CHROMATOGRAPHIC ISOLATION OF NITROGEN-CONTAINING COMPOUNDS IN LIQUID FUELS 1 Ti(IV) OXIDE GRAFTED ONTO SILICA AS STATIONARY PHASE

Abstract

The present work describes a novel method for the isolation of the neutral N-containing fraction from crude oil using column liquid chromatography on silica gel chemically modified with Ti(IV) oxide using a grafting method. The crude oil sample is introduced onto the column and eluted with a proper sequence of eluents. The first eluted fraction contains only hydrocarbons. The N-containing compounds are eluted in a isolated fraction. Both fractions are collected, concentrated and analyzed using HRGC with NPD detection. The method is shown to be very selective for the isolation of the neutral N-containing fractions from crude oil.     

CHROMATOGRAPHIC ISOLATION OF NITROGEN - CONTAINING COMPOUNDS IN LIQUID FUELS 2. THERMALLY TREATED SILICA GEL AS STATIONARY PHASE

In the present work we describe a novel method for the isolation of the neutral N-containing fraction from crude oil by preparative liquid chromatography using thermally treated silica gel as stationary phase. The hydrocarbons are eluted in the first two fractions and the nitrogen compounds in the third fraction. The collected fractions are analyzed by HRGC-NPD. The method is shown to be very selective for the isolation of nitrogen compounds from the neutral fractions of crude oil.     

CHROMATOGRAPHIC ISOLATION OF NITROGEN-CONTAINING COMPOUNDS IN LIQUID FUELS 1 Ti(IV) OXIDE GRAFTED ONTO SILICA AS STATIONARY PHASE

The present work describes a novel method for the isolation of the neutral N-containing fraction from crude oil using column liquid chromatography on silica gel chemically modified with Ti(IV) oxide using a grafting method. The crude oil sample is introduced onto the column and eluted with a proper sequence of eluents. The first eluted fraction contains only hydrocarbons. The N-containing compounds are eluted in a isolated fraction. Both fractions are collected, concentrated and analyzed using HRGC with NPD detection. The method is shown to be very selective for the isolation of the neutral N-containing fractions from crude oil.     

塔里木盆地原油中氮化物的分离及鉴定

由于原油中氮化物含量低且组成复杂，在用仪器分析其特征之前需要进行浓缩和预分离。采用柱液相色谱对塔里木盆地原油样品中的含氮化合物进行了分离，首先用中性氧化铝将原油分成饱和烃，芳烃和富氮馏份；然后用硅酸将富氮馏份进一步分离，得到了中性吡咯氮，和碱性吡啶等馏分。     

Behavior of asphaltene and asphaltene fractions films on a Langmuir–Blodgett trough and its relationship with proposed molecular structures

Abstract

Asphaltenes were precipitated from a Venezuelan Ayacucho crude oil and separated into two fractions (A1 and A2) by the p-nitrophenol method. The asphaltenes and the fractions A1 and A2, as well as mixtures of the two fractions were tested in a Langmuir–Bodgett trough. It was found that the asphaltenes and the fraction A2 had similar behavior and higher compressibility than the fraction A1. This is because the molecules of A2 are more flexible than the molecules of A1 as they have aliphatic chains that bond aromatic structures while the A1 has an aromatic nucleus.     

STUDIES ON LARGE CRUDE OIL ALKANES. II. ISOLATION AND CHARACTERIZATION OF AROMATIC WAXES AND WAXY ASPHALTENES.

ABSTRACT

Isolation of very large alkane components as described in the first paper within this series, fail in some cases. This work describes two non-routine isolation procedures applied to two different non-typical petroleum fractions. The first one comprises a chromatographic approach applied for the separation of alkanes from alkylaromatic compounds derived from paving asphalt waxes. The second separation procedure was developed for the isolation of alkane fractions associated with asphaltenes that precipitated during long crude oil storage periods, resulting in highly insoluble organic composites

In the first case, the isolated fractions were characterized by spectroscopic and chromatographic methods. The evidence showed that long chain naphtheno-aromatic molecules behave like waxy asphalt components, which interact by unusual mechanisms with solid sorbents. Their chromatographic behavior was found to be between typical alkanes and typical aromatics. This behavior is caused by the simultaneous presence of three functionalities

The second sample type was characterized by spectroscopic methods only. The results permitted to assess that the waxy composite from crude oil tank sediments precipitated selectively, including highly aromatic and long alkyl chain asphaltenes as well as very large n-alkanes.     

INVESTIGATION OF NITROGEN COMPOUND TYPES IN HIGH-BOILING PETROLEUM DISTILLATES FROM SAUDI ARABIAN CRUDE OILS

ABSTRACT

Acids, bases and neutral nitrogen compounds from high-boiling petroleum distillates were separated and further fractionated into fractions containing nitrogen compound types by HPLC on neutral alumina. Acids and bases were separated with anion and cation exchange resins respectively while the neutral nitrogen compounds were removed by complexation with ferric chloride supported on Attapulgus clay. The HPLC fractions were characterized by potentiometric titration for their basic and nonbasic nitrogen contents while infrared spectroscopy was used for the quantitative determination of major compound types present which are pyridines, pyrroles, amides, phenols and carboxylic acids. Characterization of individual nitrogen compounds was accomplished using gas chromatography and gas chromatography -mass spectrometry. The nitrogen compounds identified belong to three compound types which are pyridine, pyrrole and amide.     

Characterization of the isolated wetting crude oil components with infrared spectroscopy

To improve the understanding of wettability, especially the influence of different crude oil colloids, wetting experiments on quartz sand and kaolin were performed with an asphaltene rich oil. A two-step procedure was developed to investigate the wetting behavior. In the first step, those crude oil components were extracted, which preferentially wet solid surfaces. The extracted crude oil components were characterized in a second step. The composition of the fractions extracted with different solvents are different. The acetone fractions extracted from quartz sand are rich in compounds containing nitrogen, whereas the compounds containing sulphur predominate in the chloroform fraction extracted from quartz sand. IR spectroscopy of the extracted fractions shows that carbonyl compounds are abundant in the methanol/chloroform and acetone/chloroform fractions extracted from quartz sand. The chloroform fraction is poor in carbonyl group-containing compounds. In agreement with elemental analysis, a strong signal for C–N groups in the IR spectra is found for acetone/chloroform and methanol/chloroform fractions, extracted from the quartz sand system. On the other hand, a significant, strong IR-peak representing S=O containing components is observed in the acetone and acetone/chloroform fractions, extracted from quartz sand.     

克拉玛依原油中各组分的乳化性质

用沉淀法和色谱分离法将克拉玛依原油分离成沥青质，极性物和抽余油三组分，红外光谱分析表明，沥青质和极性物中存在一些含氧官能团的羧酸类或酚类以及含氮化合物，而抽余油则主要为烃类物质，因而沥青质和极性物的界面活性大于抽余油，沥青质具有较强的油包水（W／O）乳化能力，是造成克拉玛依原油W／O乳化的主要组分，极性物具有较强的水包油（O／W）乳化能力，是造成克拉玛依原油O／W乳化的主要组分，抽余油的乳化能力很弱。     

DETERMINATION OF NITROGEN COMPOUND DISTRIBUTION FROM THREE SOURCE FUELS

ABSTRACT

As part of a world-wide survey of middle distillate fuel instability, three fuels were chosen for detailed GC/MS analysis. These fuels are identified by number and country of origin; FL-2577 was from Burnaby, British Columbia, Canada; FL-2599 was from Abamadj, Kuwait; and FL 2592 was from Chiba, Japan. The organo-nitrogen compounds in the three fuels were separated by mild acid extraction followed by silica gel absorption. This treatment yielded three fractions for each fuel; a basic nitrogen compounds fraction, BNC; a non-basic nitrogen compounds fraction in methylene chloride, mcl, NBNC-mcl; and a non-basic nitrogen compounds fraction in methanol, meoh, NBNC-meoh. The three fractions from each fuel were analyzed by combined capillary gc/ms. The organo-nitrogen compounds from each fraction were identified and quantitated.     

不同结构破乳剂对原油及其酸碱组分表面膜的影响

 采用Langmuir-Blodgett(L-B)技术测定孤岛原油及其酸碱四组分表面膜膜压随水相破乳剂浓度的变化,考察了4种不同结构的破乳剂对原油及其酸碱四组分表面膜膜压的影响。结果表明,破乳剂对原油及其酸碱四组分的表面膜膜压降低程度与其结构和浓度有关。支链型破乳剂AE8025可以显著降低原油及其酸碱四组分的表面膜膜压,并随着破乳剂浓度的增加,表面膜膜压逐渐降低;其降低酸性分、碱性分和两性分表面膜膜压的程度大于对中性分的。与直链型破乳剂相比,支链型破乳剂降低孤岛原油及其酸碱组分表面膜膜压的能力更强,说明支链型破乳剂对原油及其组分乳状液中界面活性物质的顶替作用更强,破乳效果更优;当破乳剂浓度相同时,破乳剂对原油酸性分表面膜膜压的影响远大于其它3种组分的。     

鄂尔多斯盆地西峰油田原油含氮化合物分布特征与油气运移

为了给鄂尔多斯盆地西峰油田进一步勘探决策提供油气运移方面的依据，根据对该油田延长组原油的中性含氮化合物研究探讨油气运移问题。结果表明，原油的中性含氮化合物在平面和剖面方向均存在着明显的运移分馏效应．但是长。油层组原油中咔唑类化合物的绝对丰度和异构体参数值变化较小，说明该油层组油气经历了短距离运移。根据含氮化合物的运移分馏特征认为，平面上长s油层组油气主要从北东方向注入并向南西运移，部分原油从南部西33井地区注入并向北部运移；纵向上长s油层组油气由上向下运移，研究区西部长8、长3和延8油层组油气则自下而上从长。油层组向延s油层组方向运移。这种油气运移方向与研究区流体压力的指向一致。依据油气运移途径推断，该区油气主要来自长7段油源层。图5表2参10     

TLC-FID Calibration and Accurate Weight Determination of SARA Fractions in Heavy Crude Oil

Abstract

The authors specifically aimed to separate and characterize clean saturates, aromatics, resins, and asphaltenes (SARA) fractions and develop standards for accurate quantification purposes. A standard method ASTM D4124-86 was employed for the SARA separation of an Athabasca crude oil. These four recovered fractions were analyzed by using an Iatroscan thin-layer chromatograph with flame ionization detection (TLC-FID). The Iatroscan response to the complete burnoff of known sample weights of each fraction deposited on chromarods via known volumes of standard solutions was determined and area count versus sample weight calibration graphs subsequently obtained. From the established weight versus peak area calibration curves for each pure separated SARA fraction their accurate quantitative percentage in an Athabasca heavy crude oil was determined.     

原油中中性氮和烷基酚化合物的分离制备及分析应用

该文介绍了一种原油中中性氮化合物和烷基酚化合物分离制备的新方法.在自制的C¹⁸非极性填料的层析柱上,用正己烷淋洗除去沥青质的原油样品,除去饱和烃、芳烃,继续用正己烷淋洗,制备出中性氮化合物;再用二氯甲烷淋洗得到烷基酚化合物.实验证明,方法的稳定性和重复性令人满意,同其它的方法相比,节省试剂、分析周期短,中性氮化合物纯度较高.     

Sulfur compounds in the fuel range fractions from different crude oils

A gas chromatograph coupled with sulfur chemiluminscence detector (GC-SCD) has been used for the speciation of individual sulfur compounds in fractions of different crude oils. The crude oil fractions characterized were light naphtha (C5-90°C), heavy naphtha (90–140°C), kerosene (140–240°C), and gas oil (240–370°C) fractions obtained from true boiling point distillation process. Low boiling fractions (up to 140°C) were analyzed by existing ASTM D5623 (American Society for Testing and Materials, 2009a) method for sulfur compound speciation. As there is no standard method for the distribution of sulfur compounds in high boiling samples (up to 370°C), therefore, a methodology has been developed for the diesel range samples. The identification of individual sulfur compounds were carried out by using reference sulfur compounds. The results show that type of sulfur compounds depends upon the boiling range of the fraction and source of crude oil. The major changes in the sulfur compounds profiles of different fractions are discussed. The results of this study can be used to predict the suitability of crude oil for the production of Euro-IV and V gasoline and diesel fuels.     

稠油组分在水包油乳状液中作用机理的研究——Ⅰ．稠油组分分离及基本性质研究

本文主要研究了稠油的组分分离及其基本性质,为稠油组分在水包油乳状液中的作用机理研究提供基础数据.首次建立了将稠油分为酸性分、碱性分、两性分和中性分四组分的离子交换色谱分离技术.采用该分离技术对辽河杜-84稠油和胜利孤岛垦西稠油进行了组分分离,同时用极性分离法将稠油分为饱和分、芳香分、胶质和沥青质四组分.之后对这些纽分进行了元素、酸碱值、相对分子质量及红外光谱等组成结构测定.结果表明,杜-84稠油中酸性分、碱性分、两性分含量达36.92%;孤岛垦西稠油中酸性分、碱性分、两性分含量达20.65%.元素分析、酸碱值和红外光谱分析结果表明,分离效果较好,离子交换色谱分离法收率可达95%以上.极性四组分以沥青质相对分子质量最高(2000-3000),且辽河沥青质比孤岛沥青质要大许多,反映出辽河稠油的超稠油特性;相对分子质量大小顺序为沥青质＞胶质＞芳香分＞饱和分;官能团四组分中,碱性分相对分子质量最大(1150-1222),其它由大到小依次为两性分、酸性分、中性分.     

稠油组分在水包油乳状液中作用机理的研究 I.稠油组分分离及基本性质研究(英文)

本文主要研究了稠油的组分分离及其基本性质,为稠油组分在水包油乳状液中的作用机理研究提供基础数据。首次建立了将稠油分为酸性分、碱性分、两性分和中性分四组分的离子交换色谱分离技术。采用该分离技术对辽河杜-84稠油和胜利孤岛垦西稠油进行了组分分离,同时用极性分离法将稠油分为饱和分、芳香分、胶质和沥青质四组分。之后对这些组分进行了元素、酸碱值、相对分子质量及红外光谱等组成结构测定。结果表明,杜-84稠油中酸性分、碱性分、两性分含量达36.92%;孤岛垦西稠油中酸性分、碱性分、两性分含量达20.65%。元素分析、酸碱值和红外光谱分析结果表明,分离效果较好,离子交换色谱分离法收率可达95%以上。极性四组分以沥青质相对分子质量最高(2000-3000),且辽河沥青质比孤岛沥青质要大许多,反映出辽河稠油的超稠油特性;相对分子质量大小顺序为:沥青质>胶质>芳香分>饱和分;官能团四组分中,碱性分相对分子质量最大(1150-1222),其它由大到小依次为两性分、酸性分、中性分。     

Evaluation of Trace Metals and Physical Properties of Nigerian Crude Oil Saturate Fraction

Analyses of trace elements and physical properties of the saturate fraction of Nigerian crude oil were done in order to establish the characteristics that may aid the developmental processes of the natural resources. Crude oil samples were collected from three different oil fields in Niger-Delta area of Nigeria. The saturate fractions were eluted by column chromatography using n-hexane. The saturate fractions were investigated for functional groups using Fourier transform infrared spectrometry (FT–IR); the elemental concentrations were determined using Atomic absorption spectrometry, while the physical properties (flash point, ash content, refractive index, and color) were determined using standard analytical methods. The results revealed that the infrared spectra of the saturate fraction of the Nigerian crude oil showed mainly the presence of C-H(CH₃) and C-H(CH₂) functional groups, indicating high purity of the samples. The concentrations of the analyzed elements (Mn, Cu, Co, Zn, Fe, V, Cr, and Ni) in the saturate fraction were generally low compared to other fractions of Nigerian crude oil. This study revealed that Co has the highest mean concentration of 1.81 ± 0.36 mg/L, while Mn has the lowest mean concentration of 0.04 ± 0.02 mg/L. The t test values for the comparison of the elemental concentrations of Nigerian crude oil /saturate fraction and crude oil asphaltene/saturate fraction showed significant difference (except Mn) with respect to Nigerian crude oil /saturate fraction. The cluster analysis for the elements showed two groups, which are fairly well correlated indicating similar source and similar chemical affinity. The cross-plot analysis of the Nigerian crude oil and its saturate using elemental concentrations as the variables showed a strong positive inter element correlation since (R² = 0.71), establishing a relationship between the Nigerian crude oil and the saturate fraction. The color of the saturate fraction ranged from off-white to colorless. The results of analysis provide useful information on its conversion mechanism and environmental implications of the development of the fossil fuel deposit.     

Processing Lunpola Crude Oil

Abstract

The characteristics of crude oil from Lunpola of Xizang were studied, and the properties of different fractions were analyzed. The results indicated that this crude has great density and viscosity, solidifying points are high, and water cut is especially high. It is rich in wax and resin, but less in asphaltene, which belongs to low-sulfur intermediate-based crude oil. Looking at these characteristics, water cut oil should be more than 90°C, while dehydrated crude should be more than 100°C when it is stored, freighted, gathered, and transported; otherwise, these things will be more difficult. A reasonable processing scheme was put forward for producing diesel oil, paraffin, lube stock, and road asphalt, because it does not have a gasoline fraction but has a high diesel oil fraction and cetane number.     

辽河双南油田原油中性氮化合物的分布与运移特征研究

利用含氮化合物定量分离分析技术,研究了双南油田原油中中性氮化合物的分布、组成与浓度变化。分析结果表明原油中烷基咔唑系列呈现富和贫C-1位烷基取代2种模式,这与辽河盆地西部凹陷沙河街组烃源岩中烷基咔唑系列较好的可比性。依据原油甾萜烷成熟度参数、含氮化合物浓度和运移参数的变化特征,结合区域地质背景认为清水凹陷是双南油田的主要油源区。油气的运移方向是从双201井向双110-1井和双202井推进。