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- CCS (5) (entfernen)
Unusual Corrosion Behavior of 1.4542 Exposed a Laboratory Saline Aquifer Water CCS-Environment
(2017)
Differently heat treated coupons of 1.4542 were kept at T=60 °C and ambient pressure as well as p=100 bar for 700 h - 8000 h in an a) water saturated supercritical CO2 and b) CO2-saturated synthetic aquifer environment similar to on-shore CCS-sites in the Northern German Basin. Surface corrosion layers are homogeneous but unusually discontinuously ellipsoidal. After 8000 h at 100 bar maximum corrosion rate in the liquid phase is approximately 0.014 mm/year, with normalizing providing best corrosion resistance and approximately 0.003 mm/year in the supercritical phase where hardening+tempering at 670 °C leads to lowest corrosion rates.
X5CrNiCuNb16-4 has been proven to be sufficient resistant in corrosive environments, but shows rather unusual corrosion behaviour in CCS environment. Therefore a series of 30 specimens was tested at stress amplitudes between 150 MPa and 500 MPa (sinusoidal dynamic test loads, R=-1; resonant frequency ∼ 30 Hz). Due to the rather heterogeneous fine machined surfaces (Rz=4) the specimens are comparable with prefabricated parts. X5CrNiCuNb16-4 reached the maximum number of cycles (10 x 106) at a stress amplitude of 150 MPa and lies 60% below the stress amplitude measured in air. The scatter range TN = 1:34 is disproportionately large. Although the fracture surface exhibited the typical striations and corroded surface areas no significant differences were found. The hardness was found to be homogeneous in all specimens tested at 335 HV10. Non-metallic inclusions were found within the microstructure, but no correlation could be found between the inclusions and early rupture. Still specimens that showed inclusions at the fracture surface and its cross section endured lower number of cycles. Additionally Aluminium was analysed in specimens with low number of cycles and may be cause for early rupture during corrosion fatigue tests. These findings reveal a very high sensitivity on a homogeneous microstructure upon the corrosion and corrosion fatigue behaviour of X5CrNiCuNb16-4 and needs to be taken into account when regarding this steel as pipe steel during injection of CO2 into saline aquifers.
Properties of pipe steels for CCS (carbon capture and storage) technology require resistance against the corrosive environment of a potential CCS-site (heat, pressure, salinity of the aquifer, CO2-partial pressure). The influence of austenitzing in heat treatment routines of two different injection pipe steels (1.4034, X46Cr13 and 1.4021, X20Cr13) was evaluated. Steel coupons were austenitized at different temperatures (900- 1050 °C) for different lengths of time (30-90 min) before quenching and annealing prior to long term corrosion experiments (60°C, 100 bar, artificial brine close to a CCS-site in the Northern German Basin, Germany). In general, fewer pits are found on X46Cr13. Comparing steels with 13% chromium each the higher carbon content of X46Cr13 (0.46% C) results in a lower number of pits compared to X20Cr13 (0.20% C). It is found that neither the carbon content of the steels nor austenitizing temperature has much influence, but local corrosion behaviour is most susceptible towards austenitzing time.
Potential of martensitic stainless steel X5CrNiCuNb 16-4 as pipe steel in corrosive CCS environment
(2017)
Pipe steels suitable for carbon capture and storage technology (CCS) require resistance against the corrosive environment of a potential CCS-site (heat, pressure, salinity of the aquifer, CO2-partial pressure). X5CrNiCuNb16-4 has been proven to be sufficient resistant in corrosive environments, but shows rather unusual corrosion behaviour in CCS environment. Therefore differently heat treated coupons of 1.4542 were kept at T=60 °C and ambient pressure as well as p=100 bar for 700 h - 8000 h in an a) water saturated supercritical CO2 and b) CO2-saturated synthetic aquifer environment similar to on-shore CCS-sites in the Northern German Basin. Additionally fatigue tests were performed via push-pull tests with a series of 30 specimens was tested at stress amplitudes between 150 MPa and 500 MPa (sinusoidal dynamic test loads, R=-1; resonant frequency ~ 30 Hz). Best corrosion resistance in the liquid phase is achieved via normalizing prior to exposure and hardening+tempering at 670 °C leads to lowest corrosion rates in the supercritical phase. With no regard to atmosphere discontinuously ellipsoidal surface corrosion regions appear after exposure of 4000 h and more. The endurance limit of X5CrNiCuNb16-4 measured in air is reduced by more than 50% when exposed to CCS environment (maximum number of cycles (10 x 106) at a stress amplitude of 150 MPa) The scatter range TN = 1:34 is disproportionately large contributing to an overall unusual corrosion behaviour.
Carbon Capture Utilization and Storage (CCUS) is a promising technology for the reduction of CO2 emissions, e.g. from fossil-fuel operated power plants or cement mills. Crucial points for a sustainable and future-proof CCUS procedure are reliability and cost efficiency of the pipeline transport network. Due to the absence of certified benchmarks for upper limits, systematic experiments with impurities in the CO2 stream were carried out. For oxidation processes SO2 and NO2 acted as corrosive components, and for reductive atmosphere H2S. Carbon steel L485MB (pipeline), martensitic steel 1.4313 (compression) and austenitic steel 1.4562 (injection) were selected as specimens. Experiments were performed at 0 bar or 100 bar and within a temperature range 278 K ≤ T ≤ 313 K. High-alloyed Cr-Ni steels revealed no corrosion (1.4562, 1.4313), while for carbon steel considerable corrosion was observed. The type and intensity of corrosion was strongly coupled with the applied corrosive species and the level of humidity in the CO2 stream, leading to different compositions of acidic condensates. Applying a reducing atmosphere results in very little corrosion rates, but provokes pitting corrosion. In contrast, oxidizing or mixed settings lead to a clearly increased growth of the corrosion layer, but exhibit shallow uniform corrosion. Exceptional nitric acid results in intergranular corrosion. Investigations on the specimens were carried out by optical microscopy, XRD, SEM/EDX, and AAS/IC.