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Non-catalytic thermal decomposition of naphthenic acids of petroleum crudes

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Abstract

The thermal decomposition of naphthenic acids was carried out in a 50 mL glass vessel equipped with a bottom sparger (for bubbling a gas: H2, N2, steam) and a removable head cap for charging the oil and also containing the gas outlet connections. Gas at a suitable flowrate (1.5–4.5 mL min−1) was used for stripping the decomposition products formed at different heating temperatures (360, 380, 400 °C). Results show that the thermal decomposition of naphthenic acids follows a second order kinetic model. Three carrier gases were tested, nitrogen, hydrogen and steam. The gases stripped the fluid phase from the produced dioxide carbon. Best results were obtained when using nitrogen as stripping gas, at 400 °C and 1.5 L h−1 stripping rate. A 90% decrease of acidity was achieved with a treatment of 4 h. This final TAN value is considered acceptable for a subsequent refining of the crude in a common refinery.

Graphical abstract

Naphthenic acid present in crude oil leads to corrosion problems within oil refineries. The objective of this study was to reduce the total acid number through non-catalytic thermal decarboxylation of the naphthenic acids using a gas–liquid reactor and different carrier gases. The results indicate an acidity reduction without significant changes to its physical properties.

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Abbreviations

C :

Concentration of naphthenic acids, TAN

A :

Arrhenius preexponential factor

E a :

Activation energy, kJ mol−1

k :

Kinetic constant

HAC:

High acid crudes

TAN:

Total acid number

NA:

Naphthenic acids

NTD:

Non-catalytic thermal decomposition

FKE:

Fitting kinetic equation

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Acknowledgements

This work was performed with the funding of CONICET (PIP grants 11220130100457CO and 11420110100235CO), Universidad Nacional del Litoral (CAI+D Grant 50420150100074LI).

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Authors and Affiliations

  1. Instituto de Investigaciones en Catálisis y Petroquímica, CONICET, Colectora Ruta Nacional 168 Km 0, Paraje El Pozo, 3000, Santa Fe, Argentina

    Mariana Busto & Carlos Román Vera

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  1. Mariana Busto
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  2. Carlos Román Vera
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Correspondence to Mariana Busto.

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Busto, M., Vera, C.R. Non-catalytic thermal decomposition of naphthenic acids of petroleum crudes. Braz. J. Chem. Eng. 39, 105–112 (2022). https://doi.org/10.1007/s43153-021-00180-9

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  • DOI: https://doi.org/10.1007/s43153-021-00180-9

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