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Organisationseinheit der BAM
The CCS technique involves the compression of emission gasses in deep geological layers. To guarantee the safety of the site, CO2-corrosion of the injection pipe steels has to be given special attention when engineering CCS-sites. To get to know the corrosion behaviour samples of the heat treated steel 1.72252CrMo4, used for casing, and the stainless injection-pipe steel 1.4034 X46Cr13 were kept at T=60 °C and ambient pressure as well as p=100 bar for 700 h - 8000 h in a CC 2-saturated synthetic aquifer environment similar to possible geological on-shore CCS-sites in the northern German Basin. The isothermal corrosion behaviour obtained by mass gain of the steels in the gas phase, the liquid phase and the intermediate phase gives surface corrosion rates around 0.1 to 0.8 mm/year at ambient pressure and much lower about 0.02 to 0.2 mm/year at 100 bar where the CO 2 is in its supercritical state. Severe pit corrosion with pit heights around 4.5 mm are only located on the 42CrMo4 steel. Main phase of the continuous complicated multi-layered carbonate/oxide structure is siderite FeCO 3 in both types of steel.
Dealing with first corrosion screening experiments to predict the reliability and safety of Germanys first Carbon Capture and Storage site in the northern Bassin of Germany, northwest of the Capital Berlin, laboratory experiments have been established to simulate the particular conditions at T=60 °C, highly saline aquifer water similar to 'Stuttgart Aquifer', but only at ambient pressure. With mounting 2 independent full 2-grade titanium autoclave systems (running up to 250 bar and 300 °C) pressures up to p=100 bar are possible. In 2010 a specific corrosion chamber of 2-grade titanium working up to 100 °C, flowing aqui fer water with different gas mixtures was designed to fit to a high cycle fatigue testing machine. Long term fatigue experiments simulating fatigue crack growth under corrosive environments will soon start. These experiments may not only help engineering a CCS site, but results can be used to improve the maintenance of geothermal energy production sites, especially moved parts such as pumps and shafts.
The CCS technique involves the compression of emission gasses in deep geological layers. To guarantee the safety of the site, C02-corrosion of the injection pipe steels has to be given special attention when engineering CCSsites. To get to know the corrosion behaviour samples of the heat treated Steel 1.72252CrMo4, used for casing, and the stainless injection-pipe Steel 1.4034 X46Cr 13 were kept at T=60 °C and ambient pressure as well as p=100 bar for 700 h - 8000 h in a C02-saturated synthetic aquifer environment similar to possible geological on-shore CCS-sites in the northern German Basin. The isothermal corrosion behaviour obtained by mass gain of the steels in the gas phase, the liquid phase and the intermediate phase gives surface corrosion rates around 0.1 to 0.8 mm/year at ambient pressure and much lower about 0.02 to 0.2 mm/year at 100 bar where the C02 is in its supercritical state. Severe pit corrosion with pit heights around 4.5 mm are only located on the 42CrMo4 Steel. Main phase of the continuous complicated multi-layered carbonate/oxide structure is siderite FeCO} in both types of Steel.
The CCS technique involves the compression of emission gasses in deep geological layers. To guarantee the safety of the site, CC>2-corrosion of the injection pipe steels has to be given special attention when engineering CCS-sites. To get to know the corrosion behaviour samples of the heat treated Steel 1.72252CrMo4, used for casing, and the stainless injection-pipe Steel 1.4034 X46Crl3 were kept at T=60 °C and ambient pressure as well as p=100 bar for 700 h - 8000 h in a CC>2-saturated synthetic aquifer environment similar to possible geological onshore CCS-sites in the northern German Basin. The isothermal corrosion behaviour obtained by mass gain of the steels in the gas phase, the liquid phase and the intermediate phase gives surface corrosion rates around 0.1 to 0.8 mm/year at ambient pressure and much lower about 0.02 to 0.2 mm/year at 100 bar where the CO2 is in its supercritical state. Severe pit corrosion with pit heights around 4.5 mm are only located on the 42CrMo4 Steel. Main phase of the continuous complicated multi-layered carbonate/oxide structure is siderite FeCCh in both types of Steel.
When engineering a Carbon Capture and Storage site (CCS) local corrosion (pitting) of the injection pipe steel may become an issue when emission gasses from oxyfuel power plants are compressed into deep geological layers. This highly corrosive environment arises when the flue gasses, mainly composed of CO2 , are injected into saline aquifer water. Immediately carbonic acid is formed causing corrosive attack of the injection steels. The influence of heat treatment on the local corrosion resistance was demonstrated in laboratory experiments at 60 °C and ambient pressure for three steels X46Cr13 (1.4034), X20Cr13 (1.4021) and X5CrNiCuNb16-4 (1.4543) under a similar liquid corrosive environment as found at a geological onshore CCS-site in the Northern German Bassin.
Oxidation of a single crystal nickel-base superalloy at 950 °C - a kinetic and microstructure study
(2008)
The nickel-base single crystal alloy investigated is a widely used material for first and second row blades in stationary gas turbines. Nickel-base superalloys are especially designed to resist high temperature oxidation by process gases. To determine this high temperature behaviour oxidation testing was carried out using samples cut perpendicular to (001)-direction. Microstructures were characterized by X-ray diffraction XRD, Light Microscopy LM, Scanning Electron Microscopy SEM, and X-ray energy dispersive spectroscopy (EDS), after a series of heat treatments (950 °C, 0 h - 1000 h). Mass gain and the respective thicknesses of the different oxide layers were measured to determine oxidation kinetics. In general, the isothermal oxidation behaviour at 950 °C, as defined by weight gain, follows a parabolic law with a parabolic rate constant around 1.4 · 10-2 mg2/(cm4 · h). A short incubation time is followed by the constitution of a multi-layered oxide scale. The oxide scale consists of a three layer structure. An outer scale contains a Ti-bearing thin film associated as TiO2 and NiTiO3 but mostly Cr attributed to Cr2O3, (Ni/Co)Cr2O4 beside NiTaO4. This outer scale is connected to a discontinuous layer of inner oxidation consisting mainly of Al2O3, which is followed by an area of γ´-depletion within the base material.
The resistance of structural steels against corrosion in CO2-H2O and CO2-H2O-O2
atmospheres at temperatures above 550°C was observed with high magnification methods.
The test atmosphere is the basic composition of an oxyfuel coal combustion atmosphere. The
analytical information base was applied to develop reaction schemes for the oxidation of
steels. It was demonstrated that the formation of phases and the kinetics of oxidation reactions
in this atmospheres is affected by the formation of intermediate iron hydroxide and a high
carbon activity. In the temperature regime above 550°C the thermal equilibrium between H2O,
CO2 and Fe reacted and formed CO. CO triggers the formation of FeO and carbides and
increases the reaction kinetics. Porosity at the interface is established by gaseous phases
such as Fe(OH)2 or H2O. H2 formation is not limited to the steel - oxide interface but can occur
in the whole oxide scale. Examples of the experimental results were compared with a
thermodynamic approach. The objective of the work was to derive qualitative rules of the basic
corrosion reactions.
The most efficient construction materials for boiler water walls and superheaters in
steam power plants are ferritic and martensitic steels. In practical operation tubes are
simultaneously exposed to combustion gas and air/steam on their opposite surfaces. The
corrosion behaviour of ferritic-martensitic steels under such dual atmospheres is nondistinctive
and has therefore been investigated in a special designed test equipment between 500 and
620°C. The power plant conditions were simulated wi th a flowing and pressurised (80 bar)
combustion gas on the inner side of the tube which mainly consists of H2O and/or CO2. On the
outer side, the tube material was exposed to air. It was discovered that under similar
temperatures the oxides formed on the air side under dual atmosphere conditions were
significantly different to the oxide scales formed when the alloy was exposed to air only. It is
assumed that the anomalous corrosion behaviour during the dual atmosphere exposure is due
to the hydrogen transport through the bulk alloy from the combustion gas side to the air side.
Samples of differently heat treated high alloyed stainless injection-pipe steels AISI 420 X46Cr13, AISI 420J X20Cr13 as well as X5CrNiCuNb16-4 AISI 630 were kept at T=60 °C and ambient pressure as well as p=100 bar for 700 h - 8000 h in a CO2- saturated synthetic aquifer environment similar to possible geological on-shore CCS-sites in the northern German Basin. Corrosion rates and scale growth are lowest after long term exposure for steels hardened and tempered at 600 to 670 °C and pits - indicating local corrosion- decrease in diameter but increase in number as a function of carbon content of the steel. Martensitic microstructure is preferred with respect to this particular CCS-site.
The combustion of coal in CO2-reduced Oxyfuel power plants requires creep resistant and corrosion
resistant materials, which can withstand high temperatures up to 600°C and CO2 rich atmospheres.
Among the heat resistant materials, the 9-12% chromium steels are proven to resist high wall
temperatures in conventional power plants and are suitable as membrane wall, superheaters and steam
piping.
During Oxyfuel combustion a flue gas is generated, which consists mainly of H2O (30 mol %) and
CO2 (70 mol %). The present paper is focused on the corrosion of 9-12% chromium steels under
oxyfuel conditions in a temperature range between 550 and 625°C.
Depending on Chromium content of the 9-12%chromium steels, carburization of the base material,
perlite formation and carbide formation were observed. Alloys with lower chromium content form a
non protective oxide scale with perlite at the scale-alloy interface. Steels with 12% chromium have a
small growing oxide scale with enlarged M23C6-particles at the scale-alloy interface. The carburization
of the base material is found to be increased for the 9% Cr-steel. Higher pressure of the flue gas results
in the formation of less resistant scales and cause accelerated carburization of the base materials.
However, the carburization has an impact on the mechanical properties at the surface and leads to an
embrittlement, which is deleterious during thermal cycling.
Oxidation kinetics, phase analysis of the scale (transmission electron microscope) and carburization
depths (microprobe) of the base materials are presented.
With CO2 being one reason for climate change carbon capture and storage (CCS) is discussed to mitigate climate change. When emission gases are compressed into deep geological layers CO2-corrosion can easily cause failure of injection pipes. Different steels 42CrMo4, X46Cr13 and X20Cr13 were tested as well as X35CrMo17 and X5CrNiCuNb16-4 in a laboratory Environment similar to the conditions of the CCS engineering site at the Northern German Bassin. Samples were exposed to synthetic aquifer water saturated with technical CO2 at a flow rate of 3 NL/h.
Corrosion rates obtained via mass loss vary in a wide range (0,005 to 2.5 mm/year). The precipitations within the corrosion scale revealed a complicated multiphase layer containing siderite FeCO3, goethite α-FeOOH, lepidocrocite γ-FeOOH, mackinawite FeS and akaganeite Fe8O8(OH)8Cl1,34 and spinelphases of various compositions.
During carbon capture and storage (CCS) CO2-corrosion of pipe steels is a relevant safety issue when emission gasses are compressed in deep geological layers. The reliability of the steels 42CrMo4, X20Cr13, X46Cr13 and X35CrMo17 is demonstrated in long term laboratory experiments up to 2 years of exposure time. Testings were carried out at ambient pressure under an equivalent corrosive environment as found at the geological onshore CCS-site at Ketzin, Germany (T=60 °C, aquifer water).
The geological storage of carbon dioxide (Carbon Capture and Storage, CCS) in depleted gas reservoirs or in saline aquifers is a widely discussed issue. Carbon dioxide may induce corrosion on the piping steels during compression, transportation and injection. Therefore,
selection of appropriate piping steels is a key factor in order to increase the safety and reliability of the CCS technology, and to keep the processes cost-effective.
The here described subproject of the COORAL project (German acronym for “C02 purity for capture and storage”) deals with the levels of impurities in the C02 stream that will be acceptable when using specific steels. Material exposure to carbon dioxide (C02) containing
specific amounts of water vapor, oxygen (02) sulfur dioxide (S02), nitrogen dioxide (N02), carbon monoxide (CO) can be a challenge to steels. Within this subproject 13 different Steels are tested for suitability as materials used for compression, transportation and injection Units within the CCS chain.
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.
Kohlendioxid (C02), das z.B. aus dem Abgas von fossilgefeuerten Kraftwerken, Stahlwerken oder Zementwerken abgetrennt wird, enthält Verunreinigungen. Dies sind beispielsweise Wasserdampf, 02, S0X, NOx und H2S. Derartige Gasmischungen sind instabil und ihre Komponenten können zu weiteren Produkten reagieren. Wenn Wassermoleküle zur Verfügung stehen, können saure Lösungen kondensieren. Die Korrosion von Werkstoffen und Bauteilen in Kontakt mit den transportierten Gasmischungen wird an der BAM in Laborversuchen untersucht, Das wichtigste Ziel ist, sichere und bezahlbare Kombinationen von zugelassenen Konstruktionswerkstoffen und Grenzwerten für Verunreinigungen im C02-Strom vorzuschlagen. In den bisherigen Arbeiten hat sich herausgestellt, dass für eine verlässliche Aussage die Experimente möglichst realitätsnah durchgeführt werden sollten. Hierfür müssen die Parameter: hoher Druck (um 100 bar), Temperatur (um 60 °C), Strömungsverhältnisse (laminar oder turbulent) sowie mechanische Spannung kombiniert werden. Für diese Anforderungen wurden Prüfstände entwickelt und Experimente durchgeführt.
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.
The ageing of Fe-Cr model alloys in 0.5 % SO2 and 99.5 % Ar atmosphere was investigated to aim in a fundamental and systematic analysis of the combined oxidation and sulfidation mechanism. The crystallization and reaction paths for oxide and sulfide formation were followed in-situ by energy dispersive X-ray diffraction (EDXRD) in an early stage of corrosion (30 s – 24 h). For this technique, high energetic white synchrotron X-ray radiation (10-100 keV) was used as radiation source. Diffraction pattern were collected continuously in an early stage of corrosion up to 24 h during the complete ageing experiment.
The crystalline phases, growing on top of the coupons, were identified directly via their specific dhkl values. The evolution of the extracted integral intensities of specific reflections of the corrosion products as a function of time access direct information about the kinetics of the nucleation and growth. The results presented here show for iron with 2 wt% Cr wuestite formation first. Wuestite vanishes after 10 min of reaction only and magnetite and hematite appear. Magnetite formation proceeds simultaneously with sulfide formation. Sulfides growth proceeds after an incubation time, which differs for low alloyed (2 wt% Cr) and high alloyed (9 wt% Cr) material.
Proben unterschiedlich wärmebehandelter, hochlegierter, rostfreier Stahlqualitäten, die potenziell als Injektionsrohr-Stähle eingesetzt werden können - AISI 420 X46Cr13, AISI 420J X20Cr13 und AISI 630 X5CrNICuNb16-4 - wurden bei 60 °C sowohl bei Normaldruck als auch bei 100 bar für 700 bis 8.000 Stunden in einem C02-gesättigtem, synthetisch hergestellten Laboraquiferwasser ausgelagert. Dieses Laboraquiferwasser entspricht der erwarteten Zusammensetzung des Aquiferwassers des norddeutschen Beckens, in das im CCS- Versuchsfeld von Ketzin (CCS Carbon Capture and Storage) über zwei Jahre hinweg technisch reines C02 injiziert wurde. Die Korrosionsraten und Schichtwachstumsraten auf den Stählen sind am niedrigsten für Stähle, die vor der Langzeitauslagerung gehärtet und anschließend zwischen 600 °C und 670 °C angelassen wurden. Lokale Korrosion (Lochfraß) zeigt sich in Form von kleinsten Löchern auf der Stahloberfläche. Der Durchmesser dieser Löcher nimmt mit steigendem Kohlenstoffgehalt des Stahls ab. Gleichzeitig nimmt die Anzahl der gezählten Löcher auf der Oberfläche zu. Insgesamt wird festgestellt, dass Stähle mit einer martensitischen Gefügestruktur in dieser nachempfundenen CCS-Atmosphäre die beste Korrosionsbeständigkeit gegenüber dem C02-gesättigten, salinen Aquifer bietet.
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.
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.
This work examined the droplet corrosion of CO2 pipeline steels caused by impurities in CO2 supercritical/dense phase at 278 K, simulating the underground transport condition. The wetting properties of carbon steels (X52 and X70) as well as martensitic steel UNS S41500, and superaustenite UNS N08031 were studied by contact angle measurement, revealing reactive wetting behavior of carbon steels. Exposure tests with CO2 saturated water droplet on steel surface showed that the impurities (220 ppmv SO2 and 6700 ppmv O2) diffused into the droplet and then reacted with metal coupons in supercritical/dense phase condition, forming the corrosion product instantly during pumping process. Due to the active wetting behavior, the carbon steels suffered from heavily attack, while negligible corrosion product was observed in cases of martensitic steel UNS S41500 and superaustenite UNS 08031 coupons. Condensation experiments that were carried out on fresh polished coupons in CO2 with 1200 ppmv H2O showed that the formation and aggregation of droplet is dependent on the presence of impurities. Without SO2 and O2, the same concentration of H2O did not cause observable corrosion process after a week of exposure. With 220 ppmv SO2 and 6700 ppmv O2 even low water concentration (5-30 ppmv) still resulted in heterogeneous nucleation and subsequent growth of droplets, leading to corrosive process on carbon steel surface albeit to a lesser extent.
In this work, the focus was set on the corrosion process of condensate as drops on the surface of carbon steels (X52, X70), martensitic steel UNS S41500, and superaustenite UNS N08031 in CO2 atmosphere with impurities at 278 K (to simulate the transportation condition in a buried pipeline). Exposure tests were performed at both normal pressure and high pressure where CO2 is supercritical or in dense phase. The drop, 1 ‑ 10 μL in volume, was prepared by dropping CO2 saturated ultra-pure water onto the surface of steel coupons in a one-liter-autoclave. The CO2 gas stream, simulating the oxyfuel flue gas with varying concentration of impurities (SO2 and O2 ), was then pumped into the autoclave to observe the condensation and corrosion impacts of impurities. Comparable exposure tests were carried out with the same gas mixture and the same volume of water as vapor to observe the drop formation and the corrosion process that follows. The wettability and stability of drops on the surface of steel coupons in CO2 supercritical/dense phase environment was evaluated additionally by contact angle measurement.
In CCS environment (carbon capture and storage) pipes are loaded statically and/or cyclically and at the same time exposed constantly to the highly corrosive hot thermal water. Experimental procedures such as ambient pressure immersions tests, in-situ corrosion fatigue experiments using a flexibly designed corrosion chamber at ambient pressure and a specially designed corrosion chamber at high pressure. Experimental set-ups for push/pull and rotation bending load are introduced. The corrosion behavior and lifetime reduction of high alloyed steels (X46Cr13, 1.4043), (X5CrNiCuNb16-4, 1.4542) and (X2CrNiMoN22-5-3, 1.4462) is demonstrated (T=60 °C, geothermal brine: Stuttgart Aquifer flow rate: 9 l/h, CO2 ).
During carbon sequestration the CO2-induced corrosion of injection pipe steels is a relevant safety issue when emission gasses are compressed into deep geological layers. The reliability of the high alloyed steel X35CrMo17 suitable as injection pipe for the geological onshore CCS-site (Carbon Capture and Storage) in the Northern German Basin, is demonstrated in laboratory experiments in equivalent corrosive environment (T = 60 °CC, p = 1–100 bar, aquifer water, CO2-flow rate of 9 L/h, 700–8000 h exposure time). Corrosion kinetics and microstructure were characterized and compared to other potential injection pipe steels (42CrMo4, X46Cr13, X20Cr13 and X5CrNiCuNb16-4).
Coupons of X5CrNiCuNb16-4 that may be used as injection pipe with 16% Chromium and 0.05% Carbon (1.4542, AISI 630) were exposed for 3000 h to CO2-saturated saline aquifer water similar to the conditions in the Northern German Basin at ambient pressure and 60 °C. Surface corrosion layers and pits reveal carbonate corrosion products on the surface such as FeCO3 and FeOOH as the main precipitation phases with no dependence on the original surface roughness. Corrosion rates for polished and technical surfaces were below 0.005 mm/year compared to corrosion rates of 0.035 mm/year after shot peening.
The commercial usage of latent thermal energy storages primarily depends on the development of a suitable phase change material (PCM). For industrial high temperature applications above 400 °C multicomponent chloride eutectics are promising and therefore discussed seriously. The profound thermodynamic investigation of such eutectics requires a much greater amount of specimen material than conventional calorimeter can handle. Therefore, a special adiabatic calorimeter was developed and designed. With a specimen mass of > 100 g the typical thermodynamic measurements with a commercial calorimeter can be extended by cycle stability measurements, which are often decisive for practical application of PCM. Furthermore, by implementing corrosion specimens inside the calorimeter high temperature corrosion experiments according to ISO 21608 can be performed inside the calorimeter. Adiabatic measuring conditions can be provided by using two separate heating systems. Therefore, the outer “protective system” follows the temperature curve of the inner “measuring system” minimizing the temperature difference between the heating systems and simultaneously preventing heat losses from the measuring systems.
The work presents the microstructure, chemical composition and mechanical properties of Inconel 686 coatings after high - temperature corrosion in environment of aggressive gases and ashes. To produce the Ni - based coatings the QS Nd:YAG laser cladding process was carried out. As the substrate used 13CrMo4-5 boilers plate steel. Ni - base alloys characterize the excellent high-temperature corrosion resistance, good strength and ability to work in aggressive environments. Formed clad were characterized by high quality of metallurgical bonding with the substrate material and sufficiently low amount of the iron close to the clad layer surface. After corrosion experiment the oxide scale on the substrate and clad created. The scale on 13CrMo4-5 steel had 70 μm thickness while the scale of the clad had less than 10 μm. The microstructure, chemical composition of the obtained clad and scales were investigated by scanning electron microscope (SEM) and electron probe microanalyzer (EPMA) equipped with the EDS detectors.
Specific amounts of oxidizing and reductive impurities as well as some moisture were added to dense phase CO2 to replicate CO2 streams from sources in a CCS pipeline network. Due to the moisture content being only 50 ppmV no visible acid condensation took place. To simulate stress conditions at the inside pipeline surface due to fluid pressure (10 MPa) specimens were preloaded using a load frame. Experiments conducted at 278 K and at 313 K revealed the highest corrosion rate at lower temperature. Corrosive effect of impurities was strongest applying mixed atmosphere, containing oxidizing and reductive components, closely followed by CO2 streams with pure oxidizing character. By far, the lowest corrosion rate (10x lower) resulted from reductive atmosphere. In general, at constant temperature and pressure the CO2 stream composition strongly influences the morphology, thickness and composition of the corrosion products. Applying oxidizing or mixed impurities, iron hydroxides or oxides (e.g. goethite, hematite) occur as dominating corrosion products, capable to incorporate different amounts of sulfur. In contrast, using reductive atmosphere very thin corrosion layers with low crystallinity were developed, and phase identification by XRD was unfeasible. SEM/EDX analysis revealed the formation of Fe-O compounds, most likely attributed to the oxygen partial pressure in the system induced by CO2 (≥0.985 volume fraction) and volatile H2O. In addition to the surface covering corrosion layer, secondary phases had grown locally distributed on top of the layer. These compounds are characteristic for the applied atmosphere and vary in number, shape and chemical composition.
Carbon Capture and Storage (CCS) is identified as an excellent technology to reach the target of CO2 reduction. However, the safety issue and cost effectiveness hinder the future of CCS. For the reliability and safety issues of injection wells the corrosion resistance of the materials used needs to be determined.
In this study, representative low cost materials including carbon steel 1.8977 and low alloyed steel 1.7225 were embedded in cement to mimic the realistic casing-cement interface. Electrochemical studies were carried out using these metal-cement specimens in comparison with those made of metal only in CO2 saturated synthetic aquifer fluid, at 333 K, to reveal the effect of cement on the steel performance. The results showed the protective effect of cement on the performance of pipeline metals during polarisation process. However, the corrosion current density was high in all cases, with and without cement, indicating that the corrosion resistance of these materials is low. This conclusion was supported by the surface analysis of the polarized specimens, which revealed both homogenous and pitting corrosions.
Pipe steels suitable for carbon capture and storage technology (CCS) require resistance against the corrosive environment of a potential CCS-site, e.g. heat, pressure, salinity of the aquifer, CO2-partial pressure. Samples of different mild and high alloyed stainless injection-pipe steels partially heat treated: 42CrMo4, X20Cr13, X46Cr13, X35CrMo4 as well as X5CrNiCuNb16-4 were kept at T=60 °C and ambient pressure as well as p=100 bar for 700 h - 8000 h in a CO2-saturated synthetic aquifer environment similar to possible geological on-shore CCS-sites in the northern German Basin. Main corrosion products are FeCO3 and FeOOH. Corrosion rates obtained at 100 bar are generally much lower than those measured at ambient pressure. Highest surface corrosion rates are 0.8 mm/year for 42CrMo4 and lowest 0.01 mm/year for X5CrNiCuNb16-4 in the vapour phase at ambient pressure. At 100 bar the highest corrosion rates are 0.01 mm/year for 42CrMo4, X20Cr13 (liquid phase), X46Cr13 and less than 0.01 mm/year for X35CrMo4 and X5CrNiCuNb16-4 after 8000 h of exposure with no regard to atmosphere. Martensitic microstructure offers good corrosion resistance.
This work presents the microstructure and chemical composition of oxide scales created on Ni – base coating after corrosion experiments in aggressive gases and ashes. The Inconel 686 coating applied on the low carbon steel 13CrMo4-5 was performed by a CO2 laser cladding process. The experiments were carried out in oxidizing gas atmospheres containing O2, COx, SOx. The second Variation of corrosion experiments were performed in a reducing atmosphere with ashes containing elements such as: Na, Cl, Ca, Si, C, Fe, Al etc. After 240 h and 1.000 h corrosion experiments the oxide scales on the substrate and overlay were created in both cases.
The sulfur compounds were found on the top of the coating surface (EPMA) and also higher contents of silica compounds were revealed on specimens covered by ashes during the experiments. The microstructure and chemical composition of the clad and scales were investigated by means of a light microscope and an electron microscope (SEM)equipped with an EDS detector.
Immersion tests of potential injection pipe steels 42CrMo4, X20Cr13, X46Cr13, X35CrMo4 and X5CrNiCuNb16-4 at T=60 °C and ambient pressure and p=100 bar were performed for 700 h - 8000 h in a CO₂-saturated synthetic aquifer environment similar to CCS-sites in the Northern-German-Basin. Main corrosion products are FeCO₃ and FeOOH. Highest surface corrosion rates at ambient pressure are 0.8 mm/year for 42CrMo4 and lowest 0.01 mm/year for X5CrNiCuNb16-4. Corrosion rates at 100 bar (max. 0.01 mm/year for 42CrMo4, X20Cr13, X46Cr13) are generally lower than at ambient pressure (<0.01 mm/year for X35CrMo4, X5CrNiCuNb16-4). Heat treatment to martensitic microstructure offers good corrosion resistance.
In CCS environment (carbon capture and storage) pipes are loaded statically and/or cyclically and at the same time exposed constantly to the highly corrosive hot thermal water. Experimental procedures such as ambient pressure immersions tests, in-situ corrosion fatigue experiments using a flexibly designed corrosion chamber at ambient pressure and a specially designed corrosion chamber at high pressure. Experimental set-ups for push/pull and rotation bending load are introduced. The corrosion behavior and lifetime reduction of high alloyed steels (X46Cr13, 1.4043), (X5CrNiCuNb16-4, 1.4542) and (X2CrNiMoN22-5-3, 1.4462) is demonstrated (T=60 °C, geothermal brine: Stuttgart Aquifer flow rate: 9 l/h, CO₂).