Nachdem im Verbundprojekt COORAL das Hauptaugenmerk auf überkritisches CO2 gelegt wurde, d. h. Transport über kurze Strecken bei erhöhter Temperatur, wurde in CLUSTER ein größeres lokales Transport-Netzwerk betrachtet, bei dem CO2 bei geringeren Temperaturen, also vorwiegend im flüssigen Zustand transportiert wird. Wurden in COORAL die CO2-Ströme von Kohlekraftwerken untersucht, ging es in CLUSTER zusätzlich um die Emissionen von relevanten Industrien, deren CO2-Emissionen nicht ohne Weiteres vermieden werden können.
Aufgrund der Erfahrungen in COORAL konnte eine Auswahl von kommerziellen Werkstoffen getroffen werden, die für einen konkreten Einsatz für CCS zur Verfügung stünden. Die gemischten und fluktuierenden CO2-Zusammensetzungen sind bei geeigneten Begrenzungen der Begleit¬stoffe im CO2 bezüglich Korrosionsvorgänge beherrschbar. Die Machbarkeit eines lokalen CCS-Clusters erscheint daher gegeben, soweit dies die Anlagen für Kompression, Transport und Injektion betrifft.
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.
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.
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 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.
To mitigate carbon dioxide emissions CO2 is compressed and sequestrated into deep geological layers (Carbon Capture and Storage CCS). The corrosion of injection pipe steels is induced when the metal is in contact with CO2 and at the same time the geological saline formation water. Stainless steels X35CrMo17 and X5CrNiCuNb16-4 with approximately 17% Cr show potential as injection pipes to engineer the Northern German Basin geological onshore CCS-site. Static laboratory experiments (T = 60 ◦C, p = 100 bar, 700–8000 h exposure time, aquifer water, CO2-flow rate of 9 L/h) were conducted to evaluate corrosion kinetics. The anomalous surface corrosion phenomena were found to be independent of heat treatment prior to exposure. The corrosion process is described as a function of the atmosphere and diffusion process of ionic species to explain the precipitation mechanism and better estimate the reliability of these particular steels in a downhole CCS environment.
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.
Corrosion fatigue specimen with different surfaces (technical surfaces after machining and polished surfaces) of high alloyed martensitic stainless steel X46Cr13 (1.4043) and duplex stai nless steel X2CrNiMoN22 3 2 (1.4462) were compared at load amplitudes from 175 MPa to 325 MPa in the geothermal brine of the N orthern German Basin at 98 °C. Surface corrosion layers and pits reveal carbonate corrosion products on the surface such as FeCO 3 and FeOOH as the main precipitation phases with no dependence on the original surface roughness . At high stress amplitudes above 275 MPa technical surfaces (P50% at σa 300 MPa=5 × 10 5 ) resulted in more cycles to failure than polished (P50% at σa 300 MPa=1.5 × 10 5 ). The greater slope coefficient for technical surfaces k = 19.006 compared to polished surfaces k =8.78 demonstrate s earlier failure at given stress amplitude σa .