POROUS TUBULAR SUPPORTED THIN OXYGEN MEMBRANES PREPARATION FOR - - PowerPoint PPT Presentation

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POROUS TUBULAR SUPPORTED THIN OXYGEN MEMBRANES PREPARATION FOR OXIDATIVE COUPLING OF METHANE N B ADIOLA 1,3,4) , D. F RANK 2) , E. F ERNANDEZ 1) , M.A.L LOSA T ANCO 1) , P.L. A RIAS E RGUETA 4) , M. V AN S INT A NNALAND 3) , U. W ERR 2) , F. G

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POROUS TUBULAR SUPPORTED THIN OXYGEN MEMBRANES PREPARATION FOR OXIDATIVE COUPLING OF METHANE

This project is supported by the European Union’s HORIZON2020 Programme (H2020/2014-2020) for the SPIRE Initiative under grant agreement nº 679933

Duration: 4 years. Starting date: 01-October-2015 Contact: nerea.badiola@tecnalia.com ; alfredo.pacheco@tecnalia.com

The present publication reflects only the author’s views and the European Union is not liable for any use that may be made of the information contained therein.

N BADIOLA1,3,4), D. FRANK2), E. FERNANDEZ1), M.A.LLOSA TANCO1) , P.L. ARIAS ERGUETA4),

  • M. VAN SINT ANNALAND3) , U. WERR 2) , F. GALLUCCI 3) , D.A. PACHECO TANAKA 1)

1) TECNALIA, GROUP OF MEMBRANE TECHNOLOGY (SPAIN) 2) RAUSCHERT HEINERSDORF-PRESSIG GMBH (GERMANY) 3) TU EINHOVEN CHEMICAL PROCESS INTENSIFICATION GROUP (THE NETHERLANDS) 4) UNIVERSITY OF BASQUE COUNTRY, DEPARTMENT OF CHEMICAL AND ENVIRONMENTAL ENGINEERING (SPAIN)

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Summary

▪ Motivation: Why OCM? ▪ Support preparation ▪ Membrane preparation

▪ CGO membranes ▪ BSCF membranes

▪ Conclusions

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Motivation: Why OCM?

Ethylene

Methane

2

+

Oxygen

+ 2

Water

Allows the direct production of ethylene OCM reaction(Oxydative coupling of methane) High impact process and large market share Feedstock cost reduction and diversification (Use of NG) Reduce the enviromental impact Limitations:

  • Very exothermic reactions.
  • With packed bed reactor the C2 yield is low

MEMBRANE REACTOR TECHNOLOGY Oxygen membranes introduces oxygen in ditributive way Increase the C2 yield

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MEMERE PROJECT

OBJECTIVE Development of oxygen separation membranes for OCM membrane reactors with improved flux and selectivity, and thermal, chemical and mechanical stability under operating conditions (T=800-950ºC).

Two options in material selection:

CO2-TOLERANT OXYGEN MEMBRANES

Not tolerant to CO2:

  • High

flux perovskites (e.g. BSCF, LSCF) CO2 tolerant (lower O2 flux):

  • Sr(Fe, M)O3 ; M = Sb,Ta, Nb,…
  • Ce0.9Gd0.1O2 (CGO)
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  • 1. Capillary membranes

 (self-supported)

MEMERE PROJECT

Two possible configuration : High permeation but very fragile

  • 2. Thin membranes supported
  • n porous ceramic tubes

Alternative Advantages:

  • Easier sealing
  • Better mechanical stability
  • Thin membrane allows high permeation

SUPPORT: Function : 1.Oxygen/Air ditribution 2.Mechanical stability MEMBRANE: Funtion: oxygen separation

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MEMERE PROJECT

Al2O3 Support

  • Asymmetric
  • Good surface quality
  • Commercially available (Rauschert RKV)

Al2O3 MgO

MgO Support

  • Symmetric
  • Experimental development (Rauschert RHP)

CGO CO2 Tolerant Need of CO2 protective layer CO2 Tolerant CGO BSCF No CO2 Tolerant

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Support preparation

Porous MgO supports (Rauschert Heinersdorf-Pressig GmbH)  Based on MgO-powder < 25 µm

1st Manufacturing of 14/7 mm tubes:

 Iron oxide impurities from the preparation unit  Cracks after firing

2nd manufacturing

  • f 14/7 mm tubes:

 No more iron oxide impurities after fixing the preparation unit  No cracks due to reduced heating rate

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Support preparation

Porous MgO supports (Rauschert Koster Veilsdorf GmbH)  Based on MgO-powder < 25 µm

 Tubes are usually fired on refractory supports, touching the outer surface  10/7 mm tubes have been fired on inserted alumina rods

▪ Smoother surface, closer to commercial surface quality ▪ Avoid bending

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Membrane preparation

Dip-coating technique

T (ºC), t (h)

Dry Sintering

T (ºC), t (h)

Advantages of dip-coating:

  • Easy to perform
  • Cheap equipment required in comparison with
  • ther techniques
  • Good reproducibility of the membrane layers
  • Possibility of very thin layer deposition

Dip coating Dip coating

T (ºC), t (h)

Dry Sintering

T (ºC), t (h)

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CGO membrane

▪ The layer looks dense but there are still defects in the

  • surface. So we proceed to do multiple coatings.

Membrane thickness: 1.76 µm

1 Coating CGO on MgO

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CGO membranes: Multiple coatings

Coating 1+ Coating 2 Coating 3 Coating 4

Defects: 4,11-2,87µm Defects: 900nm-400nm

Thickness: 2,93µm-627nm- 882nm Thickness: 1,21µm-840nm

Thickness: 3,18-1,08µm

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BSCF membrane

Membrane thickness: 9.72 µm

  • Apparently there is a phase segregation of

BSCF

Ba Co Fe Sr

Phase 1= Ba+Sr Phase 2= Fe+Co

EDX 1 Coat BSCF on porous Alumina

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BSCF membrane

1 6 11 16 21

Al2O3 rod New layer Membrane layer BSCF

  • ×

Al2O3 × × × Ag × × × Ba0.717Al11O17.282

  • ×

BaAl2O4

  • ×

(Fe0.868Al0.132)8(Fe0.066Al0.934)16O32

  • ×

Ba0.5Sr0.5CuAl10O17

  • ×

CoAl2O4

  • ×

Ag2O3

  • ×

CuO

  • ×
  • Ag3Al22O34
  • ×
  • CuAl2O4
  • ×
  • Results
  • bserved

with the synchrotron show that there is an intermediate layer between alumina support and the BSCF. Need of intermediate layer

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Conclusions and future work

▪ MgO surface has been improved modify the mixture of the raw materials and sintering process. ▪ Develop new support of MgO with the goal of obtaining similar surface quality of commercial Al2O3 asymmetric supports  Obtain membranes without defects. ▪ Thin continuous BSCF coating

  • nto

Al2O3 asymmetric support

  • f

Rauschert (RKV) and thin CGO coating onto MgO support symmetric support of (RHP) have been obtained by a simple dip coating technique. ▪ There is a chemical interaction between the Al2O3 support and the BSCF supports which caused a segregation of the BSCF material not making it oxygen permeable. ▪ A intermediate layer will be develop as a sacrificial layer to avoid the BSCF disaggregation.

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Acknowledgements

We thank Finden for the support given us, carrying

  • ut the BSCF membrane analysis in the

Synchrotron. This project is supported by the European Union’s HORIZON2020 Programme (H2020/2014-2020) for the SPIRE Initiative under grant agreement nº 679933 Website: https://www.spire2030.eu/memere MEthane activation via integrated MEmbrane REactors

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Thank you for your attention

Contact info: Nerea Badiola: nerea.badiola@tecnalia.com