preparation and hydrogen permeation studies of ultrathin ... · 10-13/07/2017 / page 3 (disclosure...

Preparation and hydrogen permeation studies of ultrathin palladium and

carbon membranes

D. ALFREDO PACHECO TANAKA1, MARGOT A. LLOSA TANCO1,

JOSE MEDRANO2, JON MELENDEZ1, EKAIN FERNANDEZ1, MARIA

NORDIO2, MARTIN VAN SINT ANNALAND2 FAUSTO GALLUCCI2.

July 10-13 2017. Houston, Texas

13th International Conference onCatalysis in Membrane Reactors

1 2

ObjectiveDeveloping of an advanced high performance, cost effective separation

technology for direct separation of hydrogen from natural gas networks

10-13/07/2017 / (Disclosure or reproduction without prior permission of TECNALIA is prohibited).

13th ICCMR, July 10-13, 2017 Texas, Pd membranes

Thin and ultra thin supported Pd/Ag membranes

D. ALFREDO PACHECO TANAKA1, JON MELENDEZ1,

EKAIN FERNANDEZ1, MARIA NORDIO2,

FAUSTO GALLUCCI2

(3-5 µm thick)

Poster ULTRA-THIN PALLADIUM-SILVER MEMBRANES FOR PURE HYDROGEN PRODUCTION AND SEPARATION: MODELLING

AND EFFECT OF SWEEP GAS

Thin Ultra thin

(≈1 µm thick)

http://www.google.es/url?sa=i&source=images&cd=&cad=rja&uact=8&docid=D3rDsyyQ2Bo5QM&tbnid=yqrGTsP12_sV6M:&ved=0CAgQjRw&url=http://www.catolicas.com.ar/portal/index.php?option=com_content&view=article&id=336:derechos-humanos-de-las-mujeres&catid=25&Itemid=155&lang=es&ei=2SOQU_7FMIWI0AWxj4Fo&psig=AFQjCNEWstYb67OKJgXorZ4645RdSIFcqw&ust=1402041689879526

10-13/07/2017 / Reproduction without prior permission of TECNALIA is prohibited).

13th ICCMR, July 10-13, 2017 Texas,

MesoporousCeramics (nm)

Zeolites Carbon

MicroporousCeramics (Å)

PalladiumPalladium alloys

0.1

1

1000

100

10

10 100 1000 10000 ∞

Re

lati

ve H

ydro

gen

pe

rme

atio

n

H2/N2 selectivity

Membranes for hydrogen separation




H H

H H HH

H H

Adsorption

Splitting

DiffusionPd membrane

H2 permeation in Pd membranes

Recombination

Desorption

resistance of support

Ultra-thin membranes

-Surface interference- H2 splitting




Ceramic supported Pd-based

(3-4 µm thick) membrane

T=400 ºC

Membraneactivation

Helmi et al., Molecules 21 (2016) 376




• H2 permeance 400 ºC: 0.9 x 10-6 mol m-2 s-1 Pa-1

• H2/N2 ideal selectivity 400 ºC: >150,000 for >1200 h

Long term permeation test at 400 °C

Metallic supported Pd-Ag membranes

(5 µm thick)

Medrano et al., Int. J. Hydrogen Energy 41 (2016) 8706-8718




• At >500 ºC and after >800 h, H2/N2 ideal selectivitydropped to from 223000 to 2650

Long term permeation test at more than 500 °C

Metallic supported Pd-Ag membranes

Medrano et al., Int. J. Hydrogen Energy 41 (2016) 8706-8718




Ultra-thin Pd-Ag membranes ≈ 1μm

Melendez et al., Journal of Membr. Sci. 528 (2017) 12–23

Thickness vs plating time

H2/N2 selectivity and H2 permeancevs thickness




Activation energy of Ultra-thin Pd-Ag membranes


7.81 KJ mol-1

Ea vs thickness


10-13/07/2017 / (Reproduction without prior permission of TECNALIA is prohibited).

13th ICCMR, July 10-13, 2017 Texas, Carbon membranes

Membrane thickness 1.30 um


H2 flux at various gas mixtures and pressures at 400°C

Effect of dilution H2 and N2

Effect of COAt H2 /N2 60/40

Replacing some N2with CO





Thickness 1.30 um3 bar total pressure, vacuum at the permeate

H2 flux at various gas mixtures and pressures at 400°C




Long term test Pd-Ag membranes ≈ 1,3 μm


H2

N2




DOE 2015

1 µm Pd / ceramic

3-4 µm Pd / ceramic

5 µm Pd / metallic

DOE 2015

Gallucci et al., Chem. Eng. Sci 92 (2013) 40–66

DOE 2015 target :Purity > 99.99%>100 𝑵𝒎𝟑/𝒎𝟐. 𝒉 (6.9 bar ΔP)

Pd alloy membrane properties at TECNALIA


10-13/07/2017 / (Disclosure or reproduction without prior permission of TECNALIA is prohibited).


Carbon Molecular Sieves Membranes (CMSM)

D. ALFREDO PACHECO TANAKA1, MARGOT A. LLOSA

TANCO, JOSE MEDRANOJON MELENDEZ1,

FAUSTO GALLUCCI2

Poster

BIOGAS UPGRADING WITH CARBON MEMBRANES: EXPERIMENTAL DEMONSTRATION AND BENEFITS

EVALUATION




Mechanism

Pore size

0.5 – 0.7 nm

16

Porous membranes for gas separation




Molecular sieves membranes

Zeolite membranes▪ Difficult to obtain crack-free

▪ Intercrystallite voids affecting selectivity

Carbon Molecular sieves membranesCarbonization of a polymer precursor under inert atmosphere or vacuum

Presence of micropores and ultramicropores




0.2

9 0.3

3 0.3

8

Kinetic diameter of various gases




T/ °C t/h

Dry

calcination

450-1000 °C t/h 1°C/min inert

vacuum

Dip coating

Preparation of composite-Alumina-CMSM

19




SEM and TEM of the Al-CMSM

Composite phenolic resin CMSM, exeira, Campo, Tanaka, Llosa, Magen, Mendes, Carbon 49 (2011) 4348

20




Effect of carbonization temperature

Fresh membrane

Llosa , Pacheco et.al Int J.hydrogen energy 40 (2015) 5653 40 (2015) 3485

After one day

O2 and N2 very low flux




CMSM-500 after 14 days

N2 permeation of c-CMSM-500 in functionof the temperature at 400 kpa

0

5

10

15

20

25

50 100 150 200 250 300 350 400

N2

Pe

rmea

tio

n

[ m

lmin

-1]

Temperature [ °C ]

N2 permeation of fresh membrane 66.8 ml min-1




N2 permeation at 400 kPa for CMSM-500 in function of the time of water adsorption

0

5

10

15

20

25

30

0 50 100 150 200 250 300 350 400

N2

Per

mea

tio

n

[ m

lmin

-1]

Time [ min ]




Just aftercarbonization

Active placesreact with water(water chemisorption)

Water physisorption

-OH

-OH

-OH

=O

-OH

-OH

-OH

=O

N2 66 ml/min

N2 20 ml/min

water

Modification on the porous

24




0.000

0.005

0.010

0.015

0.020

0.025

0.030

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

F [

cm3

g-1n

m]

Pore width [nm ]

750 °C 550 °C

Pore size distribution at various carbonization temperatures




Gas permeance as a function of temperatureAl-CMSM carbonized at 500 °C



13th ICCMR, July 10-13, 2017 Texas,

Ea

Activation Energy (Ea) at various activation heat treatments




Activation energy of c-CMSM-500 membraneat various temperatures of pemeation, for various gases

The values correspond to the average of permeation dataperformed at different temperatures from 40°C to 100°C

28




Single H2 and CH4 gas flow as a functionof temperature and pressure

H2 CH4




H2 and CH4 gas ideal perm-selectivity as a functionof temperature




Testing

temp

(°C)

H2 in

feed mixture

(%)

H2 purity in the permeate

(%)

Measured Calculated

40

5 93.3 95.7

10 96.6 98.0

20 96.7 99.0

80

5 65.2 65.7

10 76.4 80.2

20 84.8 90.1

H2 purity (%) at various H2 contents in the mixturePressure: out 7.5, in 0.01 bara, inlet 2 L min-1

H2, CH4 mix gas permeation




Testing

temp

(°C)

H2 in

feed mixture

(%)

H2 purity in the permeate

(%)

Measured Calculated

40

5 93.3 95.7

10 96.6 98.0

20 96.7 99.0

80

5 65.2 65.7

10 76.4 80.2

20 84.8 90.1

Total flow H2- CH4 mixed gas Pressure: out 7.5, in 0.01 bara, inlet 2 L min-1




H2-CH4 mixed gas tests (10% of H2)(Pressureout: 7.5 bara; Pressurein: 0.01 bara, inlet 2 L min-1)

Testing

temperature

(°C)

H2 purity in the

permeate (%)

80 76.4

60 85.4

40 96.6

30 99.4

Exceeds the H2 purity

requirement of Grade A (98.0 %)

and is close to Category 3

(99.9%).


Acknowledgements

This project has received funding from the Fuel Cells and

Hydrogen 2 Joint Undertaking under grant agreement No

700355. This Joint Undertaking receives support from

the European Union’s Horizon 2020 research and

innovation programme and Hydrogen Europe and

N.ERGHY.

The present publication reflects only the author’s view and the FCH JU and the Union

are not liable for any use that may be made of the information contained herein.

preparation and hydrogen permeation studies of ultrathin ... · 10-13/07/2017 / page 3 (disclosure...

Documents