原油中三芳甾烃的色谱质谱定量分析

三芳甾烃是原油芳烃组分中的常见化合物,其色谱质谱分析结果对寻找油气有着重要的意义.以往原油中芳烃色谱质谱分析大多忽略了各三芳甾烃化合物的绝对含量,而仅得出各化合物的相对量,使三芳甾烃的应用受到了限制.我们采用人工合成的二氘代化合物d2C28三芳甾烃加入原油中作内标,进行三芳甾烃的色谱质谱定量分析,该内标化合物是将原油中自然存在的1种C28三芳甾烃化合物进行氘代反应,合成得到的d2C28三芳甾烃与原油中的三芳甾烃系列化合物有着相似的结构和质谱分裂特征,并在色谱质谱分析时与原油中的化合物不产生共流.该定量分析方法可以为油气勘探提供更多的信息.     

利用气相色谱/质谱-化学计量学分辨法分析川芎挥发性成分

采用加速溶剂萃取法提取挥发性成分,气相色谱-质谱(GC-MS)联用分析,并借助化学计量学分辨方法,对川芎的挥发性成分进行了定性定量分析。通过采用子窗口因子分析法对重叠色谱峰进行分辨,从而获得每一组分的纯色谱和质谱。依靠每一组分纯质谱在NIST质谱库进行相似性检索而定性分析,用总体积积分法进行定量分析。在川芎挥发油中共分辨出67个色谱峰,通过质谱库检索得到其中56个组分的定性定量结果,占总含量的87.67%。该方法增加了可鉴定化合物的数目,提高了定性的准确度,能用于川芎的质量控制。     

大叶桉叶挥发油的化学成分研究

用挥发油提取器提取大叶桉干叶中的挥发油,利用色质联用(GC/MS)产生的双线性数据,藉化学计量学分辨方法,得到了各组分的纯物质色谱峰和质谱图。根据色谱保留时间,同时利用解析所得的纯物质质谱图在NIST质谱数据库进行相似检索来对各个组分进行定性分析;采用色谱峰面积归一法计算各化合物的相对含量。共分离了113个化合物,鉴定了其中90个,占总挥发油的93.28%。主要为萜类、萜醇类等化合物,还成功地检测出一些色谱分离不完全和低含量的组分。     

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。     

气相色谱-质谱法与化学计量学分辨法分析当归须挥发油中化学成分

本文借助化学计量学分辨方法,建立了用气相色谱-质谱(GC-MS)联用法分析当归须挥发油成分的方法.对重叠色谱峰采用直观推导式演进特征投影算法进行分辨,从而获得每一组分的纯色谱和质谱,依靠每一组分纯质谱在NIST质谱库进行相似性检索而定性分析,用总体积积分法进行定量分析.在当归须挥发油中共分辨出86个色谱峰,通过质谱库检...     

稠油中饱和烃复杂混合物成分解析及其意义

利用两根极性不同的毛细柱,在全二维气相色谱上分析辽河油田遭受严重生物降解形成的稠油饱和烃组分,可以将传统色谱分析时形成的“基线鼓包”即不可分辨的复杂混合物（Unresolved Complex Mixtures）分开．根据饱和烃全二维气相色谱谱图的族分离特点和瓦片效应,结合飞行时间质谱提供的质谱信息初步解析不可分辨的复杂混合物主要成分．发现常规色谱分析时形成的所谓“基线鼓包”是由成千上万、含量相对较低的不同取代基的环状化合物组成,这些化合物在一维色谱上以分子量递增的顺序排列,在二维色谱上以极性的差异或者环的多少排列．C24之前的第一组不可分辨的复杂混合物主要由环己烷为基本单元的单环、双环和三环烷烃类化合物组成,信噪比在100以上的化合物数量约为饱和烃总数量的75％,质量分数是饱和烃总量的80％以上,是饱和烃的主要组成部分．C24之后出现的第二组不可分辨的复杂混合物主要由四个环或者五个环为基本单元的化合物组成,信噪比在100以上的化合物数量约为饱和烃总数量的17％,质量分数是饱和烃总量的0．5％．对稠油中这些不可分辨的复杂混合物的解析有助于对其成因机理的认识和高效开采方案的制定．     

陈皮挥发油的气相色谱/质谱分析

用ＧＣ／ＭＳ分析复方制剂平胃散中的一种单味药材陈皮的挥发油化学成分及其相对含量,对色质联用仪产生的二维数据借助直观推导式演进特征投影法来分辨以得到组分的纯色谱和质谱,根据组分的色谱保留时间和质谱对组分进行定性,继而用总体积积分法定量。本文分离出５３个组分,其中鉴定了３４个组分,约占其挥发油总量的９６．０８％。     

一种新的汽油辛烷值的气相色谱测定方法

 建立了一种新的气相色谱结果关联计算汽油辛烷值的方法。采用高分辨毛细管柱对汽油的组成进行测定,根据汽油单体烃组分的含量和纯组分辛烷值乘积的大小,将单体烃组分分为两组,每一组为一个变量,建立实测辛烷值与两个变量间的回归模型。实际分析时,根据不同的样品类型选择不同的模型进行关联计算即可获得色谱分析样品的辛烷值。对模型建立和应用过程中已知结构的化合物的辛烷值数据采用文献值。对只知碳数和类型而不能确定其化合物结构的组分,通过对文献数据进行统计计算,得到平均辛烷值与组分的碳数和类型的关系曲线,据此得到其平均辛烷值用于计算。与采用标准方法测定催化裂化汽油辛烷值的结果相比,该方法测定辛烷值的偏差约0.5个单位。该方法操作简单,用样量少,模型建立过程快速、简便,适合于微型反应器产物评价或炼厂稳定工艺装置的汽油辛烷值的监测。     

原油中芳香硫化合物形态分布的研究

建立了原油中多环芳香硫化合物形态分布的研究方法。采用氯化钯/硅胶配位交换色谱分离原油中的芳香硫化合物,并用气相色谱/质谱分析、气相色谱-硫化学发光检测法结合色谱保留指数,鉴定出原油中的100多个多环芳香硫化物,包括含烷基取代基的苯并噻吩和二苯并噻吩类硫化物。定量分析表明,二苯并噻吩类化合物的含量占芳香硫化合物总量的91%左右。该方法可用于不同来源的原油中芳香硫化合物的形态分布研究。     

用熵最小算法解析桂郁金挥发油GC-MS重叠谱

采用气相色谱-质谱(GC-MS)联用技术对桂郁金中提取的挥发油成分进行检测,同时用熵最小算法对其中的共流物色谱峰进行解析,并通过质谱库检索和程序升温保留指数相结合的方式对解析得到的各纯组分进行定性分析。将桂郁金挥发油各组分的质谱数据直接与美国国家标准及技术研究所(NIST)数据库进行比对,鉴定出38个化合物;在挥发油的色谱图中,存在一些因分离不完全而导致的共流物色谱峰,以保留时间为1 106.52~1 108.38 s及1 184 s的色谱峰为例,经熵最小算法解析,共发现5个纯组分。采用熵最小算法可以清楚地对共流物色谱峰进行解析并得到所包含的各个纯组分,该法可提高复杂成分定性定量分析结果的准确性。     

Identification of structures of nitrogen-containing compounds in crude oils in conjunction with chemometric resolution

A universal method was established for the systematically structural identification of nitrogen-containing compounds in crude oils. Pre-fractionation of the non-hydrocarbons in a crude oil sample into 7 fractions was performed by di-adsorption column chromatography using neutral aluminum oxide and silica gel; subsequent high-resolution separation of individual components was achieved by using capillary column gas chromatography, and compound types were detected by mass spectrometer. The two-dimensional data from the compounds in the fractions were further resolved by a chemometric method to obtained the deconvoluted chromatogram and mass spectrum of every compound, and then, the nitrogen-containing compounds were identified in combination with the retention indices. This method could relieve the difficulty of classical analysis in identifying those species with very low contents or incompletely separation, particularly in the cases where the authentic standards were not available for addition into the unknown samples in order to reveal what indeed existed in them. The structures of 168 nitrogen-containing compounds in a crude oil sample were determined by this method with satisfactory results.     

多环芳烃指纹用于渤海采油平台原油的鉴别

采用气相色谱/质谱方法,对渤海海上4个不同区块、5个平台的6口油井原油进行了烷基化多环芳烃系列化合物和美国环保署（EPA）优先控制多环芳烃系列化合物的准确定性定量分析。通过多环芳烃原始指纹谱图、多环芳烃组分分布模式和特征比值的比较对上述原油进行鉴别。结果证明不同区块的原油中多环芳烃指纹信息不尽相同,即使在同一平台不同油井中所产的原油其指纹也存在一定差异。为确保原油鉴别的准确性,分析过程中必须在仪器的稳定性和样品前处理方面实施严格的质量控制措施。     

Systemic analysis of structures and contents of nitrogen-containing compounds and other non-hydrocarbons in crude oils in conjunction with chemometric resolution technique.

A method is described for the systemic identification and quantitative analysis of nitrogen-containing compounds and other non-hydrocarbons in crude oils. The pre-fractionation of a crude oil sample into 7 fractions was performed by di-adsorption column chromatography using neutral aluminum oxide and silica gel. A subsequent high-resolution separation of individual components was achieved by using capillary column gas chromatography, and compound types were detected by a mass spectrometer. In conjunction with a chemometric method, the compounds in the fractions were further resolved or separated, which made it possible to identify some nitrogen-containing compounds and other non-hydrocarbons in crude oils. To a certain extent, this method could relieve the difficulty of classical analysis in identifying those species with very low contents or incompletely separation, particularly in the cases where authentic standards were not available for addition into the unknown samples in order to reveal what indeed existed in them. The structures and contents of 168 nitrogen-containing compounds in one crude sample and 60 non-nitrogen-containing compounds in one of non-hydrocarbon fractions of this oil sample were determined, and the addition-recovery examination of some standard compounds showed that the analytical veracity was satisfactory.     

Hydrocarbon type analysis by thin-layer chromatography with flame-ionization detection: vacuum gas oils, heavy feeds, and hydroprocessed products

Thin-layer chromatography with flame-ionization detection (TLC-FID) provides quantitative hydrocarbon type data as well as distribution of aromatics by ring number. This method has been applied to obtain amounts of saturates, aromatics, and polars in heavy oil distillates such as light vacuum gas oils and heavy vacuum gas oils derived from different crude sources. TLC-FID chromatograms and resultant quantitative hydrocarbon type data show that these distillates vary markedly in aromatic contents and aromatic ring types. Similar observations are made with several fluid catalytic cracking feeds. Effects of process parameters such as operating pressure and temperature on hydroconversion of aromatics and polars from a heavy oil are assessed by TLC-FID. It has been demonstrated that there is a preferential reduction of higher polycyclic aromatic hydrocarbons and polars with an increase of both hydrogen partial pressure and reactor temperature.     

Molecular characterization of organically-bound sulfur in crude oils. A feasibility study for the application of Raney Ni desulfurization as a new method to characterize crude oils

Five crude oils with varying sulfur contents (0.1 – 4.7%) were characterized on a molecular level for organically-bound sulfur. Aromatic fractions were analyzed by GC-(MS) and asphaltene and polar fractions were analyzed by flash pyrolysis-GC-(MS). The polar fractions were also desulfurized with Raney Ni and the hydrocarbons formed were analyzed by GC-MS. Major sulfur compounds in the aromatic fractions were identified as alkylbenzo- and alkyldiben-zothiophenes. The flash pyrolyzates of the asphaltene contained alkylthiophenes and alkylbenzothiophenes as major compounds, depending on the thermal maturity of the oil. Generally, the sulfur-rich crude oils contained relatively more sulfur compounds. The flash pyrolyzates of polar fractions contained a variety of sulfur compounds (alkylthiolanes, alkylthianes, terpenoid sulfides, alkylbenzothiophenes) with substantial differences between different crude oils. Raney Ni desulfurization of the polar fraction yielded hydrocarbons dominated by n-alkanes, but isoprenoid alkanes, n-alkylcyclohexanes, mid-chain methylalkanes, tricyclic terpanes, hopanes and steranes were also present. These hydrocarbons show a potential to fingerprint crude oils since their distribution patterns are more characteristic than those of the hydrocarbons present in the saturated hydrocarbon fraction.     

气流吹扫-注射器微萃取-全二维气相色谱法用于原油组分的表征

建立了气流吹扫-注射器微萃取(GP-MSE)与全二维气相色谱/飞行时间质谱(GC×GC/TOFMS)联用分析原油成分的方法。为了找到适用于原油样品分析的GP-MSE条件,用饱和烃混合标准溶液和15种芳烃的混合标准溶液进行了条件优化,得到的最佳条件如下:取样量5 mg、萃取溶剂正己烷20μL、载气流速2 mL/min、加热时间3min、加热温度300℃、冷凝温度-2℃。处理后的样品在全二维色谱/飞行时间质谱上进样分析,得到了满意结果。方法的检出限为34~93μg/L,线性相关系数(R2)>0.99,对50种烃类化合物的回收率在82.0%~107.3%之间,相对标准偏差<10%(n=5)。结果表明GP-MSE-GC×GC/TOFMS法是一种新型绿色、高效、灵敏的分析方法,非常适合原油中挥发性与半挥发性组分的分析。     

Thermal analysis of crude oils and comparison with SIMDIST and TBP distillation data

Four commercial Saudi Arabian crude oils were characterized by thermogravimetry (TG) and differential thermal analysis (DTA). These crude oils, Arab Berri (AB), Arab Light (AL), Arab Medium (AM) and Arab Heavy (AH), were also subjected to the traditionally employed true boiling point (TBP) distillation and simulated distillation (SIMDIST). The TG/DTA data show that the hydrocarbons present in these crude oils fall into four groups: the volatiles, the low molecular weight, the medium molecular weight and the high molecular weight compounds. These four types of hydrocarbons were observed to display certain trends, such that the volatile and low molecular weight hydrocarbons increased, while the medium and high molecular weight hydrocarbons decreased with the lightness of the crude. The volatile contents of AB, AL, AM and AH crude oils up to 280°C were 50.1, 42.2, 42.3 and 38.5 mass percent, respectively. This confirms that AB is the lightest of these crude oils with maximum volatile content. The mass percentage loss from the TG results is in good agreement with the percentage distilled from TBP (ASTM D 2892) and SIMDIST. During evaporation, the TG mass loss follows a similar trend to those of the TBP and SIMDIST results and thus behaves like distillation. During the oxidative degradation, the TG curve shows a higher mass loss as compared to the distillation data. The higher deviation of the TG mass loss and percentage distilled at the higher-temperature end of the curve may be attributed to the higher content of asphaltenes and carbonaceous material present in AH as compared to the AB crude oil. At around 200°C, the TG mass loss curve intersects the TBP and SIMDIST curves and shows a derivation from distillation behaviour. This intersection temperature of the TG and distillation curves is observed to decrease with the heaviness of the crude and can be an indication of the onset of thermal degradation of hydrocarbons present in the crude oil. On the whole, the TG data closely resemble the distillation results.     

A new quick method of determining the group hydrocarbon composition of crude oils and oil heavy residues based on their oxidative distillation (cracking) as monitored by differential scanning calorimetry and thermogravimetry

A calorimetric-thermogravimetric method is described of determining mass percent contents of distillate fractions, paraffins, base oils, resins, asphaltenes and carbines in various crude oils. The method is based on recording DSC curves of a 10–15 mg sample heated in air in a calorimetric-cell at a rate of 40–50 °C/min. Additionally, weight loss of sample is found at temperatures before and after the reaction. At temperatures from 220 °C or higher distillation of the hydrocarbon mixture starts to be accompanied by its exothermic oxidation, thereby making possible monitoring the distillation (oxidation) of consecutive HC fractions by simple calorimetric-techniques. Differential scanning calorimeter “Thermodat” of high-calorimetric-resolution and sensitivity equipped with dedicated software was used for conducting the experiments and performing all the calculations. Percent contents of the main constituents in a number of heavy and light crude oils were determined and formulas for establishing paraffinic, base oil and coke-forming potentials of crude oils and oil residues derived. One full analysis of a sample takes no longer than 1.0–1.5 h. The method can be used for on-line quality control of various petroleum products, such as atmospheric and vacuum oil residues, cracking residues, lubricants, ceresins and paraffins.