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Mechanical stress often accelerates the failure of polymer materials. The aim of this research is to study the interaction between the sealing material FKM and biofuels B10 (heating oil with 10% biodiesel). The mechanical stress test was carried out in a special apparatus. Both mechanical and non-mechanical stress tests were conducted on specimens at 20, 40, and 70 °C for 28 days to document changes in mass, volume, and tensile properties. Both increasing temperature and mechanical stress have a significant effect on the tensile strength of the FKM polymer when exposed to B10. The combination of increasing temperature and mechanical stress induced rupture within 2 h. It was also established that FKM polymer with pre-exposure in B10 survived longer during mechanical stress compared to specimens exposed only to air. With the support of infrared (IR) spectroscopy, we were able to confirm the penetration of B10 into the FKM polymer.
Since 2016 ISO Technical Committee (TC) 265 is working on standardization the whole CCS-process chain. Around 30 countries are working together to provide international guidelines. As ISO 27913 was the first standard finished within these activities it is already in the stage of first revision.
The objective of ISO 27913 is “to provide specific requirements and recommendations on certain aspects of safe and reliable design, construction and operation of pipelines intended for the large-scale transportation of CO2 that are not already covered in existing pipeline standards such as ISO 13623, ASME B31.8, EN 1594, AS 2885 or other standards. Existing pipeline standards cover many of the issues related to the design and construction of CO2 pipelines; however, there are some CO2 specific issues that are not adequately covered in these standards. The purpose of this document is to cover these issues consistently. Hence, this document is not a standalone standard, but is written to be a supplement to other existing pipeline standards for natural gas or liquids for both onshore and offshore pipelines.”
This contribution shall provide information on the content, the current stage of the revision process, encourage to contribute to this standard and make listeners aware to consider the influence of ISO standard on documents currently in draft.
Das gesellschaftliche Ziel der Defossilisierung der Energieversorgung erfordert eine disruptive Veränderung der Wärmebereitstellung. In Berlin und in den größten Brandenburger Städten Potsdam und Cottbus werden noch über 80 % der Nutzwärme über fossile Energieträger bereitgestellt. Die notwendigen Veränderungen erfordern Lösungen, die den tiefen Untergrund der Region nutzen. Allein die Nutzung der tiefen Geothermie kann mindestens 25% des Wärmebedarfs in Deutschland decken. Die Infrastruktur zur Verteilung dieser erneuerbaren Wärme ist bereichsweise vorhanden. Sie muss allerdings lokal und in ländlichen Gebieten weiter ausgebaut werden.
Für die Sektoren Strom und Verkehr steht zwar Energie insbesondere aus Sonne und Wind bereit, aber wegen des zeitlich variablen Angebots besteht ein erheblicher Bedarf an großtechnischen Speichern für Strom und Wärme oder auch für Energieträger (z. B. Wasserstoff). Die saisonale oder temporale Überproduktion an Strom und Wärme aus erneuerbaren Energien zwingt dazu, eine urbane Speicherinfrastruktur aufzubauen, um eine grundlastfähige und bedarfsgerechte Lieferung zu realisieren. Hinzu kommt die Aufgabe das Treibhausgas Kohlendioxid aus der Atmosphäre zu reduzieren und unterirdisch dauerhaft zu lagern. Auch hier werden Speichertechnologien und ‐räume benötigt.
Die nachhaltige energetische Nutzung des unterirdischen Raumes ist geeignet, entscheidende Beiträge zu einer zukünftigen Energiewirtschaft ohne fossile Brennstoffe zu leisten. Diese große interdisziplinäre Aufgabe erfordert die Zusammenarbeit vieler Fach‐, und Forschungseinrichtungen, die im Raum Berlin‐
Brandenburg vorhanden sind und in einer regionalen Forschungsallianz gebündelt werden sollen. Für die Region Berlin‐Brandenburg ergibt sich daraus die Chance, eine Schlüsselrolle in der Grundlagen‐ und angewandter Forschung zur Transformation des Energiesystems zu übernehmen und weltweit als Vorbild zu dienen.
Im vorliegenden Papier werden die Formen einer nachhaltigen Geoenergienutzung, das geologische Potenzial der Region Berlin Brandenburg und dessen bisherige geoenergetische Nutzung dargestellt. Aus diesem Wissen wird der Ist‐Zustand hinsichtlich des energiewirtschaftlichen Potenzials und der sich daraus ergebenden Nutzungsoptionen abgeleitet, um darauf aufbauend Maßnahmen darzustellen, mit denen spürbare Beiträge zur Dekarbonisierung erreicht werden können. Daraus ergeben sich Handlungsempfehlungen für die Region, verbunden mit einem möglichen Beitrag der GEB² zum Risikomanagement, Investitionen in Schlüsseltechnologien, der Aus‐ und Weiterbildung, sowie der Akzeptanzerhöhung für geoenergetische Projekte.
Since geothermal wells are a feasible energy source to replace fossil fuel supply, many technologies have been developed to take advantage of geothermal energy. Nevertheless, service conditions in geothermal facilities are in many cases extreme in terms of corrosion due to the chemical composition of hydrothermal fluids and temperatures. Therefore, materials selection based on preliminary material qualification is essential to guarantee a secure and reliable operation of the facilities. During operation of a geothermal research facility in Groß Schönebeck copper and lead effects have been found downhole. Occurring mechanisms and measures to prevent precipitation or scaling needed to be investigated as well as potential influences of such precipitates on corrosion resistance of metallic materials used for equipment.
This contribution deals with the evaluation of the corrosion behavior of carbon steel and corrosion resistant alloys in copper and/or lead containing artificial geothermal water, simulating the conditions in the Northern German Basin.
The behavior of these materials in an artificial geothermal water obtained by electrochemical measurements and exposure tests are presented. While carbon steel exhibits precipitation and deposition, higher alloyed material shows different response to such species and a higher resistance in saline geothermal water.
Basing on these results the suitability of the investigated corrosion resistant alloy is given for use in such conditions, whereas carbon steel creates difficulties due to its susceptibility to Cu- and Pb-precipitation.
Corrosive geothermal brines are a major challenge to geothermal power-plants. For cost reasons, plant designers favorize low alloyed steels, e.g., carbon steel, which are susceptible to uniform and localized corrosion when exposed to geothermal brines having acidic and saline properties. To solve such problem, coatings or inhibitors would be a protective solution as an alternative to the use of high alloyed materials.
This study investigated a coating system consisting of polyaniline/silicon dioxide basing on locally available resources. Protection against corrosion of carbon steel is shown by long-term exposure and electrochemical tests of coated carbon steels, performed in an artificial acidic and saline geothermal brine, comparable to real conditions at a site in Indonesia.
Therefore, an integrated coating system is presented for corrosion protection, combining the electro-chemical functionality of polyaniline and the physical advantages of silica.
Integrated Coating System for Corrosion Protection of Carbon Steel in Artificial Geothermal Brine
(2022)
Corrosive geothermal brines are a major challenge to geothermal power-plants. For cost reasons, plant designers prefer to use carbon and low alloyed steels, which are susceptible to uniform and localized corrosion when exposed to geothermal brines having acidic and saline properties. To solve such problem, coatings or inhibitors would be a protective solution as an alternative to the use of high alloyed materials.
This study investigated a coating system consisting of polyaniline/silicon dioxide based on resources locally available in Indonesia. Protection against corrosion of carbon steel was shown by long-term (28 day) exposure and electrochemical tests of coated carbon steels, performed in an artificial acidic and saline geothermal brine, comparable to the conditions encountered at a site in Indonesia.
Therefore, an integrated coating system is proposed for corrosion protection, combining the electrochemical functionality of polyaniline and the physical advantages of silica.
To reveal the corrosion resistance of casing steel/mortar interface in CO2 injection condition, sandwich samples were prepared and exposed up to 20 weeks in aquifer fluid under 10 MPa and 60 °C. Cross section analysis revealed the crevice corrosion as main mechanism instead of pitting corrosion, which would be expected to happen in the extremely high Chloride concentration. Detailed analysis using EDS line scan shown the slow diffusion of Chloride, suggesting why pitting did not happen after 20 weeks. To mimic the passivated steel surface, the steel coupon was passivated in simulated pore solution having pH 13.5 for 42 days. The passivated coupon was further exposed to NGB solution for 28 days. Electrochemical characterization was performed along the exposure processes to reveal the change in impedance, indicating the corrosion resistance of steel casing/mortar interface.
Influence of Precipitating Brine Components on Materials Selection for Geothermal Applications
(2021)
Since geothermal wells are a feasible energy source to replace fossil fuel supply, many technologies have been developed to take advantage of geothermal energy. Nevertheless, service conditions in geothermal facilities are in many cases extreme in terms of corrosion due to the chemical composition of hydrothermal fluids and temperatures. Therefore, materials selection based on preliminary material qualification is essential to guarantee a secure and reliable operation of the facilities. During operation of a geothermal research facility in Groß Schönebeck copper and lead effects have been found downhole. Occurring mechanisms and measures to prevent precipitation or scaling needed to be investigated as well as potential influences of such precipitates on corrosion resistance of metallic materials used for equipment.
This contribution deals with the evaluation of the corrosion behavior of carbon steel and corrosion resistant alloys in copper and/or lead containing artificial geothermal water, simulating the conditions in the Northern German Basin.
The behavior of these materials in an artificial geothermal water obtained by electrochemical measurements and exposure tests are presented. While carbon steel exhibits precipitation and deposition, higher alloyed material shows different response to such species and a higher resistance in saline geothermal water.
Basing on these results the suitability of the investigated corrosion resistant alloy is given for use in such conditions, whereas carbon steel creates difficulties due to its susceptibility to Cu- and Pb-precipitation.
Biodiesel (FAME) from rapeseed is an environmentally friendly alternative to common fossil fuels. It is also suitable to serve as blending component to fuels like heating oil. If the fuel composition is changed, materials compatibility must be guaranteed. Adding polar biodiesel to nonpolar heating oil, changes the blend’s solvency and might cause swelling, extraction and solvation of polymers. The objective of this research was to investigate the compatibility of polymeric materials, which are commonly used for components in middle distillate facilities, along with blends of heating oil and 20 % biodiesel (B20). For this propose, ACM, HNBR, FKM, PE, PA 6, POM, PUR and PVC were exposed to heating oil and B20 for 42 and 84 days at 40 °C. In addition, the polymers HNBR, FKM, PA, POM and PVC were also exposed at 70 °C. Furthermore, the resistance of polymers in eight-year aged B10 at 40 °C was evaluated. Ageing of biodiesel increases acidity which might propagate polymer corrosion. The materials were evaluated as resistant, if the loss in tensile properties (tensile strength and elongation at break) and Shore hardness remained under 15 % compared to the initial unexposed material values. For investigations under compressed conditions, the compression set was determined for specimens of ACM, FKM and HNBR after exposure in heating oil B0 and B20 for 3,7,14, 28, 56 and 90 days at 40 °C according to ISO 815-1. It was found that the resistance in B20 at 40 °C was given for all tested polymers except PUR. In the 8 years aged B10, PUR and POM were not compatible and ACM just conditionally compatible. At 70 °C, FKM and PVC were resistant in B20, whereas HNBR and PA 6 were not compatible. Swelling occurred for the elastomers ACM, HNBR and PUR.
The collaborative project “Impacts of impurities in CO2 streams captured from different emitters in a regional cluster on transport, injection and storage (CLUSTER)” aimed to set up recommendations on how to define “reasonable minimum composition thresholds” that CO2 streams should meet when accessing CO2 transport pipeline networks. Within CLUSTER, we investigated potential impacts of CO2 streams with different and temporally variable compositions and mass flow rates along the whole CCS chain. Investigations included, amongst others, impacts on: Corrosion of pipeline steel, pipeline network design and related transport costs, alteration of well bore cements, pressure development and rock integrity, geochemical reactions, and petrophysical and geomechanical rock properties.
All investigations are based on a generic CCS chain scenario. In this scenario, CO2 streams are captured from a spatial cluster of eleven emitters and collected in a regional pipeline network. Emitters comprise seven fossil fuel-fired power plants equipped with different capture technologies, two cement plants, one refinery and one integrated iron and steel plant. In total, 19.78 Mio t CO2 (including impurities) are captured in the emitter cluster annually. The combined CO2 stream is transported in a trunk line with a length of 400 km (100 km of these offshore) and is injected into five generic storage structures. The storage reservoirs are saline aquifers of the Buntsandstein.
The investigations revealed beneficial and deteriorating impacts of different impurities and combinations thereof. Overall, no fundamental technical obstacles for transporting, injecting and storing CO2 streams of the modelled variable compositions and mass flow rates were observed. Based on the results, the CLUSTER project team recommends not to define “minimum composition thresholds” for CO2 streams as strict threshold values for each individual impurity in the stream. Instead, CO2 stream compositions and variabilities for specific CCS projects should be constrained with regard to a set of parameters including i) the overall CO2 content, ii) maximum contents of relevant impurities or elements, iii) acceptable variability of CO2 stream composition, and iv) impurity combinations to be avoided.
Al2O3 coatings are often used as protective layers on steels against electrochemical and high-temperature corrosion because they are chemically inert and stable at elevated temperatures. This study presents preliminary work on the possibilities of using Al2O3 sol-gel coatings for corrosion protection of martensitic stainless steels in geothermal environments. Al2O3 sol-gel coatings were applied on UNS S42000, which is known to be susceptible to uniform and localized corrosion. The coated steel specimens were then tested in two types of artificial geothermal water, which simulate the geothermal fluids found in Sibayak (SBY), Indonesia, and North German Basin (NGB), Germany, respectively. SBY has pH 4 and 1.5 g/L of chloride ions, whereas NGB has a pH of 6 and 166 g/L of chloride ions. All experiments were carried out in autoclaves at 150 °C and 1 MPa under the deaerated condition. Evaluations were performed by investigating the surface profiles of both uncoated and coated steels before and after the corrosion test using a Laser Scanning Microscope (LSM) and Scanning Electron Microscope (SEM). Finally, Electrochemical Impedance Spectroscopy (EIS) was performed to compare the corrosion resistance of Al2O3 coated steels in SBY and NGB solutions. It was observed from the corrosion test that Al2O3 coatings are more suitable for use in the geothermal water with a higher pH.
The collaborative project “Impacts of impurities in CO2 streams captured from different emitters in a regional cluster on transport, injection and storage (CLUSTER)” aimed to set up recommendations on how to define “reasonable minimum composition thresholds” that CO2 streams should meet when accessing CO2 transport pipeline networks. Within CLUSTER, we investigated potential impacts of CO2 streams with different and temporally variable compositions and mass flow rates along the whole CCS chain. Investigations included, amongst others, impacts on:
• corrosion of pipeline steel,
• pipeline network design and related transport costs,
• alteration of well bore cements,
• pressure development and rock integrity,
• geochemical reactions, and
• petrophysical and geomechanical rock properties.
All investigations are based on a generic CCS chain scenario. In this scenario, CO2 streams are captured from a spatial cluster of eleven emitters and collected in a regional pipeline network. Emitters comprise seven fossil fuel-fired power plants equipped with different capture technologies, two cement plants, one refinery and one integrated iron and steel plant. In total, 19.78 Mio t CO2 (including impurities) are captured in the emitter cluster annually. The combined CO2 stream is transported in a trunk line with a length of 400 km (100 km of these offshore) and is injected into five generic storage structures. The storage reservoirs are saline aquifers of the Buntsandstein.
The investigations revealed beneficial and deteriorating impacts of different impurities and combinations thereof. Overall, no fundamental technical obstacles for transporting, injecting and storing CO2 streams of the modelled variable compositions and mass flow rates were observed. Based on the results, the CLUSTER project team recommends not to define “minimum composition thresholds” for CO2 streams as strict threshold values for each individual impurity in the stream. Instead, CO2 stream compositions and variabilities for specific CCS projects should be constrained with regard to a set of parameters including i) the overall CO2 content, ii) maximum contents of relevant impurities or elements, iii) acceptable variability of CO2 stream composition, and iv) impurity combinations to be avoided.
Study of Polyaniline/Silicon Dioxide based Coating on Carbon Steel in Artificial Geothermal Brine
(2021)
Geothermal brines are corrosive in nature because of their salt contents and high temperatures. Therefore, they pose a major challenge to geothermal power-plants, which are mostly built of low alloyed steels, e.g., carbon steel. Carbon steel is susceptible to uniform and localized corrosion when exposed to geothermal brines having acidic-saline properties. To overcome this limitation, geothermal power plants should be built by either high alloyed materials or by integrating protection systems on carbon steel, such as coatings and inhibitors. We studied a coating system containing polyaniline/silicon dioxide basing on locally available resources that provides protection against corrosion of carbon steel and enhance the thermal resistance in geothermal environments. Here, exposure and electrochemical tests of coated carbon steels were performed in an artificial geothermal brine. The solution had a pH of 4, with the composition of 1,500 mg/L of chlorides, which is based on the chemical analysis of geothermal brine found in Sibayak, Indonesia. All exposure tests were conducted using autoclaves at 150 °C with a total pressure of 1 MPa, which was performed for up to six months to evaluate the durability of the coating system. Post-experimental analyses were performed by assessing the surface of specimens using optical and electron microscopes. On the other hand, electrochemical tests were performed for seven days at 25 °C and 150 °C to investigate the kinetics of electrochemical reactions by measuring open circuit potential and electrochemical impedance spectra. Experimental results showed the corrosion resistance of PANI/SiO2 composite coatings, where polyaniline and SiO2 play their roles as stabilizers.
Carbon Capture Utilization and Storage (CCUS) is a promising technology to reach the target for 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 whole process chain, including separation of CO2 from the source, compression of CO2, its subsequent transportation to the injection site and injection into geological formations, e.g. aquifers.
Most components that are in contact with CO2-stream consist of steel. Depending on the operating conditions (e.g. temperature, pressure, and CO2-stream composition) specific suitable steels should be used. The compressed CO2-stream is likely to contain process specific impurities; small amounts of SO2 and NO2 in combination with oxygen and water are most harmful.
One approach, as currently preferred by pipeline operators, is to clean the CO2-stream to such levels, acceptable for carbon steel, commonly used as pipeline material. Another consideration would be, to use more corrosion resistant alloys for CO2-streams with higher amounts of impurities.
Due to the absence of certified benchmarks for upper limits, systematic experiments with impurities in the CO2-stream were carried out reflecting mainly transport and injection conditions.
Within the COORAL project (German acronym for “CO2 purity for capture and storage”) levels of impurities in the CO2-stream, being acceptable when using specific steels, were evaluated. Material exposure to dense or multiphase carbon dioxide (CO2) containing specific amounts of water vapor, oxygen (O2) sulfur dioxide (SO2), nitrogen dioxide (NO2), carbon monoxide (CO) can be a challenge to steels. In some situations, condensation of impurities and reaction products from the CO2 stream can occur.
CO2 saturated brine is supposed to rise in the well when the injection process is interrupted. The material selection shall ensure that neither CO2 nor brine or a combination of both will leak out of the inner tubing.
This COORAL-work was extended by a follow-up project, called CLUSTER. Here the additional influence of impurities was investigated when merging CO2 streams from different sources, combined within a “so-called” cluster.
Results are summarized within the following table regarding suitability for different parts of the process chain.
Im Vorhaben wurde eine forcierte Prüfmethode zur Bestimmung der Beständigkeit von metallenen Werkstoffen gegenüber Brennstoffen aus Mitteldestillaten und Gemischen aus Mitteldestillat und paraffinischen Kohlenwasserstoffen, die jeweils Fettsäuremethylester (FAME) als biogene Komponente enthalten, entwickelt. Bei der Prüfmethode werden Prüfkörper des jeweiligen Werkstoffes in speziellen Prüfmedien ausgelagert. Die Zusammensetzung von zwei Prüfmedien wurde im Vorhaben erarbeitet. Diese Prüfmedien erfassen die Effekte der Alterung des FAME, die zu erwarten sind, wenn der Brennstoff länger als 2 Jahre im Feld lagert. Sie decken den Bereich bis 20 % (V/V) FAME-Anteil ab. Die Auslagerung kann bei geringem Aufwand unter Atmosphärendruck durchgeführt werden.
Die Eignung einer Auswahl von metallenen Werkstoffen und Polymerwerkstoffen, die für Versorgungsanlagen für Mitteldestillat relevant sind, wurde durch Auslagerung in folgenden nicht gealterten Brennstoffen bestimmt: Heizöl EL schwefelarm (B0), Heizöl EL schwefelarm mit 20 % (V/V) FAME (B20), FAME (B100) und hydriertes Pflanzenöl (HVO). Die Werkstoffe wurden auch in einem 1 Jahr gealterten B20 und einem 8 Jahre gealtertem B10 ausgelagert. Die Temperatur bei der Auslagerung betrug 50 °C für die metallenen Werkstoffe und 40 °C und 70 °C für die Polymerwerkstoffe. Die Ergebnisse der Beständigkeitsbewertung wurden in Beständigkeitslisten zusammengefasst. Die mit B20 erhaltenen Bewertungen gelten generell für Gemische aus Heizöl EL schwefelarm und FAME mit einem FAME-Gehalt bis 20 % (V/V). Sie sind auch auf Gemische aus Dieselkraftstoff und FAME mit einem FAME-Gehalt bis 20 %(V/V) übertragbar.
Die forcierte Prüfmethode kann insbesondere KMUs bei der Weiterentwicklung von bestehenden Produkten und der Entwicklung von neuen Produkten als ein kostengünstiger Schnelltest zur Überprüfung der Werkstoff- und Bauteilbeständigkeit gegenüber Mitteldestillaten mit hohem FAME-Anteil dienen. Sie kann für die Hersteller die Sicherheit erhöhen, dass Bauteile die Freigabeprüfungen der Bauaufsicht bestehen, wobei die Freigabe jedoch nur für Deutschland gültig ist.
Die Erkenntnisse des Forschungsvorhabens können in eine harmonisierte Europäische Norm für alternative Brenn- und Kraftstoffe einfließen. Diese ist für die Bauteilhersteller die Voraussetzung für die Erschließung des europäischen Marktes.
By exposure and electrochemical tests in the laboratory the Cu-effect on corrosion behavior of carbon steel, high-alloyed steels and Ti-alloy can be assessed.
Critical materials specific properties were determined by static exposure and electrochemical tests in an artificial geothermal water with high salinity and low pH, containing Cu. Conclusions were drawn using characteristic potential values.
It could be shown that significant Cu-deposition and -precipitation only occurred in combination with carbon steel. High-alloyed materials (S31603, S31653, S31700, S31703, S31803 and N08904) prevent the disturbing Cu-agglomeration. Therefore, they are suitable to be chosen for future design of the piping system, either in massive or in cladded form, if formation of crevices with non-metallic materials can be excluded.
From the interactions and pitting corrosion point of view, R50400 seems to be most favorable.
According to the results of the experiments carried out, the following points can be concluded:
1. Exposure tests showed that specimens with the addition of SiO2 particles and polyaniline particles exhibit better corrosion resistance than specimens with the addition of only polyaniline particles or binder only.
2. Open circuit potential measurements showed that in the beginning of the experiments, both coatings had an open circuit potential 100 mV higher than carbon steel. Within one day of immersion, the potential of carbon steel increased significantly, indicating the formation of oxide layer. After extended exposure the carbon steel potential sat between PS1 (which had higher potential) and PS2 (which had a lower potential) and all three were in the range –600 mV to –500 mV vs Ag/AgCl.
3. Both coatings PS-1 and PS-2 were degraded with increasing exposure time, shown by the decrease of absolute impedance value at low frequency range after 2, 4, and 6 days exposure.
4. Potentiodynamic test was performed after 3 hours and 6 days exposure, and it was shown that the coating in the initial stage exhibited more passive behavior than the specimens exposed for 6 days.
Recent studies have shown that even at a very low concentration of impurities (less than 100 ppmv of SO2, NO2, O2 and H2O) the droplet formation and condensation of sulfuric and nitric acids in dense phase CO2 are possible and observable. To reveal the mechanism of droplet corrosion in dense phase CO2 at high pressure and low temperature, further studies on factors that affect wettability and resulting corrosion behaviors of transport pipeline steels are needed. In this study, effects of surface morphology were investigated by varying surface roughness of carbon steel coupons exposed to CO2 stream containing impurities to measure the wettability by contact angle and to observe the condensation as well as possible droplet corrosion that followed. Other considered factors were: pH of the droplet, temperature, droplet volume, and exposure time.
Geothermal energy is one of the most promising energy resources to replace fossil fuel. To extract this energy, hot fluids of various salts and gases are pumped up from a geothermal well having a certain depth and location. Geothermal wells in volcanic regions often contain highly corrosive CO2 and H2S gases that can be corrosive to the geothermal power-plants, which are commonly constructed of different steels, such as carbon steel. This research focuses on the corrosion behaviour of carbon steel exposed to an artificial geothermal fluid containing CO2 gas, using an artificial acidic-saline geothermal brine as found in Sibayak, Indonesia. This medium has a pH of 4 and a chloride content of 1,500 mg/L. Exposure tests were conducted for seven days at 70 °C and 150 °C to simulate the operating temperatures for low and medium enthalpy geothermal sources. Surface morphology and cross-section of the specimens from the above experiments were analysed using scanning electron microscope (SEM) and energy dispersive X-ray (EDX). Electrochemical tests via open circuit potential (OCP) and electrochemical impedance spectroscopy (EIS) were performed to understand the corrosion processes of carbon steel in CO2-containing solution both at 70 °C and 150 °C. Localized corrosion was observed to a greater extent at 70 °C due to the less protectiveness of corrosion product layer compared to that at 150 °C, where FeCO3 has a high corrosion resistance. However, a longer exposure test for 28 days revealed the occurrence of localized corrosion with deeper pits compared to the seven-day exposed carbon steel. In addition, corrosion product transformation was observed after 28 days, indicating that more Ca2+ cations incorporate into the FeCO3 structure.
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 investigated in simulated pore water at 333 K and under CO2 saturation condition to represent the worst-case scenario: CO2 diffusion and aquifer fluid penetration. These simulated pore waters were made from relevant cement powder to mimic the realistic casing-cement interface. Electrochemical studies were carried out using the pore water made of cement powder dissolved in water in comparison with those dissolved in synthetic aquifer fluid, to reveal the effect of cement as well as formation water on the steel performance. Two commercially available types of cement were investigated: Dyckerhoff Variodur® and Wollastonite. Variodur® is a cement containing high performance binder with ultra-fine blast furnace slag which can be used to produce high acid resistance concrete. On the other hand, Wollastonite is an emerging natural material mainly made of CaSiO3 which can be hardened by converting to CaCO3 during CO2 injection.
The results showed the pH-reducing effect of CO2 on the simulated pore water/aquifer (from more than 10 to less than 5) leading to the active corrosion process that happened on both 1.8977 and 1.7225. Electrochemical characterization showed negative free corrosion potential and polarisation curves without passive behaviors. The tested coupons suffered from pitting corrosion, which was confirmed by surface analysis. Interestingly, basing on the pit depth measurements from the tested coupons and the hardness of cement powder, it is suggested that Variodur® performed better than Wollastonite in both aspects. The electrochemical data was compared to that resulted from exposure tests to give a recommendation on material selection for bore-hole construction.
This contribution provides current findings regarding materials susceptibility for carbon capture, utilization and storage (CCUS) applications. Basing on results gathered in 2 German long-term projects (COORAL and CLUSTER) suitable materials are introduced as well as dominating impurities of the CO2-stream and corrosion mechanisms. Investigations cover the whole CCUS process chain and provide material recommendations for certain parts.
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.
The electrochemical behavior of UNS(1) N08031 was investigated as a function of electrode potential in Green-Death(2) solution at 40 °C. The UNS N08031 surface is in a stable passive state during cyclic potentiodynamic polarization without an initiation and/or propagation of localized corrosion. In potentiostatic polarization of UNS N08031 for 3600 s, passive current density increases with an increase in the passivation potential from 0.7 to 1.0 VSSE (silver/silver chloride reference electrode in saturated potassium chloride) Electrochemical impedance spectroscopy (EIS) and Mott-Schottky (M-S) analysis showed that a more defective n-type semiconductive passive film forms as the potential increases. X-ray photoelectron spectroscopy (XPS) revealed that passive film consists of mainly chromium and minor iron and nickel oxides. The mechanism of the defective passive film formation is discussed. The increase of the applied potential is considered to be a reason for the change in passive film stability.
Geothermal brine is a complex system containing a wide variety of dissolved salts resulting from the condition s in a geothermal well. These fluids lead to corrosion in pipes and other parts of geothermal system construction and necessitate intense research efforts in finding new suitable materials. Carbon steel is susceptible to corrosion in geothermal brine especially when it is exposed to a high temperature and high-pressure medium, which is considered to be an aggressive environment. An artificial geothermal water, bas ed on a brine composition found in Indonesia, was used to investigate the performance of high alloyed materials. The electrolyte has pH 4 and contains 1,500 mg/l Cl-, 20 mg/l SO4 2-, 15 mg/l HCO3 -, 200 mg/l Ca 2+, 250 mg/l K+, and 600 mg/l Na+. In order to protect the bare material in geothermal application, it is necessary to either use high alloyed material s or coatings. In this research, a coating system consisting of polyaniline and silicon dioxide was investigated regarding its behavior to protect carbon steel. In detail, the effect of SiO2 and polyaniline (PANi) addition was evaluated by exposure and electrochemical tests for 7 days, i.e. electrochemical impedance spectroscopy (EIS) and open circuit potential (OCP ) at room temperature and 150 °C with 1 MPa pressure .
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.
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.
Corrosion Resistance of the Super-Austenitic Stainless Steel UNS S31266 for Geothermal Applications
(2017)
Super-austenitic stainless steels cover grades with high chromium (20 to 27 %), high nickel (18 to 31 %) and high molybdenum (4 to 6 %) contents. Within this family, the 6%Mo high nitrogen grade S31266 was developed to combine the beneficial influence of chromium, tungsten, molybdenum and nitrogen on its mechanical and corrosion properties. Due to 22 % nickel, 24 % chromium and 0.4 % nitrogen additions, this alloy exhibits a very stable microstructure, being less prone to intermetallic phase precipitation than the other highly alloyed super-austenitic stainless steels.
This paper deals with the corrosion resistance of S31266 in artificial geothermal water with moderate salinity and low pH. Long-term static exposures and electrochemical tests were conducted at various temperatures to evaluate the pitting, crevice and stress corrosion cracking resistance of this material.
The results show that S31266 is resistant up to 220 °C. As a consequence, it can be a good candidate material for geothermal applications involving a highly corrosive environment, especially salinity and low pH.
CCUS-Technologie (CO2-Abtrennung; Nutzung und Speicherung, engl. Carbon Dioxide Capture, Utilization and Storage) gilt als eine vielversprechende Methode zur Abschwächung des Beitrags von fossilen Emissionen zur globalen Erwärmung. Dabei wird das in den Verbrennungsprozessen entstandene Treibhausgas aufgefangen, zu verschiedenen Lagerstätten transportiert und langzeitig gespeichert bzw. einer chemischen Nutzung zugeführt.
In bisher veröffentlichten Untersuchungen wurde gezeigt, dass die CO2-Transport-Pipelines in hohem Maße gefährdet sind, wenn sie korrosiven Begleitstoffen des CO2-Stroms, wie SOx, NOx bei einem hohen Wasserdampfanteil ausgesetzt sind. Screening-Tests zeigten, dass bei einer Konzentration von 1000 ppmv H2O die Reaktionen und Kondensation von SO2 und NO2 mit O2 und H2O zu Säuretropfen (pH ~ 0,5) auf der Oberfläche von Metall-Prüfkörper und Gefäß führen. Die Werkstoffe 1.0582, 1.8977, 1.4313 und 1.4562 wurden in CO2-gesättigtem Kondensat mit unterschiedlichem Verhältnis der säurebildenden Komponenten untersucht. Diese Studien zeigten grundsätzlich den Mechanismus sowie die Rolle jedes CO2-Strom-Begleitstoffes auf den Korrosionsprozess. Allerdings spiegeln die bei Auslagerung und elektrochemischen Messungen in der künstlichen CO2-gesättigten Kondensat-Lösung auftretenden Bedingungen nicht im Detail die Realität in der Praxis, wo sich nur Tröpfchen bilden, wider.
Diese Arbeit konzentriert sich auf den Korrosionsprozess von Kondensat in Form von Tröpfchen, auf der Oberfläche von Rohrleitungswerkstoffen unter CO2-Atmosphäre bei 5 °C (Simulation des Transportzustandes). Die Experimente wurden nicht nur für Auslagerungsversuche, sondern auch für elektrochemische Tests mit nur einem Tröpfchen (weniger als 20 µL) konzipiert. Die Auslagerungs-versuche wurden sowohl unter Normaldruck als auch bei hohem Druck (> 70 bar) durchgeführt, wobei das CO2 als dichte – den Tropfen umgebende - Phase vorliegt. Die korrodierten Prüfkörper wurden rasterelektronenmikroskopisch (REM) und mittels Energiedispersiver Röntgenspektroskopie (EDX) analysiert, um nicht nur Korrosionsform, sondern auch die Elementverteilung der Korrosionsprodukte zu zeigen.
Synergistic effects of impurities in the condensate on the corrosion of CO2 transport pipeline
(2017)
For the reliability of transport pipelines the corrosion resistance of the materials used needs to be determined in conditions, which are possible during the transport process. In some situations condensation of components out of the CO2 stream can occur. To study the effect of condensate on transport pipeline steel, a “worst-case scenario” gas mixture, containing 2.5 % H2O, 1.8 % O2, 1000 ppmv NO2, and 220 ppmv SO2, was proposed, fed (1.5 L/min) into a glass reactor containing coupon-shaped specimens for 120 600 h at 278 K (to simulate the underground pipeline transport), and resulted in the condensate containing 0.114 M H2SO4 and 0.0184 M HNO3 (pH 2.13). Basing on this “original” condensate, exposure tests and electrochemical characterization together with pH and conductivity in CO2 saturated condition at the same temperature were carried out. The role of each gas impurity and the combination of them, when the condensate is formed, was studied by investigating the role of individual and varying combination of acidic components in the condensate on the corrosion behaviors of the commercial pipeline-steel (L360NB). It can be concluded that although the condensation of NOx in form of HNO3 causes faster corrosion rate, it is the condensation of SOx or the combination of SOx and NOx that may cause much more severe problems in form of localized and pitting corrosions. Different to the corrosion products formed in CO2 atmosphere without impurities (mainly iron carbonate) the corrosion products resulted from these acidic condensation have no protectability, indicating the need of controlling gas quality during the transportation within the pipeline network.
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.
Within the last years the use of feasible alternative energy sources has risen and is going to replace fossil resources more and more. Nevertheless, service conditions in solar facilities are due to the chemical composition of heat transmission media and temperatures, in many cases, extreme in terms of corrosion. Since the construction of power plants shall be economical with maximum life service, materials selection based on preliminary material qualification is essential to guarantee a secure and reliable operation of those facilities.
The materials selection depends on the operation temperature of a power plant on the chemical composition of the transmission fluid used. In high corrosive environments Ni-based alloys are often used as an all-round solution for the construction of corrosion resistant parts, because of their good corrosion properties. However, there might be limits for their use regarding their corrosion behavior, with which this contribution deals.
By means of electrochemical measurements and exposure tests the suitability of two high alloyed materials X8NiCrSi38 18 and NiCr25FeAlYB in molten nitrate salt (60 % NaNO3/40 % KNO3) was characterized at 600 °C.
Since geothermal wells are a feasible energy source to replace fossil fuel supply, many technologies have been developed to take advantage of geothermal energy. Nevertheless, service conditions in geothermal facilities are due to the chemical composition of hydrothermal fluids and temperatures, in many cases, extreme in terms of corrosion. Therefore, materials selection based on preliminary material qualification is essential to guarantee a secure and reliable operation of the facilities.
This contribution deals with the evaluation of the corrosion behavior of duplex steel S31803 (318LN, X2CrNiMoN22-5-3, 1.4462) conducted by electrochemical measurements and exposure tests in artificial geothermal waters simulating the conditions in different locations with geothermal potential in Germany.
The duplex steel S31803 shows limited suitability for applications in artificial geothermal waters due to its susceptibility to pitting and crevice corrosion.
For low saline geothermal waters it can be considered suitable at moderate temperatures. Slight crevice corrosion susceptibility needs to be considered.
Results are being incorporated into a materials catalogue for geothermal applications which shall provide basic information for designers and users of geothermal facilities.
Carbon Capture, Utilization and Storage (CCUS) has been proposed as a promising technology for the mitigation of CO2 emissions into the atmosphere from fossil-fuel-operated power generation plants. As the reliability and cost effectiveness of the pipeline transport network is crucial to the overall operability and resilience of the CCUS system, it is vital to realize the possible corrosion risks of the employed pipeline steels corresponding to the impurity level of the gas source.
Recent studies have shown that even the high alloyed materials might be susceptible to general and/or localized corrosion by the condensates forming from the impurities such as SOx, NOx, CO, O2 and water [1]. Up to now, however, there is no regulation procedure which defines the maximum acceptable level of impurities and the combination of them for each employed pipeline steels. Herein, systematic experiment series were conducted by mixing pure CO2 gas with varying concentration of each impurity and with the varying combination of them. Each time, the mixture was then fed (1 L/min) into the reactor containing 12 specimens for 120-600 h at 5°C (to simulate the sub-level pipeline transport). The resulted condensate was collected and analyzed by ionic chromatography and atomic absorption spectroscopy to determine the chemical composition. In this study, the “worst-case scenario” gas mixture, containing 2.5 % H2O, 1.8 % O2, 1000 ppm NO2, and 220 ppm SO2 as impurities, resulted in the condensate containing H2SO4 0.114 M and HNO3 0.0184 M (pH 2.13). This “original” condensate was then re-produced to carry out exposure tests and electrochemical characterization including corrosion potentials and impedance spectroscopy in CO2 saturated condition for 7-14 days at the same temperature. The corrosion rate was also measured by mass loss method.
We can conclude that, at the initial stage, HNO3 plays the dominant role in Fe dissolution process, while H2SO4 is responsible for the pit initiation followed by pitting corrosion. Future studies will be focused on the combination effect from the impurities and the exposure test under the regularly changing condensate to mimic the real CO2 pipeline system.
Since geothermal wells are a feasible energy source to replace fossil fuel supply, many technologies have been developed to take advantage of geothermal energy. Nevertheless, service conditions in geothermal facilities are due to the chemical composition of hydrothermal fluids and temperatures, in many cases, extreme in terms of corrosion. Therefore, materials selection based on preliminary material qualification is essential to guarantee a secure and reliable operation of the facilities.
The corrosion behavior of different high-alloyed metals including duplex and austenitic stainless steels as well as a nickel alloy have been evaluated in artificial geothermal fluids simulating the conditions in some locations with geothermal potential in Germany as well as two sites in Indonesia.
The suitability of carbon steel 25CrMo4, stainless steels X2CrNiMo17-12-2, X2CrNiMo-22-5, X2CrNiMoCuWN25-7-4 and super austenitic steel X1CrNiMoCu32-28-7 in these geothermal fluids obtained by electrochemical measurements and exposure tests is limited. The nickel alloy NiCr23Mo16Al shows an excellent corrosion resistance against pitting corrosion. Excluding its high cost, it is a very good alternative to be used in the construction of geothermal facilities having highly saline brines. Stainless and duplex steels exhibit a limited corrosion resistance concerning pitting and crevice corrosion.
Beside of the higher alloyed materials, also the low-alloyed steel 25CrMo4 could be employed as a constructional material for the geothermal power plant in stagnant highly acidic non saline environments, as long as the wall thickness of the material vs. corrosion rate is taken into account.
Within the last years the use of feasible alternative energy sources has risen and is going to replace fossil resources more and more. Nevertheless, service conditions in solar facilities are due to the chemical composition of heat transmission media and temperatures, in many cases, extreme in terms of corrosion. Since the construction of power plants shall be economical with maximum life service, materials selection based on preliminary material qualification is essential to guarantee a secure and reliable operation of those facilities.
The materials selection depends on the operation temperature of a power plant on the chemical composition of the transmission fluid used. In high corrosive environments Ni-based alloys are often used as an all-round solution for the construction of corrosion resistant parts, because of their good corrosion properties. However, there might be limits for their use regarding their corrosion behavior, with which this contribution deals.
Experiences from the electrochemical characterization of materials in aqueous solutions are transferred to molten salts, providing a good addition to common exposure tests at temperatures from 450 0C to 600 0C.
By means of electrochemical measurements and exposure tests the suitability of high alloyed materials in molten nitrate salt (60 % NaNO3/40 % KNO3) can be characterized. The method was verified on different Ni-based alloys (UNS N08810, UNS N06600) and Titanium (UNS R50250).
In the literature there are not much data available to describe the corrosion behavior of titanium, nickel alloys and special stainless steels in acids at high temperature, in particular above the boiling point. Therefore, a laboratory testing program was performed with two titanium alloys (UNS R50400 and UNS R53400) to obtain corrosion data in formic acid, acetic acid, phosphoric acid, polyphosphoric acid, p-toluene sulfonic acid and lactic acid at 200 °C. Results were compared to previously published ones obtained on UNS N08031, UNS N06059 and UNS N10665.
From the results it can be concluded that titanium does not always show better corrosion resistance than Ni-based alloys.
UNS N06059 was the best choice for formic and acetic acids at temperatures of 200 °C. Both Ti-alloys are resistant in acetic acid. Some slight differences were observed for formic acid, where UNS R50400 is only resistant up to a 20 % solution and UNS R53400 in concentrated acid too. The phosphoric acid is extremely corrosive and none of the investigated materials was resistant. In the diluted acid (5 %) only UNS R53400 is resistant, whereas in 1 % solution all investigated materials performed satisfactory. UNS N10665 and UNS N06059 showed the best behavior in polyphosphoric acid. In 30 % concentrated p-toluene sulfonic acid at 200 °C all alloys tested were unsuitable. In very diluted acid (0.1 %) both Ti-alloys and the other three alloys behaved well. In lactic acid at 180 °C increased corrosion underneath deposits was detected; the best performance was observed for UNS N06059 and UNS R50400.
In the literature there are not much data available to describe the corrosion behavior of titanium, nickel alloys and special stainless steels in acids at high temperature, in particular above the boiling point. Therefore, a laboratory testing program was performed with two titanium alloys (grade 2 - UNS R50400 and grade 12 - UNS R53400) to obtain corrosion data in formic acid, acetic acid, phosphoric acid, polyphosphoric acid, p-toluene sulfonic acid and lactic acid at 200 °C. Results were compared to previously published ones obtained on alloy 31 (UNS N08031), alloy 59 (UNS N06059) and B-2 (UNS N10665).
From the results it can be concluded that titanium does not always Show better corrosion resistance than Ni-based alloys,
Alloy 59 was the best choice for formic and acetic acids at temperatures of 200°C. Both Ti-alloys are resistant in acetic acid. Some slight differences were observed for formic acid, where Ti grade 2 is only resistant up to a 20 % solution and grade 12 in concentrated acid too. The phosphoric acid is extremely corrosive and none of the investigated materials was resistant. In the diluted acid (5 %) only Ti grade 12 is resistant, whereas in 1 % solution all investigated materials withstand. Alloy B-2 and alloy 59 showed the best behavior in polyphosphoric acid. In 30 % concentrated p-toluene sulfonic acid at 200 °C all alloys tested were unsuitable. In very diluted acid (0.1 %) both Ti-alloys and the other three alloys behaved well. In lactic acid at 180 °C increased corrosion underneath deposits was detected; the best performance was observed for alloy 59 and Ti grade 2.
In the last years, geothermal power has become a reliable and significant energy source. Because service conditions in geothermal facilities from deeply located aquifers are usually critical in terms of corrosion, materials selection is a very important issue. Preliminary evaluation of the material's suitability represents therefore a valuable strategy to ensure a secure and reliable operation of the facilities. In geothermal applications, the use of high-alloyed materials such as superaustenitic stainless steels, duplex stainless steels, and nickel-based alloys has been considered as a good alternative because of their remarkable corrosion resistance and appropriate mechanical properties. Nevertheless, the corrosion behavior of those metallic materials in geothermal fluids at service conditions has not been determined in many cases. In this work, laboratory tests including electrochemical investigations and exposure tests at 100 degrees C and 150 degrees C (1,500 kPa) showed the limits of suitability concerning localized corrosion of three different, corrosion-resistant alloys in the highly saline fluid of the North German Basin.
The corrosion behavior of different high-alloyed metals including duplex and austenitic stainless steels as well as a nickel alloy have been evaluated in artificial geothermal fluids simulating the conditions in some locations with geothermal potential in Germany as well as two sites in Indonesia.
The suitability of low alloyed steel UNS G41300, stainless steels UNS S31603 UNS S31803, UNS S32760 and super austenitic steel UNS N08031 in these geothermal fluids, investigated by electrochemical measurements and exposure tests, is limited. The nickel based alloy UNS N06059 shows excellent corrosion resistance against pitting corrosion. Excluding its high cost, it is a very good alternative to be used in the construction of geothermal facilities having highly saline brines. Stainless and duplex steels exhibit a limited corrosion resistance concerning pitting and crevice corrosion.
Beside of the higher alloyed materials, also the low-alloyed steel UNS G41300 could be employed as a constructional material for the geothermal power plant in non-saline environments, as long as the wall thickness of the material vs. corrosion rate is taken into account.
This study aims to evaluate which of the materials currently available on the market could overcome the Problem of corrosion and withstand highly aggressive conditions in the exploitation of geothermal resources in volcanic environments. Our investigations were triggered by the conditions on Lahendong geothermal field (North Sulawesi, Indonesia): well LHD-23 presents one of the greatest challenges due to its capacity of producing > 20 MWe of energy from a single well and in the same time having very low pH (2-3) and relatively high Chloride (1,500 mg/L) and sulphate (1,600 mg/L) concentration. Three different Steel grades (low-alloyed Steel UNS G41300, stainless Steel UNS S31603 and high-alloyed stainless Steel UNS N08031) were selected, and their corrosion behavior was evaluated by means of short-term electrochemical methods (potentiodynamic polarization) and long-term exposure tests (up to 6 months). The research was carried out in the laboratory under stagnant conditions in the artificial LHD-23 geothermal brine (1,500 mg/L Chlorides, 1,600 mg/L sulphates, pH 2) at 100 °C (100 kPa) and 175 °C (900 kPa), simulating the conditions present at the site.
Since geothermal wells are a feasible energy source to replace fossil fuel supply, many technologies have been developed to take advantage of geothermal energy. Nevertheless, service conditions in geothermal facilities are due to the chemical composition of hydrothermal waters and temperatures, in many cases, extreme in terms of corrosion. Therefore, materials selection based on preliminary material qualification is essential to guarantee a secure and reliable operation of the facilities.
This contribution deals with the evaluation of the corrosion behavior of different steels in flowing low saline, slightly alkaline, artificial geothermal water simulating the conditions in the Molasse-Basin, a location with geothermal potential in Germany.
Test results for steels UNS S31603 and UNS S31803 exposed to this geothermal water obtained by electrochemical measurements and exposure tests are presented. Results obtained in static and flowing water condition show good performance of both alloys with a possible onset of localized corrosion at UNS S31603 in static conditions.
Corrosion resistance of high-alloyed and alternative materials in an artificial geothermal water
(2014)
Many technologies have been developed to take advantage of geothermal energy, which became a feasible energy source to replace fossil fuel supply. Nevertheless, service conditions in geothermal facilities are due to the chemical composition of hydrothermal fluids and involved high temperatures, in many cases, extreme in terms of corrosion. Therefore, materials selection based on preliminary material qualification is essential to guarantee a secure and reliable operation of the facilities.
This contribution deals with the evaluation of the corrosion behavior of two high-alloyed metallic materials and α-Al2O3 in an artificial geothermal fluid simulating the conditions in the Northern German Basin, a location with high geothermal potential. The suitability of the super austenitic stainless steel UNS N08031 and the nickel base alloy UNS N06059 in this geothermal fluid obtained by electrochemical measurements and exposure tests is addressed. As an alternative to the suitable but costly UNS N06059 that showed excellent corrosion resistance against pitting corrosion, ceramic made of α-Al2O3 represents an interesting possibility for selected components to be used in the construction of geothermal facilities
Many technologies have been developed to take advantage of geothermal energy, which became a feasible energy source to replace fossil fliel supply. Nevertheless, Service conditions in geothermal facilities are due to the Chemical composition of hydrothermal fluids and involved high temperatures, in many cases, extreme in terms of corrosion. Therefore, materials selection based on preliminary material qualification is essential to guarantee a secure and reliable Operation ofthe facilities.
This contribution deals with the evaluation of the corrosion behavior of two high-alloyed metallic materials and a-A1203 in an artificial geothermal fluid simulating the conditions in the Northern German Basin, a location with high geothermal potential. The suitability of the super austenitic stainless Steel, alloy 31, and the nickel base alloy 59 in this geothermal fluid obtained by electrochemical measurements and exposure tests is addressed. As an alternative to the suitable but costly alloy 59 that showed excelient corrosion resistance against pitting corrosion, ceramic made of a-A1203 represents an interesting possibility for selected components to be used in the construction of geothermal facilities.
C02-corrosion on piping steels might cause problems during injection of flue gases for their storage in deep geological aquifer fluids. Therefore, the selection of appropriate piping steels is a key factor to increase safety and reliability of the Carbon Capture and Storage (CCS) technology, and to keep the process cost-efficient.
Within the project COORAL (German acronym for “C02 purity for capture and storage”) corrosion studies on injection piping steels exposed to C02 and artificial brine with high Chloride concentration have been carried out. Corrosion of the injection pipe in C02-rich aquifer fluid may occur within the aquifer brine or when at injection interruptions the aquifer fluid may flow back into the injection pipe. Because of high salinity of aquifer brine and C02-corrosion an appropriate material ranking of injection piping steels should be made.
Corrosion resistance of steels 1.4034, 1.4021, 1.4542, 1.4162 and 1.4562 was investigated in a corrosive environment using electrochemical and metallographic techniques. Electrochemical experiments in order to investigate the surface corrosion kinetics and polarization measurements in order to investigate localized corrosion phenomena have been carried out. Critical pitting potentials and repassivation potentials were determined by polarization curves of investigated materials and compared with measured corrosion potentials. Measured values were used in order to determine the suitability and performance of tested steels in C02-injection conditions.
In der DIN 6601 - Beständigkeit der Werkstoffe von Behältern/Tanks aus Stahl gegenüber Flüssigkeiten (Positiv-Flüssigkeitsliste) ist die Beständigkeit unlegierter Stähle, austenitischer CrNi- und CrNiMo-Stähle gegenüber den reinen Ottokraftstoffen bewertet. Mit der verstärkten Verwendung bioethanol- und biodieselhaltiger Kraftstoffe und Heizöl stellt sich auch die Frage nach der Beständigkeit der handelsüblichen Tank- und Behälterwerkstoffe sowie der Dichtungswerkstoffe unter dem Einfluss dieser Medien.
Comparison of the corrosion resistance to dangerous goods of austenitic CrNiMo and duplex steels
(2014)
The “BAM-List - Requirements for Tanks for the Transport of Dangerous Goods” is the basis in Germany for substance-related prototype approvals for tank Containers in Germany. Compatibility evaluations of selected metallic materials and polymeric materials under the influence of approximately 7200 dangerous goods have been published in the BAM-List since 1989. The austenitic CrNi- and CrNiMo-steels - UNS S30403, UNS S31600, UNSS31603 and UNS S31635 - are the materials mostly used worldwide for transport tanks. The duplex Steel UNS S31803 has been put on the BAMList due to the great interest of tank producers and transport Companies. Using UNS S31803 instead of 316L, the weight of the tanks can be reduced, and the list of transportable goods can be extended. The objective of these investigations was to compare the corrosion resistance of duplex Steel UNS S31803 and austenitic Steel UNS S31603. Therefore, test specimens of both steels were exposed to selected corrosive substances, such as formic acid, acetic acid, phosphoric acid, sulfuric acid, nitrating acid, monochloroacetic acid and trichloroacetone at 55 °C (30 °C, 70 °C). The test results have shown that the duplex Steel UNSS31803 is a good alternative to austenitic CrNiMo-steel UNS S31603 for tanks carrying corrosive dangerous goods.
In Germany the “BAM-List - Requirements for Tanks for the Transport of Dangerous Goods” is the basis for substance-related prototype approvals for tank Containers undertaken by the BAM1 - Federal Institute for Materials Research and Testing. Compatibility evaluations of selected metallic materials as well as of polymeric gasket and lining materials under the influence of approximately 7200 dangerous goods have been published in the BAM-List since 1989.
The ferritic Steel UNS S44400 (X2CrMoTil8-10, 1.4521) was originally developed as alternative for the austenitic grade AISI316L (X2CrNiMo 17-12-2, 1.4404). Due to its characteristic profile this Steel was qualified for applications requiring high strength values at concomitant adequate corrosion resistance. Because of the lack of Nickel this Steel is a cost-efficient alternative to the Ni-containing austenites. No corrosion test results of UNS S44400 under the influence of dangerous goods were published in the BAM-List so far. Only data on the behavior of AISI 316L are listed. Therefore test specimens of this Steel were exposed to selected corrosive substances in order to compare both steels.
Due to the reduced alloy content a reduced corrosion resistance of the Steel UNS S44400 in acidic substances, such as formic acid, acetic acid and sulfuric acid, in comparison to the austenitic CrNiMosteels was expected but not observed. Tests in an alkaline medium showed sufficient resistance.
Use of higher-alloyed metallic materials and duplex steels for transport tanks of dangerous goods
(2011)
Compatibility evaluations of selected metallic materials under the influence of dangerous goods are published in the BAM-List - Requirements for Tanks for the Transport of Dangerous Goods” as basis for substance-related prototype approvals for tank Containers designed for the carriage of dangerous goods.
There is a request of the tank manufacturing industry and transportation Companies to incorporate additional materials into the BAM-List, especially corrosion-resistant materials because of the large number of corrosive dangerous goods. One solution to solve corrosion Problems is to line the tank with a polymer, an alternative solution is the application of high-alloyed stainless steels and nickel-based alloys as there are 1.4529 (XINiCrMoCu 25-20-7, alloy 926), 1.4562 (X1NiCrMoCu32-28-7, alloy 31) and 2.4605 (NiCr23Mo16AI, alloy 59).
There is an interest to use cost-efficient steels with high strength values and concomitant adequate corrosion resistance such as duplex steel 1.4362 (X2CrNiN23-4).
This steel grade was originally developed as a substitute for the austenitic grades 1.4404 (X2CrNiMo17-12-2) and 1.4571 (X6CrNiMoTi17-12-2). Due to the lower content of the alloy elements nickel and molybdenum this duplex steel is a cost-efficient alternative to molybdenum containing austenite.
Due to the limited number of corrosion test results with welded test samples of these high-alloyed materials and the duplex steel under the influence of corrosive dangerous goods a comprehensive test Programme was performed with these materials in Cooperation with ThyssenKrupp VDM and Deutsche Edelstahlwerke GmbH. It can be concluded from the test results that the superaustenitic steels 1.4529 and 1.4562 as well as the nickel-based alloy 2.4605 are a really good alternative as tank materials for the transport of dangerous goods in comparison to the lining of the tanks. The nickel-based alloy 2.4605 shows the best resistance and is suitable as material for tanks transporting all tested corrosive substances. One exception is the temperature limit during the transport of hydrochloric acid.
The superaustenit 1.4562 is a resistant material with a wide ränge of application. Exceptions for use are: ammonium bifluoride, brine, 34 % calcium Chloride solution, hydrochloric acid, perchloric acid, 90 % 2-chloropropionic acid, nitrating acid with nitric acid content > 50 % and molten monochloroacetic acid. The alloy is limited suitable for allyl Chloride, aluminum Chloride, copper (II) -Chloride and ferric Chloride. The superaustenit 1.4529 showed the lowest resistance compared to the other two materials. This steel is not resistant in hydrochloric acid, perchloric acid, sodium Chlorite and sodium hypochlorite. The application is limited in the concentration ränge of aqueous Solutions of aluminum Chloride, copper (II) Chloride and ferric Chloride. Due to the reduced alloying content of the duplex steel 1.4362 (X2CrNiN23-4) compared to the austenitic CrNiMo-steels, a lower resistance especially in acidic media like formic, acetic or sulfuric acid was observed. Within the more than 7.000 substances contained in the BAM-List there is a large amount of dangerous goods such as hydrocarbons, alcohols, aldehydes, ketones, ethers, esters, and inorganic alkaline substances which have a large transport volume and do not corrode the duplex steel 1.4362 (X2CrNiN23-4).
The test results are included in the actual 11th edition of the BAM-List and therefore available for the costumer.
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.