原油非烃化合物结构与含量的馏分分离及联用色谱信息获取通用方法

用正己烷将沥青质从油样中分离,再根据类组分之间极性差别,用中性氧化铝-硅胶双层析柱将原油样其余部分分成脂肪烃、芳香烃和7个非烃馏分。各馏分回收完全。用色-质联用技术,将非烃馏分再分离并获取实验数据,为原油非烃结构和含量测定奠定有关的信息基础。不同油井样品研究和重复实验表明,方法对各种原油非烃化合物分离和信息测定有很好的重现性。     

Supercritical fluid chromatography and some of its applications: A review

The general topic of supercritical fluid chromatography (SFC) is introduced, and historical aspects of its development are discussed. The physical properties of supercritical fluids, gases and liquids are tabulated. SFC is compared and contrasted with the classical forms of chromatography - gas chromatography (GC) and high performance liquid chromatography (HPLC). The selectivity of SFC, GC, and HPLC are discussed and compared. Instrumentation employed for supercritical fluid chromatography is depicted. A wide variety of SFC applications are introduced. New examples of the use of SFC for analysis of a variety of complex oligomeric mixtures indcluding polypropylene glycol, polysiloxanes, fluorocarbon oligomers (i.e. -3M's fluoro-chemical surfactant Fluorad 171, and Kel-F) and high molecular weight normal alcohols are shown. The use of SFC for separation of mono-, di-, and triglycerides at low operating temperatures is described. Lastly, the use of SFC for separations of complex hydrocarbon mixtures from liquid fuels, polycyclic aromatic hydrocarbons, synthetic alpha-olefins, and petroleum functional group separations are depicted.     

Metal selective flame ionization detection after supercritical fluid chromatography

This work describes the construction and operation of a flame ionization detector for the selective detection of metal-containing compounds after capillary supercritical fluid chromatography. Using optimal conditions for achieving metal sensitive flame ionization responses which have been established for the detector after capillary gas chromatography, initial evaluation of the detector after SFC proved promising. Like the carbon sensitive FID, it appears that the metal sensitive FID is compatible with SFC when pure carbon dioxide is used as the mobile phase. Response characteristics were found to be similar to those observed when the detector is used in gas chromatography.     

Supercritical fluid chromatography of fish,shark and seal oils

Summary Various natural and treated fish, shark liver and seal oils have been analyzed by supercritical fluid chromatography (SFC) using a non-polar capillary column. The lipids are separated according to molecular mass. The lipid groups found included free fatty acids, cholesterol, squalene, vitamins, wax esters, cholesterol esters, diglycerides, triglycerides and ether lipids. Methods for the analysis of the marine oils depend on components present in the oil. When co-eluting lipid groups were present, modifications such as hydrogenation or TLC fractionation of the oils had to be made. In this paper applications of SFC on fish, seal and shark liver oils are presented.     

Determination of nitrated-polyaromatic hydrocarbons (nitro-PAHs) in environmental samples by high resolution chromatographic techniques

An analytical procedure is described for the fractionation of organic compounds present in environmental samples and the determination of nitro polyaromatic hydrocarbons (nitro-PAHs). Both low and high resolution liquid chromatography are employed for the prefractionation of the soluble organic fraction (SOF) extracted from particulate matter or gaseous pollutants collected on adsorption traps. High resolution gas chromatography is used to analyze four fractions containing alkanes, PAHs, nitro-PAHs, and other polar PAHs. Nitrogen-containing species are separated by GC and detected specifically using an alkali flame (NPD) detector. Flame ionization (FID) detection, GC-MS of positive ions, and negative ion chemical ionization MS of the whole fraction is used for the identification and quantitation of the various components. The composition of SOF extracted from particulate matter emitted from diesel exhausts is elucidated and a large number of nitro-PAHs identified by the combination of the various techniques.     

Improvement of mineral oil saturated and aromatic hydrocarbons determination in edible oil by liquid–liquid–gas chromatography with dual detection

Mineral oils, which are mainly composed of saturated hydrocarbons and aromatic hydrocarbons, are widespread food contaminants. Liquid chromatography coupled to gas chromatography with flame ionization detection represents the method of choice to determine these two families. However, despite the high selectivity of this technique, the presence of olefins (particularly squalene and its isomers) in some samples as in olive oils, does not allow the correct quantification of the mineral oil aromatic hydrocarbons fraction, requiring additional off‐line tools to eliminate them. In the present research, a novel on‐line liquid chromatography coupled to gas chromatography method is described for the determination of hydrocarbon contamination in edible oils. Two different liquid chromatography columns, namely a silica one (to retain the bulk of the matrix) and a silver‐ion one (which better retains the olefins), were coupled in series to obtain the mineral oil aromatic hydrocarbons hump free of interfering peaks. Furthermore, the use of a simultaneous dual detection, flame ionization detector and triple quadrupole mass spectrometer allowed us not only to quantify the mineral oil contamination, but also to evaluate the presence of specific markers (i.e. hopanes) to confirm the petrogenic origin of the contamination.     

超临界流体色谱在生物工程中应用的新进展

超临界流体色谱（SFC）是高效液相色谱（HPLC）和气相色谱（GC）的重要补充技术。用SFC可以分离多数不能用GC分离的低挥发性物质。与传统的HPLC相比，SFC的分离速度更快、效率更高。本文综述了SFC在生物分子分离分析方面应用的新进展。引用文献74篇。     

全二维气相色谱/飞行时间质谱用于柴油组成的研究

将全二维气相色谱法(GC×GC)用于柴油馏分的组成分布研究,建立了两种GC×GC方法,一种用于柴油组成的详细表征,另一种用于柴油族组成的快速分离和定量,两种方法均不需要样品预处理。用前一种方法对柴油馏分中的烃类化合物、主要的含硫化合物与含氮化合物组成进行了研究;对催化裂解柴油中的27种含氮化合物和42种含硫化合物进行了定性;用后一种方法在70 min内即可完成柴油馏分族组成的定量分析,应用所建立的方法测定了4个不同来源的柴油馏分中非芳烃、一环芳烃、二环芳烃、三环芳烃的含量,定量结果与ASTM D2425法     

Feasibility of preparing and analyzing gas standards containing heavy hydrocarbons (C10–C16)

State and federal agencies are beginning to monitor ambient air for compounds related to diesel exhaust. The National Institute of Standards and Technology (NIST) was asked to develop standards containing heavy (C10-C16) alkanes which could then be used in air monitoring and exhaust studies. Several primary gravimetric standards, containing heavy (C10-C16) alkanes in nitrogen, were developed and analyzed by gas chromatography (GC) with flame-ionization detection (FID). The results of this research indicate that accurate gas standards containing these hydrocarbons can be prepared. However, the analytical results show that the temperature of the transfer system from the gas cylinder to the GC column (including the gas-sample valve) must be heated in order to prevent adsorption of these compounds within the analytical system. The results indicate that even at elevated temperatures these compounds are being absorbed within the system. The results show that quantitative results cannot be obtained by using one compound such as hexane, as an internal standard to determine the concentration of other hydrocarbons. Quantitative and accurate results are best obtained if standards for each hydrocarbon of interest are used to determine concentrations of unknowns for the respective hydrocarbon.     

烷基苯生产中循环烷烃的液固吸附色谱预分离和气相色谱/质谱分析

 利用 10 0目～ 2 0 0目的硅胶 ,选择正戊烷和二氯甲烷作为洗脱剂 ,采用吸附色谱法将烷基苯生产中的循环烷烃分离为饱和烃 (烷烃 +环烷烃 )及芳烃两部分。然后将饱和烃及芳烃分别进行色谱 /质谱 (GC/MS)联用分析 ,得到了有关循环烷烃构成的定性定量结果。定性结果如实地反映出烷基苯生产中的副反应产物 ,可直接用于指导生产。从定量结果可以看出 ,经过硅胶吸附分离后 ,试样中含量要求很低的芳烃被浓缩 ,提高了分析的准确度和灵敏度 ,可以检测出循环烷烃中含量很低的物质 ,为全面分析样品组成提供了有力的证据。     

煤系重质油的仪器分析及系统考察Ⅰ.烃族分析

采用薄层棒色谱／氢火焰离子化检测（TLC／FID）,对煤系重质油的烃族组成分析进行了研究。确定了最佳分析条件、烃族的定量因子等。在此基础上,对山西省焦化厂的典型重质油产品进行了系统测定。     

Physicochemical Principles and Applications of Supercritical Fluid Chromatography (SFC). New analytical methods (19)

In supercritical fluid chromatography (SFC) compressed gases in the region of their critical temperature are used as mobile phases. SFC has important advantages over gas chromatography (GC) for the separation of low-volatile or thermally unstable substances. Like high pressure liquid chromatography (HPLC) and gel chromatography, it is used for various special applications and preparative separations, e.g. in the petroleum industry and in the separation of oligomers. SFC is of great interest in fundamental research on fluid extraction and for the determination of the physicochemical properties of fluid systems. In this contribution the most important physicochemical, methodological, and instrumental principles of SFC are summarized; characteristic physicochemical applications are the determination of capacity ratios, partition coefficients, partial molar volumes, interaction second virial coefficients, and difusion coefficients.     

Application of capillary supercritical fluid chromatography to the analysis of a middle distillate fuel

Summary The application of capillary supercritical fluid chromatography (SFC) to the analysis of a middle distillate fuel is described. Small diameter (50m i.d.) fused-silica capillary columns coated with crosslinked 50% phenyl polymethylphenyl siloxane provided high separation efficiency and good compatibility with flame ionization detection. High resolution separations of the chemical class fractions obtained by adsorption chromatography on alumina were obtained using carbon dioxide as the supercritical mobile phase and simple pressure programming techniques. In addition to the less polar fuel components, supercritical carbon dioxide allowed chromatography of the nitrogen-containing polycyclic aromatic hydrocarbon fraction and the hydroxylated polycyclic aromatic materials.     

Improved separation of furocoumarins of essential oils by supercritical fluid chromatography

Separation of furocoumarins has become of a great interest for cosmetic industry and human health, since the recent directive of the European Union. Furocoumarins are a class of compounds presenting varied substituents linked mainly in two positions to an identical skeleton made by a furan ring bonded to a coumarin nucleus (Psoralen). The substituents are mainly methoxy, or alkyl chains, which can contain double bonds, hydroxyl or epoxy groups. Due to the variety of compounds, and their subtle structure differences, their separation requires high-performance methods. Multi-gradient high-performance liquid chromatography (HPLC) and two-dimensional chromatography are usually applied. This paper describes a new approach, by using super/subcritical fluid chromatography (SFC), with a green mobile phase: CO₂–ethanol. The choice of the stationary phase from varied types of phases, and the effects of numerous analytical parameters (flow rate, modifier percentage, temperature and outlet pressure) are studied, described and discussed, on the basis of the separation of a complex sample: lemon residue. From these studies, isocratic conditions are determined to obtain a satisfactory separation in 10 min. A two-dimensional analysis was also investigated, by performing first a class fractionation of compounds on an ethylpyridine (EP) phase, then by separating each class on a pentafluorophenyl phase (Discovery HS F5) with the selected isocratic mobile phase. A gradient elution is also studied to improve separation of some minor compounds. Structure of the eluted compounds was determined by comparison with standards, HPLC-DAD, HPLC–MS analysis, and NMR analysis of collected fractions. All these approaches allow relating structure of compounds to retention behaviour, which is unusual due to the selected pentafluorophenyl stationary phase.     

Analysis of polychlorinated biphenyls in transformer oils by automated on-line coupling reversed phase liquid chromatography-gas chromatography using the through oven transfer adsorption desorption (TOTAD) Interface

An automated method for the direct analysis of polychlorinated biphenyls (PCBs) in transformer oil is presented. The proposed method uses the TOTAD (through oven transfer adsorption desorption) interface for the on-line coupling of reversed phase liquid chromatography and gas chromatography (RPLC-GC). In this fully automated system, the oil is injected directly with no sample pre-treatment step other than dilution with n-propanol and filtration. In the LC step, PCBs are separated from other components of the oils using methanol/water (90:10 v/v) as mobile phase, at a flow rate of 1?mL?min^?1. The LC fraction containing the PCBs is automatically transferred to the GC by the TOTAD interface and GC analysis enables the separation of the PCB congeners. The proposed method is compared with two other methods: the European Norm (UNE-EN-61619) and that of the American Society for Testing and Materials (ASTM) (D4059-00). The proposed method practically eliminates the time-consuming sample preparation step and avoids errors caused by sample manipulation. The total PCB concentrations obtained with the three methods are similar.     

Modern analytical supercritical fluid chromatography using columns packed with sub-2 μm particles: A tutorial

This tutorial provides an overview of the possibilities, limitations and analytical conditions of modern analytical supercritical fluid chromatography (SFC) using columns packed with sub-2 μm particles. In particular, it gives a detailed overview of commercially available modern SFC instrumentation and the detectors that can be employed (UV, MS, ELSD, FID, etc.). Some advice on the choice of the stationary phase dimensions and chemistries, the nature of the mobile phase (choice of organic modifier and additives) and its flow rate as well as the backpressure and temperature are also provided. Finally, several groups of potentially problematic compounds, including lipophilic compounds, hydrophilic substances and basic drugs, are discussed in detail. All these families of analytes can be resolved with SFC but require specific analytical conditions.     

Two-dimensional supercritical fluid chromatography/mass spectrometry for the enantiomeric analysis and purification of pharmaceutical samples

A new analytical two-dimensional supercritical fluid chromatography/mass spectrometry system (2D SFC/SFC/MS) has been designed and implemented to enhance the efficiency and quality of analytical support in drug discovery. The system consists of a Berger analytical SFC pump and a modifier pump, a Waters ZQ 2000 mass spectrometer, a set of switching valves, and a custom software program. The system integrates achiral and chiral separations into a single run to perform enantiomeric analysis and separation of a racemic compound from a complex mixture without prior clean up. The achiral chromatography in the first dimension separates the racemate from all other impurities, such as un-reacted starting materials and by-products. Mass-triggered fractionation is used to selectively fractionate the targeted racemic compound based on its molecular weight. The purified racemate from the achiral chromatography in the first dimension is then transferred to the chiral column in the second dimension to conduct the enantiomeric separation and analysis. A control software program, we coined SFC2D, was developed and integrated with MassLynx to retrieve acquisition status, current sample information, and real time mass spectrometric data as they are acquired. The SFC2D program also monitors the target ion signal to carry out mass-triggered fractionation by switching the valve to fractionate the desired peak. The 2D SFC/SFC/MS system uses one CO(2) pump and one modifier pump for both first and second dimension chromatographic separations using either gradient or isocratic elution. Similarly, a preparative 2D SFC/SFC/MS system has been constructed by modifying an existing Waters preparative LC/MS system. All components except the back pressure regulator are from the original LC/MS system. Applications of the 2D SFC/SFC/MS methods to the separation and the analysis of racemic pharmaceutical samples in complex mixtures demonstrated that an achiral separation (in first dimension) and a chiral separation (in second dimension) can be successfully combined into a single, streamlined process both in analytical and preparative scale.     

油品族组成的详细分析和燃油中芳烃的分析

用毛细管液相色谱-毛细管气相色谱联用方法详细分析了航空煤油、各种柴油、润滑油、抽出油和塔底油的族组成。在毛细管液相色谱上分离得到的单环、双环、三环、四环和稠环芳烃族,经过多位存储接口后,顺序进入毛细管气相色谱,通过毛细管气相色谱对每个族组分作详细分析及定量。用单检测器的二维毛细管气相色谱切割-反吹方法定性定量分析汽油、航空煤油中的各种芳烃,从第一维柱流出的组分和第二维柱流出的组分都先后进入同一氢火焰离子化检测器中,因此能用质量校正响应因子归一化方法准确定量分析而不需要标准样。用上述技术分析实际样品,证明了     

Analysis of sterols in vegetable oils using off-line SFC/capillary GC-MS

Summary The analysis of sterols in vegetable oils by off-line SFC followed by capillary GC-MS is described. The fractionation of the sterols from the complex oil matrix is achieved by SFC on aminopropyl silicagel in less than 8 minutes. Injection and collection of the sterol fraction is fully automated and time controlled. The sterols are analysed without derivatisation by capillary GC-MS. Identification is performed by full scan electron ionisation and quantitation is carried out by extracted ion chromatography at m/e 107, with cholesterol as internal standard. The analyses of the sterols from the sunflower oil and two olive oils illustrate the possibilities of the method.     

复杂基体中痕量多环芳烃分析测定方法的研究进展

介绍了环境样品（水和土壤）以及植物油中痕量多环芳烃的分析检测方法。对样品的预处理过程和分析方法做了评价。采用一些新的预处理方法（包括液相色谱法、固相萃取法、超临界二氧化碳萃取法）,并结合色谱-质谱在线联用分析检测方法能够获得比较理想的分析结果。引用文献52篇。