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Chemistry

On-line Analysis of Nitrogen Containing Compounds in Complex Hydrocarbon Matrixes

Published: August 5th, 2016

DOI:

10.3791/54236

1Laboratory for Chemical Technology, Faculty of Engineering and Architecture, Ghent University

A method combining comprehensive two-dimensional gas chromatography with nitrogen chemiluminescence detection has been developed and applied to on-line analysis of nitrogen containing compounds in a complex hydrocarbon matrix.

The shift to heavy crude oils and the use of alternative fossil resources such as shale oil are a challenge for the petrochemical industry. The composition of heavy crude oils and shale oils varies substantially depending on the origin of the mixture. In particular they contain an increased amount of nitrogen containing compounds compared to the conventionally used sweet crude oils. As nitrogen compounds have an influence on the operation of thermal processes occurring in coker units and steam crackers, and as some species are considered as environmentally hazardous, a detailed analysis of the reactions involving nitrogen containing compounds under pyrolysis conditions provides valuable information. Therefore a novel method has been developed and validated with a feedstock containing a high nitrogen content, i.e., a shale oil. First, the feed was characterized offline by comprehensive two-dimensional gas chromatography (GC × GC) coupled with a nitrogen chemiluminescence detector (NCD). In a second step the on-line analysis method was developed and tested on a steam cracking pilot plant by feeding pyridine dissolved in heptane. The former being a representative compound for one of the most abundant classes of compounds present in shale oil. The composition of the reactor effluent was determined via an in-house developed automated sampling system followed by immediate injection of the sample on a GC × GC coupled with a time-of-flight mass spectrometer (TOF-MS), flame ionization detector (FID) and NCD. A novel method for quantitative analysis of nitrogen containing compounds using NCD and 2-chloropyridine as an internal standard has been developed and demonstrated.

The reserves of light sweet crude oils are gradually diminishing, and hence, alternative fossil resources are being considered to be used in the energy and petrochemical industry. In addition, renewables such as bio-oils produced by fast pyrolysis of biomass are becoming a more attractive resources of bio-based fuels and chemicals. Nevertheless, heavy crude oil is a logical first choice because of the large proven reserves in Canada and Venezuela1-3. The latter are being recognized as the largest crude oil reserves in the world and their composition is similar to the composition of natural bitumen. Similar to bio-oils, heavy crude oils differ from light cru....

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Caution: Please consult relevant material safety data sheets (MSDS) of all compounds before use. Appropriate safety practices are recommended. Solutions and samples should be prepared in the fume hood, while using personal protective equipment. Best practice implies use of safety glasses, protection laboratory gloves, lab coat, full length pants, and closed-toe shoes. The reactor should be properly sealed as several reactants and reaction products can be acutely toxic and carcinogenic.

1. Offline GC × GC–.......

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The chromatogram obtained using the offline GC × GC–NCD for characterization of nitrogen containing compounds in a shale oil sample is given in Figure 3. The following classes were identified: pyridines, anilines, quinolines, indoles, acridines, and carbazoles. Moreover, detailed quantification of the individual compounds was possible. The gathered data was used to determine the individual compound concentrations, and the obtained values are presented in

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The described experimental procedures enabled a successful comprehensive off-line and on-line identification and quantification of nitrogen containing compounds in the studied samples.

The separation of nitrogen containing compounds in shale oil was accomplished using GC × GC–NCD, as shown in Figure 3. Since the NCD cannot be used for identification, the retention times of the observed species need to be established in advance by carrying out analyses on the GC .......

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The SBO project “Bioleum” (IWT-SBO 130039) supported by the Institute for Promotion of Innovation through Science and Technology in Flanders (IWT) and the ‘Long Term Structural Methusalem Funding by the Flemish Government’ are acknowledged.

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Name Company Catalog Number Comments
2-Chloropyridine, 99% Sigma Aldrich C69802 Highly toxic
Shale oil Origin Colorado, US Piceance Basin in
Colorado, USA
Toxic
Pyridine, 99.8% Sigma Aldrich 270970 Highly toxic
Carbon Dioxide, industrial grade refrigerated liquid PRAXAIR CDINDLB0D Wear safety gloves and glasses
Helium, 99.99% PRAXAIR 6.0
Hydrogen, 99.95% Air Liquide 695A-49 Flammable
Oxygen Air Liquide 905A-49+ Flammable
Air Air Liquide 365A-49X
Nitrogen Air Liquide 765A-49
Hexane, 95+% Chemlab CL00.0803.9025 Toxic
Heptane, 99+% Chemlab CL00.0805.9025 Toxic
Nitrogen, industrial grade refrigerated liquid PRAXAIR P0271L50S2A001 Wear safety gloves and glasses
Autosampler Thermo Scientific, Interscience AI/AS 3000
High temperature 6 port/2 position valve Valco Instruments Company Incorporated SSACGUWT
Gas chromatograph Thermo Scientific, Interscience Trace GC ultra
Rafinery Gas Analyzer Thermo Scientific, Interscience KAV00309
rtx-1-PONA column Restek Pure Chromatography 10195-146
BPX-50 column SGE Analytical science 54741
TOF-MS Thermo Scientific, Interscience Tempus Plus 1.4 SR1 Finnigan
NCD Agilent Technologgies NCD 255
Chrom-card Thermo Scientific, Interscience HyperChrom 2.4.1
Xcalibur software Thermo Scientific, Interscience 1.4 SR1
Chrom-card software Thermo Scientific, Interscience HyperChrom 2.7
GC image software Zoex Corporation GC image 2.3

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