IMPROVED METHOD FOR THE REDUCTION IN ACIDITY IN CRUDE OILS WITH A HIGH NAPHTHENIC ACID CONTENT BY MEANS OF CATALYTIC HYDROGENATION

It has been discovered that the naphthenic acids present in crude oil are carboxylic acids, characterised by being one (or more) aliphatic or naphthenic ring having an associated alkyl group, which is ended by a carboxylic acid group. The naphthenic acids produce atypical corrosion phenomena, given...

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Hauptverfasser: QUIROGA, Haydee, GARZÓN, Laura, HOYOS MARÍN, Luis Javier, ALMANZA RUBIO, Luis Oswaldo
Format: Patent
Sprache:eng ; fre ; spa
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Zusammenfassung:It has been discovered that the naphthenic acids present in crude oil are carboxylic acids, characterised by being one (or more) aliphatic or naphthenic ring having an associated alkyl group, which is ended by a carboxylic acid group. The naphthenic acids produce atypical corrosion phenomena, given that they can cause a localised attack without the presence of water at temperatures between 473 K and 693 K, hindering the processing of this type of crude oils in refineries. The invention relates to a catalytic hydrogenation process that permits the selective removal of naphthenic acids present in heavy and extra heavy crude oils with a low production of hydrogen sulphides, in particular in crude oil that has not previously been fractionally distilled. The catalyst is formed by an aluminium and/or magnesium-aluminium spinel-type support having active Fe-Mo phases. In addition, the applicant has discovered that the hydrogenation process using Fe and Mo catalysts and/or mixtures thereof surprisingly permits an acid number of 1 mg KOH/g to be reached in crude oils with TAN greater than 4 gm KOH/g, reducing unwanted reactions in the process and prolonging the useful life of the catalyst via the low deposition of metal sulphurs. Se ha descubierto que los ácidos nafténicos presentes en el crudo, son ácidos carboxílicos, caracterizados por ser un anillo alifático (o varios) o nafteno con un grupo alquilo asociado, que termina en un grupo ácido carboxílico. Los ácidos nafténicos producen fenómenos de corrosión atípicos, puesto que son capaces de producir un ataque localizado sin la presencia de agua a temperaturas entre 473 K y 693 K dificultando el procesamiento de este tipo de crudos en refinerías. La presente invención describe un proceso de hidrogenación catalítica que permite la remoción selectiva de ácidos nafténicos presentes en crudos pesados y extrapesados con baja producción de sulfuros de hidrógeno, más específicamente en crudo que no ha sido previamente destilado en fracciones. El catalizador está compuesto por un soporte de tipo alúmina y/o espinela de aluminio-magnesio con fases activas de Fe-Mo. Adicionalmente, el solicitante ha encontrado de manera sorprendente el proceso de hidrogenación empleando catalizadores Fe y Mo y/o mezclas entre ellos permite alcanzar número de ácidos de 1 mg KOH/g en crudos con TAN superior a 4 mg KOH/g, logrando disminuir reacciones no deseadas en el proceso y prolongando la vida útil del catalizador por la baja deposición