Chemical Analysis PIONA+ Analyzer Characterization of Engine Fuels by Hydrocarbon Group Type think forward Gas Chromatography
Bruker 450 PIONA+ Analyzer Bruker s innovative PIONA+ TM Analyzer provides a highly flexible GC analysis platform to obtain comprehensive characterization and quantitative information, including hydrocarbon group types, saturated and unsaturated paraffins and naphthenes, aromatics and oxygenates per carbon number for spark emission fuels. Unparalleled operational flexibility. The inherent flexibility of the analyzer s design allows the operator to conduct analyses in any one of a number of different operational modes including PNA, PONA, PIONA, O-PONA and O-PIONA. Compliant with industry standard methods. Due to the outstanding operational flexibility of the analyzer, it can be utilized for any of the following established standard methods: ASTM D6839, ASTM EN-ISO-22854, ASTM D5443, ASTM D1319, IP-382, IP-526, EN 14157, UOP 870 and DIN-51448. A complete and fully integrated solution. Bruker s PIONA+ TM Analyzer is based on the powerful 450-GC gas chromatograph and comes complete with ultra high performance columns and traps, Galaxie chromatography data handling software, dedicated PIONA+ data analysis and report generation software, factory test/certification, calibration/reference standards, PIONA+ manual and on-site installation/performance verification. A single vendor solution. All of Bruker s GC analyzers are built and tested at our factory using all Bruker components. On-site installation and performance verification is then performed by Bruker trained and certified engineers. A powerful analyzer yet very easy to use. Bruker s high performance 450-GC, ultrastable columns and traps and powerful Galaxie data system with built-in PIONA+ software all contribute to the analyzer s ability to generate outstanding analysis results day after day. However, a powerful system does not necessarily have to mean that only highly skilled operators are able to use it. Figure 1: The Bruker PIONA+ TM Analyzer is based on the powerful 450-GC with Galaxie Data System.
Key Benefits PIONA is the preferred technique today to characterize petroleum streams by hydrocarbon group type. The technique is based on the separation of individual hydrocarbon groups by utilizing a complex yet fully automated multi-dimensional gas chromatography approach. Analysis challenge Since the first description of PNA (hydrocarbon type) group analysis in the 1980s, the multi-dimensional gas chromatography based technique has gone through continuous improvement and change. Although the technique has evolved and is now commonly used to obtain hydrocarbon group-type information for paraffins, iso-paraffins, naphthenes, olefins, aromatics and oxygenated components (see Tables 1a & 1b) by refinery laboratories worldwide, the basic chromatographic selectivity required to do so has remained fundamentally unchanged. From a gas chromatography hardware standpoint, several different approaches have been used in the past, but the exchange of columns and traps within the multi-dimensional system has always been the most problematic aspect of the analysis. Recent developments in thermal management techniques and mechanical interconnection devices by Bruker have enabled the development of a new class of hydrocarbon group analyzer based on the 450-GC (see Figure 1). The analyzer is not only fully capable of performing a complete analysis as described in ASTM D6839 (and similar methods) but provides unprecedented analysis flexibility and simplified operation through the use of a novel approach to column/trap heating and exchange (see Figure 2). Figure 2: Traps are easily accessible and do not require any tools to install or replace. Table 1a: Example of a Mass% Report. Carbon Number Group Paraffins 1 0.00 2 0.00 0.00 Cyclic 3 0.03 0.00 0.00 0.00 4 0.91 0.00 0.09 0.00 5 16.84 0.43 0.46 0.15 6 9.85 2.18 1.09 0.24 0.84 7 7.14 3.59 0.66 0.30 6.37 8 6.94 0.49 0.67 0.13 15.45 9 1.17 0.15 0.17 0.10 11.26 10 0.28 0.03 0.00 0.00 3.74 Total 43.16 6.87 3.14 0.92 37.66 BP>185 C 1.01 Oxygenates O-content MTBE 7.24 1.32 Tot. Oxygen 1.32 Table 1b: Example of Volume% Report. Carbon Number Group Paraffins 1 0.00 2 0.00 0.00 Cyclic 3 0.05 0.00 0.00 0.00 4 1.17 0.00 0.11 0.00 5 20.00 0.43 0.52 0.17 Naphthenes Aromatics Naphthenes Aromatics 6 11.07 2.13 1.19 0.26 0.70 7 7.72 3.51 0.69 0.32 5.44 8 7.30 0.47 0.69 0.14 13.19 9 1.20 0.14 0.17 0.10 9.55 10 0.29 0.02 0.00 0.00 3.12 Total 48.80 6.70 3.37 0.99 32.00 BP>185 C 0.89 Oxygenates MTBE 7.24
450 PIONA+ TM Analyzer Reduced analysis time and increased sample throughput efficiency through the use of concurrent heating A unique aspect of the design of the Bruker 450 PIONA+ system is the ability to independently heat the individual traps. As shown in Figure 3, when the PIONA+ system is operated in the normal mode, a total analysis time of 180 minutes is required to elute all of the component groups. However, as shown in Figure 4, a reduction in total analysis time from 180 minutes to 95 minutes can be obtained. Such a reduction in analysis time is achieved by carefully optimizing the temperature settings of the various traps and columns, and independently heating the Molsieve traps. This is referred to as concurrent heating. This approach enables a fast PIONA mode, which results in the elution of the paraffins immediately after their naphthene and iso-paraffin counterparts. However, the elution integrity of the component groups remains intact with no negative influence on either naphthene or iso-paraffin groups, (see Figure 4 inset for a close up view of the resulting elution sequence). By employing this technique, sample throughput can be nearly doubled compared to systems that do not offer this unique capability. Figure 3. Chromatogram of a calibration mix in conventional PIONA+ mode. min Figure 4. Chromatogram of a calibration mix using concurrent heating in fast PIONA+ mode.
Table 2: The 450 PIONA+ TM Analyzer is extremely flexible and can be configured to run a wide variety of methods. Extreme Flexibility EN 14517 EN-ISO-22854 PNA PONA PIONA O-PONA O-PIONA X X ASTM D6839 X x DIN 51448-2 X x x Determining total olefin content is now practical The stability, sample loading and lifetime for all of the critical chromatographic components have been improved and thoroughly optimized in the Bruker 450 PIONA+ TM Analyzer. However, the most noteworthy improvement has been increasing the sample loading capacity of the olefin trap. As a result, it is now possible to analyze streams with olefin content as high as 35-40 % or more. This makes it quite practical to employ a single analytical method to obtain total olefin content (see example report in Table 3). 450-GC based PIONA+ TM Analyzer includes Bruker 450-GC high performance gas chromatograph equipped with: Direct injection port Bruker high performance capillary column(s) (dependent on method specified at the time of order) ASTM D1319 (FIA) X x x x DIN 51448-1 X x x x x ASTM D5443 X x x x x UOP 870 X x x x x IP 382 X x x x x = Compliant with Method = Reports Available PIONA+ column/trap/valve cabinet Flame ionization detector (FID) Full electronic flow control (EFC) of all gases CP-8400 or CP-8410 automatic liquid sampler Galaxie data system software for system control, data acquisition and report generation Galaxie PIONA+ application software Computer/monitor Pre-loaded standard methods Factory test Reference chromatogram Reference standard for use in conducting onsite performance verification Table 3: Example weight % report for a gasoline sample with very high olefinic content; in this case 46 % (highlighted in red). Saturates Unsaturates Carbon Cyclic Iso Normal Cyclic Iso Normal Aromatics Oxyg Total 3 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 4 0.00 0.00 0.06 0.00 0.03 0.54 0.00 0.00 0.64 5 0.31 11.33 2.98 0.87 9.91 7.57 0.00 0.03 32.99 6 3.17 9.95 1.40 2.40 8.58 4.40 1.72 0.04 31.67 7 4.31 6.77 0.00 2.14 4.76 1.91 7.46 0.00 27.35 8 1.42 3.12 0.00 0.39 2.06 0.00 0.07 0.00 7.05 9 0.01 0.00 0.00 0.04 0.02 0.00 0.03 0.00 0.10 10 0.01 0.00 0.00 0.09 0.00 0.03 0.01 0.00 0.13 11 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Total 9.23 31.17 4.43 5.93 25.36 14.46 9.29 0.07 99.93
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