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
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
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).
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,
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
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
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
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
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.
Models development for fouling/slagging/corrosion
Developments of coatings for base materials
Structural materials for co-combustion N° CCS –WEC 18.10.2011
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
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
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.
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
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