advanced materials in ccs
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Advanced materials Advanced materials in CCSin CCS
The content of this document is confidential and is reserved for the Customer only
Egidio Zanin Egidio Zanin Centro Sviluppo Materiali SpA
Business Development & InnovationBusiness Development & InnovationProject Leader Energy & TransportProject Leader Energy & Transport
CCS –WEC 18.10.2011
CSM company in figuresCSM company in figures
Annual turnover: ~ 31 M€Annual turnover: ~ 31 M€
Turnover repartition:Turnover repartition:o85% from industry85% from industryo15% from institutions15% from institutions((researchresearch projects) projects)
DALMINE (R&D Unit)
TERNI (R&D Unit)
ROMAHeadquarters
PULA-PERDASDEFOGU(Oil & Gas Lab)
NAPOLI (Massive Calculation)
LAMEZIA TERME
(Renewables)
300 Researchers 300 Researchers
Policentric StructurePolicentric Structure
SHAREHOLDERS SHAREHOLDERS (Tenaris, Techint, (Tenaris, Techint, ThyssenKrupp, Fincantieri, Finmeccanica, ThyssenKrupp, Fincantieri, Finmeccanica, Vesuvius, ACEA, AMA, etc.)Vesuvius, ACEA, AMA, etc.)
Company EvolutionCompany Evolution
N°2 CCS –WEC 18.10.2011
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CSM activities in Energy SectorCSM 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°3 CCS –WEC 18.10.2011
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 CO2 in a state pure enough to meet
the requirements and legislation for transport and storage.
Technical needs in CCS developmentTechnical needs in CCS development
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Materials for CCSMaterials 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 CO2 Capture
Overview on main Research activities Overview on main Research activities in the Field of Materials for CCSin the Field of Materials for CCS
In Japan, long term R&D projects have been initiated to reduce the amount of CO2 emission by adopting steam temperature higher than700°C and the pressure of 35Mpa.
The Australian research in Australia is bases around the CO2CRC and has a research focusinto 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°6 CCS –WEC 18.10.2011
A key step of CCS technologies is gas separation
CO2 and N2 in the case of post-combustion capture CO2 and H2 for pre-combustion capture O2 from air in oxy-fuel combustion.
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
Few words about key functionalFew words about key functional materialsmaterials
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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 Targets, Needs for functional materials
N°8 CCS –WEC 18.10.2011
Example functional materials for CCSExample functional materials for CCS
CCS Technology
Process Notes / Example materials
Pre-combustion capture
Physical Solvents Rectisol, Selexol, Purisol.
Solid Sorbents Low temperature – activated carbons, zeolites, other porous solids
High temperature – SEWGS ( Sorption-Enhanced Water-Gas Shift) type materials
Membranes Metal and ceramic types for CO2 – H2 separation
Post–Combustion Capture
Chemical Solvents
Alkano/ amine based materials, advanced solvent systems
Solid Sorbents Low temperature - zeolites, MOFs, activated carbons, supported amines (silica, polymer etc supports) hydrotalcites
High temperature – CaO, etc
Ionic Liquids molten salts that do not evaporate
Oxyfuel-combustion
Membranes OTM / ITM power cycle ( Oxygen/ion Transport Membranes)
Gas separation (air separation)
Chemical looping Metal oxides.
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°9 CCS –WEC 18.10.2011
Key routes to materials degradationKey routes to materials degradation
Process Potential and Impact
Chemical degradation / alteration
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.
Thermal Degradation Thermal breakdown of materials during capture and regeneration cycles. For some high temperature materials this can result from agglomeration and sintering reactions.
Oxygen Oxidative degradation reported to be main degradation processes for solvent systems.
Interaction with other gases (SO2, NO2, HCl,
H2S, HCN, COS)
Other acid gases reacting irreversible with CO2 reactive sites.
Resulting in loss of capacity and eventual breakdown of materials.
Particulates Fly ash not removed from combustion process in the case of coal. Causing clogging of porous materials, associated systems.
Water Reduction in CO2 capture capacity (competition for pores),
hydrolysis, swelling, pore blocking, dissolution, corrosion and hydrolysis reactions.
Attrition Break down of particles / pellets of solid materials in the capture system and subsequent loss.
N°10 CCS –WEC 18.10.2011
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 challengesStructural materials main challenges
A-USC boilers
Oxycombustion boilers
IGCC/Gas turbine
CO2 Transport
Structural materials
N°11 CCS –WEC 18.10.2011
Structural materials for A-USCStructural 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 turbinesImproved (better creep resistance and corrosion) nickel base alloys
N°12 CCS –WEC 18.10.2011
Integrated Gasification Combined Cycle (IGCC) plants are able to effectively separate CO2 and to generate synthesis gases for fuel, methanol, H2 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 Structural materials for IGCC
N°13 CCS –WEC 18.10.2011
Co-combustion (biomass)
Critical aspectsCo-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.
NeedsModels development for fouling/slagging/corrosion in co-combustion. Developments of coatings for base materials protection.
Structural materials for co-combustionStructural materials for co-combustion
N°14 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 CO2/H2O 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-combustionStructural materials for oxy-combustion
N°15 CCS –WEC 18.10.2011
A multipartner project, MACPLUSA multipartner project, MACPLUS
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MACPLUS: Material-Component Performance-driven Solutions for Long-Term EfficiencyIncrease in Ultra Supercritical Supercritical Power Plants
Budget: 18,2 M€ (10.7 EU funding) Coordinator: Centro Sviluppo MaterialiOther 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 materialsAdvanced 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 surfaceLaser-treatment on refractory surface
N°18 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
Protective coatings (oxidation/corrosion)Protective coatings (oxidation/corrosion)
MCrAlY for turbine blade protection,(M=Ni, Co + Iridium, Rhenium) depositionwith 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 “O2Gen” for long term exposure tests in industrial plant.
N°19 CCS –WEC 18.10.2011
600 m
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 COOverview on CO22 transportation transportation
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Issues under study:
-Effect of quality composition of CO2 mixture (impurities, H2O) 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
COCO22 Transport Cost Estimates for Large-Scale Transport Cost Estimates for Large-Scale
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Safe and reliable COSafe and reliable CO2 2 Transportation Transportation Pipeline (SARCO2)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 CO2 transportation pipelines,• Definition of European Guideline for safe design of CO2 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 CO2
pipeline transportation hazards.
N°22 CCS –WEC 18.10.2011
ConclusionsConclusions
• 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°23 CCS –WEC 18.10.2011
