Investigating Corrosion in Supercritical Fluids

Lead Research Organisation: CRANFIELD UNIVERSITY
Department Name: School of Water, Energy and Environment

Abstract

This project proposes to study how turbine materials may fail in a new specialist energy production environment. The materials to be studied are superalloys, which are nickel- and cobalt-based alloys that can resist and work at high temperatures. These superalloys can be coated with thin ceramic layers, known as a thermal barrier coating (TBC), or metallic layers, to help protect them when they are in a high temperature environment.

It is important to know how the materials respond because they may be used in a new type of power plant which will expose them to an environment which is very unusual. This power cycle burns a fuel to drive a turbine and generate electricity when there is demand. The fuel can be natural gas or a synthetic gas made from coal, biomass or waste meaning that fuel supply is secure and power can be dispatched when needed. Unlike current power cycles using combustion, only oxygen, rather than air, is present with the fuel meaning carbon dioxide (CO2) and steam are the main products. The steam can be condensed out, and the CO2 kept. The CO2 then flows past the turbine at such high temperatures and pressures that it enters a special condition where it is neither liquid nor gas and is called supercritical-CO2.

This new type of power cycle has many potential advantages. As the superciritcal-CO2 is very dense, it's very good at pushing the turbine, so the energy from burning the fuel has a high efficiency of conversion into electricity, meaning electricity may be cheaper. It also means the turbine can be very small compared to other power cycles, so the new power plant can fit into small parcels of land, and can be put next to existing industrial structures for localised power generation. Finally, because the CO2 from burning the fuel is captured to drive the turbine, it doesn't have to be released into the atmosphere where it may contribute to climate change. Instead this CO2 can be captured, transported and used or stored. CO2 can be captured at 99% purity; this is better than specialist plant trying to remove CO2 from other power cycles, which aim to have 90% CO2 purity. This means the cycle can help make low-CO2 power while other renewable energy sources and storage options are developed.

However, in the supercritical-CO2 going through the turbine, there can be small amounts of chemical contaminants that can degrade the materials it is made from. As this power cycle recycles CO2 before transportation and use (it is a 'semi-closed' system), these chemicals can build up in concentration. To make sure that the plant built lasts for a long time and that there are no unexpected interruptions to power generation, it is important to know whether the turbine materials can survive these conditions as the supercritical-CO2 is at very high temperatures and pressures. By investigating the reliability of these materials, we can contribute to the confidence in these new, cleaner energy production systems, driving investment in and the spread of these options, rather than other cycles which may give off more CO2.

To meet this project's aim of understanding materials' degradation in this contaminated supercritical-CO2 operating environment experimental research much be carried out. Superalloy and ceramic coated samples will be provided by industry (see letters of support). These will be exposed at high temperatures (metal samples at 800-1000 C; TBC samples at 1100 C to simulate the cooling gradient anticipated through the component under operational conditions), high pressures (300 bar) and with chemical contaminants (such as H2O, SOX and NOX). Different superalloys will be used to see how differences in their chemistry, manufacturing and internal microstructure alters their reaction with supercritical-CO2. After a thousand hours exposure the samples will be looked at using specialist microscopy techniques to see how much metal has been lost and if any changes have taken place with the internal structure.

Planned Impact

This project's impact is in providing enhanced understanding of long-term degradation mechanisms for turbine materials to inform the construction and operation of advanced, high efficiency, low plant-footprint advanced semi-closed supercritical-CO2 cycles. Despite the power cycle's potential, little is known about long-term effects on materials exposed to such operating conditions. Developing this understanding is especially important for the turbine's first stage, where blades experience combinations of high temperatures, pressures and corrosive contaminants. This research will provide confidence in the long-term use of specific superalloys and coatings, and oxidation/carburisation data obtained will directly impact industry, allowing the benefits of semi-closed supercritical CO2 power generation cycles to be realised, to the benefit of a wide range of stakeholders. Impact includes:

*Business/industry. The Materials and Manufacturing KTN vision places the UK at the forefront of new industries and associated supply chains by building on materials research. Examples of supply chain beneficiaries to this project include original equipment manufacturers (e.g. Siemens Corporation, Siemens Industrial Turbomachinery, Doosan Babcock Technology and Engineering), power generators, and companies supplying specialist components or maintenance services. Industry will benefit from long-term degradation data under simulated supercritical power generation cycle conditions and improved understanding of fundamental degradation mechanisms. This will aid future plant design, engagement in plant supply chains and inform safe operating guidance. Globally, research into this cycle is taking place in the USA. UK companies would benefit from access to materials performance know-how at higher temperatures than currently exists and the quantification of coatings to compete for work, thus this research would help keep UK research and industry at the forefront of new developments and contribute to UK economic success. Further, as this cycle has a small plant footprint, it can be located close to existing plant, or to novel fuel sources, allowing industries to integrate this technology, when developed, onto existing sites where space is often at a premium, prohibiting the use of other generation cycles.

*The Public Sector. Knowledge generated will provide governmental energy policy makers with more options when choosing which power generation methods to encourage. When setting policy, they must consider the cost, supply security and environmental impact. Uptake of this cycle can help lower CO2 emissions (in line with UK legislation e.g. the Climate Change Act and ratification of the Paris Treaty to cut greenhouse gases linked to limiting climate change). Additionally, the cycle's fuel flexibility (natural gas, coal, biomass and wastes) improves the UK's energy portfolio security and does not require the development of new energy storage technologies unlike other proposed low-carbon power generation techniques. Thus, this cycle can contribute to the UK's Industrial Strategy "Building a Britain Fit for the Future" by producing clean energy to drive growth.

*The general public. Semi-closed supercritical-CO2 based power cycles can be coupled to carbon capture and utilisation technologies for a clean energy supply. Benefits can be maximised by using alternative fuel sources to further reduce CO2 emissions and thus climate change. Fuels include biomass; conventionally considered a low carbon fuel as CO2 given off is assumed to be reabsorbed when the next crop grows. Using alternative fuel sources increases energy security by reducing dependence on a single source, reducing volatility in availability or cost of energy. Another advantage for the general public is related to the high efficiency of the cycle (generation efficiencies of 52-59% compared to 33-40% in coal plant), which has the potential to reduce power costs and thus lower electricity bills.

Publications

10 25 50
 
Description Small changes in bare alloy oxidation/carburisation responses have been found if trace impurities exist within CO2. This will potentially have an impact on how power generation cycles based on these fluids are set up, as well as raising, for future research, research questions around other potential impurities.
Exploitation Route Research findings from this award are directly relevant for a power generation cycle based on supercritical-CO2. This cycle is being demonstrated currently in the USA. Research findings have been of interest to colleagues in Oak Ridge National Lab and Sandia National Lab (USA), and to industrial companies such as Siemens Corporation.

Remaining research questions are currently being addressed at Cranfield by a PhD student, using the facilities. Additional questions have been found around the role of impurities in the fluid, and we are currently looking at developing a collaboration with colleagues in Germany to assess this.
Sectors Energy

 
Description The research carried out is to assess the likely failure mechanisms linked to high CO2 rich, extreme operating environments linked to novel power generation cycles such as the Allam cycle. These cycles are highly efficient, and, for the semi-closed cycles, can be linked to carbon capture and storage to minimise the environmental impact of generating energy, as more sustainable systems are developed. Currently the data found has been shared with industry partners, although the long term impact is still unclear. Engagement includes data transfer to Siemens Corporation, NETL and with researchers in the UK. This has been facilitated by the PI, Dr Sumner, chairing 2 conferences over the course of this project (see Engagement activities), at which events sessions on sCO2 were arranged. Additional data sharing has been facilitated at 6 monthly meetings through the UK-US Energy Materials Network. Evidence includes a joint publication (Materials at High Temperature, 2023) with a senior member of staff, at Siemens Corporation, Anand Kulkarni, and the production of 2 MSc thesis (PhD project is ongoing as it started out of sink with the main project.) This is working towards impact in new projects around Allam cycles and other CO2 linked research, to improve the lifetime of components in power plant and so reduce costs. This has also followed onto an industrially funded piece of research.
First Year Of Impact 2023
Sector Energy
Impact Types Economic

 
Description Karlsruhe Institute of Technology 
Organisation Karlsruhe Institute of Technology
Country Germany 
Sector Academic/University 
PI Contribution The collaboration has been to assess the impact on oxidation/carburisation grain boundary diffusion of potential contaminant species (e.g. sulphur). For this, we have produced samples in our test conditions under representative conditions.
Collaborator Contribution The collaboration has been to assess the impact on oxidation/carburisation grain boundary diffusion of potential contaminant species (e.g. sulphur). KIT have given access to their atom probe tomography system to assess multiple sites on the sample, and evaluate the location of species. This work is carried out at much higher resolution than is possible with Cranfield's facilities, and has given insight into the damage mechanisms.
Impact Submitted abstract to Eurocorr 2024 Conference (Norman et al). Paper in draft, but awaiting final results form KIT.
Start Year 2022
 
Description University of Brimingham 
Organisation University of Birmingham
Country United Kingdom 
Sector Academic/University 
PI Contribution We have been looking at the impact of advanced manufacturing compared to conventional alloy production in these extreme environments. We have contributed testing and analysis time.
Collaborator Contribution University of Birmingham have supplied a large number of samples to add into the test program, as well as contributing to discussions between our two research teams.
Impact We have an abstract submitted to EuroCORR 2024 (international conference) and a paper relating to this is currently in draft. Initial data has been disseminated at a previous Conference (EuroCORR 2023) as well as through a networking group (UK-US Energy Materials Network).
Start Year 2023
 
Description 10th International Charles Parsons Turbine and Generator Conference 
Form Of Engagement Activity A formal working group, expert panel or dialogue
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Industry/Business
Results and Impact The PI, Dr Sumner, chaired this conference, run by the Institute of Materials, Minerals and Mining.
In the conference, industry and researchers with an interest in turbomachinery discussed the findings of current research, including the Allam cycle and the performance of key component materials in supercritical fluids.
Year(s) Of Engagement Activity 2019
 
Description INWED Open Day (Cranfield) 
Form Of Engagement Activity Participation in an open day or visit at my research institution
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Schools
Results and Impact 32 female students from 3 local schools (and teachers) attended on the 5th May 2022 linked to INWED. Students were shown current cutting edge research projects and related activities. This included the influence of sCO2 for novel power generation systems (this award). In addition, this allowed the associated PhD student to engage with the school students and explain her research to a general audience. It seemed to go well, with lots of interest from the school students in research. We are in discussions about repeating this outreach in coming years.
Year(s) Of Engagement Activity 2022
URL https://www.cranfield.ac.uk/about/community-and-public-engagement/inwed-2022
 
Description Microscopy of Oxidation 11, International Conference 
Form Of Engagement Activity A formal working group, expert panel or dialogue
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Industry/Business
Results and Impact The PI, Dr Sumner, chaired and ran the 11th Microscopy of Oxidation conference. This brought together members of academia, industry and research institutes working to understand materials responses in extreme environments, and sharing best practice. sCO2 performance was debated between the attendees.
Year(s) Of Engagement Activity 2022
URL https://www.cranfield.ac.uk/events/events-2022/microscopy-of-oxidation-11
 
Description UK-US Energy Materials Network 
Form Of Engagement Activity A formal working group, expert panel or dialogue
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Industry/Business
Results and Impact This working group/network was established to encourage cross-collaboration between the UK and USA on precompetitive areas, historically relating to fossil fuels (this has shifted in recent years).
Within this group, research institutes, companies and policymakers can discuss specific topics related to energy generation. For the duration of this research project, pre-competitive results have been shared with the network, to encourage uptake and improve research plans. This has also resulted in a joint publication.
Year(s) Of Engagement Activity 2019,2020,2021,2022,2023,2024
URL https://fossil.energy.gov/usuk/
 
Description Utility Week Article 
Form Of Engagement Activity A magazine, newsletter or online publication
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Industry/Business
Results and Impact A trade article for Utility Week in winter 2022 entitled "The material component of the energy transition". This covers a number of current challenges posted by materials for the energy sector, including sCO2 based power generation systems. Please note that I do not have numbers for how many people have read the article, as such, I have approximated 51-100.
Year(s) Of Engagement Activity 2022
URL https://utilityweek.co.uk/the-material-component-of-the-energy-transition/