Center for Research and Technology-Hellas Chemical Process Engineering Research Institute Laboratory of Inorganic Materials

CERAMIC MEMBRANES IN ENERGY AND ENVIRONMENT RELATED APPLICATIONS

Research at the Center of Research and Technology-Hellas

V.T. Zaspalis

CONTENTS
What is a membrane

Separation of gas mixtures Low Temperature Applications: Water treatment

Hydrogen from renewable sources High Temperature Applications: Environmental friendly combustion of natural gas CONCLUSIONS

What is a membrane

A ceramic membrane is a thin semi-permeable film made of inorganic oxidic materials It can be porous so that selective transport takes place though the pores and through various mechanisms It can be non porous so that selective transport takes place through crystalline lattice diffusion It can be self-supported when is thick and strong enough, or supported on substrates when is thin and mechanically weak porous systems Flux through research goals

dense systems selectivity of permeating substances

What is a membrane

34cm

8mm

14mm

us poro nano

us oporo macr trate subs

mesoporous bridge layers

laye r

What is a membrane Ceramic membranes at CERTH are prepared:

Step 1:

Synthesis of stabilized nanoparticle dispersions by metal-alkoxide hydrolysis

Step 2:

Membrane layer formation by dip-coating on porous substrates

Step 3:

Eventual further pore surface modification or size reduction by wet impregnation or vapor deposition techniques

Porous membranes, Separation of gas mixtures

Scientific principle I:

Knudsen law FK = ADK

dC A2 k rm v m P = 3RT dx L

vm =

8RT M

In simple words: At nanopore level small molecules move faster than large ones

This principle can form the basis for the development of separation techniques where mixtures of light (e.g. hydrogen) and heavy (e.g. hydrocarbons) components can be enriched in the light components

Porous membranes, Separation of gas mixtures

5.E-08 F (mol s-1 m-1 Pa-1) 5.E-08 4.E-08 4.E-08 3.E-08 3.E-08 2.E-08 2.E-08 1.E-08 5.E-09 0.E+00 0.E+00 1.E+05 2.E+05 3.E+05 4.E+05 5.E+05 (Pa)

Hydrogen Helium

Nitrogen

Hydrogen

Propane Mixture 50/50 Membrane

Hydrogen

Propane Mixture 82/18

Porous membranes, Separation of gas mixtures

Scientific principle II:

Kelvin law

RT

2 cos Pt = ln M P0 r

Vapor pressure of liquid concave in a pore is lower than that of the same liquid on a flat surface, it therefore condenses much earlier

This principle can form the basis for the development of separation techniques on mixtures containing a condensable and noncondensable and non-soluble component

Porous membranes, Separation of gas mixtures Propane C3H8

7,5 Separation factor 7 6,5 6 5,5 5 20 30 40 Temperature (oC) 50 60 5 4 3 2 1 0 permeability x 1015 mol/m/s/Pa 8 6

Propylene C3H6 Similar molecules very difficult to separate

C3H6: 50

C3H8: 50

C3H8: 12 C3H6: 88

H2: 50

C3H8: 50

H2: 2

C3H8: 98

Porous membranes, Separation of gas mixtures

Scientific principle III : Activated microporous diffusion The pore is reduced down to the molecular dimensions and separation occurs by sieving Vapor deposition techniques

H2: 50

CO2: 50

H2: 98.8

CO2: 1.2

Porous membranes, Water treatment

3 layers

4 layers

5 layers

Pure Water
Monovalent ions Multivalent ions Viruses

Bacteria
Suspended solids
1

0 0,1 0,01 d p (m) 0,001 0,0001

4th 3rd 2nd 1st

Porous membranes, Water treatment

Removal of toxic metals (As, Cr) from water

1 ln Q Q = K ad t ln Qc e
7 6 ln(1/(Qe-Q)) 5 4 3 2 1 0 0 20 40 60 80 100 120 140 Contact time, min

As: 1ppm Fe2O3 nanoparticles

Purified water product

1 As ion concentration (ppm)

Fe: 2000 ppm

Fe: 0,001 ppm

0,1

Current maximum allowable limit 50ppb

0,01 feed product

5nm

Dense Membranes, Hydrogen from renewable sources

One of the most promising and long-term sustainable routes for the production of energy is:
H2O H2 + 0.5 2

The process currently under intensive research is the socalled RedOx process
hydrogen production

Dense Membranes, Hydrogen from renewable sources Our research-proposal is based on a dense oxygen conducting membrane reactor

H2O

. 2 o o 2
compartment 1

Vo, e

compartment 2

Oo
Membrane Mixed Conductor

1. O+ O + V 2 e o2 o 2
O2

H2

Dense Membranes, Hydrogen from renewable sources

Hydrogen in compartment 1, T=900oC, P1=P2=1bar CO off

0 3.0E-08 2.5E-08 H 2 Ion Current (A) 2.0E-08 1.5E-08 1.0E-08 5.0E-09 1 2 Time (hr) 3 4 5 6

Inactive state

CO+H2O

CO2+H2

steady state: (~39 mmol H2 m-2 hr-1) H2O 1/2O2+H2

steady state (~13 mmol H2 m-2 hr-1)

baseline (0 mmol H2 m-2 hr-1)

0.0E+00 0 5000 10000 Time (s) 15000 20000

CO in (compartment 2) (activation)

Dense Membranes, Environmental friendly combustion of natural gas

H Air 2O

Methane (CH4)
Vo, e
compartment 2

. 2 o o 2
compartment 1

Oo
Membrane Mixed Conductor

1. O+ O + V 2 e o2 o 2
O2

H2

CH4+2O2

CO2+2H2O + Energy
pure CO2 STORAGE

Dense Membranes, Environmental friendly combustion of natural gas

Material: La0.7Sr0.3Cu0.05Fe0.95O3 Oxygen available in the solid for reaction

200

CH
4

oxy gen

150

ck pi s up

T=980oC

100

50

0 0 20 40 60 80 100 120

-50

Reactor loop number

Air

del iv

e rs

y ox n ge

CONCLUSIVE REMARKS Porous ceramic membranes (specially modified to the nanoporous region) can give high separation factors and give rise to the development of efficient process, in particular for the separation of hydrogen

Porous ceramic membranes can provide technological solutions to many water treatment case-problems. The technology is quite mature to leave the laboratories

Dense oxygen conducting membranes can give rise to the development of green high temperature processes towards either hydrogen production from renewable sources or CO2-capture oriented combustion of natural gas

ACKNOWLEDGEMENTS L. Nalbandian Research staff of the Laboratory of Inorganic Materials S. Sklari A. Evdou A. Pagana

T. Tsilipiras Technical staff of CERTH: N. Georgiou A. Moudiotis

The vapor deposition modifications of the membranes are being done in cooperation with: Prof. G. Sakellaropoulos, dr. S. Kaldis and S. Koutsonikolas of the department of Chemical Engineering of the Aristotle University of Thessaloniki