hydrogen embrittlement in pipelines transporting sour hydrocarbons

Abstract Lamination-like defects in pipeline steels can be of both metallurgical and operational origin. In pipelines transporting hydrocarbon usually such defects are not a big challenge since they do not propagate under operating conditions. Nonetheless, in presence of a corrosion phenomenon and sour gas (H2S), it is possible to observe blisters and cracks which may propagate in the steel. The observed damage mechanisms is Hydrogen Embrittlement and in spite of a huge amount of study and publications available, it is quite difficult for a pipeline owner to get practical data (crack propagation rate for instance) allowing a reliable estimate of the fitness for service of a pipeline. Taking advantage of a pipeline spool containing internal defects that was in service for more than 10 years and recently removed, a comprehensive study is underway to obtain a complete assessment of the pipeline future integrity. The program is comprehensive of study and comparison of ILI reports of the pipeline, to determine the optimum interval between inspections, assessment of inspection results via an accurate nondestructive (UT) and destructive examination of the removed section, to verify ILI results, lab tests program on specimens from the removed spool at operating conditions (75-80 bar and 30°-36° C) in presence of a small quantity of water, H2S (5%) and CO2 (7%), in order to assess defect propagation and to obtain an estimate of crack growth rate, and test in field of available methods to monitor the presence of Hydrogen and/or the growth of defects in in-service pipelines. This quite ambitious program is also expected to be able of offering a small contribution toward a better understanding of HE mechanisms and the engineering application of such complex, often mainly academic, studies

engineering thoughts on hydrogen embrittlement

Abstract Hydrogen Embrittlement (HE) is a topical issue for pipelines transporting sour products. Engineers need a simple and effective approach in materials selection at design stage. In other words, they must know if a material is susceptible to cracking, to be able of: selecting the right material and apply correct operational measures during the service life. Following ASTM F2078, HE is "a permanent loss of ductility in a metal or alloy caused by hydrogen in combination with stress, either externally applied or internal residual stress". In many cases, hydrogen can play a role in crack propagation, as for instance in Stress Corrosion Cracking (SCC) and Corrosion Fatigue (CF). Three parameters are required to cause failure: presence of hydrogen, tensile stress, and material susceptibility. The two previous ones are triggering the failure, while the root cause is usually material susceptibility. This is why material selection is the important step to safely manage engineering structural materials. As an example, material selection for sour service pipeline is the object of well-known standards, e.g. by Nace International and EFC: they pose some limits in the sour service of steels, with reference to surface hardness. These standards have shown some weak points, namely: In the definition of sour service; In defining the role of crack initiation and propagation, considering that in Hydrogen embrittlement, stress state and stress variations are very important. As for the second point, in hydrogen generation anodic processes shall be taken into account too. For instance, there is a relationship between corrosion resistance and crack susceptibility. In carbon and low alloy steels, cracking will not normally occur when there is a significant corrosion rate. If a brittle layer (or a brittle spot) is present on the metal surface, this one can initiate a crack

Test Conditions for Pipeline Materials Selection with High Pressure Sour Gas

Acid gases, such as CO2, H2S, and/or sulfur in oil industry's production fluids, can be responsible for both general and localized corrosion, acting with different mechanisms, which depend on chemical and physical properties of the produced fluids. Materials selection for handling such fluids is performed by combining experience with suggestions from standards and regulations. A good deal of knowledge is available to predict corrosion rates for CO2-containing hydrocarbons, but the effect of high H2S pressure is less understood, mainly due to the difficulty of performing laboratory tests in such challenging conditions. For instance, the so-called NACE solution to assess SSC (Sulfide Stress Cracking) susceptibility of steels is a water-based solution simulating production fluids in equilibrium with one bar bubbling H2S gas. This solution does not represent environments where high gas pressure is present. Moreover, it does not take into account the corrosive properties of sulfur and its compounds that may deposit in such conditions. Besides, properties of high pressure gases are intermediate between those of a gas and those of a liquid: high pressure gases have superior wetting properties and better penetration in small pores, with respect to liquids. These features could enhance and accelerate damage, and nowadays such conditions are likely to be present in many production fields. This paper is aimed to point out a few challenges in dealing with high pressure gases and to suggest that, for materials selection in sour service, a better correspondence of test conditions with the actual field conditions shall be pursued

An investigation on corrosion protection layers in pipelines transporting hydrocarbons

Chemical reactions between carbon steel, water and chemical species produce corrosion layers (scales) on the internal surface of pipelines transporting hydrocarbons. Scales act as a diffusion barrier and prevent the progress of corrosion, a dangerous failure initiator. The protective film (10-100 m thickness) can be removed locally by the action of the internal flow, or by other mechanisms. Adhesion with the substrate and the failure modes of the corrosion layer can be tested by indentation. Some results are presented of experiments performed on specimens with scales grown in a controlled environment

Modelli per la previsione della corrosione da CO2: confronto e applicazione a casi reali

La corrosione interna da CO2 è il meccanismo di danno più importante per le condotte che trasportanoidrocarburi. Per un adeguata scelta dei materiali di costruzione è necessario essere in grado di prevederel evoluzione della corrosione in funzione delle caratteristiche del fluido trasportato, e la resistenza dellediverse classi di acciai. Sono disponibili vari modelli predittivi che sulla base dei principali parametri chimicofisicipermettono di valutare la velocità di corrosione attesa. La maggior parte di questi modelli si fondasull interpolazione di dati sperimentali, rielaborati e corretti a partire da osservazioni di campo. Esiste poi unmodello più complesso, elaborato dall Università dell Ohio, che è basato sul comportamento chimico-fisico delmetallo descritto da equazioni di stato. Gli autori di questo lavoro hanno svolto un esercizio comparativoconsistente nell applicazione di diversi modelli ad alcuni casi reali. I risultati ottenuti sono stati confrontatitra di loro e, ove possibile, paragonati con osservazioni e misure disponibili. In generale si può affermare che imodelli a disposizione danno un utile indicazione per la selezione materiali e per l interpretazione di casi dirottura; in genere però i dati che si ottengono sono conservativi e non sono in accordo con le velocità dicorrosione effettivamente misurate in campo. Se l’obiettivo è quello di riuscire ad ottenere un valore numericoche sia veramente significativo per la previsione della vita di un componente, è necessario approfondire lostudio delle diverse metodologie

PROVE DI CORROSIONE AD ALTA PRESSIONE DI CO2 PER I POZZI DI STOCCAGGIO

Nell’ambito del progetto ENI “GreenHouse Gases” è stata effettuata una attività sperimentale volta alla scelta materiali per i pozzi di stoccaggio. Utilizzando un sistema esperto per la scelta dei materiali dei pozzi è stata preparata una tabella che possa servire da guida per la selezione dei materiali per pozzi in funzione delle impurezze contenute nella CO2 e dei parametri di processo. I risultati forniti dal sistema esperto sono stati validati mediante prove sperimentali. Le prove svolte sono state: test di corrosione in autoclave, prove meccaniche, analisi chimica, indagini metallografiche

A new approach to quantitative propagation of chaos for drift, diffusion and jump processes

This paper is devoted the the study of the mean field limit for many-particle systems undergoing jump, drift or diffusion processes, as well as combinations of them. The main results are quantitative estimates on the decay of fluctuations around the deterministic limit and of correlations between particles, as the number of particles goes to infinity. To this end we introduce a general functional framework which reduces this question to the one of proving a purely functional estimate on some abstract generator operators (consistency estimate) together with fine stability estimates on the flow of the limiting nonlinear equation (stability estimates). Then we apply this method to a Boltzmann collision jump process (for Maxwell molecules), to a McKean-Vlasov drift-diffusion process and to an inelastic Boltzmann collision jump process with (stochastic) thermal bath. To our knowledge, our approach yields the first such quantitative results for a combination of jump and diffusion processes.Comment: v2 (55 pages): many improvements on the presentation, v3: correction of a few typos, to appear In Probability Theory and Related Field