Application Note # CA-270368 Detailed Hydrocarbon Analysis of Naphtha

Introduction
Individual hydrocarbon components of spark-ignition engine fuels and their mixtures can be determined with well-known detailed hydrocarbon analysis methods such as ASTM D 5134, D 6729 and D 6730. These methods use long (50 to 100 m), narrow bore capillary (250 m) columns to meet the high resolution specifications of the methods. The analysis time, however, usually exceeds two hours. Improving the speed of DHA analysis is possible with shorter columns having a smaller column internal diameter. By choosing the proper column dimensions, the plate number (i.e. separation performance) is kept constant. Table 1 shows a comparison table of columns with identical plate numbers for different column dimensions.
Table 1: Comparison between column dimensions with identical plate number. Column ID (mm) 0.25 (standard) 0.15 0.10 Column length (m) 100 60 40 Column head pressure (kPa) 260 550 800

Software: GC Control and Data Handling: Galaxie Chromatography software DHA Calculations: DHA plug-in software fully integrated into Galaxie

Materials and reagents

Column: PONA CB, 40 m x 0.1 mm x 0.2 m Samples: Light naphtha, naphtha

Conditions
Carrier Gas: Helium, 95 psi Injector: split 700:1, 250 C Injection Volume: 1 L Oven: 35 C (5 min), @ 20 C/min to 45 C (6 min), @ 2.5 C/min to 60 C (6 min), @ 5 C/min to 220 C (2.5 min) Detector: 300 C

Results and discussion

To validate the performance between a standard DHA and a fast DHA a light naphtha sample is analyzed on both analyzers. Figure 1 shows a fraction of the analysis between the two methods with cyclohexane and toluene as reference components to synchronize both analyses. Note that the time scale for the fast DHA is stretched to match time scale of the standard DHA. In effect the fast DHA fraction is 9 min long while the standard DHA fraction is 28 min. The resolution of both analyses is similar, resulting in an identical separation performance using the fast DHA method. Note that the (relative) elution order for some components of the fast DHA example differs compared to the standard method as result of non-optimized method conditions.

This application note describes a fast DHA method. By using a 40 m x 0.1 mm x 0.2 m PONA CB column, the analysis time is reduced, depending on the sample type, by 20 to 40 minutes. This is a factor 3 to 4 shorter analysis time compared to the conventional 100 m column DHA application.

Instrumentation
Technique: DHA Analyzer for fast DHA Injector: 1177 S/SL Split/splitless with full EFC control Detection: FID with full EFC control Autosampler: Bruker CP-8400 AutoSampler

Identical high separation performance

250m x 100m upper chromatogram 100m x 40m lower chromatogram

Figure 1: Comparison between standard and fast DHA of a Naphtha sample.

53

40

58

Synchronized with cyclohexane and toluene

42 45 50

66 38

60

36

28 min

9 min

Table 2: Peak identification.

Fast detailed hydrocarbon analysis

3 8 11 22 26 23

35

53

40

80 42 45 58 66 70

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46

propene iso-butane butane t-2-butene neo-Pentane c-2-butene cyclobutane iso-pentane 1-pentene iso-Propanol pentane t-2-pentene c-2-pentene 2-methyl-2-butene 2,2-dimethylbutane 4-methyl-1-pentene cyclopentene 3-methyl-1-pentene cyclopentane MTBE 2,3-dimethylbutane 2-methylpentane 3-methylpentane 2-methyl-1-pentene 1-hexene hexane t-2-hexene t-3-hexene 2-methyl-2-pentene t-3-methylcyclopentene t-3-methyl-2-pentene 1-hexyne c-2-hexene 2,2-dimethylpentane methylcyclopentane 2,4-dimethylpentane 2,2,3-trimethylbutane benzene 3,3-dimethylpentane cyclohexane t-4-methyl-2-hexene 2-methylhexane 2,3-dimethylpentane 2-methyl-1,5-hexadiene 3-methylhexane c-1,3-dimethylcyclopentane

47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92

1,1-dimethylcyclopentane t-1,3-dimethylcyclopentane 3-ethylpentane t-1,2-dimethylcyclopentane 1-heptene 2,2,4-trimethylpentane heptane c-3-heptene t-3-methyl-2-hexene t-2-heptene c-1,2-dimethylcyclopentane methylcyclohexane 1,1,3-trimethylcyclopentane ethylcyclopentane 2,4-dimethylhexane ctc-124-trimethylcyclopentane 3,3-dimethylhexane 2,3,3-trimethylpentane ctc-123-trimethylcyclopentane toluene 3-methyl-3-ethylpentane c-1,3-dimethylcyclohexane 3,4-dimethylhexane (D) 2-methylheptane 4-methylheptane 3-methylheptane 3-ethylhexane 1,1-dimethylcyclohexane t-1,3-ethylmethylcyclopentane t-1,2-ethylmethylcyclopentane 1,1-ethylmethylcyclopentane t-1,4-dimethylcyclohexane cycloheptane octane iso-propylcyclopentane c-12-ethylmethylcyclopentane c-1,2-dimethylcyclohexane 2,4-dimethylheptane 4,4-dimethylheptane 2,6-dimethylheptane 3,5-dimethylheptane 2,5-dimethylheptane 3,3-dimethylheptane ethylbenzene 2,3,4-trimethylhexane ctt-1,2,4-trimethylcyclohexane

93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138

2,3,3-trimethylhexane p-xylene 3,4-dimethylheptane(L) 2,3-dimethylheptane 4-ethylheptane 4-methyloctane 2-methyloctane ctc-124-trimethylcyclohexane 3-ethylheptane 3-methyloctane o-xylene 1-nonene t-1-methyl-4-ethylcyclohexane c-1-methyl-4-ethylcyclohexane t-1-me-2-n-propylcyclopentane nonane t-1-methyl-2-ethylcyclohexane iso-propylcyclohexane 3,3,5-trimethylheptane 2,2-dimethyloctane 2,5-dimethyloctane sec-butylcyclopentane 2,6-dimethyloctane 2,3,6-trimethylheptane 3,3-dimethyloctane 2-methyl-3-ethylheptane n-propylbenzene 1-methyl-3-ethylbenzene 1-methyl-4-ethylbenzene 2,5,5-trimethylheptane 2,3-dimethyloctane 4-methylnonane 1-methyl-2-ethylbenzene 3,3,4-trimethylheptane 3-ethyloctane iso-butylbenzene decane 1,2,3-trimethylbenzene 1-methyl-4-isopropylbenzene 1-methyl-2-isopropylbenzene 1-methyl-3-n-propylbenzene 1-methyl-4-n-propylbenzene 1-methyl-4-n-propylbenzene 1,4-diethylbenzene 1,2-diethylbenzene undecane

108

38

72 87

89 90 94 97 103 129

10

15

20

25

30

35

Min

40

Figure 2: Complete analysis of a Naphtha sample by fast DHA.

High resolution analysis

8 11

22

23

26

35

53

Figure 3: Magnified section of a Naphtha sample from neo-pentane up to heptane.

21 19 38 14 5
3 4

40

42

45

43 39
8

48 49 47

50

15

36 34
5 6

37

44
9 Min 10

For the fast detailed hydrocarbon analyzer a standard sample mixture containing n-alkanes is used for calibration. The retention times of the n-alkanes are used to calculate the retention indices of the sample components. These retention indices are compared with a database and peaks are assigned accordingly. Table 2 shows a number of the components in the database, which contains more than 450 components. This approach is very powerful, with virtually all peaks identified. A good example of this is shown in the magnified fraction of the chromatogram (from Figure 2), depicted in Figure 3. After each analysis, the fast DHA results are converted using the database of the DHA plug-in software. This database contains component information such as density, Motor Octane Number (MON) and Research Octane Number (RON) values, vapor pressure and others. Together with the chromatographic results, the DHA software makes the appropriate calculations and generates associated results. Different reports, depending on the type of information needed, can be generated. In the component identification report, the weight and volume percent for each component is listed (Table 3). The number of components listed in the report can be over the 450. In order to create a composition overview, similar components mostly isomers, are grouped as paraffins, isoparaffins, olefins, naphthenes, aromatics and oxygenates

per carbon number by weight and volume percent in the PIONA report (table 4). Further summarization of the sample composition results in the sample properties report. The report includes boiling range, MON, RON and density and other sample properties as shown in table 5. The naphtha sample is analyzed multiple times to demonstrate the systems repeatability. A summary of the results is given in table 6, which shows excellent repeatability for both individual components like benzene and toluene, and sample properties like RON, MON and density. Shown also in table 6 are the repeatability results for hexane and heptane, demonstrating that the fast DHA analyzer is capable of measuring components at a higher concentration level. Figure 4a and 4b illustrates that the fast DHA method generates a weight percent repeatability for benzene and toluene that fits perfectly within the repeatability window specified by different DHA methods of ASTM. In order to validate the dynamic range of the Fast DHA analyzer three Naphthas are analyzed that have significant different component concentrations. Figure 5 demonstrates a perfect peak overlap of the components in the C8 region ensuring repeatable identification and quantification of the components.

Table 3: Component identification report.

FAST DHA Analyzer Analysis according to FAST DHA Sample Info N.A. Sample Type Sample Analyst ADMINISTRATOR Vial 12 Data File \Naptha\FastDHA Naptha.DATA Method \450 Fast DHA\450 Fast DHA Samples\450-GC Fast DHA.dha Description FastDHA Naptha Instrument 450-GC 110117 Detailed Hydrocarbon Analysis ID 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 RT 2.642 2.809 2.954 3.029 3.487 3.778 4.059 4.325 4.901 4.937 5.035 5.361 5.798 6.523 6.601 6.725 6.923 7 .452 7 .678 7 .827 CRT 2.642 2.809 2.954 3.029 3.487 3.766 4.059 4.325 4.901 4.937 5.019 5.361 5.775 6.523 6.601 6.725 6.923 7 .452 7 .678 7 .827 Index 300.00 354.91 400.00 410.32 468.31 500.00 517 .52 532.37 561.62 563.33 567 .18 582.60 600.00 622.55 624.75 628.19 633.56 647 .19 652.72 656.28 * * * * Name * * propane iso-butane butane neo-Pentane iso-pentane pentane 2-methyl-2-butene 2.2-dimethylbutane cyclopentane 2.3-dimethylbutane 2-methylpentane 3-methylpentane hexane 2.2-dimethylpentane methylcyclopentane 2.4-dimethylpentane 2.2.3-trimethylbutane benzene 3.3-dimethylpentane cyclohexane Area 8.5 144.0 931.8 6.5 1644.7 2451.6 1.8 33.2 212.9 144.0 1096.7 699.0 1905.2 16.6 633.5 55.3 3.6 150.1 9.8 379.0 Area Percent 0.04 0.72 4.67 0.03 8.24 12.29 0.01 0.17 1.07 0.72 5.50 3.50 9.55 0.08 3.18 0.28 0.02 0.75 0.05 1.90 Weight Percent 0.06 0.93 5.57 0.04 9.07 13.52 0.01 0.18 1.17 0.79 5.80 3.70 9.19 0.08 3.20 0.28 0.02 0.62 0.05 1.92 Volume Percent 0.08 1.13 6.53 0.04 9.93 14.65 0.01 0.18 1.07 0.94 6.02 3.77 9.46 0.08 2.90 0.28 0.02 0.48 0.05 1.67

Table 4: Weight percent profile PIONA report.

FAST DHA Analyzer Analysis according to FAST DHA Sample Info N.A. Sample Type Sample Analyst ADMINISTRATOR Vial 12 Data File \Naptha\FastDHA Naptha.DATA Method \450 Fast DHA\450 Fast DHA Samples\450-GC Fast DHA.dha Description FastDHA Naptha Instrument 450-GC 110117 Weight Percent Profile Saturates Carbon 1 2 3 4 5 6 7 8 9 9+ Total 14.01 1.17 5.14 5.06 1.49 1.15 0.90 9.04 10.48 5.52 4.92 4.61 1.64 37 .11 0.06 5.46 13.44 9.22 5.02 3.77 2.46 0.61 40.05 0.22 0.05 0.16 0.01 0.62 1.56 1.55 0.88 0.18 4.79 0.08 1.34 2.10 0.32 3.83 0.06 6.37 23.66 25.46 17 .39 13.07 11.25 2.74 100.00 Cyclic Iso Normal Unsaturates Cyclic N+ Iso Aromatics Oxyg Unknown Total

Table 5: Properties report.

FAST DHA Analyzer Analysis according to FAST DHA Sample Info N.A. Sample Type Sample Analyst ADMINISTRATOR Vial 12 Data File \Naptha\FastDHA Naptha.DATA Method \450 Fast DHA\450 Fast DHA Samples\450-GC Fast DHA.dha Description FastDHA Napth Instrument 450-GC 110117 Physical Properties MON Value RON Value 57 .6 58.6 Net Heat Gross Heat 44.2 48.0 kJ/g kJ/g

Reid Vapor P .

14.64

mm Hg TBP Report

Density

0.6903

g/ml

Recovery Percentage TBP % OFF IBP 5% 10 % 20 % 30 % 40 % 50 % 60 % 70 % 80 % 90 % 95 % FBP -0.5 9.5 36.1 36.5 36.5 63.3 71.8 90.0 99.2 119.4 143.0 153.5 176.1 D86 % OFF

100.0

Conclusion
The Bruker Fast Detailed Hydrocarbon Analyzer is specially designed for analyzing individual hydrocarbon components, as well as oxygenates present in spark ignition fuels and light hydrocarbon streams such as naphtha. The analyzer is equipped with a 40 m x 0.1 mm PONA CB column. The analysis time is significantly reduced compared to conventional DHA while maintaining separation power and ensuring analytical results of high quality. Being able to calculate corrected retention times is a real benefit when using narrow bore columns. The peak shape from components at a higher level in the sample tend to show overloading and thus retention time shifting. The DHA software calculates the corrected retention time based on peak skewing, ensuring correct peak assignment.

The fast DHA analyzer yields all required reports. A detailed hydrocarbon analysis report gives, per component, the content in weight% and volume%, as well as (corrected) retention times and retention index. PIONA reports can be generated, in weight% and or volume%, where sample components are grouped in chemical classes, e.g. iso-, cyclic and normal paraffins and olefins, aromatics and oxygenates. In conclusion, a sample properties report can be generated which gives the MON and RON values, as well as read vapor pressure, density, net heat and gross heat, and a boiling point distribution. The fast DHA analyzer is perfectly capable of analyzing relative light hydrocarbon streams such as naphtha. Peak identification via retention index and comparison with a database proved to be a very powerful methodology.

Fast DHA Benzene concentration Average Repeatability according ASTM D 6730

Weight % 0.70

Repeatability according ASTM D 5134

Repeatability according ASTM D 6729

Table 6: Repeatability results of the naphtha sample.

Naphtha
0.65

Run 1 2 3 4 5 6 7 8 9 10 11 12
Fast DHA Toluene concentration Average Repeatability according ASTM D 6730

MON 57 .3 58.4 58.0 58.6 58.6 58.5 58.6 57 .6 57 .9 58.4 57 .5 58.5 58.5 56.7 58.0 58.0 58.5 58.2 57 .6 58.8 58.1 0.54 0.93

RON 58.2 59.5 59.0 59.8 59.9 59.7 59.8 58.6 59.2 59.6 58.5 59.7 59.8 57 .6 59.2 59.2 59.7 59.2 58.8 59.9 59.2 0.63 1.07

Density (g/mL) 0.6889 0.6886 0.6890 0.6888 0.6897 0.6890 0.6892 0.6903 0.6899 0.6890 0.6893 0.6891 0.6883 0.6897 0.6897 0.6891 0.6890 0.6903 0.6893 0.6880 0.6892 0.0006 0.09

Hexane Wt% 9.20 9.19 9.19 9.22 9.19 9.23 9.19 9.20 9.23 9.20 9.22 9.24 9.25 9.24 9.22 9.22 9.19 9.21 9.13 9.23 9.2 0.027 0.29

Heptane Wt% 5.00 5.02 5.01 5.02 5.01 5.03 5.00 5.01 5.04 5.02 5.05 5.03 5.03 5.08 5.04 5.06 4.99 5.02 4.97 5.03 5.0 0.025 0.49

Benzene Wt% 0.62 0.62 0.62 0.62 0.62 0.63 0.62 0.62 0.62 0.62 0.62 0.63 0.62 0.62 0.62 0.62 0.62 0.62 0.62 0.62 0.6 0.0031 0.50

Toluene Wt% 1.55 1.55 1.55 1.55 1.55 1.56 1.55 1.55 1.56 1.55 1.56 1.56 1.56 1.57 1.56 1.57 1.54 1.55 1.54 1.56 1.6 0.0083 0.53

0.60

0.55

10

15

Run

20

Figure 4a: Repeatability results of Benzene in Naphtha.

13 14 15 16 17 18 19 20 Average St.dev. RSD%

Weight % 1.70

Repeatability according ASTM D 5134

Repeatability according ASTM D 6729

1.60

1.50

1.40

10

15

Run

20

Figure 4b: Repeatability results of Toluene in Naphtha.

Naphtha 1 Naphtha 2 Naphtha 3

14

15

16

17

Min

18

Figure 5: Elution profile of three different Naphthas in the C8 region at different concentration levels.

References
ASTM D 5134-98, 2003, Standard Test Method for Detailed Analysis of Petroleum Naphthas through n-Nonane by Capillary Gas Chromatography, ASTM International, West Conshohocken, PA, www.astm.org. ASTM D 6729-04, Standard Test Method for Determination of Individual Components in Spark Ignition Engine Fuels by 100 Meter Capillary High Resolution Gas Chromatography, ASTM International, West Conshohocken, PA, www.astm.org. ASTM D 6730-01, 2006e1, Standard Test Method for Determination of Individual Components in Spark Ignition Engine Fuels by 100 Meter Capillary (with Pre column) High Resolution Gas Chromatography, ASTM International, West Conshohocken, PA, www.astm.org.

Keywords Naphtha Fast GC analysis High Resolution Chromatography

Instrumentation & Software Bruker DHA Analyzer for fast DHA Galaxie Chromatography software DHA plug-in software

For research use only. Not for use in diagnostic procedures.

Bruker Daltonik GmbH

Bremen Germany Phone +49 (0)421-2205-0 Fax +49 (0)421-2205-103 sales@bdal.de

Bruker Daltonics Inc.

Billerica, MA USA Phone +1 (978) 663-3660 Fax +1 (978) 667-5993 ms-sales@bdal.com

www.bruker.com/chemicalanalysis

Bruker Daltonics is continually improving its products and reserves the right

to change specifications without notice. Bruker Daltonics 01-2011, #CA-270368