Development of Innovative Gas Separation Membranes Through Sub-Nanoscale Materials Control

Transcription

1 GCEP Research Symposium 2006 Wednesday, September 20, 2006 Carbon Mitigation, Capture, and Separation Development of Innovative Gas Separation Membranes Through Sub-Nanoscale Materials Control Yuichi Fujioka, Shingo Kazama,, Katsunori Yogo, Teruhiko Kai, Naoki Yamamoto, Kousuke Uoe,, and Koichi Yamada, RITE (Research Institute of Innovative Technology for the Earth) 1

2 Contents 1. Application for Membrane 2. Development of carbon membrane a. Defect of membrane and performance b. Pore size orientation 3. Development of Functionalized mesoporous oxide membrane 4. Development of zeolite membrane a. Crystal face orientation method b. Rubbing method 2

3 Technological ptions for 550 ppmv Stabilization Carbon emissions and reductions (GtC/yr) Energy Saving Fuel Switching Biomass Photovoltaics Wind Power Hydro & Geoth. Nuclear Power cean Seq. Aquifer Seq. Gas Well Seq. ER Reforestation Net C2 Emission Net Carbon Emissions in Reference Case Net Carbon Emissions in 550ppmv Case Energy Saving Fuel Switching among Fossil Fuels Biomass Photovoltaics Wind Power Hydro & Geoth. Nuclear Power cean Seq. Aquifer Seq. Gas Well Seq. Reforestation Year 3

4 C 2 chemical absorption efficiency (Coal fired power plant) 1. Separation Energy of Chemical absorption = 3.0 GJ/t-C 2 Absorber C 2 < 2% HEX Regenerator Solvent Chemical absorption C 2 > 99% Reboiler Heating of absorbent 0.75 (25%) C 2 desorption reaction 1.91 (63%) Absorbent transport 0.38 (13%) 2. Efficiencies % Coal = 13.3 GJ/t- C Theoretical separation energy (10%, 50 degree-c) = 0.18 GJ/t- C 2 Separation efficiency % 4

5 Future C 2 Separation and Capture Coal PC PC Gasifier Flue gas Absorber C 2 < 2% HEX Solvent Regenerator Chemical absorption C 2 > 99% Reboiler Gasifier S/T G G/T Water-Gas shift Reactor G Membrane Chemical absorption Membrane 5

6 C2 Separation Membranes Through Sub-Nanoscale Materials Control Membrane concept C 2 N 2 Selective Layer Sub-Nanoscale Materials Control C 2 affinity Pore diameter No structural defect Porous Substrate High C 2 selectivity and permeability 6

7 2. Development of carbon membrane a. Defect of membrane and performance b. Pore size orientation by carbonization 7

8 Definition of Permeance & Selectivity Feed Retentate p1, x C2, x N2 x (-): molar fraction in feed y (-): molar fraction in permeate p1 (Pa): total pressure in feed p2 (Pa): total pressure in permeate Ft (m 3 s -1 ): total gas flux of permeate A (m 2 ): membrane area Permeate Ft, p2, y C2, y N2 C 2 permeance (m 3 m -2 s -1 Pa -1 ) : Q C2 = Ft y C2 / (p1 x C2 -p2 y C2 ) / A N 2 permeance : Q N2 = Ft y N2 / (p1 x N2 - p2 y N2 ) / A C 2 /N 2 selectivity : α C2/N2 = Q C2 /Q N2 8

9 Concept for High C2 Selectivity C2 0.32nm N2, H2etc. 0.26, 0.22 nm Candidate materials Polyamidoamine(PAMAM) dendrimers H 2 N N H HN H 2 N NH 2 N N N H NH NH 2 C2/N2 separation: A. S. Kovvali, H. Chen, and K. K. Sirkar J. Am. Chem. Soc. 2000, 122, C2 Molecular Gate H 2 N H N H H HN H 2 N N N N H NH C2/H2 separation: S. Kazama et al., 8th Intl. Conf. on Greenhouse Gas Control Technologies(GHGT-8), Trondheim, Norway (2006) NH 2 H H NH 2 9

10 Dendrimer Composite Membrane Modules #1, 2 200, 800 mm, 3/8 inch #3 1 mm 1100 mm in length, 1 inch in diameter Cross section of membrane Module # Membrane Area cm Dendrimer: conventional PAMAM dendrimer Temperature: 25 C C2/N2 Selectivity α C2/N

11 Design of Precursor (1) Selection of functional group, polymer unit and polymer Cardo moiety: Low volatility & Large chain distance + Unit X1 + Unit X2 + UnitX3 + UnitY1+UnitY2 Chain distance (nm) High volatility pore-size controller C 2 affinity enhancer Polymer Chain 12

12 Design of Precursor (2) Chain distance control in sub-nano size Unit X1 Chain distance (nm) A B C C N C C N C C N C C CF 3 C CF 3 C C N C C N n C C N n n Polymer Chain X-ray diffraction A B C 13

13 Carbonization Manufacturing larger pore size of carbon membrane through carbonization process (temperature, pressure, atmosphere) Membrane Unit X2 (High volatility) Cardo Polymer (Low volatility) Positive phase separation with Controlling Pore Size Carbonization Image precursor Porous substrate nm 1-2 nm Strict pore size control 14

14 Pre- & post Carbonization Membrane Precursor-coated membrane Carbon membrane Substrate: porous alumina 15

15 Porous Carbon Membrane (PCM) Top View Top View 300nm Carbon membrane prepared from Cardo polyimide 300nm Carbon membrane prepared from Cardo polyimide and Poly(ethylene glycol)(peg) Pore size : ca. 10 nm 16

16 Surface morphology of PCM Top View 300nm Porous Carbon Membrane Schematic image 100nm riginal photo was contrasted with black and white 17

17 SEM images and pore diameter distribution Top View 0.10 Pore size distribution nm Surface of carbon layer Kelvin diameter [nm] Pore size distribution using Nano-permporometer SEM photograph and pore size distribution of carbon membrane prepared from polyimide/poly(ethylene glycol) precursor. 18

18 Future work: Enhancement of C 2 Affinity Modification of pore property for high C2 affinity Modification of pore surface N 2, H 2 : C 2 Pore size: nm Modified wall Ideal C 2 Molecular Gate -Insertion of molecule having C 2 molecular gate function N 2, H 2 : C 2 Pore size: 1-2 nm Molecule insertion C 2 Molecular Gate 19

19 3. Development of Functionalized mesoporous oxide membrane 20

20 Amine-modified modified MCM-48 C2=0.33nm APS=0.7nm MCM-48(2nm pore) is promising MCM nm APS: H 2 N Si(CH 2 CH 3 ) 3 3-aminopropyltrietoxysilane 2.2 nm APS/MCM-48 21

21 MCM-48 Membrane MCM-48 membrane synthesized by spin coating. SEM image Cross view TEM image Top view MCM-48 (300nm) Pore diameter : 2 nm 22

22 Pore size distributions of mesoporous silica (dv/ddp) (cm 3 /nm/g) MCM-48 APS/MCM-48 Surface area (m 2 g - 1 ) Pore Volume (cm 3 g -1 ) MCM Dp: Pore diameter (nm) APS/ MCM APS: H 2 N Si(CH 2 CH 3 ) 3 3-aminopropyltrietoxysilane (measured at powder) 23

23 Ammonium carbamate formation Absorbance ν NH 3439 ν NH IR spectrum ν CH C2 (gas) NHC Wave number (cm -1 ) b a δ NH2 C2 NH2 Si NH2 Si C2 adsorption: NHC - NH3 + Si Ammonium carbamate formation on the pair site of amino-group Si a: Dried APS/MCM-48 b: After C 2 adsorption Amino group on pore surface is effective for C 2 adsorption 24

24 Comparison of C 2 separation performances C 2 selectivity Target zeolite T (Kita et al., 2004) Na-Y zeolite (Kusakabe et al., 1997) K-Y zeolite (Kusakabe et al., 1999) Cs-Y zeolite (Kusakabe et al., 2002) SAP-34 (Falconer et al., 2000) silicalite (Ando et al., 1998) B-, Na-ZSM-5 (Santamaría et al., 2004) Carbon (Kusakabe et al., 1998) Si 2 -Zr 2 (JFCC, 2000) Anodic-treated Al 2 3 (JFCC, 2000) APS/MCM-48 (RITE) C 2 permeance (m 3 (STP) m -2 s -1 Pa -1 ) 1. Ammonium carbamate is too stable 2. Not enough space to move molecule 3. Membrane defect 25

25 Future work: Functionalized mesoporous oxide membrane Selection of optimum porous structure Membrane preparation & Functionalization Target pore size/structure chemical composition rganic hybrid Preparation of ultra thin separation layer: Dip coating Hydrothermal synthesis Affinity control : selection of functional group carbamate formation N-atom density High permeability Permeance 1000 times High selectivity α C2/N2 =

26 4. Development of zeolite membrane a. Crystal face orientation method b. Rubbing method 27

27 Zeolite Membrane Zeolite Highly ordered structure with same pore diameter High thermal stability Zeolite membrane N H H H (SDA:Structuredirecting agent) D : 0.3 ~ 1.3 nm rientation Secondary growth Uniform shape crystal Mono-layer of crystals Membrane 28

28 Silicalite synthesized by conventional method Silicalite (MFI) Former Crystal view (010) pore size : nm 1k cps Intensity (a.u.) (101) (020) (121) (002) (102) (202) (112) (312) (102) (421) (501) (432) (133)(303) (104) (352) (503) (080) (10 00) (0 10 0) 500 nm twin crystal crystal size ( μm) θ / deg. (Cu Kα) 29

29 Synthesis of Uniform crystal 1 μm Crystal size ( μm) Morphology controlled crystallization (rate of nucleation / crystal growth) θ / deg. (Cu Kα) Control addition rate of SDA 30 Intensity (a.u.) (101) (020) (121) (002) (102) (202) (112) (312) (102) (421) (501) (432) (133)(303) (104) (352) (503) (080) (10 00) (0 10 0) 1k cps Random Crystal face

30 Crystalline orientation ph control ζ potential is dependent on ph Surface (minus) charge of crystal is dependent on the ζ potential Force of repulsion between crystals is dependent on the surface charge ζ potential ph Force of repulsion makes crystal face orientation 31

31 rientation by ultrasonic oscillation Water evaporation under ultrasonic oscillation Crystal suspended solution ph = 11 I (020) /I (002) =6.8 ph =12.5 I (020) /I (002) = μm 100 μm Crystals is oriented monolayer by ultrasonic oscillation 5 μm 5 μm 32

32 rientation of silicalite seed crystals Intensity (a.u.) (020) (040) (060) (080) (10 0 0) 1k cps θ / deg. (Cu Kα) seed crystals mono-layer Uniform Crystal face substrate 5 μm 33

33 Zeolite membranes after secondary growth Monolayer of seed crystals Secondary growth A-type Silicalite Y-type top view top view top view 1 μm 10 μm 5 μm cross-section cross-section cross-section 1 μm 2 μm 5 μm α C2/N2 = 4.5 α C2/N2 = 2.5 α C2/N2 =

34 Defect in zeolite membrane Rhodamine B staining of a silicalite membrane C 2 permeance: m3 m-2 s-1 Pa-1 C 2 selectivity:1.33 A lot of defect larger than 2 nm Silicalite pore size : nm Free space pace dose mot disappear after secondary growth Movement & Slow diffusion of raw materials into the space 35

35 Membrane by rubbing method Fixation of seed crystal into the inside of substrate secondary growth Silicalite membrane Zeolite Y membrane top view top view H. Kita et al., Sep. Purif. Techol., 2001, 25, cross-section cross-section Silicalite composite layer substrate Zeolite Y composite layer substrate Formation of mixed layer by growth of seed crystal inside of substrate 36

36 Performance of Membranes by rubbing method Silicalite membrane Zeolite Y membrane C 2 permeance : m 3 m-2 s-1 Pa-1 C 2 permeance : m3 m-2 s-1 Pa-1 α C2 /N 2 = 3.24 α C2 /N 2 = 69.3 Evaluation method : soaking in 0.2 mmol/l Rhodamine B ethanol solution Condition of permeation measurement : gas composition C 2 20%(N 2 Balance) feed gas pressure 0.05 MPa temperature 298 K C 2 selectivity : Crystal face orientation << Rubbing 37

37 Mechanism of Decreasing Defect Zeolite Y membrane (0.7μm) α (C2/N2) =69.3 Few defects Crystals grow up at a limited space Growing point is often broken or Direction of Crystal face is often moved by stress. New space where new solution can enter is generated. Generation and destruction around crystals decrease the defects during secondary growth. 39

38 Comparison of C 2 separation performances C 2 /N 2 selectivity Target C 2 permeance (m 3 (STP) m -2 s -1 Pa -1 ) zeolite T (Kita et al., 2004) Na-Y zeolite (Kusakabe et al., 1997) K-Y zeolite (Kusakabe et al., 1999) Cs-Y zeolite (Kusakabe et al., 2002) SAP-34 (Falconer et al., 2000) silicalite (Ando et al., 1998) B-, Na-ZSM-5 (Santamaría et al., 2004) Carbon (Kusakabe et al., 1998) Si 2 -Zr 2 (JFCC, 2000) Anodic-treated Al 2 3 (JFCC, 2000) APS-MCM-48/Al 2 3 (RITE) Zeolite Y(RITE) 38