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 power plant ） recovery amount:1Mt-CO 2 /yr 、 distance:20km 、 pressure:7MPa injection method ： ERD 、 injection amount ： 0.1Mt-CO 2 /yr/well Power loss for extraction steam from low pressure turbine: 0.05kWh/MJ New plant NET storage 分離回収 Separation coal fired plant ＝ 670/1000 石炭火力新設～帯水層 昇圧 Pressurization to aquifer Transportation 輸送 Injection 貯留 Existing plant income 収入 NET storage 石炭火力既設改造～帯水層 Existing ＝ 502/1000 coal fired plant to aquifer 0 2,000 4,000 6,000 8,000 10,000 12,000 14,000 avoided cost JPY/t-CO 2 アボイデッドコスト 円/t-CO2 Upgrading desulfurization facilities Capture cost CCS total cost & Auxiliary coal fired boiler 4,200JPY/t-CO 2 7,300JPY/t-CO 2 2

CO 2 capture methods for various Sources 1. CO 2 Sources Power plant Natural Gas Blast-furnace Gasification (Combustion) Fossil Fuel EOR Shift Bio-Mass reaction 2. CO 2 Capture (Chemical Research Group ) R. & D. Absorption Membrane Adsorption CO 2 > 99% CO 2 < 2% CO 2 < 2% CO 2 > 95% Regenerator CO 2 < 2% Absorber CO 2 > 97% HEX absorbent Polymer Zeolite, Absorbent Zeolite Mesoporous silica Novel process Carbon Chemical absorption pilot Plant Waste heat utilization Nano composite material (COURSE50: NEDO Project) Source: Nippon Steel Eng. HP. Plant analysis for the decreasing energy and cost 3. Storage ( CO 2 Storage Group ) Geological Utilization Ocean 3

Schematic of IGCC with CO 2 Capture Product H 2 After WGS Coal Steam H 2 , CO 2 O 2 Heat Exchanger CO 2 Gasifier WGS reactor Advantage in -2 to 4 MPa Membrane -ca 40%CO 2 Separation -CO 2 /H 2 Insufficient Separation Selectivity 4

Prospect for CO 2 Separation Cost of Membrane Separation Out put ： 300MW Gas Membrane CO 2 Gas Pres. Performance Source Comp. Membrane (Target) Area ： 100,000 m 2  CO 2 /H 2 : 30 H 2 Prod. CO 2 :40% CO 2 Permeance * 4 MPa Plant H 2 , H 2 O :1x10 -9 (m 3 m -2 s -1 Pa -1 ) Ref. 4 MPa Amine solution (MDEA-Flash) Absorption 4 MPa Phys Absorption Amine solution (KS solution) 0.1 MPa 2,000 4,000 6,000 JPY / t-CO 2 * Duration period Facility:15 years Membrane:5 years Membrane Skid Cost: 50,000JPY/m 2 5

CO 2 Molecular Gate for CO 2 /H 2 Separation CO 2 H 2 0.29 nm 0.33nm Conventional Polymeric Membrane: Feed CO 2 H 2 High Pressure Difference Low Membrane CO 2 /H 2 Selectivity: <1 Permeate O NH 2 O Excellent CO 2 selectivity H 2 N N N H H N N NH HN O NH 2 O H 2 N 6

Possible Model of H 2 Perm. Blockage CO 2 CO 2 H 2 H 2 O O H H H H Carbamate Formation R N C R N C O O N R N R H H H H O O H H H H R N C R N C O O N R N R H H H H Pseudo-cross-linkage CO 2 HCO 3 CO 2 HCO 3 R NH 2 R NH 2 H 2 N R H 2 N R H 2 permeation blockage O O H H H H R N C R N C O O N R N R H H H H CO 2 CO 2 7

Dendrimer Membrane for CO 2 Capture from Pressurized Gas Stream O NH 2 O H 2 N N N H H N N NH HN O UV NH 2 O H 2 N Curing O-OH-PAMAM dendrimer + + PEGDMA + TMPTMA 8

Dendrimer membrane for CO 2 capture from a pressurized gas stream -10 10 1000 α CO CO 2 /H 2 Selectivi 2 （ Q ） / （ m 3 (STP)/(m 2 s Pa) ） H 2 -11 10 100 CO 2 vity ty -12 10 α α （ CO 2 /H 2 ） / （－） 10 -13 10 Permeance H 2 -14 10 1 0 1 2 3 4 5 6 7 CO 2 Partial pressure P CO2 , atm PAMAM/PEGDMA/TMPTMA = 50/37.5/12.5, Feed : 100 mL/min,Sweep : 20 ml/min, T = 313 K, R.H. = 80% 9

Temperature and Performance 50 40 CO 2 /H 2 Selectivity 55 ºC 30 40 ºC 25 ºC 20 10 PAMAM/ PEGDMA/ 0 TMPTMA = -14 -13 -12 -11 -10 -9 10 10 10 10 10 10 50/37.5/12.5 CO 2 /H 2 Permeance / m 3 (STP)/(m 2 s Pa) Thickness: 500 m m 10

CO 2 /H 2 Separation Properties of Dendrimer Membranes at High Pressure 50 RITE CO 2 /H 2 Selectivity (-) 40 9 7 10 30 6 8 11 4 5 2 3 12 20 1 Science (1) 10 0 -14 -13 -12 -11 -10 -9 10 10 10 10 10 10 CO 2 Permeance / m 3 (STP)/(m 2 s Pa) (1) H. Lin, B.Freeman et al., Science , 311 , 639-642 (2006) 11

Separation of CO 2 /CH 4 using molecular gate membranes CO 2 conc. CO 2 conc. in Permeance, Separation factor,  CO2/CH4 in Feed Permeate Q CO2 7.6  10 -12 Membrane 79.6 99.2 30 A 1.2  10 -11 Membrane 74.5 99.9 260 B Temperature: 40  C, Total pressure in feed gas: 0.1 MPa, Relative humidity in Feed gas: 80%, He sweep gas at permeate side. Molecular gate membranes possess high potential for separation of CO 2 /CH 4 mixed gas 12

Dendrimer Composite Membrane Substrate of UF Membrane (commercial) 1 m mm Selective Layer 300 nm 0OH Dendrimer/ Polymeric Matrix Porous Substrate For CO 2 separation from ambient pressure gas stream (1 st Term) 13

Dendrimer Composite Membrane Module #1, 2 200, 800 mm, 3/8 inch #3 1 1 m mm Cross section 1100 mm in length, 1 inch in diameter of membrane Module Membrane CO 2 /N 2 # Area Selectivity  CO2/N2 cm 2 1 17 290 2 180 150 3 4000 150 Dendrimer: conventional PAMAM dendrimer (0OH), Temperature: 25  C For CO 2 separation from ambient pressure gas stream (1 st Term) 14

Long-term Stability in Permeate CO 2 Conc. 100 average 95% [%] minimum 90% 90 80 1000 10 CO2 Permeance Q(CO 2 ) X 10 10 Separation Factor,  CO 2 /N 2 9 8 7 [m 3 (STP) m -2 s -1 Pa -1 ] 6 ) 2 5 /N 100 Selectivity (CO 2 4 [ - ] 3 10 2 1 1 0 200 400 600 800 1000 1200 Test period [ [ h h ] Test period [hour] 800mm-3/8inch module Feed gas mixture: CO 2 /N 2 (32/68 v/v%) containing unknown amount of water vapor Measured temperature: 14-25 o C, Pressure difference between feed and permeate: 0.1MPa 15

Membrane modules Spiral-wound Module Hollow-fiber module ： (flat-sheet membranes) ： Merits ： Merits: ・ Well-studied structure for gas separation ・ Pressure durability up to 10MPa (water) ・ Large membrane area per unit volume ・ Easy to coat flat-sheet membranes Issues ： Issue ： ・ Pressure durability up to 4MPa ・ Membrane area per unit volume ・ Coating method for hollow-fibers Permeate Permeate Feed Feed gas Feed gas spacer gas Retentate Retentate Feed gas Permeate Permeate gas spacer Molecular gate Molecular gate Permeate tube Hollow-fiber membranes flat-sheet membranes 16

Cooperation with private companies （ Development of Membrane module ） Cooperation with Four membrane companies (Kuraray, Daicel, Toray, Nitto-Denko) Engineering company (Nippon Steel Engineering) Dendrime imer/ Polyme meric ic matri rix 500 m ｍ 10 m ｍ 3 m ｍ 17

Membrane module test using syngas Testing apparatus at ECOPRO Gasifier, Nippon Steel Corporation (Yawata plant), Nippon Steel Engineering Co., Ltd. ECOPRO ： JCOAL project supported by METI 18

Acknowledgements This study is supported by: - Ministry of Economy, Trade and Industry (METI), Japan. - Nippon Steel Engineering Co., Ltd. 19

20 Thank you for your attention! Research Institute of Innovative Technology for the Earth Contact: kai.te@rite.or.jp kazama@rite.or.jp 20