Fast Analysis of Paraffins, iso-Paraffins, Naphthenes and Aromatics in Hydrocarbon Streams Using Concurrent Temperature Programming

 

Topics Covered

Introduction to PIONA Gas Chromatography
Temperature programming of PIONA Gas Chromatograph
Results and Discussion of Application
Conclusion
About Bruker CAM

Introduction to PIONA Gas Chromatography

 

Gas chromatography is a widely-used method of chemical analysis that analyses the chemical make-up of a substance that has been vaporised. The moving phase in a gas chromatographer (an inert gas) carries the vapour desired through a tube lined with a stationary phase. The main physical components of a gas chromatographer are the auto samplers, inlets and detectors.

Gas chromatography is used in a large range of industries, including the engine fuels industry, for the characterisation of hydrocarbons.

POINA gas chromatography is specifically used for characterising Paraffins, Iso-paraffins, Olefins Naphthenes and Aromatics in gasoline-range materials. It is currently the favoured technique to characterise petroleum streams by hydrocarbon group type. It does this using a ‘multidimensional’ approach, which allows the recognition of different hydrocarbon groups.

‘Multidimensional’ gas chromatography analysis is now very common in refinery laboratories across the globe. Although many improvements have been made since it was first introduced, there are still improvements that can be made.

One improvement that can be implemented is a decrease in the time it takes to analyse samples. This is an extremely useful improvement which would be of benefit to many industries, including the fuel industry.

 

 

Temperature programming of PIONA Gas Chromatograph

Faster PIONA analysis is thought to be achievable by using concurrent heating.

The new Bruker PIONA+™ Analyser has made great strides in this respect.  This machine was developed to provide flexibility in determining the composition of spark ignition fuels by hydrocarbon group-type through the use of multi-dimensional gas chromatography.

The Bruker PIONA+™ Analyser has various ‘traps’ that help to group various hydrocarbons by carbon numbers.

Temperature programming of the Bruker Molsieve 5A trap so that is it ‘concurrent’ with the Bruker Molsieve 13X trap results in several large advantages.

Firstly, the application range for wide samples is greatly increased. Also, Quantification of volatile hydrocarbons in wide range samples is improved.

Importantly, the application range analysis time is reduced significantly.

Below is a review of an application to demonstrate how these advantages are achieved.

Results and Discussion of Application

The Instrumentation used in this application was: Bruker PIONA+ Analyzer, Software, CompassCDS, and Chromatography Software from Bruker with PIONA+ plug-in software.

In this application, the PIONA+ system was set up to separate normal and iso-paraffins, naphthenes and aromatics (PINA). In conventional mode, there can be breakthrough of volatile n-paraffins from the Bruker Molsieve 5A trap, which can make quantification quite difficult. Also, co-elution is possible for high C number isoparaffins and corresponding naphthenes. In addition, the total analysis time is approximately two hours.

Figures 1 shows some of the quantification problems encountered using conventional PINA analysis. A calibration mix was analyzed and breakthrough is apparent. The separation per component group and per carbon number is clearly shown. However, breakthrough of the volatilen-paraffins challenges the software, for example, in the case of nP5 from 7 to 9.5 minutes as shown in Figure 1b. This effect is particularly evident around 9 minutes when the N6 (napthenes C6) elutes.

Figure 2 clearly shows the improved performance of the fast PINA system, enabling easier quantification and reduced analysis time. In the regular PINA mode analysis time is about 95 minutes. In fast PINA mode, this is reduced to 55 minutes.It is also apparent that the analysis time reduction is achieved without adaptations in hardware and without any negative effect on chromatographic separation. This means that the chromatographic specifications remain unchanged.

Conclusion

It is shown in this test that concurrent temperature programming of the Molsieve 5A trap together with the Molsieve 13X trap in the Bruker PIONA+ Analyzer greatly extends the application range for wide samples. Quantification of volatile hydrocarbons in wide range samples is also improved. The reduction of analysis time in this example was 40 minutes, or nearly 45 %.

About Bruker CAM

Bruker is the new name in chemical analysis. Accurate and comprehensive analysis of exogenous and discrete elements in a wide range of sample matrices are key applications for many analytical chemistry groups. To address the needs and challenges of analysts working in those areas, Bruker has expanded their product family to provide, and expertly support, a series of fully integrated solutions including:

· Gas Chromatography-Mass Spectrometers (GC/MS and GC/MS/MS)

 

· Inductively Coupled Plasma Mass Spectrometers (ICP-MS)

 

· Gas Chromatography Systems (GC)

Widely used in food and consumer safety testing, forensic, industrial, environmental, and clinical laboratories, these systems are well accepted and established market leaders that universally deliver outstanding performance at a premium value.

This information has been sourced, reviewed and adapted from materials provided by Bruker CAM.

For more information on this source, please visit Bruker CAM.

Date Added: Jun 15, 2012 | Updated: Jun 18, 2012
Ask A Question

Do you have a question you'd like to ask regarding this article?

Leave your feedback
Submit