Journal of Chromatography A, 1090 (2005) 116–125 Multidimensional gas chromatography for the detailed PIONA analysis of heavy naphtha: Hyphenation of an olefin trap to comprehensive two-dimensional gas chromatography Colombe Vendeuvre a , Fabrice Bertoncini a,∗ , Didier Espinat a , Didier Thi´ ebaut b , Marie-Claire Hennion b a DirectionPhysiqueetAnalyse,InstitutFran¸ caisduP´ etrole,BP3, 69390Vernaison,France b ESPCI,LaboratoireEnvironnementetChimieAnalytique,10rueVauquelin, 75235ParisCedex05,France Received 11 March 2005; received in revised form 3 June 2005; accepted 7 June 2005 Available online 8 August 2005 Abstract A multidimensional method providing the composition of a heavy naphtha in paraffins, isoparaffins, olefins, naphthenes, and aromatics (PIONA) in the C 8 –C 14 range is presented. The analytical set-up consists in a silver modified silica olefin trap on-line coupled to comprehensive two-dimensional gas chromatography (GC × GC). In this configuration, hydrocarbons are separated, in gaseous state, in two fractions, saturate and unsaturate, each fraction being subsequently analysed by GC or by GC × GC. The resolution between saturates and olefins was found to be improved compared to a single GC × GC run. The characterisation of the olefin trap highlights the benefits and the limits related to the use of that stationary phase as a double bond selective fractionation medium. © 2005 Published by Elsevier B.V. Keywords: Comprehensive two-dimensional; Multidimensional; Gas chromatography; Olefin trap; PIONA analysis; Olefins; Heavy naphtha; Hydrocarbons 1. Introduction The detailed analysis of petroleum cuts is required for refinery processes monitoring and for product specifications. Two gas chromatographic (GC) techniques, providing dif- ferent levels of detail, have been normalised to obtain the chemical composition of commercial gasoline (boiling up to 200 ◦ C) [1,2]. The first one is to achieve a high resolutive GC separation that provides individual components analysis with an identification based on retention indices [1]. The second possibility, widely used in refineries, is a multidimensional method (PIONA analyser) based on the separation of each different constituting chemical group (alkanes or paraffins, isoalkanes or isoparaffins, alkenes or olefins, cycloalkanes ∗ Corresponding author. Tel.: +33 4 78022 935; fax: +33 4 78022 745. E-mailaddress: fabrice.bertoncini@ifp.fr (F. Bertoncini). or naphthenes, aromatics) in a dedicated column or trap [2]. Since the introduction of the PNA analyser in 1971 [3] to determine the content of paraffins, naphthenes and aromatics for each carbon atoms through C 10 by sequential separations on polar, non-polar and 13× molecular sieve columns, the system has evolved to extend the analysis to olefins using an olefin trap [4] and to isoparaffins using a 5A molecular sieve column. However, these techniques are limited when analysing refinery cuts having a higher boiling range, such as heavy naphtha (C 8 –C 14 ). Using high resolution GC, sig- nificant coelution may indeed occur above C 10 , especially if blending cuts derived from fluid catalytic cracking (FCC) – olefinic naphtha – are analysed, because the high num- ber of components is not compatible with the peak capacity of the GC column. The limitation of the PIONA analyser is related to the maximum number of carbon atoms (C 10 ) of molecules to be handled, principally owing to the high 0021-9673/$ – see front matter © 2005 Published by Elsevier B.V. doi:10.1016/j.chroma.2005.06.087