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Application No.: VEV0080
Version 1  12/2017

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​Determination of mono- and polyaromatic hydrocarbons in diesel fuels with HPLC using RI detection

Lilit Avagyan¹, Stephanie Hutfless², Kate Monks¹; applications@knauer.net 
1KNAUER Wissenschaftliche Geräte GmbH, Hegauer Weg 38, 14163 Berlin
²Haltermann Carless Deutschland GmbH, Hamburg, Germany

Determination of mono- and polyaromatic hydrocarbons in diesel fuels with HPLC using RI detection

Summary

The content of aromatic hydrocarbons in diesel fuel has an influence on exhaust emission and its combustion characteristics. Here we present the determination of aromatic hydrocarbons under normal phase conditions with an isocratic AZURA® Analytical HPLC system and detection via refractive index detector AZURA RID 2.1L.

Introduction

It is well known that the best performance and maximum lifetime of an engine can be reached, when the amount of aromatic hydrocarbons in diesel and aviation turbine fuels is as low as possible. Since the aromatic hydrocarbon content can affect the cetane number of fuels and cause emissions due to incomplete burning, there are different regulations to protect the environment and public health. Below, we describe a method according to DIN EN 12916 [1] for the the determination of mono- and polyaromatic hydrocarbons, like 1,2-dimeth ylbenzene, fluorene, and phenanthrene in diesel fuel samples.

Results

The chromatographical results show that all three aromatic hydrocarbons in standard solutions were successfully separated under normal phase conditions and current instrumental settings. Fig 1 shows the overlay of chromatograms from three repetitions. The standard deviation value for retention time and peak area is 0.05 % – 0.06 % and 0.09 % – 0.22 %, respectively (Tab 2). The correlation factor for all compounds, obtained due analysis of three concentration levels (standard solutions A, C, and D) is > 0.9999. The corresponding overlay chromatograms are presented in Fig 2. In the chromatogram of the diesel fuel sample all three compounds could be identified (Fig 3). The highest amount of aromatic hydrocarbons was detected for 1,2-dimethylbenzene. The calculated value is 19.26 %. The values for all three hydrocarbons are presented in Tab 3.

Fig. 1  Overlay chromatogram of three replicates of standard solution C

Fig.1 Overlay chromatogram of three replicates of standard solution C

Tab.1 Amount of components in m% of standard solutions A, C, and D

Compound name

Solution A

Solution C

Solution D

1,2-Dimethylbenzene

1.515

1.348

6.557

Fluorene

0.062

0.785

2.017

Phenanthrene

0.072

0.221

0.479

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Fig. 2  Overlay chromatogram of two replicates each for standard solutions A (red), C (blue), and D (green)

Fig.2 Overlay chromatogram of two replicates each for standard solutions A (red), C (blue), and D (green)

Tab. 2 Reproducibility of standard solution C

Compound name

Ret. time (min)

RSD (%)

Area (µRIU·s)

RSD (%)

1,2-Dimethylbenzene

4.18

0.06

967.67

0.22

Fluorene

6.54

0.06

1067.25

0.09

Phenanthrene

8.59

0.05

355.25

0.17

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Fig. 3  Chromatogram of a diesel fuel sample

Fig.3 Chromatogram of a diesel fuel sample

Tab.3 Calculated amount of identified components in diesel fuel

Compound name

Amount (m%)

1,2-Dimethylbenzene

19.26

Fluorene

1.53

Phenanthrene

0.04

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Materials and Methods

For the analysis of mono-, and polyaromatic hydrocarbons we used the following HPLC system setup: isocratic AZURA P6.1L pump with 10 mL pump head, AZURA AS 6.1L autosampler, AZURA RID 2.1L detector and AZURA CT 2.1L thermostat. The separation was performed on normal phase column ZORBAX®, NH2 250 x 4.6 mm. The used mobile phase was n-heptane. For calibration three concentration levels were used. The amounts of 1,2-dimethylbenzene, fluorene and phenanthrene in corresponding solutions A, C and D are presented in Tab 1. The samples from the respective diesel fuel batches were diluted to 10 % with n-Heptan and analyzed.

Conclusion

This application demonstrates, that the AZURA isocratic analytical HPLC system in combination with AZURA RID 2.1L detector suitable for determining of mono- and polyaromatic hydrocarbons in diesel fuel according to DIN EN 12916.

Additional Materials and Methods

Tab. A1 Method parameters

Eluent

n-heptane

Gradient

isocratic

Flow rate

1.2 mL/min

Run time

12 min

Column temperature

25 °C

Injection mode

Full loop

Injection volume

5 µL

Data rate

20 Hz

Detection

RI

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Tab.A2 System configuration

Instrument

Description

Article No.

Pump

AZURA® P6.1L

APH30ED

Autosampler

AZURA® AS 6.1L

AAA00AA

Detector

AZURA® RID 2.1L

ADD31

Column

ZORBAX®, NH2 250 x 4.6 mm

Thermostat

AZURA® CT 2.1

ATC00

Software

ClarityChrom 7.2

A1670-11

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KNAUER System Configuration

References

DIN EN 12916:2016 Petroleum products – Determination of aromatic hydrocarbon types in middle distillates – High performance liquid chromatography method with refractive index detection, German version

Related KNAUER Applications

VEV0078 – Systematic HPLC Method Development and Robustness Evaluation of 13 Carbonyl DNPH Derivatives Using DryLab®

VEV0081 – GPC vs. SPE and subsequent determination of polycyclic aromatic hydrocarbons using GC/MS

Application details

Method

HPLC

Mode

NP

Substances

1,2-Dimethylbenzene, Fluorene, Phenanthrene

CAS number

n/a

Version

Application No.: VEV0080 | Version 1  12/2017 | ©KNAUER Wissenschaftliche Geräte GmbH

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