Ligand exchange chromatography: a vital dimension for the reliable characterization of heterocycles in crude oils and refined products

In the present study, we established a statistical distribution pattern of indigenous sulfur, nitrogen, and oxygen species in Arabian Heavy crude oil and its distilled fractions: naphtha, gas oil, and vacuum gas oil (VGO) using chemical derivatization with methyl iodide and subsequent characterization by positive electrospray Fourier transform mass spectrometry. It was observed that sulfur species for naphtha and gas oil were accumulated at lower double bond equivalent values and at lower carbon numbers compared to VGO, whereas crude oil encompassed a complete range of the sulfur species detected in all distilled fractions. Moreover, the use of alumina column chromatography and ligand exchange chromatography (LEC) on a palladium-bonded silica stationary phase revealed additional structural features of sulfur heterocycles in terms of condensed and non-condensed thiophenes. During LEC separation, in addition to sulfur heterocycles, interesting results were obtained for oxygen-containing compounds. Ortho-substituted alkyl phenols were separated from meta- and para-substituted alkyl phenols on a palladium-bonded silica stationary phase.     

Metal complex catalysts for oxidative demercaptanization of sulfur compounds in crude oil

Demercaptanization of sulfur compounds in crude oil in the presence of metal complex oxidation catalysts was studied. The adsorption capacities of the catalysts and industrial mercaptane scavengers were compared. The possibility of using these catalysts for the removal of light sulfur impurities in the field oil preparation was shown.     

An improved method for determination of light hydrocarbons in stabilized crude oil

Summary This paper reports a quick, and simple method for quantitative determination of C₂ to C₆ hydrocarbons in stabilized crude oil without using a back flush system. A mixture of crude oil and internal standard is injected into a GC equipped with a 6 meter length of fused silica capillary as a guard column. The light hydrocarbons are separated individually up to the last peak of the hexane group with the heavier components trapped in the guard column. The total analysis time for each sample is 15 minutes. The base line is table for up to 15 consecutive analyses. The guard column and the injector port are then reconditioned by simply heating them for one hour at 300 °C.     

Determination of petroleum sulfonates in crude oil by column-switching anion-exchange chromatography

A column-switching anion-exchange chromatography method was described for the separation and determination of petroleum monosulfonates （PMS） and petroleum disulfonates （PDS） in crude oil that was simply diluted with the dichloromethane/methanol （60/40）. The high performance liquid chromatography （HPLC） system consisted of a clean-up column and an analytical column, which were connected with two six-port switching valves. Detection of petroleum sulfonates was available and repeatable. This method has been successfully applied to determine PMS and PDS in crude oil samples from Shengli oil field.     

Determination of volatile and non-volatile nickel and vanadium compounds in crude oil using electrothermal atomic absorption spectrometry after oil fractionation into saturates, aromatics, resins and asphaltenes

In recent work, it has been shown that electrothermal atomic absorption spectrometry (ET AAS) can be used to differentiate between volatile and non-volatile nickel and vanadium compounds in crude oil. In the present work, the distribution of these two groups of compounds over different fractions of crude oil was investigated. For this purpose two crude oil samples were separated in two steps: firstly, the asphaltenes were precipitated with n-heptane, and secondly, the maltenes were loaded on a silica column and eluted with solvents of increasing polarity. The four fractions of maltenes eluted from silica column were: F1, saturated and light aromatics; F2, polyaromatics; F3, resins; and F4, polar compounds. Fractions F1 and F2 were further investigated using gas chromatography, and all fractions were characterized by CHN analysis, confirming the increase of aromatics in the fractions 2, 3, 4 and asphaltenes. For the determination of Ni and V by ET AAS, oil-in-water emulsions were prepared. The speciation analysis was carried out measuring without chemical modifier (stable compounds) and with 20 μg palladium (total Ni and V) and the volatile fraction was calculated by difference. The limits of detection were 0.02 μg g⁻¹ and 0.06 μg g⁻¹, for Ni and V, respectively, based on an emulsion of 2 g of oil in 10 mL. The volatile species of Ni and V were associated with fractions F3 and F4, while only thermally stable Ni and V was precipitated in part together with the asphaltenes.     

Hydrogen isotope type-curves of very hot crude oils

Several crude oil accumulations in the Pannonian Basin are trapped in uncommonly hot (>170°C) reservoirs. Their maturities range from mature to very mature on the basis of cracking parameters of their biological marker homologous series (ratio of products to reactants). A stable carbon isotopic study of these oils, poor in biological markers commonly used for correlation purposes, did not provide a reliable oil-to-oil correlation. As an alternative tool, the hydrogen isotope compositions of oil fractions separated on the basis of different polarities were measured, and hydrogen isotope type-curves were generated for a set of mature to very mature crude oil samples. This method of presenting hydrogen isotope composition of fractions as type-curves is novel. Nineteen samples (17 crude oils from SE-Hungary, 1 oil condensate and 1 artificial oil) were chosen for the present study. The aim was to examine the applicability of hydrogen isotope type-curves in oil-to-oil correlation and to test the simultaneous application of carbon and hydrogen isotope type-curves in the field of petroleum geochemistry. We have shown that, although the conventionally used co-variation plots proved to be inadequate for the correlation of these hot and mature oils, the simultaneous use of carbon and the newly introduced hydrogen isotope type-curves allows us to group and distinguish oils of different origins.     

Electrochemical sensing of gases based on liquid collection interfaces

Although many electrochemical gas sensors have been reported, electrochemical gas sensors based on liquid collection constitute a smaller subset. Minimally, a liquid interface based electrochemical gas sensor is composed of two electrodes and an ion conducting electrolyte. There is a large number of possible arrangements of these parts, and many choices exist for their composition and preparation methods. This results in a diverse and rich technology now available for gas sensing. The measurement of some analyte gases of interest, notably ozone, nitrogen oxides, hydrogen peroxide, formaldehyde, ammonia, sulfur dioxide and hydrogen sulfide are specifically discussed. Finally, the recent reviews that are likely to be the most relevant to the further development of electrochemical detection approaches for gases with a liquid collection interface are cited and discussed.     

A comprehensive analysis of the properties of light crude oil in oxidation experimental studies

The analysis of light crude oil for oxidation reaction experiments is a kind of important technological for evaluating an air injection project in a reservoir. In this study, the paper comprehensively analyzes the variations of Jilin crude oil composition comparing crude oil component’s variations before and after oxidation, and investigates the effluent gas composition and hydrocarbon, analyzes the mechanism of low temperature oxidation reaction (LTO), and rebuilds the light crude oil cracking reaction of intermediate component in a new pattern. In the early stage of the oxidation reaction, firstly, oxygen is captured by forming chemical bond in liquid hydrocarbon. And then oxygen takes part in the free radical chain reaction by forming hyperoxide and decomposes to ketones, aldehydes, alcohols, and so on. Meanwhile, chain scission reaction comes up. Research result shows that the intermediate components (C_7–17) of crude oil make great contribution to crude oil cracking. The experimental result shows that Jilin reservoir has the potential of implementing air injection project.     

Ion chromatographic measurement of sulfide, methanethiolate, sulfite and sulfate in aqueous and air samples

Simultaneous measurement of sulfur species was investigated using ion chromatography. Sulfide, methanethiolate, sulfite and sulfate are representative of sulfur species. The aqueous sulfur species were simultaneously measured using a two-detector system: suppressor-type conductivity detector for sulfite and sulfate, and fluorometric or electrochemical detector for the reduced sulfur compounds. The major sulfur-containing gases, hydrogen sulfide, methyl mercaptan and sulfur dioxide are collected into aqueous solution as the species listed above. Collection of sulfur gases using a membrane-based cylindrical diffusion scrubber was investigated. Atmospheric hydrogen sulfide and sulfur dioxide are measured by the diffusion scrubber collection and subsequent measurement by ion chromatography without an enrichment column. In addition to the two gases, methyl mercaptan was also determined using a dual scrubber system.     

Evaluation of gas chromatography-mass spectrometry in conjunction with chemometric resolution for identification of nitrogen compounds in crude oil

A chemometric resolution method is described for the identification of nitrogen compounds in crude oil. Prefractionation of crude oil into discrete chemical classes was performed by adsorption column chromatography using small quantities of neutral aluminum oxide and silicic acid. Subsequent high-resolution separation of individual components was achieved by using capillary column gas chromatography, and compound types were detected by mass spectrometer. In conjunction with a combined chemometric method, each principal chemical class was further resolved and separated, which made it possible to identify some nitrogen compounds in the investigated oils. To a certain extent, this method could relieve classical analysis of difficulty in identifying those species with poorly low contents or partially chromatographic overlaps, particularly in the cases where authentic standards were not available for addition into the unknown analytical systems to reveal what indeed existed in them.     

Thermo-elastic and thermodynamic properties of light and heavy crude oil

Three different experiments, viz., ultrasound interferometry, differential scanning calorimetry, and density measurements were carried out over a wide range of temperature varying from 20°C to 70°C in light, heavy, and a mixture of light and heavy crude oil samples which differ considerably in its American Petroleum Institute gravity. The properties of the mixture have been discussed in terms of its deviation from the ideal values of mixing. The directly measured quantities such as the compression wave velocity, the specific heat at constant pressure, and the density were used to evaluate the temperature dependence of adiabatic compressibility, coefficient of volume expansion and the acoustic impedance. A correlation between thermo-elastic and thermodynamic functions of crude oils has been investigated. In particular, the ratio of the specific heats has been determined by making use of the thermo-elastic functions, which was further used to estimate the specific heat at constant volume. The values of the isothermal compressibility and the coefficient of volume expansion are used to evaluate the pressure–temperature dependence of crude oil conforming to in-situ reservoir conditions.     

The determination of water in crude oil and transformer oil reference materials

The measurement of the amount of water in oils is of significant economic importance to the industrial community, particularly to the electric power and crude oil industries. The amount of water in transformer oils is critical to their normal function and the amount of water in crude oils affects the cost of the crude oil at the well head, the pipeline, and the refinery. Water in oil Certified Reference Materials (CRM) are essential for the accurate calibration of instruments that are used by these industries. Three NIST Standard Reference Materials (SRMs) have been prepared for this purpose. The water in these oils has been measured by both coulometric and volumetric Karl Fischer methods. The compounds (such as sulfur compounds) that interfere with the Karl Fischer reaction (interfering substances) and inflate the values for water by also reacting with iodine have been measured coulometrically. The measured water content of Reference Material (RM) 8506a Transformer Oil is 12.1+/-1.9 mg kg(-1) (plus an additional 6.2+/-0.9 mg kg(-1) of interfering substances). The measured water content of SRM 2722 Sweet Crude Oil, is 99+/-6 mg kg(-1) (plus an additional 5+/-2 mg kg(-1) of interfering substances). The measured water content of SRM 2721 Sour Crude Oil, is 134+/-18 mg kg(-1) plus an additional 807+/-43 mg kg(-1) of interfering substances. Interlaboratory studies conducted with these oil samples (using SRM 2890, water saturated 1-octanol, as a calibrant) are reported. Some of the possible sources of bias in these measurements were identified, These include: improperly calibrated instruments, inability to measure the calibrant accurately, Karl Fischer reagent selection, and volatilization of the interfering substances in SRM 2721.     

Analysis of seven chlorobiphenyl congeners by multidimensional gas chromatography

Chlorobiphenyl congeners (CBs) are used as indicator compounds in analysis performed to determine whether or not PCB concentrations in food products, waste mineral oil, and environmental samples comply with the maximum levels permitted by legislation. Seven of these compounds have been checked for coelution with other CB congeners by means of a multidimensional gas chromatographic method utilizing a combination of two narrow bore columns, one coated with a conventional non-polar stationary phase and the other with a liquid crystalline (smectic) stationary phase. Peaks of the relevant CBs have been transferred, by heart cutting, from the non-polar column to the liquid crystal column, on which unambiguous separation from possible coeluting CB congeners was obtained. It has been shown that if the seven congeners are analyzed solely on a single, non-polar capillary column the results obtained for two of them may be affected by coelution of other compounds.     

改进的广义回归神经网络用于基于气相色谱法的原油密度定量分析

在油气勘探开发领域,快速识别储集层原油性质对于工程技术人员有非常重要的指导意义.地球化学录井技术是用于判断储集层原油性质的常规手段,能为储集层综合评价提供专业认识.该文研究了地化录井中的岩石热解分析和气相色谱分析的原理,提出了一种利用色谱谱图对原油密度进行定量分析的新方法,再结合原油性质密度划分标准,可快速判断储集层原...     

Analysis of metal ions in crude oil by reversed-phase high performance liquid chromatography using short column

In this study a rapid, simultaneous analysis of V, Ni, Fe and Cu in crude oil was achieved by high performance liquid chromatography using 10 cm length reversed-phase C18 column. Since the amount of metal ions is at a very low level, in this work, solvent extraction of metals by a ligand such as 8-hydroxyquinoline from acidic media was investigated with some modification to previous procedures. Average extraction recoveries were 99, 85, 94 and 96 for V, Ni, Fe and Cu, respectively. The proposed method was successfully applied to the crude oil which was obtained from Koshk area in southern Iran. Fast analysis of metal ion in reversed-phase short column was achieved with methanol/water (55/45, v/v) and the detection limits measured as three times the background noise were obtained. Also it was shown that if small amount of 8-hydroxyquinoline was added to the mobile phase, the peak height and the peak symmetry were improved. A typical chromatogram for the separation of the 8-hydroxyquinoline complexes of V (V), Ni (II), Fe (III) and Cu (II) in crude oil was obtained in less than 4 min.     

Analysis of sulfur-containing compounds in crude oils by comprehensive two-dimensional gas chromatography with sulfur chemiluminescence detection

This paper reports an analytical method for separating, identifying, and quantifying sulfur-containing compounds in crude oil fraction (IBP-360 degrees C) samples based on comprehensive two-dimensional gas chromatography coupled with a sulfur chemiluminescence detector. Various sulfur-containing compounds and their groups were analyzed with one direct injection. 3620 peaks were detected including 1722 thiols/thioethers/ disulfides/1-ring thiophenes, 953 benzothiophenes, 704 dibenzothiophenes, and 241 benzonaphthothiophenes. The target sulfur compounds and their groups were identified based on the group separation feature and structured retention of comprehensive two-dimensional gas chromatography as well as standard substances. The quantitative analysis of major sulfur-containing compounds and total sulfur was based on the linear response of the sulfur chemiluminescence detector using the internal standard method. The sulfur contents of target sulfur compounds and their groups in 4 crude oil fractions were also determined. The recoveries for standard sulfur-containing compounds were in the range of 90-102%. The quantitative result of total sulfur in the Oman crude oil fraction sample was compared with those from ASTM D 4294 standard method (total S by X-ray fluorescence spectrometry), the relative deviation (RD%) was 4.2% and the precision of the method satisfactory.     

Application of solid‐phase microextraction to the determination of polycyclic aromatic sulfur heterocycles in Bohai Sea crude oils

A simple and rapid solid‐phase microextraction approach for the isolation of polycyclic aromatic sulfur heterocycles from the aromatic fraction of crude oil is described. 8‐Hydroxyquinoline silica gel impregnated with palladium chloride was used as a sorbent material for extraction. Operational parameters of the extraction solvents have been evaluated and optimized. Benzothiophene, dibenzothiophene, and benzo[b]naphtho[1,2‐d]thiophene and their C₁–C₄ alkyl derivatives were identified and quantified by GC–MS. Under optimum conditions, the limits of detection for benzothiophene, dibenzothiophene, and benzo[b]naphtho[1,2‐d]thiophene were 0.277, 0.193, and 0.597 μg/g oil, respectively. The recoveries for the polycyclic aromatic sulfur heterocycles ranged from 81.5 to 92.1%, and the linear dynamic range was from 10 to 1000 ng/mL. The developed methodology was tested in the characterization of crude oil samples collected at the DY, SZ, ZH, and HC petroleum oil fields of the Bohai Sea. The results proved that SPE coupled with GC–MS is a promising tool for the quantitative analysis of polycyclic aromatic sulfur heterocycles in crude oils, especially for oil samples with low concentrations of polycyclic aromatic sulfur heterocycles.     

High performance liquid chromatographic separations of gas oil samples and their hydrotreated products using commercial normal phases

Three commercially available high performance liquid chromatography columns are used in normal phase or quasi-normal phase mode for the separation of gas oil samples. The columns are tested with 20 analytical standards to determine their suitability for separations of petroleum samples and their ability to separate the nitrogen group-types (pyrrole and pyridine) found in petroleum. The columns studied are polymeric hypercrosslinked polystyrene (HGN), a biphenyl phase, and a Chromegabond "DNAP" column from ES Industries. The HGN column separates gas oils based on both ring structure and heteroatom, while the biphenyl phase has low retention of most compounds studied in quasi-normal phase mode. The "DNAP" column is selective for nitrogen-containing compounds, separating them from PAHs as well as oxygen and sulphur compounds. Retention data of standards on all three columns is shown, along with chromatograms of gas oil samples on the HGN and "DNAP" columns.