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Matteo Bientinesi. H2 Separation From Gas Mixtures Through Palladium Membranes On Metallic Porous Supports
Matteo Bientinesi. H2 Separation From Gas Mixtures Through Palladium Membranes On Metallic Porous Supports
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
H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports
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)
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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports
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
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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports
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
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
Sensitization Activation
ELP deposition
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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports
Sensitization Activation
ELP deposition
Electroless Plating
Reaction.
Operating conditions.
T
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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H2 permeability
H2/CO2 selectivity
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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports
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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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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports
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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
No
4
500
4
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%
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
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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Membrane T6 Support abrasion: YES Support oxidation: 500C Film thickness: 29.5 m
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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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N2 and CO2 permeation flow-rate non detectable (< 0.01 mol/m2s) for pressures up to 30 bar!!!
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0.4
2 s] H2 flow [mol/m
0 x 10
-4
0.5
1.5
2.5
x [m]
2 s] CO2 flow [mol/m
0.5
1.5
2.5
x [m]
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H2 Separation from Gas Mixtures through Palladium Membranes on Metallic Porous Supports
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 [%]
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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ICheaP-10
The Ninth International Conference on Chemical and Process Engineering
8-11 May 2011 Florence, Italy
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