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Advanced materials in CCS
Advanced materials in CCS
Advanced materials in CCS
Advanced materials in CCS
Advanced materials in CCS
Advanced materials in CCS
Advanced materials in CCS
Advanced materials in CCS
Advanced materials in CCS
Advanced materials in CCS
Advanced materials in CCS
Advanced materials in CCS
Advanced materials in CCS
Advanced materials in CCS
Advanced materials in CCS
Advanced materials in CCS
Advanced materials in CCS
Advanced materials in CCS
Advanced materials in CCS
Advanced materials in CCS
Advanced materials in CCS
Advanced materials in CCS
Advanced materials in CCS
Advanced materials in CCS
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Advanced materials in CCS

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    • 1. Advanced materials in CCS The content of this document is confidential and is reserved for the Customer only Egidio Zanin Centro Sviluppo Materiali SpA Business Development & Innovation Project Leader Energy & Transport CCS –WEC 18.10.2011
    • 2. CSM company in figures
      • Annual turnover: ~ 31 M€
      • Turnover repartition:
        • 85% from industry
        • 15% from institutions
        • ( research projects)
      • 300 Researchers
      • Policentric Structure
      • SHAREHOLDERS (Tenaris, Techint, ThyssenKrupp, Fincantieri, Finmeccanica, Vesuvius, ACEA, AMA, etc.)
      Company Evolution N° CCS –WEC 18.10.2011 DALMINE (R&D Unit) TERNI (R&D Unit) ROMA Headquarters PULA-PERDASDEFOGU (Oil & Gas Lab) NAPOLI (Massive Calculation) LAMEZIA TERME ( Renewables )
    • 3. . CSM activities in Energy Sector
      • Advanced materials development (steels, special alloys, ceramics, coatings)
      • Materials/component prototyping and validation in different working conditions (HT, corrosion, wear, fatigue) , full scale testing
      • Advanced modeling for improving degradation mechanisms understanding and more in general materials/component behavior during fabrication (casting, forging, welding, coating) and exercise
      • Process control (heat treatments design & testing, combustion/gasification, automation)
      N° CCS –WEC 18.10.2011
    • 4.
      • Technically, CCS can be implemented today, but the capture steps are too expensive or too energy intense.
      • Requirements needed for capture technologies:
      • to operate with a minimum energy penalty on power plant,
      • reasonable cap-ex and op-ex and plant footprint
      • to achieve capture targets
      • to produce CO 2 in a state pure enough to meet
      • the requirements and legislation for transport
      • and storage.
      Technical needs in CCS development N° CCS –WEC 18.10.2011
    • 5. Materials for CCS
      • Development of new materials and improvement of the existing one are required for
        • Structural materials  Coal, Gas and co-fired power plants, Transport
        • Functional materials  CO 2 Capture
    • 6. Overview on main Research activities in the Field of Materials for CCS
      • In Japan, long term R&D projects have been
      • initiated to reduce the amount of CO 2 emission
      • by adopting steam temperature higher than
      • 700°C and the pressure of 35Mpa.
      • The Australian research in Australia is bases
      • around the CO 2 CRC and has a research focus
      • into a range of functional materials for carbon
      • capture, for example solid sorbents, membranes and cryogenic systems.
      • Large EU-projects funded through FP7 and entirely focussed or dealing with aspects of structural (e.g. MACPLUS , COMTES , ENCIO, H2-IGCC, and RECOMBIO) and functional (incl. CACHET II, CAESAR, CASTOR) materials.
      •  Outside the EU, the principal research programs developing structural materials for high efficiency power plants are the USA (large project on materials for USC boilers funded by DOE in collaboration with NETL).
      N° CCS –WEC 18.10.2011
    • 7.
      •  A key step of CCS technologies is gas separation
          • CO 2 and N 2 in the case of post-combustion capture
          • CO 2 and H 2 for pre-combustion capture
          • O 2 from air in oxy-fuel combustion.
      Few words about key functional materials N° CCS –WEC 18.10.2011
      • CCS Functional materials
      • Absorbent liquids
      • Adsorbent materials
      • Oxygen carriers for chemical looping
      • technologies
      • Membranes for gas separation technologies
      Physical solvents Chemical solvents Pre-combustion capture Post-combustion capture Oxy-fuel combustion Capture Technologies
    • 8.
      • Further efforts in synthesis and screening of adsorbents experimentally and theoretically, integration of the full process are needed
      • To the efficiency and cost of capture are important
          •  kinetics (mass transport),
          • capacity and selectivity for carbon dioxide,
          • mechanical robustness
          • thermal properties
      • The main challenges for current technologies (specific for each technology)
          • a high selectivity,
          • fast reaction kinetics to achieve separation to the required purity,
          • acceptable energy penalty
          • resistant to the aggressive chemical/physical demands of fuel gas streams
          • durable and economic
      Targets, Needs for functional materials N° CCS –WEC 18.10.2011
    • 9. Example functional materials for CCS Absorption based stripping of carbon dioxide with amines in water (e.g. MEA), chilled ammonia are probably the first technologies to be deployed on a large scale for CCS. Full-scale demonstration units are currently being constructed. N° CCS –WEC 18.10.2011 Metal oxides. Chemical looping Gas separation (air separation) OTM / ITM power cycle ( Oxygen/ion Transport Membranes) Membranes Oxyfuel-combustion Ionic Liquids molten salts that do not evaporate High temperature – CaO, etc Low temperature - zeolites, MOFs, activated carbons, supported amines (silica, polymer etc supports) hydrotalcites Solid Sorbents Alkano/ amine based materials, advanced solvent systems Chemical Solvents Post–Combustion Capture Metal and ceramic types for CO2 – H2 separation Membranes High temperature – SEWGS ( Sorption-Enhanced Water-Gas Shift) type materials Low temperature – activated carbons, zeolites, other porous solids Solid Sorbents Rectisol, Selexol, Purisol. Physical Solvents Pre-combustion capture Notes / Example materials Process CCS Technology
    • 10. Key routes to materials degradation N° CCS –WEC 18.10.2011 Break down of particles / pellets of solid materials in the capture system and subsequent loss. Attrition Reduction in CO 2 capture capacity (competition for pores), hydrolysis, swelling, pore blocking, dissolution, corrosion and hydrolysis reactions. Water Fly ash not removed from combustion process in the case of coal. Causing clogging of porous materials, associated systems. Particulates Other acid gases reacting irreversible with CO 2 reactive sites. Resulting in loss of capacity and eventual breakdown of materials. Interaction with other gases (SO 2 , NO 2 , HCl, H 2 S, HCN, COS) Oxidative degradation reported to be main degradation processes for solvent systems . Oxygen Thermal breakdown of materials during capture and regeneration cycles. For some high temperature materials this can result from agglomeration and sintering reactions. Thermal Degradation A potential problem for chemically active functional materials where repeat cycles can lead to degradation. For example carbamate polymerisation for 1  or 2  amines as observed in amine solvents above 100  C . Chemical degradation / alteration Potential and Impact Process
    • 11. Life time prediction and assessments of critical components (optimization of materials design and elaboration of behaviour models: creep, creep-fatigue. oxidation, ….) Improved materials and protective systems (coatings) under new operating conditions (USC, Gas turbines, Co- and oxy- combustion). Production and verification of large components and welded joints (advanced steam turbine, USC) of currently state of art materials. Improvement of monitoring methods. Structural materials main challenges A-USC boilers Oxycombustion boilers IGCC/Gas turbine CO2 Transport Structural materials N° CCS –WEC 18.10.2011
    • 12. Structural materials for A-USC
      • Trend: increasing steam working temperature > 650 °C
        • up to 700°C/720 °C and 350 bar.
      • Boilers
      • Optimization of F/M steels up to 650 ºC; Protective coating system
      • Advanced martensitic steels (up to 17-20%Cr) to be used up to 670°C
      • Advanced steam turbines
      • Advanced Fe-Ni alloys (Ni less than 40%);
      • USC boiler and steam turbines
      • Improved (better creep resistance and corrosion) nickel base alloys
      N° CCS –WEC 18.10.2011
    • 13.
      • Integrated Gasification Combined Cycle (IGCC) plants are able to effectively separate CO2 and to generate synthesis gases for fuel, methanol, H 2 and SNG production.
      • Critical aspects
        • - Oxidation/corrosion in the hot gas path.
        • adaptation of gas turbines to hydrogen rich
        • fuel gases.
      • Needs
      • - high temperature creep resistant metal
      • substrates (intermetallics).
      • - durable thermal barrier coatings (TBCs) and effective cooling techniques.
      • - Ceramic and fibre reinforced materials could be an interesting alternative for hot gas components in gas turbines.
      Structural materials for IGCC N° CCS –WEC 18.10.2011
    • 14.
      • Co-combustion (biomass)
      • Critical aspects
      • Co-utilisation of biomass or wastes promotes operational problems such as slagging, fouling and corrosion of boiler materials.
      • Transferability between lab and plants is not straightforward.
      • Needs
      • Models development for fouling/slagging/corrosion
      • in co-combustion.
      • Developments of coatings for base materials
      • protection.
      Structural materials for co-combustion N° CCS –WEC 18.10.2011
    • 15.  Flue gases in an oxy-combustion coal plant are rich in CO2 and steam water , NOx and SOx: oxidation/corrosion issue.  For oxy-fuel gas turbines with a mixture of CO 2 /H 2 O as working medium, an adaptation of the available technology for gas turbine and future developments should be available by 2020. Needs: Improvement of failure mode mechanisms. Ceramic and refractory materials for very aggressive environments. Structural materials for oxy-combustion N° CCS –WEC 18.10.2011
    • 16. A multipartner project, MACPLUS N° MACPLUS : Ma terial- C omponent P erformance-driven Solutions for L ong-Term Efficiency Increase in U ltra S upercritical S upercritical Power Plants Budget : 18,2 M€ (10.7 EU funding) Coordinator : Centro Sviluppo Materiali Other Partners : Dong Energy, RWE, Endesa, E.ON, Doosan Babcock, Alstom, Foster Wheeler, Ciuden, Tubacex, TUV, Cogne Acciai speciali, Flame Spray, TU GRAZ, NPL, Un. Loughborough, FZ Juelich, DTU, Imperial College, VTT, Goodwins Steel, Salzgitter Mannesmann, Aubert & Duval, Saarschmiede, Welding Research Institute VUZ, Royal Technical Univ. ( KTH ), Fraunhofer-Freiburg ( IWM ), Research, FZ Jülich Industrial realisation and testing of innovative material-component solutions is envisaged: ceramic refractory, advanced WJs in MARBN steels, super heaters in optimised austenitic steel and Ni-base alloy, improved SRC thick-walled pipe, coated solutions for boiler pipes. Advanced modelling for production of high alloy steel and Ni-base alloy for steam turbine components (rotor, casing), as well as integrated advanced design and testing criteria for HT components development, integration and standardization Full-scale prototypes of candidate material-component solutions installed into industrial plant(s) and/or test loop(s) / rig(s) CCS –WEC 18.10.2011
    • 17. Advanced Refractory materials The conditions occurring in oxy-combustion plants, coupled with the fuel flexibility, represent a critical factor for refractory materials, New low cost solutions are required. CSM, is developing a functionally graded material consisting of a low cost refractory substrate coated with a protective layer having superior corrosion resistance that will be tested in Ciuden plant.
    • 18. Laser-treatment on refractory surface N° The content of this document is confidential and is reserved for the Customer only Laser treated surface Untreated surface
      • CSM is testing laser treatment on refractory surface for:
      • Reducing surface porosity
      • Depositing a protective layer of superior compositional and physical properties on a low quality refractory substrate by laser cladding
      • Objective: to improve the lifetime of refractory
    • 19. Protective coatings (oxidation/corrosion)
      • MCrAlY for turbine blade protection,
      • (M=Ni, Co + Iridium, Rhenium) deposition
      • with thermo spray technique o HVOF
      • ( High Velocity Oxy Fuel ).
      Aluminisation for heat exchanger tubes. Coatings on carbon steel tubes by HVOF technology. The produced coated tubes are used within the projects “Macplus” and “O 2 Gen” for long term exposure tests in industrial plant. N° CCS –WEC 18.10.2011
    • 20.
      • Existing infrastructures for CO2 transportation are relatively short connections between plants and nearby storage sites or situated in remote areas.
      • CO2 transport lines will probably cross populated areas.
      Overview on CO 2 transportation N°
      • Issues under study:
      • Effect of quality composition of CO2 mixture
      • (impurities, H 2 O) due to the characteristics of the point
      • of capture or the capture process adopted;
      • Supercritical transportation (to avoid two phase flow), P > 82 bar ;
      • - CO2 behavior in case of pipeline failure:
        • ductile Fracture propagation (CO2 decompression behavior);
        • leak before break event;
      CCS –WEC 18.10.2011
    • 21. CO 2 Transport Cost Estimates for Large-Scale N°
    • 22. Safe and reliable CO 2 Transportation Pipeline (SARCO2)
      • Partners: CSM, Salzgitter Mannesmann Forschung, ENI G&P, GDF
      • SUEZ, E.ON Ruhrgas, National Grid
      • Start: 1/7/2011
      • Targets:
      • evaluation steel pipe requirements for anthropogenic CO 2
      • transportation pipelines,
      • Definition of European Guideline for safe design of CO 2 pipeline
      • network using high steels grades as well as crack arrestors and
      • reinforced pipes.
      • Improvements on:
        • Definition of toughness requirements to control running ductile fracture propagation;
        • Definition of requirements to control pipe steel corrosion and to minimize the occurrence of stress corrosion cracking;
        • Selection and calibration of existing analytical tools to evaluate the most relevant CO 2 pipeline transportation hazards.
      N° CCS –WEC 18.10.2011
    • 23. Conclusions
      • Materials are a key factor in the development/application of novel processes.
      • Each application is characterized by its peculiarities (T, atmosphere composition, pressure, dimensions, cycling conditions).
      • No general purpose materials are available.
      • The development of new materials needs a long term qualification process in order to assure safety aspects.
      • The right balance costs/performance improvements is a key factor for enabling new solution under commercial point of view.
      • Large-scale CCS requires the development of a transport infrastructure equivalent to the current hydrocarbon infrastructure
      N° CCS –WEC 18.10.2011
    • 24. Thank you For any request: Egidio Zanin e-mail [email_address] Tel +39 065055830 N°

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