Characterization of Functional Groups of Asphaltenes in Vacuum Residues Using Molecular Modelling and FTIR Techniques

Asphaltenes are components of crude oil, and their average chemical structures are characterized with difficulty. This study shows that simple Fourier transform infrared (FTIR) analysis spectroscopy could be adapted to the determination of aromatic hydrogens in asphaltenes and resins and elucidation of their average molecules. The work demonstrates the existence of a linear correlation in the infrared (IR) intensities of the symmetric and asymmetric aromatic hydrogens in methyl substituted arenes, in the 2,900 to 3,100 cm^-1 region and of the out-of-plane deformation in the 700 to 900 cm^-1 region.     

Characterization and Identification of Petroleum Hydrocarbons and Biomarkers by GC-FTIR and GC-MS

Abstract

Identification of petroleum hydrocarbons from crude and distilled oils by GC-MS is well known. The distilled crude and oils contain specific group of hydrocarbons are known as biomarkers bearing the information of their geographical source or origin and the geological past. These are diamondoids (adamantanes, diadamantanes, terpanes, steranes, sesquiterpanes, hopanes, norhopanes, etc.). The present article describes the identification of hydrocarbons using their IR spectra in the molecular fingerprinting region where every molecule shows its unique and characteristic individual vibrational frequencies. GC-FTIR spectrum of each of the individual components present in distilled oils was identified by proper standard library matching with the spectrum of the individual component. The GC-MS profiles of the biomarkers of different light and middle distilled fine products of samples from three leading oil companies, namely Indian Oil Corporation (IOC), Indo-Burma Petroleum (IBP), and Bharat Petroleum Corporation (BPC), differ from each other, indicating the variation of the sources of the crudes used by the companies. But nothing specific can be said about the origin of crudes from this limited data.     

鄂尔多斯盆地三叠系延长组页岩油储层裂缝特征及常规测井识别方法

鄂尔多斯盆地三叠系延长组长7油层组底部广泛发育张家滩页岩,厚度15～60m,中间夹薄层细砂岩或泥质粉砂岩,是很好的页岩油储层。野外露头观察、岩心分析及成像测井资料解释均表明该页岩段近东西向高角度构造裂缝和近水平页理缝发育,为致密页岩油储层提供了良好的渗流通道。依据岩心分析和成像测井资料解释确定单井内裂缝类型和分布;选取对裂缝敏感的常规测井曲线自然电位、声波时差、密度、中子及深浅电阻率差比,根据岩心分析和成像测井解释结果,利用模糊神经网络推理系统确定不同测井曲线的权系数,采用综合概率指数法和分形维数法识别页岩油储层及裂缝。     

Synthesis,Characterization, and Thermal and Explosive Properties of Alkali Metal Salts of 5,7-Diamino-4,6-Dinitrobenzofuroxan (CL-14)

Potassium, rubidium, and cesium salts of 5,7-diamino-4,6-dinitrobenzofuroxan (CL-14) have been prepared by reacting sodium salt of 5,7-diamino-4,6-dinitrobenzofuroxan with alkali metal nitrate in an aqueous medium. The structure of the compounds was unequivocally confirmed by spectra data, elemental analyses, and estimation of metal content. Further, the compounds have been evaluated for explosive and thermal properties and found more suitable as compared to alkali metal salts of 4,6-dinitrobenzofuroxan (DNBF).     

Characterization of Fuel Blends by GC-MS and Multi-Way Chemometric Tools

Discrimination of fuel types in mixtures is a common need in remediation of fuel spills and the examination of fuel contamination issues. Available methods for performing these types of discrimination analyses generally rely on either spectroscopic or chromatographic analyses. However, these methods are limited when the compositions of the components of a mixture are very similar. In this study we have shown that many of these limitations can be overcome by including the additional dimension of compositional information provided by gas chromatography-mass spectrometry (GC-MS). Multidimensional chemometric techniques were successfully used to analyze GC-MS data to unravel multi-component properties of fuel blends. Both qualitative and quantitative features were derived from a series of diesel fuel and heavier heating oil blends.     

Structural Characterization of Asphaltenes and Ethyl Acetate Insoluble Fractions of Petroleum Vacuum Residues

Asphaltenes and insoluble fractions of vacuum residues (VRs) of two Indian crude oils (viz. Heera and Jodhpur) of different specific gravity were obtained by precipitation of VRs in n-hexane, n-heptane, and ethyl acetate, and also by subsequent reprecipitation of n-heptane and ethyl acetate soluble fractions by n-pentane. The effect of various solvents on average molecular structure of asphaltenes and insolubles was studied using nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FTIR), and size exclusion chromatography (SEC). The asphaltenes and insolubles of Jodhpur VR have higher amounts of high molecular weight species with a high concentration of condensed and substituted aromatic rings, branched and/or short alkyl side chains, oxygen and nitrogen functionalities, compared to that of Heera VR. Ethyl acetate insolubles comprise a higher number of substituted aromatic structures, branched aliphatic structures, complex average unit structures, nitrogen and oxygen functionalities, and high molecular weight (MW) species as compared to hexane and heptane asphaltenes. Heptane insolubles consist of more naphthenic rings condensed with aromatic rings than C6A and EAI.     

改性X分子筛甲醇/甲苯共吸附原位红外表征

采用原位红外光谱法表征了负载一定量KOH和H_3BO_3的X分子筛催化剂,分析了不同改性分子筛上甲醇/甲苯吸附的原位红外特征峰,考察了KOH浓度和不同H_3BO_3负载量对改性的X分子筛甲醇/甲苯共吸附的影响,并研究了原位红外光谱定量分析结果与催化剂性能的关联性。实验结果表明,采用甲醇吸附在分子筛上的特征峰(2 824 cm~(-1))和甲苯吸附在分子筛上的特征峰(1 596 cm~(-1))的峰面积和峰面积比值可有效定量X分子筛酸碱性对甲醇/甲苯的吸附能力的影响;原位红外光谱表征结果可与催化剂性能相关联,为开发高性能甲醇/甲苯侧链烷基化反应的催化剂提供了一种重要的研究途径。     

应用FTIR分析硫磺中残留硫化氢及多硫化氢

硫磺中硫化氢（Ｈ２Ｓ）和多硫化氢（Ｈ２Ｓｘ）的残留量是硫磺产品质量控制指标之一。介绍了利用傅立叶变换红外光谱仪（ＦＴＩＲ）定量分析硫磺中残留Ｈ２Ｓ和Ｈ２Ｓｘ的方法,并对影响分析的主要因素－温度进行了讨论,给出了温度的选择方法,该分析方法简单,快速,且分析范围,检测下限低。     

L型沸石的合成、表征及其应用

对L型沸石的合成、表征和应用研究进展进行了综述。     

基于地震物理模拟的三角洲砂体识别及刻画技术

渤海海域古近系广泛发育三角洲沉积体系,三角洲砂体是重要的油气勘探目标,对三角洲砂体地震响应特征分析以及边界的精细刻画有助于提高三角洲储层预测的准确率。以渤海辽东湾探区实际地震资料为基础,设计物理模型和参数,并对模型进行简化;制作了典型三角洲沉积模式下的物理模型,模型包括低位体系域、湖浸体系域和高位体系域共11套砂体。在实验室条件下,采集得到物理模拟三维地震数据体,并对其进行处理和解释,再分别利用常规振幅切片和谱分解技术识别砂体边界。结果表明,振幅切片对于砂体横向的岩性变化较敏感,而谱分解技术能够精细刻画出砂体的轮廓和边界。     

环烷酸的分离表征及腐蚀研究

环烷酸腐蚀一直是炼油工业多年来亟待解决的问题,认识高酸原油中环烷酸的结构、类型及腐蚀机理,对炼油企业具有十分重要的意义。从环烷酸的分离、表征及腐蚀研究三个方面综述了近年来国内外的研究进展,报道了国内外环烷酸研究的一些最新成果,以期为深入开展环烷酸腐蚀研究提供参考。     

L型沸石的合成表征及其在工业中的应用

L型沸石是具有一维孔道结构,孔径在0．71nm的大微孔分子筛,具有高的水热稳定性,用作催化和吸附材料,用于工业催化、工业烃类生产、吸附和光化学等领域。讨论了L型沸石合成过程中反应物原料、组成、晶化温度和时间、导向剂、添加物等合成条件对合成产物的晶型、粒径、稳定性等性能的影响。介绍了表征L型沸石的方法和手段(如XRD,SEM,TEM,FT—IR,NMR．TG／DTA等),对L型沸石在工业催化等领域的应用进行了总结,并对L型沸石的工业应用前景进行了展望。     

古近系陡坡扇构造-岩性复合圈闭识别与储层刻画技术及应用

生油凹陷发育的陡坡扇,由于缺乏亮点型地震反射特征,目标评价过程中的圈闭识别和储层刻画难度较大。以珠江口盆地陆丰凹陷古近系陡坡扇陆丰1-X目标为例,运用古地貌分析、三维可视化、叠前弹性反演储层预测等多种地球物理解释技术,形成了生油凹陷古近系陡坡扇构造-岩性圈闭识别与储层刻画技术,有效识别和刻画了该沉积类型的圈闭和储层展布。研究成果表明,陆丰1-X文昌组文五段发育扇三角洲储层,文五段储层西侧朵叶扇体富集程度高于东侧朵叶扇体,且扇三角洲前缘是优质储层的有利发育部位。研究成果对生油凹陷陡坡扇型构造-岩性目标的综合评价具有借鉴意义。     

Synthesis,Characterization, Detonation Performance,and DFT Calculation of HMX/PNO Cocrystal Explosive

A novel 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX)/pyridine-N-oxide (PNO) cocrystal at 1:1 molar ratio was synthesized by a solvent evaporation method, and its crystal structure was determined using X-ray diffraction (XRD). It crystallizes in the orthorhombic system with the Pbcn space group and cell parameters a = 12.712(3)Å, b = 9.315(3)Å, c = 12.909(3)Å. In addition, detonation performance of this cocrystal was estimated. The predicted detonation velocity and detonation pressure of this cocrystal are 7.47 km/s and 23.20 GPa, respectively, suggesting that it is less powerful than β-HMX. Finally, density functional theory, involving binding energy, atoms in molecule (AIM) theory, natural bond orbital (NBO) analysis, band structure, and density of states, was adopted to characterize the driving forces for the formation of this cocrystal. The results show that driving forces are dominated by the interactions between O atoms of PNO and methylene groups of HMX. It is expected that this research provides some bases for further HMX cocrystal design and preparation.     

Si、Zr取代型APO—11分子筛的合成与表征

采用水热法合成了分别由Si和Zr取代的APO－11分子筛SAPO－11和ZAPO－11，利用XRD，SEM，TG－DTA，N2吸附等多种手段对它们的晶体结构，表面形貌，孔结构等作了系统的表征。结果表明，三者具有相同的结构，其中SAPO－11与APO－11为5－10μm的球形颗粒，而APO－11为10－15μm的棒状晶粒；除了0.45nm结构的微孔外，3种分子筛还具有3.8-3.9nm的中孔结构，表面吸附和表面元素分析证实，Zr可能主要存在于分子筛的孔道内，而部分Si则已进入分子筛的骨架中，SAPO－11和ZAPO－11的稳定性可与APO－11相媲美，崩塌温度超过1000℃。     

FeY分子筛的合成、表征及其加氢裂化活性

采用水热法合成了骨架含杂原子Fe的Y分子筛,并经处理得到超稳Y(USY)分子筛超稳FeY(USFeY)分子筛。利用X射线衍射、红外光谱、紫外可见漫反射光谱(UV-V is-DRS)、热重(TG)法对FeY分子筛进行了表征,结果表明,随Fe含量的增加,FeY分子筛的晶化时间延长,结晶度降低,晶胞常数增大;FeY分子筛的骨架伸缩振动峰向低波数方向移动;FeY分子筛的UV-V is-DRS谱图上不存在非骨架Fe的特征吸收峰;在600℃通氢气处理1h后,FeY分子筛的TG曲线仍无还原峰出现,以上结果均表明Fe进入了Y分子筛的骨架中。利用吡啶吸附红外光谱测定了USY和USFeY分子筛的表面酸性,并对以USY和USFeY分子筛为载体制备的催化剂的加氢裂化活性进行了评价,实验结果表明,与USY分子筛相比,USFeY分子筛的B酸、弱L酸量及总酸量增加,催化剂的加氢裂化活性提高。     

火山岩岩性、岩相识别方法——以准噶尔盆地滴南凸起火山岩为例

准确识别火山岩岩性和岩相是进行火山机构重建及地震相刻画的基础。火山岩岩性复杂且变化快,其变化不同于砂岩分布变化服从于沉积规律,而是与火山建造和喷发期次等因素直接相关,造成目前无成熟的预测模型和较强规律性可以遵循预测。选择准噶尔盆地滴南凸起火山岩为研究对象,总结出适应火山岩复杂岩性岩相识别的技术方法,即首先利用测井、岩心等基础资料建立关键岩性电性识别图版,落实井点硬数据的岩性纵向分布;其次,建立不同岩性的地震响应特征;第三,在地震波阻抗二次刻画岩性分布范围的约束下,应用数学概率和变差函数分析技术对岩性进行精细刻画;最后,结合测井响应特征进行测井相与地震相的综合标定,建立典型的火山机构地质、测井、地震相模式,为火山岩机构识别提供依据。     

Reservoir Characterization in Balal Oil Field by Means of Inversion,Attribute, and Geostatistical Analysis Methods

Abstract

The authors focus on the Arab reservoir of Balal oil field in the Persian Gulf. The major reservoir unit in the interested area is composed of alteration of thin dolomite with anhydrite layers. In the available 3D seismic data, these layers are not resolved and generate a composite detectable seismic response, making reservoir characterization difficult through conventional seismic attribute analysis (using single-attribute transforms). In addition to resolving the major reservoir units the main aim of this study is porosity prediction and making 3D porosity volume for detailed reservoir characterization. For this purpose first the 3D seismic volume was inverted to obtain an acoustic impedance cube using 3 different inversion algorithms. Inversion integrates log and seismic data to a full band acoustic impedance model of Earth. This process improves the vertical resolution and resolving the interested reservoir layers; it is also an important layer property, which usually has close relation with reservoir properties such as porosity, water saturation, and clay content. Among the different inversion methods applied, according to cross-validation results, acoustic impedance derived from model-based inversion has been selected as the main seismic attribute. In the next step, the acoustic impedance attribute besides other attributes extracted from seismic volume were analyzed using multiattribute regression and neural networks (probabilistic, multilayer feed forward, and radial basis function). These linear or nonlinear combinations of attributes for porosity prediction result in the improved match between the derived and predicted porosity. To estimate the reliability of the derived multiattribute transforms, cross-validation is used. Finally, multiattribute transform using stepwise regression for selection of attributes with minimum cross-validation error is selected for porosity prediction. In addition to making a 3D cube of porosity, several porosity maps from different reservoir layers were prepared.     

全二维气相色谱-飞行时间质谱分析直馏柴油馏分中硫化物的分子组成

The solid-phase extraction using Pd-Al2O3 as the stationary phase was employed to pre-separate the sulfur compoundsin straight-run diesel. The isolating effect was evaluated quantitatively by gas chromatography with a sulfur chemiluminescencedetector to harvest a satisfactory result. The identification of the structure of sulfur compounds by comprehensivetwo-dimensional gas chromatography coupled with the time-of-flight mass spectrometry indicated that cyclo-sulfides,benzothiophenes, dibenzothiophenes, dihydro-benzothiophenes and tetrahydro-dibenzothiophenes were included in straightrundiesel obtained from the Arab medium crude （AM）. A total of 259 individual compounds were detected and their molecularstructures were identified. The analytical method was approved as an effective way to characterize the composition ofsulfur compounds, which reduced the interference of other compounds, facilitated the data presentation and provided moredetailed information about molecular composition of sulfur compounds.     

The Structural Characterization of Saturate,Aromatic, Resin,and Asphaltene Fractions of Batiraman Crude Oil

Abstract

The structural characterization of fractions of Batiraman crude oil, which is the heavy crude oil from a field in the southeastern part of Turkey, was investigated. Batiraman crude oil and its saturate, aromatic, resin, and asphaltene (SARA) fractions were seperated. Treatment of crude oil with n-heptane provided the separation of asphaltene. Maltene was collected by evaporating the n-heptane from the filtrate. Then, maltene was separeted into saturates, aromatics, and resins by SARA technique. Maltene was separated into saturate, aromatic, and resin fractions using column chromatography. SARA fractions were quantified on a weight percent basis. Fractions of Batiraman crude oil were characterized by elemental analysis, proton nuclear magnetic resonance (¹H NMR) analysis, electrospray ionization mass spectrometry (ESI-MS), and Fourier transform infrared (FTIR) spectroscopy techniques.