Elemental Analysis for Quality and Process Control at Refineries, for Lubricants and Wear Metals in Engine Oils

Bruker offers best-in-class turnkey elemental analysis solutions for the entire petrochemical industry – from feedstock at refineries, to catalyst elements in fluid catalytic cracking (FCC) processes, to final process and quality control – enhancing productivity and increasing profit.

Turnkey Analytical

Solutions for Refineries
Elemental analysis is vital for process control in the petrochemical refining industry. X-ray Fluorescence (XRF) spectrometry enables direct analysis of petrochemical samples, without digestion or dilution, making it the ideal technology in many cases. Equipped with polarized optics, the S2 POLAR (Figure 1) – a benchtop Energy Dispersive XRF (EDXRF) spectrometer – is the optimal analytical tool for refineries to fulfill regulatory compliance for Sulfur (S) and Ultra-Low Sulfur (ULS). The S2 POLAR allows for norm compliant analysis according to important international norms such as ASTM D7220, D4294, ISO 13032, and ISO 20847.
Figure 1: Easy-to-use EDXRF S2 POLAR with integrated TouchScreen

Other elements, such as Ni and V, are also of interest at refineries and measured according to ASTM D8252.  Chlorine (Cl) is particularly noteworthy due to its potential to increase corrosion. Chlorine determinations are often performed in compliance with ASTM D4929 in crude oil. Thanks to the multi-element capability of the S2 POLAR, both norms are fulfilled by the instrument. The polarized excitation of the S2 POLAR reduces the background for several elements substantially, resulting in excellent Lower Limits of Detection (LLD). To highlight the instrument’s outstanding Cl performance, repeatability data and calibration curve for the lower Cl concentration range are shown in Table 1 and Figure 2, respectively.
Table 1: Repeatability of 21 times freshly prepared QC diesel samples, measured on the polarized EDXRF S2 POLAR
For certain petrochemical norms, the use of Wavelength Dispersive XRF (WDXRF) technique is mandatory. For example, the analysis of Sulfur in petroleum products according to ASTM D2622 and ISO 20884 is a task for Bruker’s WDXRF instruments, the S6 JAGUAR or S8 TIGER.
The S6 JAGUAR (Figure 3) is equipped with a 400 W HighSense™ X-ray tube making it the most powerful benchtop WDXRF. Modern software with enhanced fundamental parameter algorithms and state-of-the-art hardware enables excellent analytical performance. It achieves outstanding sensitivity for a wide range of elements (F to Am), and the different configuration options allow to optimize the system for the various analytical needs. As an example for the analytical performance of the S6 JAGUAR, results for the analysis of minor elements and traces in anode coke are shown in Table 2.

Figure 3: Compact benchtop WDXRF spectrometer S6 JAGUAR, available with integrated TouchScreen and 24-position XY-loader configuration for high sample throughput

The S6 JAGUAR also excels the analysis of intermediate refinery products and final products such as Pb and Mn in gasoline according to ASTM D5059. Beside liquid products, also solids such as material from the fluid catalytic cracking process (FCC), petcoke, and bitumen can be easily analyzed.
For the lowest detection limits as well as for the analysis of traces, the S8 TIGER WDXRF spectrometer is the optimal choice. The quantification of over 30 elements in all kinds of hydrocarbons is easily possible with the universal calibration package PETRO-QUANT. Whether XRF is employed as a technique to quantify sulfur from the crude oil to refined products or to analyze refinery process impurities such as metals and catalysts: PETRO-QUANT covers it all!

Oil & Lubricant Manufacturing

Oils and lubricants serve multiple functions in engineering. Beside lubrication, they cool pistons in car engines and during metal milling, protect against corrosion, and bind particles. Precise and reliable analysis of additives at the minor and trace level is the key for high product quality. Moreover, accurate analyses allow to use expensive additives sparsely and thus to safe production cost, while ensuring the performance requirements of the product. XRF is the most important analytical method for the analysis of additives and impurities, no matter if oils, greases, or waxes need to be qualified (ASTM D6443, and D4927) and to detect engine debris in the form of wear metals (DIN 51399). The norm-compliance to DIN 51399 of the WDXRF S8 TIGER is demonstrated in Table 3.
These norms mentioned are fulfilled by WDXRF instrumentation, while the EDXRF S2 PUMA meets the requirements for the ASTM D6481 and D7751. The later one covers 7 key additive elements including Mg, Ca, and Mo in lubricating oils.

Conclusion

There is a wide variety of raw, intermediate, and final petrochemical, ranging from incoming feedstock at refineries to intermediate process streams and final automotive fuels or lubricants. These materials vary significantly in their physical properties, from highly volatile such as gasoline to viscose or even solid as greases and waxes. Each of these products requires precise and reliable elemental analysis. This article demonstrates the suitability and benefits of EDXRF and WDXRF instruments for multiple key applications in the petrochemical industry.