Grzegorz Boczkaj

Characteristics of volatile organic compounds emission profiles from hot road bitumens.

A procedure for the investigation and comparison of volatile organic compounds (VOCs) emission profiles to the atmosphere from road bitumens with various degrees of oxidation is proposed. The procedure makes use of headspace analysis and gas chromatography with universal as well as selective detection, including gas chromatography-mass spectrometry (GC-MS). The studies revealed that so-called vacuum residue, which is the main component of the charge, contains variable VOC concentrations, from trace to relatively high ones, depending on the extent of thermal cracking in the boiler of the vacuum distillation column. The VOC content in the oxidation product, so-called oxidized paving bitumen, is similarly varied. There are major differences in VOC emission profiles between vacuum residue and oxidized bitumens undergoing thermal cracking. The VOC content in oxidized bitumens, which did not undergo thermal cracking, increases with the degree of oxidation of bitumens. The studies revealed that the total VOC content increases from about 120 ppm for the raw vacuum residue to about 1900 ppm for so-called bitumen 35/50. The amount of volatile sulfur compounds (VSCs) in the volatile fraction of fumes of oxidized bitumens increases with the degree of oxidation of bitumen and constitutes from 0.34% to 3.66% (w/w). The contribution of volatile nitrogen compounds (VNCs) to total VOC content remains constant for the investigated types of bitumens (from 0.16 to 0.28% (w/w) of total VOCs). The results of these studies can also find use during the selection of appropriate bitumen additives to minimize their malodorousness. The obtained data append the existing knowledge on VOC emission from oxidized bitumens. They should be included in reports on the environmental impact of facilities in which hot bitumen binders are used.

A new procedure for the determination of distillation temperature distribution of high-boiling petroleum products and fractions

AbstractThe distribution of distillation temperatures of liquid and semi-fluid products, including petroleum fractions and products, is an important process and practical parameter. It provides information on properties of crude oil and content of particular fractions, classified on the basis of their boiling points, as well as the optimum conditions of atmospheric or vacuum distillation. At present, the distribution of distillation temperatures is often investigated by simulated distillation (SIMDIS) using capillary gas chromatography (CGC) with a short capillary column with polydimethylsiloxane as the stationary phase. This paper presents the results of investigations on the possibility of replacing currently used CGC columns for SIMDIS with a deactivated fused silica capillary tube without any stationary phase. The SIMDIS technique making use of such an empty fused silica column allows a considerable lowering of elution temperature of the analytes, which results in a decrease of the final oven temperature while ensuring a complete separation of the mixture. This eliminates the possibility of decomposition of less thermally stable mixture components and bleeding of the stationary phase which would result in an increase of the detector signal. It also improves the stability of the baseline, which is especially important in the determination of the end point of elution, which is the basis for finding the final temperature of distillation. This is the key parameter for the safety process of hydrocracking, where an excessively high final temperature of distillation of a batch can result in serious damage to an expensive catalyst bed. This paper compares the distribution of distillation temperatures of the fraction from vacuum distillation of petroleum obtained using SIMDIS with that obtained by the proposed procedure. A good agreement between the two procedures was observed. In addition, typical values of elution temperatures of n-paraffin standards obtained by the two procedures were compared. Finally, the agreement between boiling points of polar compounds determined from their retention times and actual boiling points was investigated. FigureSIMDIS and EC-GC distillation curves of fractions B, C, and D

Application of dispersive liquid-liquid microextraction and gas chromatography with mass spectrometry for the determination of oxygenated volatile organic compounds in effluents from the production of petroleum bitumen.

We present a new procedure for the determination of oxygenated volatile organic compounds in samples of postoxidative effluents from the production of petroleum bitumens using dispersive liquid-liquid microextraction and gas chromatography with mass spectrometry. The eight extraction parameters were optimized for 43 oxygenated volatile organic compounds. The detection limits obtained ranged from 0.07 to 0.82 μg/mL for most of the analytes, the precision was good (relative standard deviation below 2.91% at the 5 μg/mL level and 4.75% at the limit of quantification), the recoveries for the majority of compounds varied from 70.6 to 118.9%, and the linear range was wide, which demonstrates the usefulness of the procedure. The developed procedure was used for the determination of oxygenated volatile organic compounds in samples of raw postoxidative effluents and in effluents after chemical treatment. In total, 23 compounds at concentration levels from 0.37 to 32.95 μg/mL were identified in real samples. The same samples were also analyzed in the SCAN mode, which resulted in four more phenol derivatives being identified and tentatively determined. The studies demonstrated the need for monitoring volatile organic compounds content in effluents following various treatments due to the formation of secondary oxygenated volatile organic compounds.

Effective method of treatment of effluents from production of bitumens under basic pH conditions using hydrodynamic cavitation aided by external oxidants

Utilization of cavitation in advanced oxidation processes (AOPs) is a promising trend in research on treatment of industrial effluents. The paper presents the results of investigations on the use of hydrodynamic cavitation aided by additional oxidation processes (O3/H2O2/Peroxone) to reduce the total pollution load in the effluent from the production of bitumens. A detailed analysis of changes in content of volatile organic compounds (VOCs) for all processes studied was also performed. The studies revealed that the most effective treatment process involves hydrodynamic cavitation aided by ozonation (40% COD reduction and 50% BOD reduction). The other processes investigated (hydrodynamic cavitation+H2O2, hydrodynamic cavitation+Peroxone and hydrodynamic cavitation alone) ensure reduction of COD by 20, 25 and 13% and reduction of BOD by 49, 32 and 18%, respectively. The results of this research revealed that most of the VOCs studied are effectively degraded. The formation of byproducts is one of the aspects that must be considered in evaluation of the AOPs studied. This work confirmed that furfural is one of the byproducts whose concentration increased during treatment by hydrodynamic cavitation alone as well as hydrodynamic cavitation aided by H2O2 as an external oxidant and it should be controlled during treatment processes.

Application of dynamic headspace and gas chromatography coupled to mass spectrometry (DHS-GC-MS) for the determination of oxygenated volatile organic compounds in refinery effluents

The paper presents a new procedure for the determination of oxygenated volatile organic compounds (O-VOCs) in postoxidative effluents from the production of petroleum asphalt using dynamic headspace coupled to gas chromatography-mass spectrometry in the selected ion monitoring (SIM) mode (DHS-GC-MS). Among the GC capillary columns tested, a polar SLB-IL111 column with the ionic liquid stationary phase was found to be superior due to its high selectivity for n-alkanes and individual oxygenated volatile organic compounds. The low detection limit, good reproducibility and a wide linear range allows determination of O-VOCs at low concentration levels and applicability of the procedure to routine analyses of O-VOCs in industrial effluents with a very complex composition. The developed procedure was used for the analysis of real samples – raw effluents from the production of bitumens and effluents treated chemically through oxidation. Thirteen compounds at concentrations ranging from 0.01 μg mL−1 to 118.61 μg mL−1 were identified in the effluents. In addition, nine more compounds, mostly alcohols, aldehydes and ketones, were identified using the SCAN mode. The paper demonstrates the need for monitoring O-VOCs in processes of chemical treatment of effluents. Due to the pathways of oxidation of organic pollutants present in effluents, O-VOCs become secondary pollutants. A substantial increase in the concentration of some groups of compounds, i.e. phenol and its derivatives and aliphatic and cyclic alcohols, was found in oxidized effluents. The presence of these compounds has a negative effect on the activated sludge used in refinery wastewater treatment plants.

New procedure for the control of the treatment of industrial effluents to remove volatile organosulfur compounds

We present a new procedure for the determination of volatile organosulfur compounds in samples of industrial effluents using dispersive liquid-liquid microextraction and gas chromatography with flame photometric detection. Initially, the extraction parameters were optimized. These included: type and volume of extraction solvent, volume of disperser solvent, salting out effect, pH, time and speed of centrifugation as well as extraction time. The procedure was validated for 30 compounds. The developed procedure has low detection limits of 0.0071-0.49 μg/L and a good precision (relative standard deviation values of 1.2-5.0 and 0.6-4.1% at concentrations of 1 and 10 μg/L, respectively). The procedure was used to determine the content of volatile organosulfur compounds in samples of effluents from the production of bitumens before and after chemical treatment, in which six compounds were identified, including 2-mercaptoethanol, thiophenol, thioanisole, dipropyl disulfide, 1-decanethiol, and phenyl isothiocyanate at concentrations ranging from 0.47 to 8.89 μg/L. Problems in the determination of organosulfur compounds related to considerable changes in composition of the effluents, increase in concentration of individual compounds and appearance of secondary pollutants during effluent treatment processes are also discussed.

Research on the separation properties of empty-column gas chromatography (EC-GC) and conditions for simulated distillation (SIMDIS)

Previous studies have revealed it is possible to separate a high-boiling mixture by gas chromatography in empty fused-silica capillary tubing rather than in columns coated with stationary phase. Chromatographic separation occurs solely on the basis of the different boiling points of the substances separated. The high similarity of such separations to those in classic distillation seems advantageous when gas chromatography is used for simulated distillation. This paper presents results from further research on the separation properties of empty fused silica tubing. The efficiency of this chromatographic system has been examined. The usefulness of such conditions has been studied for simulated distillation, i.e. to determine the boiling-point distribution of complex mixtures, mainly petroleum fractions and products, on the basis of their retention relative to reference substances. The results obtained by use of empty-column gas chromatography (EC-GC) and by use of classical simulated distillation columns have been compared for solutes of different polarity. Studies revealed boiling points determined by EC-GC were more accurate than those obtained by the standard method of simulated distillation.

Highly effective degradation of selected groups of organic compounds by cavitation based AOPs under basic pH conditions

Cavitation has become on the most often applied methods in a number of industrial technologies. In the case of oxidation of organic pollutants occurring in the aqueous medium, cavitation forms the basis of numerous advanced oxidation processes (AOPs). This paper presents the results of investigations on the efficiency of oxidation of the following groups of organic compounds: organosulfur, nitro derivatives of benzene, BTEX, and phenol and its derivatives in a basic model effluent using hydrodynamic and acoustic cavitation combined with external oxidants, i.e., hydrogen peroxide, ozone and peroxone. The studies revealed that the combination of cavitation with additional oxidants allows 100% oxidation of the investigated model compounds. However, individual treatments differed with respect to the rate of degradation. Hydrodynamic cavitation aided by peroxone was found to be the most effective treatment (100% oxidation of all the investigated compounds in 60 min). When using hydrodynamic and acoustic cavitation alone, the effectiveness of oxidation was diversified. Under these conditions, nitro derivatives of benzene and phenol and its derivatives were found to be resistant to oxidation. In addition, hydrodynamic cavitation was found to be more effective in degradation of model compounds than acoustic cavitation. The results of investigations presented in this paper compare favorably with the investigations on degradation of organic contaminants using AOPs under conditions of basic pH published thus far.

New procedure for the examination of the degradation of volatile organonitrogen compounds during the treatment of industrial effluents

We present a new procedure for the determination of 32 volatile organonitrogen compounds in samples of industrial effluents with a complex matrix. The procedure, based on dispersive liquid-liquid microextraction followed by gas chromatography with nitrogen-phosphorus and mass spectrometric detection, was optimized and validated. Optimization of the extraction included the type of extraction and disperser solvent, disperser solvent volume, pH, salting out effect, extraction, and centrifugation time. The procedure based on nitrogen-phosphorus detection was found to be superior, having lower limits of detection (0.0067-2.29 μg/mL) and quantitation as well as a wider linear range. The developed procedure was applied to the determination of content of volatile organonitrogen compounds in samples of raw effluents from the production of bitumens in which 13 compounds were identified at concentrations ranging from 0.15 to 10.86 μg/mL and in samples of effluents treated by various chemical methods.

Size-exclusion chromatography for the determination of the boiling point distribution of high-boiling petroleum fractions

The paper describes a new procedure for the determination of boiling point distribution of high-boiling petroleum fractions using size-exclusion chromatography with refractive index detection. Thus far, the determination of boiling range distribution by chromatography has been accomplished using simulated distillation with gas chromatography with flame ionization detection. This study revealed that in spite of substantial differences in the separation mechanism and the detection mode, the size-exclusion chromatography technique yields similar results for the determination of boiling point distribution compared with simulated distillation and novel empty column gas chromatography. The developed procedure using size-exclusion chromatography has a substantial applicability, especially for the determination of exact final boiling point values for high-boiling mixtures, for which a standard high-temperature simulated distillation would have to be used. In this case, the precision of final boiling point determination is low due to the high final temperatures of the gas chromatograph oven and an insufficient thermal stability of both the gas chromatography stationary phase and the sample. Additionally, the use of high-performance liquid chromatography detectors more sensitive than refractive index detection allows a lower detection limit for high-molar-mass aromatic compounds, and thus increases the sensitivity of final boiling point determination.