7. CO 2 Membrane Separation Teruhiko Kai and Shingo Kazama Chemical - - PowerPoint PPT Presentation
CCS WORKSHOP Jakarta, 22 February 2011 16:00 16:25 7. CO 2 Membrane Separation Teruhiko Kai and Shingo Kazama Chemical Research Group Research Institute of Innovative Technology for the Earth (RITE) 1 Present Cost of CCS coal fired
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Teruhiko Kai and Shingo Kazama Chemical Research Group Research Institute of Innovative Technology for the Earth (RITE)
CCS WORKSHOP Jakarta, 22 February 2011 16:00 – 16:25
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Present Cost of CCS （coal fired power plant）
recovery amount:1Mt-CO2/yr、 distance:20km、pressure:7MPa injection method：ERD、 injection amount ：0.1Mt-CO2/yr/well
2,000 4,000 6,000 8,000 10,000 12,000 14,000 アボイデッドコスト 円/t-CO2 石炭火力既設改造～帯水層 石炭火力新設～帯水層 分離回収 昇圧 輸送 貯留 収入
Power loss for extraction steam from low pressure turbine: 0.05kWh/MJ NET storage ＝670/1000 NET storage ＝502/1000
New plant Existing plant
avoided cost JPY/t-CO2
coal fired plant to aquifer Existing coal fired plant to aquifer Upgrading desulfurization facilities & Auxiliary coal fired boiler
Separation Pressurization Transportation Injection income
Capture cost 4,200JPY/t-CO2 CCS total cost 7,300JPY/t-CO2
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Absorption
CO2 capture methods for various Sources
3. Storage ( CO2 Storage Group ) Geological Utilization Ocean 2. CO2 Capture (Chemical Research Group ) 1. CO2 Sources
Fossil Fuel Bio-Mass
Gasification
Shift reaction
Blast-furnace Power plant (Combustion) Adsorption Membrane
Polymer Zeolite Carbon Nano composite material Zeolite, Mesoporous silica
Plant analysis for the decreasing energy and cost
Absorbent Novel process Waste heat utilization
CO2 > 99% CO2 < 2% Absorber HEX absorbent Regenerator CO2 > 95% CO2 < 2% CO2 > 97% CO2 < 2%
Natural Gas EOR
Chemical absorption pilot Plant (COURSE50: NEDO Project) Source: Nippon Steel Eng. HP.
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Coal
O2
Steam
Separation
Heat Exchanger
CO2 Product H2 Advantage in Membrane Separation Insufficient Selectivity
After WGS H2, CO2 Gasifier WGS reactor
5 2,000 4,000 6,000 JPY / t-CO2
Out put：300MW Membrane Area：100,000 m2
CO2 Source Gas Comp. Membrane Performance (Target) H2 Prod. Plant Gas Pres. Absorption 4MPa CO2:40% H2, H2O Amine solution (MDEA-Flash) Ref.
CO2/H2: 30
CO2 Permeance :1x10-9(m3 m-2 s-1 Pa-1) Phys Absorption Amine solution (KS solution) 4MPa 4MPa 0.1MPa Membrane Skid Cost: 50,000JPY/m2 Duration period Facility:15 years Membrane:5 years
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CO2
0.33nm
H2
0.29 nm
Feed Permeate Pressure Difference High Low Conventional Polymeric Membrane: CO2 H2 CO2/H2 Selectivity: <1
Excellent CO2 selectivity Membrane
N N N H NH N H HN O O O O NH2 NH2 H2N H2N
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CO2 HCO3
CO2 H2 CO2 R N C O O N R H H H H R N C O O N R H H H H R N C O O N R H H H H R NH2 H2N R
CO2 HCO3
CO2 H2 CO2 R N C O O N R H H H H R N C O O N R H H H H R N C O O N R H H H H R NH2 H2N R
Carbamate Formation Pseudo-cross-linkage H2 permeation blockage
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TMPTMA PEGDMA
O-OH-PAMAM dendrimer
UV Curing
N N N H NH N H HN O O O O NH2 NH2 H2N H2N
+
9 PAMAM/PEGDMA/TMPTMA = 50/37.5/12.5, Feed : 100 mL/min,Sweep : 20 ml/min, T = 313 K, R.H. = 80%
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10
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10
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1 10 100 1000 1 2 3 4 5 6 7
CO
2
H
2
α
Permeance
（Q）/ （m 3(STP)/(m2 s Pa)） CO2/H2 Selectivi
vity ty
PCO2, atm α（CO2/H2）/（－） CO2 Partial pressure
H2 CO2 α
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10 20 30 40 50 10
10
10
10
10
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25 ºC 40 ºC 55 ºC Thickness: 500mm CO2/H2 Selectivity CO2/H2 Permeance / m3(STP)/(m2 s Pa) PAMAM/ PEGDMA/ TMPTMA = 50/37.5/12.5
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CO2 Permeance / m3(STP)/(m2 s Pa)
CO2/H2 Selectivity (-)
1 2 3 4 5 6 7 8 9 10 11 12
10 20 30 40 50 10
10
10
10
10
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(1) (1) H. Lin, B.Freeman et al., Science, 311, 639-642 (2006)
RITE
Science
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Molecular gate membranes possess high potential for separation of CO2/CH4 mixed gas
CO2 conc. in Feed CO2 conc. in Permeate Permeance, QCO2 Separation factor, CO2/CH4 Membrane A
79.6 99.2 7.6 10-12 30
Membrane B
74.5 99.9 1.2 10-11 260
Temperature: 40 C, Total pressure in feed gas: 0.1 MPa, Relative humidity in Feed gas: 80%, He sweep gas at permeate side.
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Selective Layer 0OH Dendrimer/ Polymeric Matrix Porous Substrate
1 m mm
Substrate of UF Membrane (commercial) 300 nm
For CO2 separation from ambient pressure gas stream (1st Term)
14 200, 800 mm, 3/8 inch
1100 mm in length, 1 inch in diameter
Cross section
CO2/N2 Selectivity
CO2/N2
Dendrimer: conventional PAMAM dendrimer (0OH), Temperature: 25 C
1 m 1 mm
Membrane Area cm2 17 180 4000 Module # 1 2 3 #1, 2 #3 290 150 150
For CO2 separation from ambient pressure gas stream (1st Term)
15 Feed gas mixture: CO2/N2 (32/68 v/v%) containing unknown amount of water vapor Measured temperature: 14-25oC, Pressure difference between feed and permeate: 0.1MPa
1 10 1 10 100 1000 200 400 600 800 1000 1200
Selectivity (CO 2 /N
2
) Test period [hour]
Test period [ [ h h ] CO2 Permeance Q(CO2) X 1010 [m3(STP) m-2 s-1 Pa-1] Separation Factor, CO2/N2 [ - ] CO2 Conc. in Permeate
[%]
90 100
minimum 90%
80 2 3 4 5 6 7 8 9
800mm-3/8inch module average 95%
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Hollow-fiber module：
Merits： ・Well-studied structure for gas separation ・Large membrane area per unit volume Issues： ・Pressure durability up to 4MPa ・Coating method for hollow-fibers
Spiral-wound Module (flat-sheet membranes)：
Merits: ・Pressure durability up to 10MPa (water) ・Easy to coat flat-sheet membranes Issue： ・ Membrane area per unit volume
Permeate tube Retentate Permeate Feed gas Feed gas spacer Feed gas Permeate gas spacer
Molecular gate flat-sheet membranes
Feed gas Retentate Permeate Permeate
Molecular gate Hollow-fiber membranes
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Cooperation with private companies （Development of Membrane module）
Dendrime imer/ Polyme meric ic matri rix
500 mｍ 10 mｍ 3 mｍ
Cooperation with Four membrane companies (Kuraray, Daicel, Toray, Nitto-Denko) Engineering company (Nippon Steel Engineering)
18 ECOPRO： JCOAL project supported by METI Testing apparatus at ECOPRO Gasifier, Nippon Steel Corporation (Yawata plant), Nippon Steel Engineering Co., Ltd.
Membrane module test using syngas
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This study is supported by:
Japan.
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Research Institute
Innovative Technology for the Earth