Research Development Center for Refinery Industry

Płock, Poland

Research Development Center for Refinery Industry

Płock, Poland
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Sitko R.,University of Silesia | Zawisza B.,University of Silesia | Kowalewska Z.,Research Development Center for Refinery Industry | Kocot K.,University of Silesia | Polowniak M.,University of Silesia
Talanta | Year: 2011

The determination of fatty acid methyl esters (FAME) in diesel fuel blends is an important aspect of production and blending process as well as quality control of distribution operations. In this study, energy-dispersive X-ray fluorescence spectrometer (EDXRF) is used for the first time for determination of FAME in biodiesel blends. The principle of the method is based on intensity difference of X-ray radiation scattered from hydrocarbons and from FAME. The experiment shows that coherent and incoherent radiation, commonly applied for evaluation of the average atomic number of the sample with light matrix, cannot be applied for FAME determination. However, the application of scattered continuous radiation gives excellent correlation between FAME concentration and intensity of scattered radiation. The best results are obtained if continuum is collected in the range of energy between 10.5 and 15.0 keV for rhodium X-ray tube, operated at 35 kV. Linear relationship between the FAME concentration and the inverse of scattered continuous radiation is obtained with the correlation coefficients of 0.999. Standard deviation of measurement is ca. 0.46% (v/v) of FAME and detection limit is 1.2% (v/v) for 600 s counting time and 50% dead-time loss using Si-PIN detector. The investigation shows that crucial issue in determination of FAME in biodiesel blends using EDXRF spectrometer is the precision of measurements resulting from the counting statistics. Therefore, much better results (0.20% (v/v) standard deviation and 0.52% (v/v) detection limit) can be expected if higher intensity of primary radiation is applied and X-ray spectrum is collected by silicon drift detector of high input count rate. For concentration of FAME from 10 to 100% (v/v), the differences between reference method (Fourier transform infrared spectrometry) and the proposed method usually do not exceed 1% (v/v) of FAME. The proposed method is fast, simple and enables FAME determination in wide range of concentration up to 100% of FAME without any sample treatment. © 2011 Elsevier B.V. All rights reserved.

Kowalewska Z.,Research Development Center for Refinery Industry | Welz B.,Federal University of Santa Catarina | Welz B.,Federal University of Bahia | Castilho I.N.B.,Federal University of Santa Catarina | Carasek E.,Federal University of Santa Catarina
Talanta | Year: 2013

The aim of this work was to investigate the influence of magnesium acetylacetonate (MgA) on the signal of organic forms of vanadium in xylene solution by graphite furnace atomic absorption spectrometry. MgA alone or mixed with palladium acetylacetonate (PdA) was considered as a chemical modifier. It has been found that MgA does not improve, but decreases significantly the integrated absorbance of V in the form of alkyl-aryl sulfonates, acetylacetonates, porphyrins and in lubricating oils, while its effect is negligible in the case of "dark products" from petroleum distillation, i.e., heavy oil fractions and residues. The decrease is also observed in the presence of Pd. The MgA (or MgA+PdA) effect on the integrated absorbance of V has been studied using the following variants: different ways of modifier application, various pyrolysis temperature, additional application of air ashing, preliminary pretreatment with iodine and methyltrioctylammonium chloride, application of various graphite furnace heating systems (longitudinal or transverse) and various optical and background correction systems (medium-resolution line source spectrometer with deuterium background correction or high-resolution continuum source spectrometer). The experiments indicate formation of more refractory compounds as a possible reason for the decrease of the integrated absorbance for some forms of V in the presence of MgA. The application of MgA as a chemical modifier in V determination is not recommended. Results of this work have general importance as, apart from the intentional use of MgA as a modifier, organic Mg compounds, present in petroleum products for other reason (e.g. as an additive), can influence the signal of V compounds and hence the accuracy in V determination. Generally, petroleum products with known amount of V are recommended as standards; however, lubricating oils can be inadequate for "dark products" from petroleum distillation. In the case of unknown samples it is recommended to check the effect of Mg using recovery tests of V in a form that is affected by MgA. © 2012 Elsevier B.V. All rights reserved.

Kowalewska Z.,Research Development Center for Refinery Industry
Spectrochimica Acta - Part B Atomic Spectroscopy | Year: 2011

For the first time, high-resolution molecular absorption spectrometry with a high-intensity xenon lamp as radiation source has been applied for the determination of sulphur in crude oil and petroleum products. The samples were analysed as xylene solutions using vaporisation in acetylene-air flame or in an electrothermally heated graphite furnace. The sensitive rotational lines of the CS molecule, belonging to the Δν = 0 vibrational sequence within the electronic transition X1Σ+ → A1Π, were applied. For graphite furnace molecular absorption spectrometry, the Pd + Mg organic modifier was selected. Strong interactions with Pd atoms enable easier decomposition of sulphur-containing compounds, likely through the temporal formation of PdxSy molecules. At the 258.056 nm line, with the wavelength range covering central pixel ± 5 pixels and with application of interactive background correction, the detection limit was 14 ng in graphite furnace molecular absorption spectrometry and 18 mg kg -1 in flame molecular absorption spectrometry. Meanwhile, application of 2-points background correction found a characteristic mass of 12 ng in graphite furnace molecular absorption spectrometry and a characteristic concentration of 104 mg kg-1 in flame molecular absorption spectrometry. The range of application of the proposed methods turned out to be significantly limited by the properties of the sulphur compounds of interest. In the case of volatile sulphur compounds, which can be present in light petroleum products, severe difficulties were encountered. On the contrary, heavy oils and residues from distillation as well as crude oil could be analysed using both flame and graphite furnace vaporisation. The good accuracy of the proposed methods for these samples was confirmed by their mutual consistency and the results from analysis of reference samples (certified reference materials and home reference materials with sulphur content determined by X-ray fluorescence spectrometry). © 2011 Elsevier B.V. All rights reserved.

Kowalewska Z.,Research Development Center for Refinery Industry | Laskowska H.,Research Development Center for Refinery Industry
Energy and Fuels | Year: 2012

The significant decrease of admissible sulfur content, wide implementation of variety of components of biological origin and adequate changes of additives packages create new challenges in terms of S determination in modern automotive fuels. Wavelength dispersive X-ray fluorescence spectrometry (WD XRF) and ultraviolet fluorescence spectrometry (UVF) are currently the obligatory methods for the determination. Both methods fulfill requirements of detection and precision (much better performance of UVF) as well as give successful results in certified reference materials analysis, proficiency testing, and intermethod comparisons. Apart from satisfactory results for good quality fuels, some difficulties can be met in crucial cases, when S admissible content is exceeded. S content can be apparently exceeded in UVF analysis due to nitrogen interference as well as apparently not exceeded in UVF, and apparently not exceeded (filtered sample) or apparently exceeded (sediment on the bottom) in WD XRF analysis in cases of inhomogenous fuel samples containing S in the solid phase. In such cases, the mandatory methods will not reveal (UVF) or will not be able to prove quantitatively (WD XRF) the contamination of automotive fuels. The work shows that the system of automotive fuels quality assessment needs improvement in terms of S content control. Simplified standard addition method turned out to be efficient for overcoming multiplicative effect of absorption by main components of matrix (C, H, and O) in WD XRF, but it does not correct N influence on UVF determination that is an effect of additive character. © 2012 American Chemical Society.

Kowalewska Z.,Research Development Center for Refinery Industry S.A | Ruszczynska A.,University of Warsaw | Jaron I.,Polish Geological Institute | Bulska E.,University of Warsaw
Atomic Spectroscopy | Year: 2012

The analytical performance of inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry GCP-MS) for the determination of Fe and Ca in alumina-based nickelmolybdenum hydrodesulphurization catalysts was evaluated. Although the typical concentration of both elements is quite high (0.02-0.4% for Fe and 0.02-0.2% for Ca), the complex matrix of the catalysts strongly influences the results. Before measurements, effective digestion using HClO4+HF, H 3BO3, and HCl was executed. The accuracy of the results was evaluated by spiking a raw catalyst sample before digestion and measuring the recoveries. In the case of ICP-OES, a 10-fold dilution of the sample digest solution yielded recoveries of 95% for Fe and 102% for Ca. In the case of ICP-MS, the use of dynamic reaction cell (DRC) with ammonia as a reaction gas along with the low mass bandpass was crucial. The optimized ICP-DRC-MS conditions were as follows: 56Fe and 42Ca as monitored isotopes, ammonia flow rate of 0.45 mL min-1, RPa of 0.00 and RPq of 0.65 mL min-1. Applying these conditions, the recovery was 97% for Fe and 89% for Ca, and the results of ICP-OES and ICPMS were in satisfactory agreement. As no appropriate reference materials are available, cross-validation of both methods turned out to be a crucial tool for confirmation of the accuracy of the results. This work also shows that the use of DRC is an effective way for spectral interference elimination in a complex matrix.

Nickel is a severe poison to cracking catalysts, therefore its content in raw material for cracking (which is a mixture of heavier oils boiling in the range 330-550°C) has to be controlled at levels below mg kg-1. A reliable, simple and fast method of Ni determination in this kind of material is proposed with a detection limit of 1.2 μg kg-1 in the initial sample at 1:5 dilution m/v. The method relies just on sample dilution in xylene and Ni determination using graphite furnace atomic absorption spectrometry, with palladium acetylacetonate and air ashing as a double modifier. The method was successfully validated using mineralization as an alternative sample preparation procedure. The following commonly used methods failed as tools for verification of analysis accuracy: Ni in the investigated cracking feed behaved completely differently than in the available certified reference materials; recovery of standard added to samples was close to 100%, while results were up to 10 times too low; pyrolysis curves did not reveal a decrease of integrated absorbance appearing in the entire investigated temperature range. Decreased evaporation of Ni porphyrins due to interaction with graphite, and increased Ni binding in the solid phase in the presence of asphaltenic matrix, should be taken into account in interpretation of technologically important information on speciation of Ni (volatile and non-volatile Ni forms). © 2013 The Royal Society of Chemistry.

Kowalewska Z.,Research Development Center for Refinery Industry
Spectrochimica Acta - Part B Atomic Spectroscopy | Year: 2012

Various organic and inorganic Ni forms were investigated using graphite furnace atomic absorption spectrometry. Experiments without chemical modification showed a wide range of characteristic mass values for Ni (from 6.7 to 29 pg) and the importance of interaction with graphite. With the aim of achieving signal unification of organic Ni forms, different ways of chemical modification were tested. Some rules that govern the behavior of Ni were found and confirmed a significant role of the organic component of the analyte molecule in the analytical process. The application of air as an internal furnace gas in the pyrolysis phase and the Pd modifier injected with the sample solution improved the signal of porphyrins, while the application of iodine and methyltrioctylammonium chloride was required for organic compounds containing oxygen-bound Ni atoms. The Ni signal was strongly diminished when an aqueous solution containing hydrochloric acid was measured with the Pd modifier injected over the sample. Using the developed analytical methods, the range of characteristic mass values for various Ni forms totally dissolved in organic or aqueous solution was 6.5-7.9 pg. © 2012 Elsevier B.V.

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