Advanced CO 2 Separation Using Molecular Gates

Transcription

1 GCEP Workshop on Carbon Capture May 27, 2011 Stanford University, Stanford, California Advanced C 2 Separation Using Molecular Gates Shingo Kazama Research Institute of Innovative Technology for the Earth (RITE)

2 utline 1. C2 Separation Membrane for IGCC 2. C2 Molecular Gate Function for C2/H2 separation 3. Dendrimer for Possible Molecular Gate 4. Dendrimer Hybrid Membrane 5. ext Generation of C2 Molecular Gate in GCEP research 6. Concluding Remarks C2 H 2

3 C 2 Capture Methods for CCS 1. C 2 Sources Fossil Fuel Bio-Mass Power plant (Combustion) Blast-furnace Gasification Shift reaction 2. C 2 Capture (Chemical Research Group in RITE ) C 2 < 2% Absorption C 2 > 99% Membrane C 2 > 95% C 2 < 2% Adsorption R. & D. Absorber HEX Regenerator absorbent Absorbent ovel process Waste heat utilization C 2 < 2% Polymer Zeolite Carbon ono composite material Plant analysis for the decreasing energy and cost Zeolite, Mesoporous silica C 2 > 97% 3. Storage ( C 2 Storage Group in RITE ) Geological Utilization cean 3

4 Driving Force in PCPP and IGCC Gas source Pulverized Coal Power Plant IGCC with WGS reaction Total press. in Feed C2 Conc./ % Total press. in Permeate Difference of C2 partial press.(initial) 101 kpa 4000 kpa 14 % 40 % 10 kpa Vacuum 101 kpa 8.9 kpa 1,470 kpa Driving force of C 2 permeation more than 150 times

5 Cost Estimation of C 2 Membrane Separation from IGCC C 2 Source Gas Pres. Gas Comp. Membrane Performance (Target in RITE) IGCC w/ WGS 4MPa C 2 :40% H 2, H 2 αc 2 /H 2 : 30 C 2 Permeance :1x10-9 (m 3 m -2 s -1 Pa -1 ) 2 Stages * Ref. Absorption 4MPa 4MPa Amine solution (MDEA-Flash) Phys Absorption 0.1MPa Amine solution (KS solution) * Duration period Facility:15 years Membrane:5 years Membrane Skid Cost: 50,000JPY/m USD / t-c 2

6 What is an ideal membrane for C 2 /H 2 separation? A hint may exist in a towel balloon. Dry Towel Wet Towel Textile Fiber Water Air Air

7 Concept of C 2 Molecular Gate for C 2 /H 2 Separation C2 0.33nm H nm Feed High Pressure Difference Low Permeate Membrane Material Excellent C2 selectivity

8 Dendrimer Membrane: A C 2 Selective Molecular Gate H 2 H 2 H H H H H 2 H 2 Polyamidoamine (PAMAM) dendrimer C2/2 separation: A. S. Kovvali, H. Chen, and K. K. Sirkar J. Am. Chem. Soc. 2000, 122,

9 Design of Dendrimer s Chemical Structure for better C 2 /H 2 separation 0H H 2 H 2 H H H H 2 riginal Polyamidoamine(PAMAM) dendrimer H H 2 H 2 H H H 2 4H H H H H H H H 2 H 2 H H H 2 H 2 H H Hydroxyl Polyamidoamine(PAMAM) dendrimer H H H 2 ewly Synthesized 3H

10 C 2 /H 2 Permeability & Selectivity of Dendrimers Permeability coefficient [m 3 (STP) m m -2 s -1 kpa -1 ] H P C2 0H 4H 0H P H2 3H 3H Separation factor H 4H 3H 4H 3H 0H Relative humidity [%] Relative humidity [%] 3H-PAMAM dendrimer P C2 = [m 3 (STP) m m -2 s -1 kpa -1 ], α C2/H2 =1,000 (at 80RH%) - Feed:(C 2 /H 2 =5/95) at 25 C, Dendrimer was supported in porous substrate - Isobaric test condition

11 H 2 Blockage by C 2 in Dendrimer H 2 Permeability [m 3 m m -2 s -1 Pa -1 ] Pure H 2 Pure gas Mixed-gas Mixed-gas (C 2 /H 2 ) RH [%] Mixed-gas Pure gas 5%C2 4H H 2 Permeability Pure gas > Mixed-gas (C 2 : 5 %) C 2 blocks H 2 permeation

12 Possible Model of H 2 Perm. Blockage C 2 H 2 H R C H R H H Carbamate Formation H R C H R H H C 2 HC 3 Pseudo-cross-linkage R H 2 H R C C 2 H 2 R H R H H H2 permeation blockage

13 Dendrimer Hybrid Membrane for C 2 Capture from Pressurized Gas Stream H H 2 2 H H H H H 2 H 2 -H-PAMAM dendrimer + + UV Curing PEGDMA + TMPTMA

14 C 2 /H 2 Separation Properties of Dendrimer Hybrid Membrane at Elevated Pres Permeance (Q)/ (m 3 (STP)/(m 2 s Pa)) C 2 α H 2 C 2 α H C 2 /H 2 Selectivity α(c 2 /H 2 )/(-) C 2 Partial pressure PC2, atm PAMAM/PEGDMA/TMPTMA, Feed : 100 ml/min, Sweep: 20 ml/min, T = 313 K, R.H. = 80%

15 C 2 /H 2 Separation Properties of Various Dendrimer Hybrid Membranes 50 C 2 /H 2 Selectivity (-) RITE Science (1) Film Thickness: 500 μm C2 partial press.: 6 bar at 313 K C 2 Permeance / m 3 (STP)/(m 2 s Pa) (1) H. Lin, B.Freeman et al., Science, 311, (2006)

16 Temperature Dependence of Membrane Performance C2/H2 Selectivity 55 ºC ºC 25 ºC C 2 Permeance / m 3 (STP)/(m 2 s Pa) PAMAM/ PEGDMA/ TMPTMA Thickness: 500μm

17 Development of Membrane Module ow fabricating dendrimer membrane modules with membrane module makers Dendrimer/ Polymeric matrix : Dendrimer Hybrid 500 μm 10 μm 3 μm

18 Feature of Dendrimer Hybrid Membrane Current Generation: High C 2 /H 2 selectivity at various C 2 partial pressure from atmospheric to elevated pressure at high relative humidity such as 80 %RH or more Required no dehumidifying process ext Generation: Should be adapted over a wide range of relative humidity GCEP s Challenge

19 C 2 permeation Model of Current Dendrimer Hybrid Membrane C 2 H 2 Gas Feed H H 2 R-H 2 R C R H H C 2 H2 R-H 2 HC - 3 Sorption Hopping C 2 H R C H R H H HC 3 - Hopping C 2 Diffusion H R C H R H H C 2 HC 3 - Desorption Permeate C 2 H 2

20 Sc-C 2 Structure Directing Method for ext Generation Membrane Inject Sc-C 2 Remove Sc-C 2 Pre-formed Solid Membrane Amino moiety C R--C- -R- carbamate formation Ion Hopping Channel

21 Set-up for Sc-C 2 Structure Directing Method Pre-formed membrane Camera Sapphire window C 2 Membrane under Sc-C2 Pressure:10 MPa Temperature:20-60 Syringe pump High-pressure view cell Back-pressure regulator

22 Concluding Remarks - Membrane application for C2 capture from a pressurized gas stream is promising way of reducing C2 capture cost and energy. - Molecular gate membrane (MGM) is proposed for high C2 selectivity over H2. - Dendrimer membrane has good C2 separation performance over a wide range of C2 partial pressure and highly humidified feed gas. - ext generation MGMs that work well in a wide range of humidity in a feed gas and have higher selectivity are now under development in GCEP project.

23 Acknowledgements Researchers: Dr. Yuichi Fujioka, Dr. Katsunori Yogo Dr. Shuhong Duan, Dr. Teruhiko Kai, Dr. Kazuya Goto, Dr. Ryo agumo, Dr. Ryosuke Shimizu, Dr. Hiroshi Machida Dr. Ikuo Taniguchi, Dr. Kouta Yamazaki Student of AIST (ara Institute of Science and Technology) : Mr. Tomoyuki Kato This study is supported by -GCEP, Stanford University -Ministry of Economy, Trade and Industry (METI), Japan. -ippon Steel Engineering Co., Ltd.

24 GHGT th International Conference on Greenhouse Gas Control Technologies - ovember Kyoto will welcome experts in greenhouse gas control technologies from across the world! 1. Dates : Sun. 18 Thur. 22 ovember, Venue : Kyoto International Conference Center, Japan 3. rganizers : RITE & IEAGHG 4. Estimated umber of Attendees: 1,600 GHGT-10 : Poster session 5. Themes of Technical Sessions (at GHGT-10, Sep. 2010, Amsterdam, the etherlands) Capture, Utilisation, Storage, Integrated, Demonstrations, Policy, egative Emissions, Legal, Public Perception GHGT-10 : Closing session GHGT-10 : Plenary session

25 25 Thank you for your attention! Research Institute of Innovative Technology for the Earth Contact: or. jp