Matteo Bientinesi. 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
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
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
11/05/2011
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
3
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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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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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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Experimental methods. Membrane preparation

Support pre-treatment Abrasion Cleaning Oxidation
Sensitization Activation
ELP deposition
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ELP deposition
Electroless Plating
Reaction.
Operating conditions.
T
= 60C Stirring pH = 10.7

11/05/2011 H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports 9

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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10
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11
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
12
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Permeability test experimental set-up at CPTM.
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13
Permeability test experimental set-up at CPTM.
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14
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
11/05/2011 H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports
Support after abrasion

16
Experimental results. Support oxydation

Support after abrasion
Support after oxydation at 800C

SEM analysis. ELP. Surface morphology.

2 ELP cycles
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18
SEM analysis. ELP. Surface morphology.

2 ELP cycles
N depositions Thickness (wt. gain) [m]

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2 7
4 11
6 14
19
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

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.
21
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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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22
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
Permeation test results. Membrane T6, selectivity

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25

N2 and CO2 permeation flow-rate non detectable (< 0.01 mol/m2s) for pressures up to 30 bar!!!
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26
Permeation test results. Membrane T8, selectivity

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27
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]
28
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]
29
H purity [%]
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.
H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports 30
11/05/2011
ICheaP-10
The Ninth International Conference on Chemical and Process Engineering
8-11 May 2011 Florence, Italy
Thank you for the attention!
11/05/2011
31

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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

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

Consorzio Polo Tecnologico Magona

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

CONSORZIO PISA RICERCHE

Consorzio Polo Tecnologico Magona

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

Why hydrogen from fossil fuels?

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

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

Thin film Pd membranes deposited on porous supports

Consorzio Polo Tecnologico Magona

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

Consorzio Polo Tecnologico Magona

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

Experimental methods. Membrane support

Porous support material

Consorzio Polo Tecnologico Magona

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

Experimental methods. Membrane preparation

Consorzio Polo Tecnologico Magona

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

Experimental methods. Membrane preparation

= 60C Stirring pH = 10.7

Consorzio Polo Tecnologico Magona

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

Experimental methods. Membrane preparation

Consorzio Polo Tecnologico Magona

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

Experimental methods. Membrane preparation

Consorzio Polo Tecnologico Magona

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

Experimental methods. Membrane characterization

Consorzio Polo Tecnologico Magona

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

Permeability test experimental set-up at CPTM.

Consorzio Polo Tecnologico Magona

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

Permeability test experimental set-up at CPTM.

Consorzio Polo Tecnologico Magona

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

Experimental results. Support abrasion

Support after abrasion

Consorzio Polo Tecnologico Magona

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

Experimental results. Support oxydation

Support after oxydation at 800C

Consorzio Polo Tecnologico Magona

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

SEM analysis. ELP. Surface morphology.

Consorzio Polo Tecnologico Magona

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

SEM analysis. ELP. Surface morphology.

N depositions Thickness (wt. gain) [m]

Consorzio Polo Tecnologico Magona

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

Palladium deposition. Tubular palladium membranes

H2N2* feeding Vacuum level

* S: single reagent dose, R: progressive feeding