Topics Covered
Introduction
Gas Chromatography-Mass Spectrometers (GC/MS and GC/MS/MS)
GC/MS Applications
Bruker PIONA+ Gas Chromotography System
Analysis of Oxygenates, Paraffins, Olefins, Naphthenes and Aromatics (O-PONA) of Hydrocarbon Streams
Conclusions
About Bruker CAM
Introduction
Accurate and comprehensive analysis of exogenous and discrete elements in a wide range of sample matrices are key applications for many analytical chemistry groups and industries.
To address the needs and challenges of analysts working in these areas, Bruker has developed and 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.
Gas Chromatography-Mass Spectrometers (GC/MS and GC/MS/MS)
Gas chromatography-Mass spectrometry is a unique combination of two methods of analysis designed to identify different substances within a test sample.
By combining Gas-Liquid Chromatography to separate and analyse chemical compounds and Mass spectrometry to determine the mass of specific particles, it is possible to very accurately identify the elemental composition of compounds or materials.
Bruker Daltonics’ GC/MS systems are designed for a wide range of chemical analysis applications for a diversity of samples and analytes.
GC/MS Applications
GC/MS solutions are designed to deliver unmatched sensitivity, flexibility, and maximum utility all at a premium value to handle even the most challenging applications including:
- Food and Product Safety Assessment
- Forensics
- Environmental Analysis
- Clinical/Toxicology Testing
- Pharmaceutical Analysis
- Chemical Analysis
- Polymer Analysis
Bruker PIONA+ Gas Chromotography System
Standard GC Analyzers: Configured for Performance and Productivity.
Bruker configures and tests its standard GC analyzers to more than meet industry standard performance requirements for a variety of widely used methods (ASTM, UOP, EN, ISO, GPA). Available in an array of configurations, Bruker Standard GC Analyzers utilize the leading analytical performance characteristics of the Bruker 400 Series of GC.
PIONA+TM Analyzer
Using a fully automated multidimensional gas chromatography approach to analyze individual hydrocarbons groups per carbon number, the PIONA+ Analyzer is especially designed and configured to be fully compliant with any of the following established methods including: ASTM D6839, EN-ISO-22854, ASTM D5443, ASTM D1319, IP-382, IP-526, EN 14157, UOP 870 and DIN-51448.
Concurrent Operation Ramps-Up Productivity
The PIONA+ Analyzer is capable of concurrent use of molecular sieve columns and carefully matched temperature programming to provide simultaneous separation of Napthalenes, iso-Paraffins, and normal Paraffins by carbon number in carbon number ranging from C4 through C11. With a traditional PIONA analysis, this separation would normally take around 180 minutes.
Taking advantage of the capabilities of the PIONA+ Analyzer reduces the analysis time by almost half-down to only 95 minutes. For some analyses, such as for gasoline with ether additives, the analysis time can be reduced even further down to 65 minutes and provide results conforming with ASTM D6839.
Making Total Olefin Content Analysis Practical
The PIONA+ Analyzer provides a powerful simplified approach for a notoriously difficult operation-that of total olefin analysis. The stability, sample loading capacity, and lifetime of the PIONA+ Analyzer have all been dramatically enhanced to meet the needs of olefin analysis.
Particularly important is the increased capacity of the "olefin trap" of the PIONA+ Analyzer. With this enhanced capability, it's possible to analyze streams with olefin content as high as 35-40% or more.
Analysis of Oxygenates, Paraffins, Olefins, Naphthenes and Aromatics (O-PONA) of Hydrocarbon Streams
The Bruker PIONA+ Analyzer is a comprehensive GC system that offers the ability to characterize and quantify components in a variety of spark ignition fuels according to an array of industry standard method protocols. For quantitative determination of oxygenates, Paraffins, naphthenes and aromatics (O-PONA) in spark ignition fuels the PIONA+ uses a multidimensional gas chromatography separation approach. The system can be operated in one of multiple method “modes” depending on the analysis requirement of a given stream type. For this particular application, the system was set up to characterize the O-PONA content of spark ignition fuels.
Using the Bruker PIONA+ Analyzer incorporating Galaxie Chromatography Software and PIONA+ Software Plug-in it is possible to accurately identify and characterize the O-PONA make-up of spark ignition fuels.
A typical Chromatograph of the O-PONA content of spark ignition fuels is shown in Figure 1.
Figure 1. Test Sample 1
In the O-PONA mode, the Bruker PIONA+ uses an olefin trap to separate the Olefins from Paraffins (Table1).
From
|
To (min) |
Components
|
Column Route
|
0
|
25.0
|
C1 to C10 N + P
|
1st OV-275 fraction via arom/eth and
olefin trap to 13x
|
25.0
|
30.0
|
>185 °C fraction
|
Back flush CP-Sil™ 5CB of 2nd
OV-275 fraction
|
30.0
|
40.0
|
ethers
|
1st OV-275 fraction via arom/eth and
CP-Sil 5CB to porous polymer column
|
40.0
|
45.0
|
C8 A and pN
|
2nd OV-275 fraction via arom/eth
and CP-Sil 5CB |
45.0
|
50.0
|
>185 °C fraction
|
Back flush CP-Sil 5CB of 2nd
OV-275 fraction |
50.0
|
60.0
|
C6 A + C7 A
|
2nd OV-275 fraction via arom/eth
and CP-Sil 5CB to porous polymer
column
|
60.0
|
90.0
|
C3 to C10 cO + O
|
Olefin trap in flow to 13x |
90.0
|
96.5
|
C8 to C10 A
|
3rd back flush OV-275 and precolumn
back flush fraction via arom/eth to
CP-Sil 5CB
|
96.5
|
105.0
|
>185 °C fraction
|
Back flush CP-Sil 5CB of 3rd OV-275
and pre back flush fraction
|
105
|
115.0
|
alcohols
|
3rd OV-275 and precolumn back flush
fraction via arom/eth and CP-Sil 5CB
to porous polymer column
|
Table 1. Elution Scheme for O-PONA
Results and Discussion of Sample Test
The chromatogram shown in Figure 1 is an example of an O-PONA analysis. In this case, a test sample is run.
Clearly made visible here is the group separation making identification and quantification very easy. The oxygenates elute without co-elution of other sample components allowing accurate and precise quantification. All conditions for the different columns and traps are set in order to obtain the elution scheme represented in Table 1. Galaxie Chromatography Software from Bruker, together with the PIONA+ plug-in software, generates a weight% and a volume% profile report.
A summary of these reports is shown in Tables 2 and 3. The amount of the different groups per carbon number is shown as well as the totals per group and per carbon number.
| Carbon |
Saturates |
Unsaturates |
Total |
Cyclic
|
Normal +Iso
|
Cyclic
|
Normal +Iso
|
Aromatics
|
Oxygenates
|
2
|
0.00
|
0.00
|
0.00
|
0.00 |
0.00 |
2.72
|
2.72
|
3
|
0.00 |
0.00 |
0.00
|
0.00 |
0.00 |
0.00
|
0.00
|
4
|
0.00 |
0.00 |
0.00 |
0.00 |
0.00 |
0.00
|
0.00
|
5
|
0.00 |
0.00 |
0.00 |
0.00 |
0.00 |
7.14
|
7.14
|
6
|
1.04
|
1.45
|
1.06
|
1.09
|
2.40
|
0.00 |
7.05
|
7
|
3.16
|
3.74
|
1.98
|
0.74
|
2.90
|
0.00 |
15.52
|
8
|
5.12
|
7.33
|
0.00
|
0.38
|
9.43
|
0.00 |
22.27
|
9
|
4.12
|
3.17
|
0.00
|
0.00
|
6.16
|
0.00 |
13.46
|
10
|
2.12
|
4.74
|
0.00
|
0.00
|
4.70
|
0.00 |
11.56
|
11
|
0.00
|
0.00
|
0.00
|
0.00
|
0.00
|
0.00 |
0.00
|
Total
|
15.57
|
20.44
|
3.04
|
2.21
|
25.59
|
9.85
|
76.70
|
|
|
|
|
|
|
|
|
Fraction >200°C
|
17.36
|
|
|
MTBE
|
7.14
|
|
Polynaphthenes
|
5.94
|
|
|
Ethanol
|
2.72
|
|
Table 2. Mass % results of a test sample - Nomalized Weight Percent Profile
| Carbon |
Saturates |
Unsaturates |
Total |
Cyclic
|
Normal +Iso
|
Cyclic
|
Normal +Iso
|
Aromatics
|
Oxygenates
|
2
|
0.00
|
0.00
|
0.00
|
0.00 |
0.00 |
2.73
|
2.73
|
3
|
0.00 |
0.00 |
0.00
|
0.00 |
0.00 |
0.00
|
0.00
|
4
|
0.00 |
0.00 |
0.00 |
0.00 |
0.00 |
0.00
|
0.00
|
5
|
0.00 |
0.00 |
0.00 |
0.00 |
0.00 |
7.65
|
7.65
|
6
|
1.09
|
1.75
|
1.08
|
1.27
|
2.17
|
0.00
|
7.37
|
7
|
3.32
|
4.34
|
2.00
|
0.84
|
2.65
|
0.00
|
15.15
|
8
|
5.24
|
8.27
|
0.00
|
0.42
|
8.65
|
0.00
|
22.58
|
9
|
4.16
|
3.48
|
0.00
|
0.00
|
5.61
|
0.00
|
13.25
|
10
|
2.09
|
5.16
|
0.00
|
0.00
|
4.21
|
0.00
|
11.45
|
11
|
0.00
|
0.00
|
0.00
|
0.00
|
0.00
|
0.00
|
0.00
|
Total
|
15.90
|
23.01
|
3.08
|
2.53
|
23.28
|
10.38
|
78.18
|
|
|
|
|
|
|
|
|
Fraction >200°C
|
15.41
|
|
|
MTBE
|
7.65
|
|
Polynaphthenes
|
6.41
|
|
|
Ethanol
|
2.73
|
|
Table 3. Volume % profile of a test sample - Normalized Volume Percent Profile
Oxygenates are reported as a group per carbon number but also per component. In Figure 2, a chromatogram of a gasoline is shown. Again, a clear view of the group type separated by carbon number and the oxygenates obtained, in this case only MTBE. From this chromatogram, volume and weight percent profile reports are generated.
Figure 2. chromatogram of a gasoline sample.
The reports are divided into several columns showing saturated and unsaturated component groups. Furthermore, a clear overview per carbon number is shown as well as the totals per group and per carbon number.
The determination of oxygenates, Paraffins, Olefins, naphthenes and aromatics with the Bruker PIONA+ Analyzer. This analyzer provides the required mass% and volume% reports and functions fully according the ASTM methods D 6839 and D 6293.
About Bruker - Chemical and Applied Markets
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 - Chemical and Applied Markets (CAM).
For more information on this source please visit Bruker by Bruker - Chemical and Applied Markets.