Effect of Crude Oil Fractions on Interfacial Tensions of Novel Sulfobetaine Solutions

The dynamic interfacial tensions (IFTs) of two novel zwitterionic surfactants with different hydrophobic groups, alkyl sulfobetaine (ASB), and xylyl substituted alkyl sulfobetaine (XSB), against kerosene, crude oil, and model oils containing crude oil fractions, such as resins, asphaltenes, saturates, aromatics, and acidic fractions, have been investigated by a spinning drop interfacial tensiometer. The experimental results show that XSB solutions show higher interfacial activity than ASB against kerosene because of the larger size of the hydrophobic part of the XSB molecule. The petroleum acids have high interfacial activity and can adsorb onto the interface. For ASB solutions, the synergism mixed adsorption of betaine and acid molecules lowers IFT values. On the one hand, the partly displacement of XSB molecules by petroleum acid at the interface results in the increase of IFTs. Therefore, resins, aromatics, and acidic fractions show strong effects on IFTs of betaine solutions. On the other hand, asphaltenes and saturates have little effect on interfacial properties. Moreover, the hydrophilic part of the betaine molecule at the interface may vary its orientation from vertical to flat with aging time. Therefore, the dynamic IFT curves of ASB solutions against model oils show “V” shape for resins, aromatics, and acidic fractions.     

Fractional and component analysis of crude oils by the method of dynamic microdistillation—Differential scanning calorimetry coupled with thermogravimetry

High-resolution differential scanning calorimetry was used to accurately establish the temperature intervals of oxidation/distillation of the major components of crude oils. Some theoretical aspects of the method of dynamic microdistillation, enabling consecutive distillation (oxidation) of the main components of hydrocarbon mixtures, are discussed. The experimental TG-DSC curves show that the temperature scan of the run can be divided into six regions, of which the first belongs to simple distillation of the sample's liquid constituent (the distillate) and the others to oxidative cracking distillation of the solid (heavy) residue. The latter occur in the order paraffins + light oils, middle base oils, heavy base oils, condensed aromatics (resins) and asphaltenes. The probable oxidation mechanisms of different classes of petroleum hydrocarbons operating in different temperature regions are discussed. Full quantitative fractional and group component analysis of a number of crude oils of different chemical classes and geological age was carried out by the combined TG-DSC techniques under specially chosen experimental conditions (those of dynamic microdistillation).     

Towards comprehensive hydrocarbons analysis of middle distillates by LC-GCxGC

The detailed characterization of middle distillates is essential for a better understanding of reactions involved in refining processes. Owing to a higher resolution power and an enhanced sensitivity, but especially to a group-type ordering in the chromatographic plane, comprehensive two-dimensional gas chromatography (GCxGC) offers unsurpassed characterization possibilities for petroleum samples. However, GCxGC fails to totally discriminate naphthenes from unsaturates occurring in hydrotreated diesel samples. This article aims at promoting the implementation of LC-GCxGC for the quantitative determination of hydrocarbon distribution in middle distillates, including naphthenes. In this configuration, liquid chromatography (LC) enables the separation of hydrocarbons into two fractions (viz., saturated and unsaturated) before the subsequent analysis of each fraction by GCxGC. In this paper, the choice of GCxGC conditions in order to achieve the separation and identification of hydrocarbons by chemical class is discussed; under these conditions, naphthenes are separated according to the number of saturated rings. For the first time, the presence of di-, tri-, and tetra-naphthenes resulting from the hydroconversion of aromatics can clearly be evidenced. A quantitative procedure for the determination of the distribution of hydrocarbons, including the distribution of naphthenes according to the number of saturated rings, is also proposed and discussed in detail. LC-GCxGC is found to provide an unequalled degree of information that will widely contribute to a better understanding of hydroconversion processes.     

Polycyclic aromatic hydrocarbons in edible fats and oils: occurrence and analytical methods

This review deals with analytical methods for polycyclic aromatic hydrocarbon (PAH) determination in oils and fats. The data reported in the introduction deal with PAH dietary intake from this group of food and contamination levels recently found by some authors in different vegetable oils, stressing the importance of establishing a method suitable for routine analyses. Traditional sample preparation relies on tedious, time-consuming procedures. They generally consist of an extraction step (liquid-liquid partition, caffeine complexation, saponification) followed by one or more purification procedures (column chromatography, thin-layer chromatography, solid-phase extraction). The analytical determination is usually carried out by HPLC and spectrofluorometric detection, or through high-resolution capillary GC coupled to flame ionisation detection or mass spectrometry. LC is a valid alternative to the traditional sample preparation, and off-line LC-LC allows performing an accurate PAH analysis in less than 2 h. Also supercritical fluid extraction, allowing performing both extraction and clean-up in one combined step, is a promising technique. Hyphenated techniques such as LC-GC and LC-LC-GC seem to be very promising. A completely on-line method for alkylated PAH determination in oils or lipidic extracts contaminated with mineral oil involves a two-dimensional LC-step with intermediate eluent evaporation and GC transfer through a vaporiser/overflow interface.     

Organic palladium and palladium-magnesium chemical modifiers in direct determination of lead in fractions from distillation of crude oil by electrothermal atomic absorption analysis

Platinum reforming catalysts are easily poisoned by increased levels of lead, therefore a sensitive atomic absorption spectrometric procedure for lead determination in fractions from crude oil distillation was developed. Lead was present in organic form in the samples analysed therefore the behaviour of various lead compounds (Pb-alkylarylsulphonate, Pb-4-cyclohexanobutyrate, tetraethyllead, Pb in fuel oil) was studied. The best procedure for the determination of lead in different petroleum products, including those containing asphaltenes includes a pretreatment with iodine and methyltrioctylammonium chloride, followed by the use of an organic Pd-Mg modifier. Under these conditions an effective matrix removal is possible at a pyrolysis temperature up to approximately 1100°C and the behaviour of lead present in different forms is unified. The characteristic mass is 11–12 pg Pb, corresponding to a detection limit of 0.25 ng g⁻¹ for 20 μl sample solution. This can be lowered by multiple injection.     

Challenge in the speciation of nitrogen-containing compounds in heavy petroleum fractions by high temperature comprehensive two-dimensional gas chromatography

Extending the knowledge related to nitrogen-containing compounds presents an important interest for the petroleum industry due to their implication in atmosphere pollution as well as their inhibitive or refractive behaviour towards hydroprocessing. Most of the nitrogenated species are concentrated in heavy petroleum cuts. As no analytical method is resolutive enough for these heavy cuts, particularly regarding nitrogen-containing compounds, a new approach is needed. For this reason, this study focuses on the development of a GC×GC technique, through the hyphenation of a specific NCD detector with a GC×GC system at high temperature. The performances of highly polar thermally stable stationary phases, in particular those composed of promising ionic liquids, were monitored in normal and reversed configurations. Subsequently, after the extraction of neutral or basic compounds by adsorption on an ion-exchange resin, a first quantitative determination was attempted for a straight-run and a direct coal liquefaction vacuum gas oils. This study led to a better understanding of the behaviour of highly aromatic N-compounds by 2D-GC including an ionic liquid phase as well as a deeper N-characterization of heavy petroleum fractions.     

Determination of vanadium in petroleum crudes and fuel oils by gas chromatography

A method is described for determining levels of vanadium as low as 0.1 μg g^-1 in petroleum oils by gas chromatography with flame-ionization detection. The method involves decomposition of the oils, derivatization and solvent extraction of vanadium as the chelate, [2,2,2',2'-tetramethyl-5,5'-(ethane-1,2-diyldiimino)bis(hex-4-en-3-onato)-(2-)] oxovanadium(IV), followed by gas chromatography on a non-polar (SE-30) column. The procedure is applied to a variety of samples, including standard reference and fuel oils used in an interlaboratory study. The results are compared with those of emission spectrography and two standard methods. The new procedure can be extended to the selective, simultaneous detection of copper, nickel and vanadium in such samples.     

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.     

Comparison of three different solid-phase microextraction fibres for analysis of essential oils in yacon (Smallanthus sonchifolius) leaves

A headspace solid-phase microextraction (HS-SPME) procedure based on three commercialised fibers (100 microm polydimethylsiloxane, 65 microm polydimethylsiloxane-divinylbenzene and 50/30 microm divinylbenzene-Carboxen-polydimethylsiloxane) is presented for the determination of a selected essential oils in dried leaves of yacon (Smallanthus sonchifolius). The extraction performances of these compounds were compared using fibers with one, two and three coatings. The optimal experimental procedures for the adsorption and desorption of target compounds were determined. Significant parameters affecting sorption process such as sample weight, sorption and desorption time and temperature were optimised and discussed. Finally, the optimised procedures were applied successfully for the determination of these compounds in various yacon species. The relative concentration factors of three characteristic components of yacon were measured for relative evaluation of the fiber efficiency. Main essential oils were isolated from dried yacon leaves by appropriate solid-phase microextraction fiber and semi-quantitative analysis of the target volatiles was conducted by gas chromatography-flame ionisation detection (GC-FID) using a capillary column. Three compounds--beta-pinene, caryophylene and y-cadinene were found as the predominant essential oils. Its relative content was important for specification of yacon varieties. Solid-phase microextraction in combination with gas chromatography enabled a rapid and simple determination of relative content of essential oils in yacon.     

Determination of low levels of methanol in crude oils by multi-dimensional gas chromatography (MDGC) using novel micro channel flow technology

The accurate and precise determination of methanol in crude oils at concentrations less than 10 ppm is of economic value to the petroleum industry. This report presents the optimization, results and long term performance of a flow switching device MDGC hardware, the Swafer?, for the rapid and precise analysis of methanol from approximately 0.4 ppm (w/w) to 1000 ppm. The use of low temperature injection and backflush technique decreases maintenance and increases sample throughput. The short term quantitative percent relative standard deviations at 1, 30 and 1000 ppm (w/w) methanol in crude oils are 5, 3 and 0.3, respectively. The MDGC procedure follows closely that described in ASTM D7059 for determination of crude oils; however, D7059 previously has not been evaluated at concentrations of less than 10 ppm. This work further extends the application of D7059 to concentrations of <10 ppm.     

Pyrolysis of vegetable oil soaps—Palm, olive, rapeseed and castor oils

Saponified, palm, olive, rapeseed and castor oils were pyrolysed (at 750 °C for 20 s) by pyrolysis gas chromatography with mass selective and flame ionisation detection (Py-GC/MSD and FID) to clarify their thermochemical behaviours. The liquefiable compounds recovered from palm, olive and rapeseed oils mainly contained linear alkenes (up to C₁₉) and alkanes (up to C₁₇), both similar to those found in gasoline (C₄-C₁₀) and diesel fuel (C₁₁-C₂₂) boiling range fractions of petroleum, whereas in the case of castor oil a significant amount of undesired oxygen-containing products (e.g., ketones and phenols) were formed. The obtained data on reaction mechanisms can also be utilised in applications where various biofuels are produced, for example, from the extractive-derived by-product (tall oil) of kraft pulping.     

全二维气相色谱用于轻质石油馏分中芳烃含量的测定

建立了采用全二维气相色谱(GC×GC)技术一次进样完成轻质石油馏分中非芳烃、一环芳烃和二环芳烃的分离、定性 和定量。通过对柱系统的选择和色谱条件的优化,实现了一次全二维气相色谱分析即完成轻质石油馏分的族组成分离以及 目标化合物的分离。方法的加标回收率为89.5%～106.1%;样品中各组分含量重复测定的相对标准偏差均不大于5.8%,能 够满足样品测定的精密度和准确性要求,且完成1次分析最多只需要30 min。     

Characterisation of heavy oils using near-infrared spectroscopy: optimisation of pre-processing methods and variable selection

In this study, chemometric predictive models were developed from near infrared (NIR) spectra for the quantitative determination of saturates, aromatics, resins and asphaltens (SARA) in heavy petroleum products. Model optimisation was based on adequate pre-processing and/or variable selection. In addition to classical methods, the potential of a genetic algorithm (GA) optimisation, which allows the co-optimisation of pre-processing methods and variable selection, was evaluated. The prediction results obtained with the different models were compared and decision regarding their statistical significance was taken applying a randomization t-test. Finally, the results obtained for the root mean square errors of prediction (and the corresponding concentration range) expressed in %(w/w), are 1.51 (14.1-99.1) for saturates, 1.59 (0.7-61.1) for aromatics, 0.77 (0-34.5) for resins and 1.26 (0-14.7) for asphaltens. In addition, the usefulness of the proposed optimisation method for global interpretation is shown, in accordance with the known chemical composition of SARA fractions.     

The comparison of solid phase microextraction-GC and static headspace-GC for determination of solvent residues in vegetable oils

The objective of these investigations has been the determination of volatile organic compounds including residue solvents present in vegetable oil samples. Some olive oil, rape oil, sunflower oil, soy-bean oil, pumpkin oil, grape oil, rice oil as well as hazel-nut oil samples were analysed. Among residue solvents the following compounds have been mentioned: acetone, n-hexane, benzene, and toluene. Some experiments for the solid phase microextraction (SPME)-GC-flame ionisation detection (FID) were performed to examine extraction conditions such as fiber exposure time, temperature of extraction, and temperature of desorption. Various SPME fibers such as polydimethylsiloxane, Carboxen/polydimethylsiloxane and polydimethylsiloxane/divinylbenzene coatings were used for the isolation of tested compounds from vegetable oil samples. After optimisation of SPME, real vegetable oil samples were examined using SPME-GC/MS. Based on preliminary experiments the qualitative and quantitative analyses for the determination of acetone, n-hexane, benzene and toluene were performed by SPME-GC-FID and static head-space (SHS)-GC-FID methods. The regression coefficients for calibration curves for the examined compounds were R(2) > or = 0.992. This shows that the used method is linear in the examined concentration range (0.005-0.119 mg/kg for SPME-GC-FID and 0.003-0.728 mg/kg for SHS-GC-FID). Chemical properties of analysed vegetable oils have been characterised by chemometric procedure (cluster analysis).     

Nitrogen compounds of petroleum oils (review)

The literature data on the quantitative percentages, group and individual compositions, and structures of nitrogen compounds of all types that have been identified in petroleum oils and directly distilled petroleum fractions are systematized. The general regularities in the structures of the molecules of petroleum nitrogen compounds and their structural relationship with other aromatic components of petroleum oils are noted. The modern concepts regarding the genesis of the most important classes of nitrogen-containing components of petroleum are discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 147–165, February, 1979.     

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

The 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.     

Size exclusion chromatography sample pretreatment for GC-AED analysis of metalloporphyrins in crude oils

Size exclusion chromatography (SEC) has been demonstrated to be an effective and reproducible sample pretreatment procedure for removal of heavy oil matrices prior to GC-AED analysis of metalloporphyrins, and for the resolution of volatile metal species into clean and defined fractions. This paper also discusses the results obtained by SEC for determination of the distribution of metallopor-phyrins in crude oils and the correlation between total metal, metal-loporphyrin, and total distillable metal content.     

The effect of sample mass and heating rate on DSC results when studying the fractional composition and oxidative stability of lube base oils

The method of dynamic microdistillation instrumented through DSC has been further elaborated and validated using distillate and residual base oils as model systems. The two major experimental factors of the method—sample mass and heating rate were varied to determine the optimal (standard) experimental conditions for better fraction resolution and thus more reliable quality assessment of petroleum products (lube oils). If these are increased, the fraction resolution ability of the method is reduced—the lighter fractions evaporate at temperatures close to those of the heavier ones, and generally all the fractions evaporate/oxidize at higher temperatures. Two major types of reactions in the heated sample were identified—the one occurring on the metal surface of the crucible leading to a polymer (lacquer) film formation and the other the oxidative cracking in the bulk of the sample leading to the formation of gaseous products. The extent of the lacquer film formation on the crucible metal surface can be reduced by increasing the heating rate and/or the sample mass, while their reduction results in better fraction resolution.     

Liquid chromatography/electrospray ionisation mass spectrometric investigations of imidazoline corrosion inhibitors in crude oils

The so-called imidazolines (2-alkyl-1-[ethylalkylamide]-2-imidazolines and 2-alkyl-1-ethylamine-2-imidazolines) are a group of surface-active compounds, complex mixtures of which are used by various industries as surfactants and corrosion inhibitors. Although their industrial synthesis was reported over 100 years ago, few methods for the determination of individual imidazolines in mixtures, including industrial matrices such as crude oils, have been reported. Here we demonstrate that spiking of crude oils with synthetic imidazolines followed by solid-phase extraction and liquid chromatography/electrospray ionisation multistage mass spectrometry (LC/ESI - MS(n)) allows an estimation of low (<10) parts per million concentrations of individual imidazolines in crude oils. Whilst non-optimised at present, the method is a significant advance and may prove useful not only for improving an understanding of the mechanisms of industrial imidazoline synthesis and for monitoring downhole and topside oilfield operations, but also for the determination of the fate of imidazoline-based oilfield corrosion inhibitors and surfactants in the environment.     

High temperature gas chromatography – atomic emission detection of metalloporphyrins in crude oils

High temperature gas chromatography-atomic emission spectroscopy is used for the detection of vanadyl, nickel, and iron porphyrins in crude oils. The operational variables are investigated with regard to the effects on performance in high temperature GC-AED. Under optimal conditions, the method provides charactersitic metal distributions for oils from different sources. The method is also advantageous in the study of decomposition of petroleum metal species. Several crude oils were analyzed for the content of the distillable metals in comparison with total metals as determined by a direct spectroscopic method.