1. Research Subject 2 Development of New Inorganic Membranes Membranes
– Ceramic membranes for H2 separation
– Ceramic membranes for CO2 separation
– Studies address mechanism of permeation
Prediction of permeation properties

2. Research Subject 2 Studies of Membrane Reactors
Selective layer
Support
Membrane preparation
Experimental and modeling studies of membrane reactors
Steam reforming CH4 + H2O CO + 2H2 Ethanol reforming C2H5OH + 3H2O H2 + 2CO2

3. Applications and New Concepts Reforming of Natural Gas
Steam reforming of methane ( oC) CH4 + H2O CO + 3 H2
Feed cleanup Steam reforming Shift
HTS
LTS
H2O
CH4
Product
H2 purification
CO2 removal
Condensate
Water-gas shift (HTS oC, LTS – 200 oC) CO + H2O CO2 + H2
Product purification with pressure swing adsorption or cryogenic distillation
P. Hacarlioglu, Y. Gu, S. T. Oyama J. Nat. Gas Chem. 2006, 15,

4. Membrane Reactor Studies: Separator
CH4 + H2O CO + 3 H2
Control box
Liquid pump
Gas chromatograph
Furnace
Condenser Ar H2 O2
CH4 P
BPR
Water Reservoir
MFC MF
Bubble Flowmeter
Vent
3-way
Membrane
Catalyst bed
4-way
Quartz wool
Quartz chips
Dense alumina tube
Quartz liner
Temperature controller
Catalyst bed
Quartz chips
Membrane
Quartz wool
Dense tube
Quartz liner
Purge gas
Combines reaction and separation

5. Reactor Modeling For a one-dimensional model
Tube side: Shell side:
F = molar flow
where
For a two-dimensional model
Tube side: Shell side:
C = concentration

6. Flow rate of CH4 (cm3 (NTP) min-1)
Pressure Dependence of MSR
CH4 + H2O
CO + 3H2
Pressure (atm) 1 5 10 15 20
Flow rate of CH4 (cm3 (NTP) min-1) 50
100
150
200
1-D model
2-D model

7. Radial and Axial Profiles of Hydrogen Flow
T = 873 K P = 10 atm
T = 873 K P = 1 atm
Membrane
Bed side
T = 873 K P = 20 atm
Empty tube side

8. When Should a 2-D Model be Used? Criterion: Order Estimation Parameter
T = 873 K P = 10 atm
Gradients expected when:
Reaction rate > flow rate
> Pe
dPL
uCo ρR 2
Permeance rate > diffusion rate PΔP DΔC/r
>
Order estimation parameter
uCo ρR 2 Pe
dPL
PΔP
DΔC/r
>
0.01
For our conditions gradients begin when P > 10 atm
R = volumetric rate ρ = density u = flow velocity Co = concentration
P = permeance P = pressure r = radius Pe = Peclet number

9. Operability Level Coefficient (OLC)
= 1/DaPe
Model I
Model II
Model I
Maximum hydrogen permeance---maximum enhancements
Model II
Correlation independent of kinetics
OLC dependent on reaction rates and permeances

10. Hollow Fiber Membranes
High surface area/volume ratio
Easily processed
Broad use
Koremade keishakouzou-wo motsu soujyou-no maku, soushite mukibushitsu-wo
matrix-to shita koremade-ni nai muki-yuuki hybrid-maku-ni tsuite ohanashi shimashita-ga, sara-ni muki-no chuu-kuu-sen-i kara naru maku-no kenkyuu-ni torikunde iku yotei desu. Taiseki-ni taishite takai hyoumenseki-wo jitsu-youka-niwa hijou-ni yuuri desu. Korerawa kantan-na process-de tsukurukoto-ga deki, hikakuteki anka-dato iu riten ga arimasu. Soshite hiroihan-i deno youto-ga kitai saremasu. Watashidomo-wa koremade ohanashi shitekita subeteno maku-ni kono chuu-kuu-sen-i makuwo support-to shite mochiiru koto-wo kenntou shiteimasu.
A final type of membrane we are working with are inorganic hollow fiber membranes. These have high surface area/volume ratio, so with high commercialization potential. They are easily processed, so relatively inexpensive. Very importantly, they have broad use. We are using them as supports for all the membranes I have described.