In the present work, CuO/SBA-15 SOx regenerable adsorbents were elaborated. Synthesis conditions were controlled in order to obtain highly dispersed Cu2+ species assumed to be Cu-O-Si species. Materials were evaluated as SOx adsorbents through multicycle adsorption/regeneration experiments. Their performances decrease along cycles due to copper species sintering and there is an optimal copper loading for a maximal SOx adsorption efficiency.
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Dorge, Sophie

Berger, Marc

Nouali, Habiba

Michelin, Laure

Josien, Ludovic

Vierling, Matthieu

Molière, Michel

Fiani, Emmanuel

Habermacher, David

Patarin, Joël

Brilhac, Jean-François

Gaudin, Pierrick

English

Engineering Conferences International

Engineering Conferences InternationalECI Digital Archives5th International Congress on Green ProcessEngineering (GPE 2016) Proceedings6-21-2016SOx trapping performances of cuo based silicamesoporous adsorbents for desulfurization ofindustrial flue gas streamSophie DorgeUniversité de Haute Alsace, France, sophie.dorge@uha.frMarc BergerUniversité de Haute Alsace ; ADEME - Agence de l'Environnement et de la Maîtrise de l'Energie, FranceHabiba Noualiersité de Haute Alsace, FranceLaure Michelinersité de Haute Alsace, FranceLudovic Josienersité de Haute Alsace, FranceSee next page for additional authorsFollow this and additional works at: http://dc.engconfintl.org/gpe2016Part of the Chemical Engineering CommonsThis Abstract and Presentation is brought to you for free and open access by the Proceedings at ECI Digital Archives. It has been accepted for inclusionin 5th International Congress on Green Process Engineering (GPE 2016) by an authorized administrator of ECI Digital Archives. For moreinformation, please contact franco@bepress.com.Recommended CitationSophie Dorge, Marc Berger, Habiba Nouali, Laure Michelin, Ludovic Josien, Matthieu Vierling, Michel Molière, Emmanuel Fiani,David Habermacher, Joël Patarin, Jean-François Brilhac, and Pierrick Gaudin, "SOx trapping performances of cuo based silicamesoporous adsorbents for desulfurization of industrial flue gas stream" in "5th International Congress on Green Process Engineering(GPE 2016)", Franco Berruti, Western University, Canada Cedric Briens, Western University, Canada Eds, ECI Symposium Series,(2016). http://dc.engconfintl.org/gpe2016/35AuthorsSophie Dorge, Marc Berger, Habiba Nouali, Laure Michelin, Ludovic Josien, Matthieu Vierling, MichelMolière, Emmanuel Fiani, David Habermacher, Joël Patarin, Jean-François Brilhac, and Pierrick GaudinThis abstract and presentation is available at ECI Digital Archives: http://dc.engconfintl.org/gpe2016/35 SOx trapping performances of CuO based silica mesoporous adsorbents for the desulfurization of industrial flue gas stream   5th International Congress  On Green Process Engineering, Mont Tremblant, Quebec, Canada, 19-24 June 2016  P. Gaudin, M. Berger, S. Dorge, H. Nouali, L. Michelin, L. Josien, M. Vierling, M. Molière, E. Fiani, D. Habermacher,  J. Patarin, J.F. Brilhac  Financial support:  Collaboration:  1 2UMR CNRS 7361   Context 2 Industrial SOx emissions Production of energy Gaseous pollutants SOx (SO2 + SO3) Fossil fuels  combustion Power Plant (e.g. turbines) Industrial boilers SOX: negative impact on: - Environment (acid rain, precursors of secondary aerosols) - Human health  5th International Congress  On Green Process Engineering, Mont Tremblant, Quebec, Canada, 19-24 June 2016  5th International Congress  On Green Process Engineering, Mont Tremblant, Quebec, Canada, 19-24 June 2016     Context 3 Industrial SOx emissions abatement Strict Regulation  at industrial level SOx emissions  abatement SOx emissions Industrial Emissions Directive  (IED)  2010/75/EU Traditional Desulfurization processes :   wet and dry scrubbing   Efficient  Non regenerative  Produce additional greenhouse gas CO2 and large amount of solid and liquide wastes  High energy cost Alternative solution :  reversible SOx trapping on solid adsorbents    promising material : supported CuO  SO2 + ½ O2   SO3 SO3 + CuO CuSO4 Oxidation catalyst: SO3 chemisorption: Regeneration: CuSO4 Δ (600-700°C) SO3 + CuO Adsorbent  requirements CuO 5th International Congress  On Green Process Engineering, Mont Tremblant, Quebec, Canada, 19-24 June 2016     Context 4 Objective  Elaboration of a regenerable  adsorbent with high SOx adsorption performances - Inert in regards with SOx  -  High specific surface aera and mesoporous volume  -  Easy diffusion of SOx in the porous network Organized Mesoporous  Silica  supports  Characterizations of the adsorbents : N2 physisorption/XRF/XRD/     and TEM analyses  Study of SOx adsorption capacity during cycling experiments at laboratory scale in fixed bed reactor SBA-15 Copper incorporation: wet impregnation in aqueous solution    Materials and methods 5 Adsorbents synthesis 5th International Congress  On Green Process Engineering, Mont Tremblant, Quebec, Canada, 19-24 June 2016  SBA-15 Copper nitrate Wet impregnation in aqueous solution : Tambiant CuO8.8/SBA-15 CuO31.7/SBA-15 CuO15.6/SBA-15 Drying : 45°C during 12 hours Calcination step:  500°C during 6 hours (ramp of 1°C.min-1) in fixed bed reactor under synthetic air flow (60 NL.-1) Three metal loadings :    8.8 wt.%     -    15.6 wt.%    -    31.7 wt.%     of CuO + +    Materials and methods 6 SO2 adsorption tests 5th International Congress  On Green Process Engineering, Mont Tremblant, Quebec, Canada, 19-24 June 2016  SO2 adsorption conditions:  - reactor: quartz, Øinternal = 6 mm - adsorbent shaping: 250-400 μm,  - mass: 150 to 200 mg - gas feed composition : 250 ppm SO2 + 10 vol.% O2 in N2  - GHSV = 25000 h-1 - temperature: 400°C Cycling experiments in fixed bed reactor Regeneration conditions:  Two different procedures at two temperatures: 1.  Under N2 at 600°C 2.Under H2 (0.5 vol.% in N2) at 280°C       (with rege. 1 under N2 at 600°C)     Results  7 Adsorbents characterizations  5th International Congress  On Green Process Engineering, Mont Tremblant, Quebec, Canada, 19-24 June 2016  Textural characterization N2 physiroption isotherms  No alteration of the mesoporous structure after impregnation and calcination steps   Decrease of the BET surface area, pore size  and porous volume after copper incorporation, more prononced for higher copper loadings Sample SBA-15 CuO8.8%/SBA-15 CuO15.6%/SBA-15 CuO31.7%/SBA-15 Color White Light blue Light green Dark green CuO (wt.%)* / 8.8 15.6 31.7 SBET (m2/g) 825 459 356 325 Pore size(nm) 6.8 6.4 6.3 6.1 Vp (cm3/g) 1.02 0.65 0.57 0.45 Color, chemical composition and textural properties of materials *Determined by XRF analysis    Results  8 Adsorbents characterizations  5th International Congress  On Green Process Engineering, Mont Tremblant, Quebec, Canada, 19-24 June 2016  TEM analyses  XRD analyses : no diffraction peak corresponding to a copper crystalline phase   TEM analyses: no copper particles observed : copper highly dispersed for all materials, probably formation of Cu-O-Si speciesa,b   CuO15.6/SBA-15  CuO31.7/SBA-15  CuO8.8/SBA-15  a Y. M. Wang, Z. Y. Wu, J. H. Zhu, Journal of Solid State Chemistry 177 (2004) 3815-3823 b X-C. Shao, L-H. Duan, Y-Y. Wu, X-C. Qin, W-G. Yu, Y. Wang, H-L. Li, Z-L. Sun, L-J. Song, Acta Phys. Chim. Sin. 28 (2012) 1467-1473 Synthesis conditions used prevent copper sintering phenomenon and generate copper species in strong interaction with the support SBA-15    Results  9 SO2 adsorption tests: cycling experiments 5th International Congress  On Green Process Engineering, Mont Tremblant, Quebec, Canada, 19-24 June 2016  Regeneration under N2 at 600°C CuO15.6/SBA-15  CuO31.7/SBA-15  CuO8.8/SBA-15   The best SO2 adsorption capacity during adsorption 1     Important deactivation from adsorption 2  No deactivation, even after 9 cycles   Strong increase of performances from the 2nd SO2 chemisorption   Interesting SO2 adsorption capacities obtained along cycling experiments with a  relatively weak deactivation   The best performances after 5 cycles SO2 breakthrough curves SO2 breakthrough curves SO2 breakthrough curves    Results  10 SO2 adsorption tests: cycling experiments 5th International Congress  On Green Process Engineering, Mont Tremblant, Quebec, Canada, 19-24 June 2016  Regeneration under N2 at 600°C The best  adsorbent Adsorbent SO2 adsorption capacity at 75 ppm (mgSO2.gads-1)* Copper sulfation rate at 75 ppm (%)** Cycle  Cycle  1 2 3 5 9 1 2 3 5 9 CuO8.8/SBA-15 21 37 39 42 44 30 52 55 59 62 CuO15.6/SBA-15 44 75 60 57 35 60 48 45 CuO31.7/SBA-15 162 54 51 49 63 21 20 19 *   SO2 adsorption capacity  calculated by integration of the SO2 curve until the outlet  SO2 concentration reaches 75 ppm * * Ratio of SO2 chemisorbed at 75 ppm/total Cu content (mol/mol)  Adsorbents CuO/SBA-15 behavior strongly depends on copper loading Low and intermediate copper loadings Formation of Cu+ species during the first regeneration, more efficient in the desulfurization reaction High copper loading High SO2 storage capacity during cycle 1  Strong deactivation during cycle 2  due to strong copper sintering    Results  11 Characterizations after SO2 adsorption experiments 5th International Congress  On Green Process Engineering, Mont Tremblant, Quebec, Canada, 19-24 June 2016  TEM analyses CuO15.6/SBA-15  CuO31.7/SBA-15  CuO8.8/SBA-15  XRD analyses Wide angle XRD patterns  CuO8.8/SBA-15 : after 9 cycles, copper species remain highly dispersed    CuO15.6/SBA-15 : small XRD peaks of CuO    CuO31.7/SBA-15 : sharp XRD CuO peaks : presence of large CuO crystallites in high quantity       Results  12 SO2 adsorption tests: cycling experiments 5th International Congress  On Green Process Engineering, Mont Tremblant, Quebec, Canada, 19-24 June 2016  Regeneration under H2 at 280°C CuO15.6/SBA-15   Regeneration at low temperature (280°C) under H2 (0.5 vol.%) is efficient  No H2S is emitted during regeneration under H2  Energetic and financial advantages   CuO15.6/SBA-15 SO2 adsorption capacity  at 75 ppm (mgSO2.gads-1)* Cycle  1 2 3 5 Regeneration under N2 600°C 44 75 60 57 Regeneration under H2 280°C 38 63 51 45 *   SO2 adsorption capacity  calculated by integration of the SO2 curve until the outlet  SO2 concentration reaches 75 ppm     Conclusions  13 Conclusions   Synthesis of CuO/SBA-15 based adsorbents with highly dispersed copper species by wet impregnation in aqueous solution    Interesting SO2 chemisorption capacities along cycling experiments    Significant increase of the adsorbent efficiency after thermal treatment at 600°C : generation of Cu+ species, more active in desulfurization reaction    The adsorbents’ behavior strongly depends on copper loading : deactivation increases with copper loading    Optimum copper loading to ensure sufficient SO2 adsorption capacity and weak deactivation   Total regeneration under H2 at 280°C without H2S emissions   5th International Congress  On Green Process Engineering, Mont Tremblant, Quebec, Canada, 19-24 June 2016  14 Thanks for your attention! Acknowledgments:  - Philippe Fioux  - Loïc Vidal  - Damaris Kehrli  - All my colleagues!  SOx trapping performances of CuO based silica mesoporous adsorbents for the desulfurization of industrial flue gas stream   5th International Congress  On Green Process Engineering, Mont Tremblant, Quebec, Canada, 19-24 June 2016  P. Gaudin1, M. Berger1,2,5, S. Dorge2, H. Nouali1, L. Michelin1, L. Josien1, M. Vierling3, M. Molière4,  E. Fiani5, D. Habermacher2, J. Patarin1, J.F. Brilhac2  Financial support:  Collaboration:  15 2UMR CNRS 7361 1 Equipe Matériaux à Porosité Contrôlée, Institut de Science des Matériaux de Mulhouse,    UMR CNRS 7361, Université de Haute-Alsace, 3 bis rue Alfred Werner, 68093 Mulhouse Cedex, France  2 Laboratoire Gestion des Risques et Environnement, Université de Haute-Alsace, 3 bis rue Alfred Werner, 68093  Mulhouse Cedex, France  3 GE Energy, 20 avenue du Marechal Juin, 90007 Belfort Cedex, France  4 Université de Technologie  de Belfort-Montbéliard, Campus de Sévenans, 90010 Belfort Cedex France  5 ADEME - Agence de l'Environnement et de la Maîtrise de l'Energie, 20 avenue du Grésillé - BP 90406, 49004 Angers Cedex 01, France  

SOx trapping performances of cuo based silica mesoporous adsorbents for desulfurization of industrial flue gas stream

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SOx trapping performances of cuo based silica mesoporous adsorbents for desulfurization of industrial flue gas stream

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