Research Article A Sensitive Method Approach for Chromatographic Analysis of Gas Streams in Separation Processes Based on Columns Packed with an Adsorbent Material I. A. A. C. Esteves, 1 G. M. R. P. L. Sousa, 2 R. J. S. Silva, 3 R. P. P. L. Ribeiro, 1 M. F. J. Eusébio, 1 and J. P. B. Mota 1 1 LAQV, REQUIMTE, Departamento de Qu´ ımica, Faculdade de Ciˆ encias e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal 2 Saudi Basic Industries Corporation (SABIC), P.O. Box 5101, Riyadh 11422, Saudi Arabia 3 Instituto de Biologia Experimental e Tecnol´ ogica (iBET), Apartado 12, 2781-901 Oeiras, Portugal Correspondence should be addressed to I. A. A. C. Esteves; iaesteves@fct.unl.pt Received 1 February 2016; Accepted 19 May 2016 Academic Editor: Fernando Lusqui˜ nos Copyright © 2016 I. A. A. C. Esteves et al. Tis is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. A sensitive method was developed and experimentally validated for the in-line analysis and quantifcation of gaseous feed and product streams of separation processes under research and development based on column chromatography. Te analysis uses a specifc mass spectrometry method coupled to engineering processes, such as Pressure Swing Adsorption (PSA) and Simulated Moving Bed (SMB), which are examples of popular continuous separation technologies that can be used in applications such as natural gas and biogas purifcations or carbon dioxide sequestration. Tese processes employ column adsorption equilibria on adsorbent materials, thus requiring real-time gas stream composition quantifcation. For this assay, an internal standard is assumed and a single-point calibration is used in a simple mixture-specifc algorithm. Te accuracy of the method was found to be between 0.01% and 0.25% (-mol) for mixtures of CO 2 , CH 4 , and N 2 , tested as case-studies. Tis makes the method feasible for streams with quality control levels that can be used as a standard monitoring and analyzing procedure. 1. Introduction Adsorption separation is a phenomenon in which one or more components of a fuid (adsorbate) are extracted via selective bonding to a solid (adsorbent) medium [1–3]. Tis is the basis for every adsorption separation process. Periodic adsorption processes, such as single or multibed Pressure Swing Adsorption (PSA), have been extensively developed and applied in industry for gas separation and are energy efcient alternatives to other separation techniques such as cryogenic distillation. Much progress has been achieved in improving their performance with respect to both the process economics and the attainable purity of the products by inves- tigating new process confgurations or giving a better reuse to some topical waste gases like biogas produced from biomass [4]. Simulated Moving Bed (SMB) is a continuous adsorptive separation process with various applications, many of which are difcult to handle using other techniques. Recently, the feasibility of SMB operation for gas separation has been addressed and its feasibility demonstrated, with focus on cyclic modulation of the internal fow rates [5, 6]. Long gone are the days where the development of SMB and PSA process schemes and their experimental validation were analyzed by manual and discrete sampling quantifca- tion chromatographic techniques. Nowadays, for the appli- cations of interest the coupling of the separation/purifcation process unit with a spectrometry system can be done through a capillary line, in order to bring the required continuous sample streams into the analyzer at the specifed pressure, while maintaining the high vacuum necessary for proper spectrometry operation. For mixtures where the identifca- tion of the masses of individual atoms and molecules that have been ionized are possible to distinguish, mass spec- trometry (MS) is a reasonably simple but unique technique Hindawi Publishing Corporation Advances in Materials Science and Engineering Volume 2016, Article ID 3216267, 9 pages http://dx.doi.org/10.1155/2016/3216267