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Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

ICheaP-10 - The tenth International Conference on Chemical & Process Engineering

H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports
Ing. Matteo Bientinesi, Ph.D.1* Prof. Luigi Petarca2
1

Consorzio Polo Tecnologico Magona 2 Dipartimento di Ingegneria Chimica, Chimica Industriale e Scienza dei Materiali (DICCISM), Universit di Pisa
Via Magona - 57023 - CECINA (LI) Italy Tel. 0586/632142 - Fax 0586/635445 www.polomagona.it info@polomagona.it

* e-mail: matteo.bientinesi@polomagona.it Florence, 11 May 2011

H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports

Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Acknowledgement
This work was partially financed by the Italian Ministry of University and Research (MIUR) in the ambit of the project FISR 2006 Integrated Systems for Hydrogen Production and Use in Distributed Generation. CONSORZIO POLO TECNOLOGICO MAGONA UNIVERSITA DI PISA
Dipartimento di Ingegneria Chimica, Chimica Industriale e Scienza dei Materiali (DICCISM)

CONSORZIO PISA RICERCHE

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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports

Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Why hydrogen from fossil fuels?


Hydrogen production from fossil fuels involves some important advantages respect to fossil fuels direct utilization.
immediate availability of hydrogen at low prices possibility of capturing and storing carbon dioxide

possibility of using hydrogen in highlyefficient applications (fuel-cells)


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automotive applications: delocalization of polluting emissions from urban centres to H2 production plants
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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports

Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Pd membranes: origin and growth of interest in recent years


Hydrogen selective dissolution in metal palladium was first observed by Graham in 1860s (Graham, T., On the absorption and dyalitic separation of gases by colloidal septa, Philosophical Transactions of the Royal Society, vol. 156, 1866, pp. 399-439). Solution diffusion mechanism

Thin film Pd membranes deposited on porous supports

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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports

Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Objectives
Optimizing the preparation of thin film palladium membranes on stainless steel porous supports through Electroless Plating. Testing the performance of the produced membranes. Develop a mathematical model for the assessment of industrial scale membranes.

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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports

Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Experimental methods. Membrane support

Porous support material

AISI 316L 0.1 m filter grade (95% rejection of particle greater than 0.1 m guaranteed) 15% porosity
Tube (o.d. 6.35 mm, i.d. 3.175 mm, length 100 mm, area 19.95 cm2) welded to non porous tubes on both sides MOTT Corporation Production method: metal powder sintering

Support geometry

Supplier

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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports

Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Experimental methods. Membrane preparation


Support pre-treatment Abrasion Cleaning Oxidation

Sensitization Activation

ELP deposition

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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports

Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Experimental methods. Membrane preparation


Support pre-treatment Abrasion Cleaning Oxidation

Sensitization Activation

ELP deposition

Electroless Plating

Reaction.

Operating conditions.
T

= 60C Stirring pH = 10.7


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Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Experimental methods. Membrane preparation


Support pre-treatment Abrasion Cleaning Oxidation

Sensitization Activation

ELP deposition

Vacuum ELP

In order to enhance the film adherence and repair defects, vacuum was applied in some experiments on the opposite side of the tubular support. A water aspirator was used in order to generate vacuum.

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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports

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Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Experimental methods. Membrane preparation

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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports

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Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Experimental methods. Membrane characterization


Weight measurement Pd ELP yield Pd film thickness Support surface Membrane Optical microscope / SEM Pd Film structure Pd film thickness Thermal annealing / Permeability test

H2 permeability
H2/CO2 selectivity
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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports

Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Permeability test experimental set-up at CPTM.

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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports

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Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Permeability test experimental set-up at CPTM.

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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports

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Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Experimental results. Support abrasion

Abrasion was performed in order to avoid the formation of local defects near the welding zone of tubular membranes (detected during nitrogen permeation tests). The abrasion treatment reduces the average dimension of the largest pores nearest to the surface.

Cleaned support
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Support after abrasion


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Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Experimental results. Support oxydation


Support after abrasion

Support after oxydation at 800C


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Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

SEM analysis. ELP. Surface morphology.


2 ELP cycles

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Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

SEM analysis. ELP. Surface morphology.


2 ELP cycles

N depositions Thickness (wt. gain) [m]


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2 7

4 11

6 14
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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports

Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Palladium deposition. Tubular palladium membranes


ID membrane Abrasion Oxydation temperature [C] N ELP cycles T1 No T2 No T3 Yes 500 4 T4 No 500 6 T5 Yes 500 6 S T6 Yes 500 6 R T7 Yes 800 6 T8 Yes 700 2

No
4

500
4

H2N2* feeding Vacuum level


Deposited Pd [g] Film thickness [m] Deposition yield

S 0.23 9.5

S 0.26 11

S 0.28 11.6

S 0.37 15.5

R 1 mH2O
0.58 24.3

R 3 mH2O
0.38 10.2

1 mH2O 1 mH2O
0.40 16.7 0.71 29.5

38%

43%

46%

41%

44%

78%

64%

81%

* S: single reagent dose, R: progressive feeding


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Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Permeation tests. Single gas tests


Feed, retentate and permeate pressure are recorded through the manometers

Feed contains a single gas with no flow regulation

Temperature in the cell and permeate flow are recorded respectively via a thermocouple and the mass flow meter. Flow per unit area can be calculated for given value of trasmembranal pressure and temperature.

Pressure in the retentate side is regulated through the back-pressure valve V27.
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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports

Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Equations for data fitting and modeling

Assumptions:

permeate flow for N2/CO2 occurs via Knudsen flow and viscous flow through membrane defects; hydrogen permeation flow occurs via two parallel mechanisms:
flow through defects via Knudsen flow and viscous flow; flow through Pd film via solution-diffusion mechanism;

pressure drops through the porous support are neglected; N2/CO2 flow data are used in order to calculate, via an error minimization algorithm, parameters inherent to membrane defects; H2 flow data are then used in order to calculate parameters inherent to Pd film.

The calculated parameters were used to set a model of an industrial membrane, by integrating on the membrane length the mass balance for H2 and CO2. Data fitting and model simulation were implemented in Matlab environment.

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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports

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Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Permeation test results. Membrane T6

Membrane T6 Support abrasion: YES Support oxidation: 500C Film thickness: 29.5 m
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Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Permeation test results. Membrane T6

Membrane T6 Support abrasion: YES Support oxidation: 500C Film thickness: 29.5 m

Membrane T6 Support abrasion: YES Support oxidation: 500C Composition: Pure Pd Film thickness: 29.5 m
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Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Permeation test results. Membrane T6, selectivity


Membrane T6 Support abrasion: YES Support oxidation: 500C Film thickness: 29.5 m

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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports

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Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Permeation test results. Membrane T8


Membrane T8 Support abrasion: YES Support oxidation: 700C Film thickness: 10.2 m

N2 and CO2 permeation flow-rate non detectable (< 0.01 mol/m2s) for pressures up to 30 bar!!!

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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports

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Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Permeation test results. Membrane T8, selectivity


Membrane T8 Support abrasion: YES Support oxidation: 700C Film thickness: 10.2 m

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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports

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Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Model simulation results.


H2 and CO2 permeation flow-rate Vs axial coordinate x
Membrane specifications: length 3 m Pd thickness 10 m T8 flow parameters OD 6.4 mm ID 3.2 mm Feed: H2 50% vol. CO2 50% vol. 0.016 mol/s (1.3 Nm3/h) total feed flow-rate Pressure: Feed side 20 bar; Retentate side 1.15 bar
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0.4
2 s] H2 flow [mol/m

0.3 0.2 0.1 0

0 x 10
-4

0.5

1.5

2.5

x [m]
2 s] CO2 flow [mol/m

1.6 1.4 1.2 1 0.8

0.5

1.5

2.5

x [m]
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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports

Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Model simulation results.


H2 and CO2 permeation flow-rate Vs axial coordinate x
Membrane specifications: length 3 m Pd thickness 10 m T8 flow parameters OD 6.4 mm ID 3.2 mm Feed: H2 50% vol. CO2 50% vol. 0.016 mol/s (1.3 Nm3/h) total feed flow-rate Pressure: Feed side 20 bar; Retentate side 1.15 bar
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100 90 80 70 99.96 99.98

H2 recovery [%]

60 50 40 30 20 10 0

99.94

99.92

99.9

0.5

1.5

2.5

99.88 3

x [m]

H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports

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H purity [%]

Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

Conclusion

The procedure of palladium deposition above porous stainless steel supports via ELP was optimized in order to form thin dense films with a minimum number of defects. The porous supports and the membrane preparation technology were chosen with the aim of facilitating the up-scaling to industrial scale membrane production. The produced thin-film Pd membranes were tested at high temperature showing hydrogen permeation rates as high as 0.25 mol/m2s at 10 bar of transmembranal partial pressure and selectivities with respect to CO2 well over 2000. No change in membrane performances was detected after over 500 h of high temperature testing. The developed model was able to fit experimental data and is useful in order to evaluate the performances of Pd membranes in industrial configurations.
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Consorzio Polo Tecnologico Magona

Icheap 10 , Florence 8-11 May 2011 - M. Bientinesi, L. Petarca

ICheaP-10
The Ninth International Conference on Chemical and Process Engineering
8-11 May 2011 Florence, Italy

Thank you for the attention!

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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports

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