Chromatographic characterization of high‐boiling petroleum fractions

Detailed investigation of solvent‐separated fractions of petroleum vacuum residues is necessary for understanding the separation mechanism using different solvents and to prepare better feedstocks for secondary conversion processes. The efficiency of different solvents to remove polars and insolubles from vacuum residues (of two Indian crude oils) has been studied. The solvents used were n‐heptane, n‐hexane, and n‐pentane (non‐polar) and ethyl acetate (polar). Soluble fractions were characterized for hydrocarbon group type analysis using high performance liquid chromatography (HPLC), average molecular weights using size exclusion chromatography (SEC), and boiling point distribution using high temperature gas chromatography (HTGC). Method development for HPLC analysis involved the study of parameters such as columns, solvent polarity, detectors, model compounds study, calibration, flow, and solvent gradient programming. The study demonstrated that ultimate soluble fractions have the least content of polar structures of the kind which can cause problems, during cracking and are least prone to cracking. The HPLC, SEC, and simulated distillation (SIMDIS) methods developed and standardized are simple, accurate, and suitable for the rapid assay needed for quick compositional surveys.     

Effects of Spatial Noncommutativity on Energy Spectrum of a Trapped Bose-Einstein Condensate

In noncommutative space, we examine the problem of a noninteracting and harmonically trapped BoseEinstein condensate, and derive a simple analytic expression for the effect of spatial noncommutativity on energy spectrum of the condensate. It indicates that the ground-state energy incorporating the spatial noncommutativity is reduced to a lower level, which depends upon the noncommutativity parameter θ. The gap between the noncommutative space and commutative one for the ground-state level of the condensate should be a signal of spatial noncommutativity.     

Internal standardization for the determination of cadmium,cobalt, chromium and manganese in saline produced water from petroleum industry by inductively coupled plasma optical emission spectrometry after cloud point extraction

In the present paper a procedure is proposed for the determination of traces of Cd, Co, Mn and Cr in petroleum industry produced water by inductively coupled plasma optical emission spectrometry. The procedure is based on cloud point extraction of these metals, as their dithizonate complexes, into the surfactant-rich phase of octylphenoxypolyethoxyethanol surfactant (Triton X-114). Extractions were carried out in solutions with salinities between 10‰ and 70‰. Since residual salinity in the surfactant-rich phase caused differences in its transport to the plasma, yttrium was used as an internal standard to correct for this effect. The simultaneous metal extraction procedure was optimized by response surface methodology using a Doehlert design and desirability function. Enhancement factors of 21, 21, 9 and 19, along with limits of quantification of 0.093, 0.20, 0.73 and 1.2 μg L^− 1, and precision expressed as relative standard deviation (n = 8, 20.0 μg L^− 1) of 5.8, 1.2, 1.7 and 5.7% were obtained for Cd, Co, Mn and Cr, respectively. The accuracy was evaluated by spike recovery tests on the high salinity water samples with salinity of 40 and 63‰.     

Vortices in Bose-Einstein condensates: A review of the experimental results

Rotating dilute Bose-Einstein condensates (BEC) of alkali atoms offer a testing ground for theories of vortices in weakly interacting superfluids. In a rotating super-fluid, quantised vortices, with a vorticity h/m, form above a critical velocity. Such vortices have been generated in BEC of alkali atoms by different techniques such as (a) wave function engineering of a two-component BEC, (b) decay of solitons, (c) rotation of a thermal cloud before cooling it below the condensation temperature, (d) stirring with an ‘optical’ spoon, (e) rotating a deformation in the anisotropic trap in which the condensate is trapped and (f) by creating Berry phase by adiabatically reversing the axial magnetic field. Since the core of a vortex is a fraction of a micrometer in diameter, it cannot be directly imaged optically. The condensate with vortices is allowed to ballistically expand till the size increases by one order before the vortices are imaged. Surface wave spectroscopy and the change in aspect ratio of a rotating cloud are the other techniques used. Studies have been made on the creation and dynamics of single vortex and on systems with more than a hundred vortices. Results have been obtained on vortex nucleation, stability of vortex structures, nature of the vortex lattice and defects in such a lattice. Important results are: (a) evidence exists that vortex nucleation takes place by a surface mode instability; but this is not the only mechanism; (b) the vortex lattice is perfectly triangular right up to the edge; (c) in the initial stages of rotation of the cloud a tangled web of vortices is seen; it takes a few hundred milliseconds before the vortices arrange themselves in a lattice; this time appears to be independent of temperature; (d) the decay of vortices appears to arise from the transfer of energy to the rotating thermal component and is dependent on temperature; (e) defects in the lattices such as dislocations and grain boundaries are seen; (f) transverse oscillations (Tkachenko modes) of the vortex lattice have been observed; and (g) giant vortices have been produced. These will be discussed.     

带调和势的超临界非线性Schrdinger方程的最佳门槛

考虑带调和势的超临界非线性Schroedinger方程，解决了该方程整体解和爆破解存在所依赖的初始条件的最佳分界门槛．通过构造两类强制变分问题和建立局部不变半流，运用势井方法和凹方法，获得了该方程在两个不同的空间中的整体解和爆破解的最佳门槛条件．     

Supercritical fluid chromatography of petroleum products using flameless sulfur chemiluminescence detection

Supercritical fluid chromatography using flameless sulfur chemiluminescence detection has been investigated for the analysis of sulfur compounds in petroleum products. The chromatography and detection system was easy to implement and exhibited good precision, linearity, selectivity, and sensitivity. A minimum detectable limit of 0.3 pg sulfur/s was obtained, and response to sulfur in different sulfur species was nearly equimolar.     

Determination of hopane biomarkers in Arabian crude oils by gas chromatography-tandem mass spectrometry

Gas chromatography-mass spectrometry with the mass spectrometer operated in the tandem mode at a constant accelerating voltage was used to analyse for triterpanes in Arabian crude oils. Specific molecular parent-daughter ion pairs were selected for quantitative measurements owing to their metastable transitions in the first field-free region. More accurate relative distribution ratios of hydrocarbon biomarkers were determined by this sequential gating technique than by the conventional diagnostic daughter ion mass fragmentogram in common GC-MS. The data and spectra obtained from MS-MS operation may serve as unique “fingerprints” for these regional crudes     

Comparison of purge and trap GC/MS and spectrophotometry for monitoring petroleum hydrocarbon degradation in oilfield produced waters

Results of using a field spectrophotometer and its appropriate protocols as a surrogate method for an oilfield produced water treatment process is presented. Methylene chloride extractions of the produced water before and after treatment maintained a yellow color pigment that was directly proportional to the hydrocarbon concentration. From this, an absorption spectrum and standard curve were developed. A resultant linear plot of the standard curve indicated that there is an excellent correlation (r²=0.9847) between the varying concentrations and the associated absorbance values at a wavelength of 400 nm. Total n-alkane concentration comparisons between the laboratory GC/MS analysis and the spectrophotometry analysis generated data of similar accuracy and precision at concentrations ranging from 1 to 137 mg/l (alpha=0.05). Linear comparisons between GC/MS and spectrophotometric coefficients were near unity, with the constant being near zero, with a correlation coefficient (r²) of 0.99. Based on this study, spectrophotometry is a complimentary method to GC/MS for determining total n-alkane concentrations in oilfield produced water samples.     

Determination of arsenic in petroleum refinery streams by electrothermal atomic absorption spectrometry after multivariate optimization based on Doehlert design

This paper reports the development of a methodology for the determination of arsenic in petroleum refinery aqueous streams containing large amounts of unknown volatile organic compounds, employing electrothermal atomic absorption spectrometry with polarized Zeeman-effect background correction. In order to make the procedure applicable, the influence of chemical modification and the drying step was examined. Also, pyrolysis and atomization temperatures and the amount of nitric acid added to the sample were optimized using a multivariate approach based on Doehlert matrix. Obtained results indicate that, in this kind of sample, arsenic must be determined by standard addition procedure with a careful control of the drying step temperature and ramp pattern. In order to evaluate the accuracy of the procedure, a test was performed in six spiked samples of petroleum refinery aqueous streams and the relative errors verified in the analysis of such samples (added As between 12.5 and 190 μg l⁻¹) ranged from −7.2 to +16.7%. The detection limit and the relative standard deviation were also calculated and the values are 68 pg and 7.5% (at 12.5 μg l⁻¹ level), respectively.     

Analysis of Petroleum Distillates from Fire Debris Using Supercritical Fluid Extraction with a Two‐Level Orthogonal Array Experimental Design

A supercritical fluid extraction (SFE) method was developed in the present study as an effective sample pretreatment technique of petroleum distillates from fire debris. Three petroleum distillates were used as target analytes, including 95 unleaded gasoline, kerosene, and premium diesel. An orthogonal array (L16) experimental design was adopted to separately evaluate primary SFE experimental factors. The SFE efficiencies of petroleum distillates at various extraction conditions were examined and the optimized SFE conditions were identified. Experimental results demonstrated that the optimized SFE method not only provided an effective extraction method for the spiked sample, but also successfully recovered residues of petroleum distillates from fire debris.