tsuru@hiroshima-u.ac.jp

tel:082-424-7714Membrane Science & Technology at Hiroshima University

2012/09/28CO2

Outline

Laboratory for Membrane Science and Technology

CO2post-combustion CO2pre-combustion CO2H2oxyfuel-combustion O2

2

(http://www.bbc.co.uk/news/science-environment-11435522)

3

Pore size [nm]

UF MF

NF

RO

1 10 1002 5 20 500.2 0.5

0

5,000,000

10,000,000

15,000,000

20,000,000

25,000,000

30,000,000

35,000,000

1990

1991

1992

1993

1994

1995

1996

1997

1998

1999

2000

2001

2002

2003

2004

2005

2006

Classified by membrane types

32,000,000 m3/d, 2006

m

3 /d

Figure is copied from The Association of Membrane Separation Technology of Japan, based on membrane manufactures in JapanIDA Inventory Report 2006

year

SWRONF+BWROMF+UF

4

All types(SWRO)

(NF+BWRO)(LP+MF+UF)

SWRO

MF+UF

60%

40%

70%

30%

43%

57%

JapanOverseasJapan

overseas

Figure is copied from The Association of Membrane Separation Technology of Japan, based on membrane manufactures in JapanIDA Inventory Report 2006

5

RO/ NF Toray (sw), Nitto (sw), Toyobo (sw)

UF Asahi Chemicals, Daicen

MF Mitsubishi Rayon, Asahi Chemicals

GS Ube Industries

PV Mitsui Shipping

Engineering Kurita, Organo, Mitsubishi Rayon

6

RO/ NF Toray, Nitto (spiral wound)Toyobo (hollow fiber)

Topics high-flux low pressure RO membranes

positron analysis for boron rejection

70%

30%JapanOverseasJapanoverseas

7RO/NF

(membrane combined with anaerobic fermentation)Aqua Renaissance (1985-1990) (METI)

MAC21 (Membrane Aqua Century 21) (1991-) NewMAC21 (1994-1996)ACT21 (Advanced Aqua Clean Technology for 21 century ) (1997-2001)E-Water, E-Water2 (2002-)

Topics:1. Membrane BioReactor in submerged system (MBR)

originally developed in Aqua Renaissance.

2. MembranesPE, PP: conventional materialsPVdF: a new and major material for membranes for water treatment

8UF/MF

MLSS

(http://blog.anua-us.com/blog/bid/50584/Membrane-Bioreactor-Wastewater-Treatment-for-Processing-Nitrogen)

9

Manufactures: Mitsui Engineering & Shipbuilding Co.Mitsubishi Chemical, Hitachi Zosen Cor. (Hitz)

Zeolite: NaA, TApplications: dehydration

Manufactures: NGK InsulatorsNoritake

Materials: Al2O3, TiO2Pore size: MF, UF (MWCO5,000)

10

Outline

Laboratory for Membrane Science and Technology

CO2post-combustion CO2pre-combustion CO2H2oxyfuel-combustion O2

11

12CO2 post-pre-oxycombustion

(Rubin et al., Progress in Energy and Combustion Science, 2012)

13

CO2

(Rubin et al., Progress in Energy and Combustion Science, 2012)

CO2H2

CH4

CO

Mo350

ZnO

Ni750-900

Fe-Cr350-400

Cu-zn200-250

CO+H2O H2+CO2

PSA

CO2

H2(

H2

H2

H2CO2

CO2

CH4+H2O 3H2+CO

CO2: 0.05CH4: 0.01CO: 0.15H2

CO2: 0.20CH4: 0.01CO: 0.01H2

CO2

H2

(

14

CO2

i

iii

iipDSpPJ

j

i

j

i

j

iji D

DSS

PP

/

15

16CO2

CO2 > H2 CO2CO2 > N2 CO2H2 > CO2 H2

(Robeson, JMS 2008)

17CO2

CO2CH3|

-( C = C-)|

H3C-Si-CH3|

CH3

PTMSP

(Robeson, JMS 2008)

CO2

18

(Baker, Membrane Technology and Applications, 2004)

H2/N2 100-200

O2/N2 6-7

H2O/air >200

CO2

/

19

SILM (Supported Ionic Liquid Membrane)

100m

20

(Bara, Noble et. al., Ind. Eng. Chem. Res. 2009)

0.20 0.30 0.40 0.50 0.60

H2 CO2 N2

CH4

C3H8 i-C4H10

kinetic diameter [nm]

C2H6

tolueneSF6He

0.70

H2O

CO2

DDR SAPO-34

SAPO34

SiSi

Si

Si Si

Si

Si

SiO

O

OO

OO

O

OH

OH

OHOH

O

SiSi

Si

Si Si

Si

Si

O

O

OO

OO

O

OH

OH

OHOH

O

21

(permeate:153kPa)

SAPO34

0

50

100

150

perm

eanc

e ra

tio [-

]

Predicted

0 1 2 3 410-10

10 -9

10 -8

10 -7

Per

mea

nce

[mol

/(m2

s P

a)]

CO2 (Pure)CO2 (Mix) CH4 (Mix)

Predicted (CH4)Predicted (CO2)

Upstream partial pressure of CO2 [MPa]

pd = 0.1 MPa

CO2

CO2

CO2SAPO50-100

22

(Ping, Noble et al., JMS 2012) (, 2010)

CO2/CH4

10 -11 10 -10 10 -9 10 -8 10 -7 10 -6 10 -510 0

10 1

10 2

CO2 Permeance [mol/(m2 s Pa)]

CO

2/ C

H4

sele

ctiv

ity [-

]

Organic

Inorganic

Fig. CO2/CH4 CO2

35 C Low pressure (this work)

DDRSAPO-34

35C High pressure (this work)

-SiO2CO2/CH4

23

(, 2010)

24Oxy-combustion

800-900

Outline

Laboratory for Membrane Science and Technology

CO2post-combustion CO2pre-combustion CO2H2oxyfuel-combustion O2

25

Membrane Reactor)

26

A+B C

D

A+B C+D

A

C

A+B C D

B

Distributor

CH4 + H2O CO + 3H2

CO + H2O CO2 + H2

Extractor

CH3OH + O2 HCHO + H2O

CO2 + H2O

A+B

A+B C (cat.)

Active Contactor

VOC+ O2 CO2+H2 O

C

CO+ O2 CO2+H2 O Pt/ zeolite-Y

MeOH DME ZSM-5

Extractor

Distributor

ActiveContactor

VOC

27

S, Cl

Pd

CVD CVDNi SiNSiC

Pd,Pd/Ag CVD

Pd

28

C7H14 =C7H8 +3H2(MCH) (TOL)

CH4+H2O CO+3H2 (SRM)CO + H2O CO2+H2 (WGS)

(150~300C)

(Tsuru et al., Sep. Sci. Tech. 2001, AIChE J 2004, App. Cat; 2006, J. Membr. Sci 2008) (Yada, Tsuru et al., ICIM10, 2008)

7.2 6.6 2.89(500~600C)

H2 CO2

H2

-

0.20 0.30 0.40 0.50 0.60

H2NH3CO2 N2

CH4C3H8 iC4H10

[nm]

C2H6tolueneSF6He

0.70

H2O

29

2NH3 N2 +3H2H=+46 kJ/mol

(400~500C)

Ru-basedalkali-promoter

CH4+2H2O CO2+4H2 H=+164.5 kJ/molC7H14 C7H8 + 3H2 H=+ 104.6kJ/mol

0

0.2

0.4

0.6

0.8

1

200 300 400 500 600 700T[C]

NH 3

Conversio

n

P=1bar

Feed:NH3100%

10bar

100bar

400-500

H2 NH32

30

NH3

CO2

NH3 methanol L-H2 propane

[g/cm3] 0.68 0.79 0.07 0.51

[wt%] 17.6 12.5 100.0 18.2

[kg/m3] 120.0 98.8 70.0 92.7

HHV [MJ/kg] 22.5 22.7 141.9 48.9

HHV [MJ/L] 15.3 17.9 9.9 24.9

CO2 [kg/kg] 0.0 1.4 0.0 3.0

31

Silica membrane

BimodalCatalyticMembraneReactor

Compact configuration

Improved catalytic performance

Proposal of a bimodal catalytic membrane reactor (BCMR) for NH3decomposition

Macropores by -Al2O3 (~1m)

Mesopores by -Al2O3 (~5nm)

Bimodal pore structures (-Al2O3/ -Al2O3):

High gas diffusivity

Improved catalyst dispersion

Momomodal [1] Bimodal [2,3] [1] Tsuru et al., AIChE J. 50 (2004) 2794-2805 [2] Tsuru et al., Appl. Catal., A 302 (2006) 78-85

[3] Tsuru et al., J. Membr. Sci., 316 (2008) 53-62

32

NH3 flow rate: 10 cc/minReaction temperature : 450CN2 sweep gas: 100 cc/min

Reaction conditions:

without sweep gas with sweep gas

withoutsweep gas

0

4

8

12

16

20

H 2flo

wra

te[m

lmin

1]

0

20

40

60

80

100NH 3

conversio

n[%

]

0 100 200 300 400 500 600 700 800Time[min]

retentatepermeate

Retentate(NH3,N2,H2)

Permeate

Feed(NH3)

sweepgas

Catalytic activitystable with time.

With H2 extractionNH3 conversion increased.H2 production rate increased.

NH3 33

(Li, Tsuru et al., J. Cata. Commun. 2011)

H2O + AcOH100kg/hW: 50A: 50

50 kg/hW:0.5A: 49.5

50 kg/hW: 49.5A: 0.5

250 kg/h

300 kg/h

162,000 kcal/h

energy-saving70%

(M. Matsukata et. al., 2011)

H2O + AcOH100kg/hW: 50A: 50

50 kg/hW: 49.5A: 0.5

35,000 kcal/h20 kg/hW:0.44A: 19.5

45.3 kg/hW: 7.7A: 37.6

15.3 kg/hW: 7.6A: 7.6

30 kg/hW: 0.06A: 30.0

95.3 kg/hW: 57.2A: 38.1

Water/AcOH=150

Water/AcOH=20

34

70%

150

35

Membrane Extraction Adsorption Distillation

855 1003 634 151

1. 1991-2011

web of Science(Membrane OR Extraction OR Adsorption OR Distillation) AND separation AND

hydrocarbon AND (1991-2011)

36

37

2 C6H5CH3 C6H6 + C6H5(CH3)2

STARMEM

STARMEM55bar4391.2%8-carbon8.8%7-carbon0.035

(L. White JMS 2006)

38MOF(Metal Frame Organic)

MOF(1)

ZIF(2) (3)

MOF(1)MOF(2)

ZnO-based MOFZIF (ZnN)

(3)

(Slash et al., IEC 2011)

(1) in-situ(2) secondary growth(3) Others

layer-by-layercouter-diffusion(4) MOF on polymer supports(5) Mixed-matrix membranes (MMM)

39MOF

(1) in-situ(2) secondary growth(3) Others

Liquid-phase epitaxy (layer-by-layer)(4) MOF on polymer supports(5) Mixed-matrix membranes (MMM)

(Pan and Lai, ChemComm 2011)

Generation-4(1) High concentration acid gas removal from natural gas(2) Propane-propylene debottlenecking(3) Shale-gas

40

2021

20

21

, CO2challenging

41

Membrane Science & Technology, Hiroshima University

Thank you very much for your kind attention!

42