2, He…)

> 4%

✓Pre-treatment is necessary for✓latter membrane systemHeat◼ water vapour◼ Acidic gases◼ Dicol◼ BTEX◼ Hydrocarbon(R. Baker and K. Lokhandwala, Ind. Eng.
Chem. Res., 47, 2109-2121 (2008))

oPure gas data

50

35 C

2000

360

as-cast1500

Selectivity (CO 2/CH4)

760 min later2(x10-107203605CA

Plasticizationpressure51000

35

CO2 permeability

360

cm (STP)cm/(cm s cmHg))

Polyimide(DCM)6FDA-TeMPD

760 min laterm)

60

2500

500

72036054030

30.6% CO2 in feed

2070.6% CO2 in feed10thermal0040500102030

Feed pressure (atm)

4050051015

Pressure (atm)2025

2Upperbound(2008)Upperbound(2008)

Wet mixed CO2/CH4POP-2POP-2ZIF-8ZIF-8

Water uptake (wt%)

CO2/CH4 selectivityCO2/CH4 selectivity

Cu-BTCCu-BTC

CarbonA ACarbonOther MMMsOther MMMs

Upper bound (2008)

12CarbonB BCarbonCarbonC CCarbon

PI PI

102

15

Cu-BTCUiO-66

9Matrimid

ZIF-8

6

Carbon CCarbon B

311010POP-2

Matrimid-based MMMsMatrimid-based MMMs

1100100101110CO2 permeability (barrer)CO2 permeability (barrer)✓

CO2/CH4 selectivity

10 102

102POP-2PI

ZIF-8UiO-66

Carbon B

10102Cu-BTCCarbon C

Carbon A010Carbon A

1020

Filler loading (wt%)

30

40

100

101CO2 permeability (barrer)

102

1.51.51.5N2

MMM (Cu-BTC)

H2S

1.0CarbonPOP-2PI

ZIF-8

0.51.0PICarbonPOP-2

0.5N2 permeability (barrer)

N2 permeability ratio

Cu-BTCN2 permeability ratio

N21.0SO2NOOriginal PIperformance

0.5Cu-BTC

H2S

ZIF-800.000204060Time (day)

✓80

100

0204060Time (day)

80

100

0204060Time (day)80100✓