Factors Controlling Naphthenic Acid Corrosion

Turnbull, A.; Slavcheva, E.; Shone, Bryan

doi:10.5006/1.3284811

Cited by 91 publications

(75 citation statements)

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“…The pronounced sensitivity of corrosion resistance in the 1.4541 regarding composition of the organic fluid phase resulted in high reaction rates especially in waste lard mixtures not only in the short run, but over longer periods, suggests the existence of an altered microstructure, lower compactness and increased solubility of metals and sulphide scales in acid containing fluid than in neat gas oils. This is in agreement with the literature [60] as naphthenic acids are most accountable for the highly corrosive nature oils [61][62][63][64]. The high corrosion rate of the St35.8 at low temperatures probably is a result of diffusion along short-circuit paths at grain boundaries or dislocations rather than of lattice diffusion, as thermal activation is high compared to over long periods when kinetic control of barrier effects besides the seldom failure of scales.…”

Section: Discussionsupporting

confidence: 80%

Hydrogen Sulphide Corrosion of Carbon and Stainless Steel Alloys Immersed in Mixtures of Renewable Fuel Sources and Tested Under Co-processing Conditions

Gergely¹,

Locskai²,

Szabó³

et al. 2016

Hungarian Journal of Industry and Chemistry

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HUNGARYIn accordance with modern regulations and directives, the use of renewable biomass materials as precursors for the production of fuels for transportation purposes is to be strictly followed. Even though, there are problems related to processing, storage and handling in wide range of subsequent uses, since there must be a limit to the ratio of biofuels mixed with mineral raw materials. As a key factor with regards to these biomass sources pose a great risk of causing multiple forms of corrosion both to metallic and non-metallic structural materials. To assess the degree of corrosion risk to a variety of engineering alloys like low-carbon and stainless steels widely used as structural metals, this work is dedicated to investigating corrosion rates of economically reasonable engineering steel alloys in mixtures of raw gas oil and renewable biomass fuel sources under typical coprocessing conditions. To model a desulphurising refining process, corrosion tests were carried out with raw mineral gasoline and its mixture with used cooking oil and animal waste lard in relative quantities of 10% (g/g). Co-processing was simulated by batch-reactor laboratory experiments. Experiments were performed at temperatures between 200 and 300ºC and a pressure in the gas phase of 90 bar containing 2% (m 3 /m 3 ) hydrogen sulphide. The time span of individual tests were varied between 1 and 21 days so that we can conclude about changes in the reaction rates against time exposure of and extrapolate for longer periods of exposure. Initial and integral corrosion rates were defined by a weight loss method on standard size of coupons of all sorts of steel alloys. Corrosion rates of carbon steels indicated a linear increase with temperature and little variation with composition of the biomass fuel sources. Apparent activation energies over the first 24-hour period remained moderate, varying between 35.5 and 50.3 kJ mol -1 . Scales developed on carbon steels at higher temperatures were less susceptible to spall and detach. Nonetheless, moderate deceleration of corrosion rates as a function of time are due to the less coherent, frequently spalling and low compactness, higher porosity of the scales evolved at lower and higher temperatures, respectively. On the surface of high alloy steels, sulphide scales of an enhanced barrier nature formed during the induction periods and the layer formation mechanism was found to be assisted by the increasing temperature as initial reaction rates considerably decreased over time. Nevertheless, corrosion-related sulphide conversion of metals and mass loss of the high alloys are strongly affected by the composition of the biomass fuel sources especially animal waste lard. Thermal activation in the first 24 hours decreased from 68.9 to 35.2 kJ mol -1 . A greater degree of failure to develop protective sulphide scales was experienced by changing to composition of the biomass fuel sources than the impact of thermal activation between a narrow temperature range at around 100ºC. In accordance with the litera...

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Section: Discussionsupporting

confidence: 80%

Hydrogen Sulphide Corrosion of Carbon and Stainless Steel Alloys Immersed in Mixtures of Renewable Fuel Sources and Tested Under Co-processing Conditions

Gergely¹,

Locskai²,

Szabó³

et al. 2016

Hungarian Journal of Industry and Chemistry

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“…[75][76][77][78][79] A relação entre TAN, conteúdo de enxofre e atividade corrosiva tem sido tema de algumas pesquisas. 25,80,81 A corrosão nas unidades de destilação da refinaria Salina Cruz (México), tanto à pressão atmosférica, quanto à pressão reduzida, foi estudada por Laredo e colaboradores.…”

Section: Relação Entre O Teor De Enxofre No Combustível E a Corrosãounclassified

Ácidos naftênicos no petróleo

Gruber¹,

Damasceno²,

Caramão³

et al. 2012

Quím. Nova

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Recebido em 22/7/11; aceito em 5/2/12; publicado na web em 15/5/12 NAPHTHENIC ACIDS IN PETROLEUM. Brazilian petroleum is known by its high acidity due to the presence of acidic constituents, especially naphthenic acids (NA). The total characterization of the NA in petrochemical samples has been receiving special attention in research and comprises an analytical challenge, mainly due to the complexity of their mixtures. Gas chromatography with mass detector (GC/MS) is the technique of analysis more used, but recently comprehensive two-dimensional gas chromatography (GC × GC) has been used, due to its high resolution, peak capacity and sensitivity. The goal of this article is to discuss the techniques for sample preparation and analysis of NA in petroleum.Keywords: petrochemicals samples; naphthenic acids; characterization of the NA. INTRODUÇÃONos últimos anos grande parte das reservas de petróleo descobertas em território brasileiro consiste de óleo pesado de baixo grau API (<20º), alta viscosidade e elevada acidez total. 1 A Empresa de Petróleo Brasileiro S/A, PETROBRAS, visando viabilizar a comercialização do petróleo vem investindo em programas de pesquisa e desenvolvimento, tais como, PRAVAP (Programa de Recuperação Avançada de Petróleo), PROTER (Programa de Tecnologias Estratégicas de Refino) e PROPES (Programa Tecnológico de Óleos Pesados).As fontes de óleo cru na América do Sul, incluindo o petróleo brasileiro, estão entre as mais ácidas do mundo.2,3 Tal acidez é responsabilizada por muitas dificuldades na utilização desta matéria-prima nas refinarias e no aproveitamento de seus resíduos.Os ácidos naftênicos (AN) são encontrados, predominantemente, em óleos imaturos, biodegradados, em óleos pesados e águas residuá-rias geradas no processo de extração do betume.4,5 Sua importância é salientada em geoquímica, aplicações comerciais, aspectos ambientais e corrosão. [2][3][4][5][6] O termo naftênico, correspondente a compostos cíclicos saturados, é usado para todos os tipos de ácidos encontrados em petróleos, mesmo os saturados lineares e os ramificados. 2,5,7 Os ácidos carboxílicos presentes no petróleo representam um grande problema para o refino e craqueamento do mesmo, devido ao seu efeito corrosivo em linhas de transferência de massa e calor, nas seções de entrada e refluxo de colunas (à pressão atmosférica e a vácuo) e nos condensadores das unidades de destilação das refinarias. 5 De forma geral, determina-se o teor de ácidos através da titulação com KOH, obtendo-se então o índice ou número de acidez naftênica. Este índice pode ser indicativo de atividade corrosiva da amostra, contudo, nada acrescenta quanto à qualidade do petróleo e à natureza dos ácidos presentes. Para caracterizar estes ácidos, é necessário extraí-los e analisá-los de forma individual. 2,5 O petróleo é constituído de uma mistura complexa de hidrocarbonetos com quantidade bastante significativa de isômeros, além destes, apresenta compostos contendo nitrogênio, oxigênio e enxofre, que dificultam as etapas de extração, isolamento e caract...

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“…Corrosivity increases with increasing total acid number (TAN) of crude oil. Yet, the spread of corrosion by NAs rely not only on TAN but also on the availability of the carboxylic acid group and the type of compounds [43,44,46]. Very few reports have been disclosed discussing NAs in reinery wastewater due to their analytical diiculties although discharged wastewater from petroleum reineries.…”

Section: Recent Insights In Petroleum Science and Engineeringmentioning

confidence: 99%

“…NAs decompose at temperatures above 400°C creating a protective ilm over the alloy [43,46]. Corrosivity increases with increasing total acid number (TAN) of crude oil.…”

Section: Recent Insights In Petroleum Science and Engineeringmentioning

confidence: 99%

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Total Acid Number Reduction of Naphthenic Acids Using Supercritical Fluid and Ionic Liquids

Mandal¹,

Sasaki²

2018

Recent Insights in Petroleum Science and Engineering

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Naphthenic acids (NAs) are complex mixture of predominately alkyl-substituted cycloaliphatic carboxylic acids and small amount of acyclic acids present in crude oil, heavy oil and in oil sands bitumen. They are toxic components in reinery wastewater and in oil sand extraction water and lead to corrosion problems within the oil reineries. Therefore, the amount of NAs needs to suppress in petroleum oils and wastewater came from petroleum industry. This paper reviews the supercritical luids (SCFs)-and ionic liquids (ILs)-based acidity reduction process from heavy oils by reviewing open literature. The potential beneits of SCFs-and ILs-based acidity reduction process of heavy oils are also explored. The reviewed articles reveal that total acid number (TAN) removal increase with increasing reaction time and temperature by the action of SCF. Supercritical methanol (SC-MeOH) has higher potentiality for removing acidity of NAs than supercritical water (SCW) without deposition of coke. TAN removal from NAs using SCF follows irst order kinetics on TAN removal. ILs can reduce acidity of heavy oil either forming zwitterionic species or building cage structure around NAs through speciic chemical bonds. Thus, non-catalytic SCF-and ILs-based TAN reduction process can open a new window to reduce acidity of heavy oils.

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Factors Controlling Naphthenic Acid Corrosion

Cited by 91 publications

References 1 publication

Hydrogen Sulphide Corrosion of Carbon and Stainless Steel Alloys Immersed in Mixtures of Renewable Fuel Sources and Tested Under Co-processing Conditions

Hydrogen Sulphide Corrosion of Carbon and Stainless Steel Alloys Immersed in Mixtures of Renewable Fuel Sources and Tested Under Co-processing Conditions

Ácidos naftênicos no petróleo

Total Acid Number Reduction of Naphthenic Acids Using Supercritical Fluid and Ionic Liquids

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