Resolution and Quantification of Ring Type Aromatics by HPLC Method Using n -Hexane Elution

Abstract

A method is described for the ring type separation of aromatic fraction of crude oils. The crude oils were dissolved in n-hexane to precipitate asphaltenes. The n-hexane dissolved portion of the crude oil was separated into saturates, aromatic types, and polars using high performance liquid chromatography. The aromatics were differentiated into monoaromatics (1R), diaromatics (2R), triaromatics (3R), tetraaromatics (4R), and polyaromatics (5R+). This method was applied to four commercial Saudi Arabian crude oils namely Arab Berri, Arab Light, Arab Medium, and Arab Heavy having API gravity in the range 28.0–38.5. The HPLC separation was carried out by n-hexane elution on a amino propylsilane silica column. The hydrocarbon group types were determined on weight percent basis. The saturates and total aromatics were found decreasing with decreasing API gravity while polars and asphaltenes increased. This trend may be due to the reason that the condensed polycyclic compounds and heteroatomic contents increase with decreasing API gravity in crude oils. This method may be applied to other crude oils for aromatic types determination.     

多产芳烃并兼产小分子烷烃的正己烷转化机理

对不同含量ZnO负载ZSM-5催化剂的物化性质和其催化正己烷芳构化反应性能进行了系统考察,利用分子模拟计算了关键反应步骤的能垒,对芳构化路径在不同阶段的变化进行了解释。结果表明：ZnO的引入强化了脱氢反应,从而提高了芳烃选择性,但过量的ZnO将加剧氢解反应,ZnO负载量以3%(质量分数)为宜;正己烷在3%ZnO/ZSM-5催化剂上的转化率小于58.02%时,生成芳烃的路径以脱氢反应为主;而转化率大于58.02%时,芳构化途径以氢转移为主,并且此时甲烷和乙烷的选择性由于氢解反应的发生而快速提高。分子模拟结果证实,氢解反应能垒较高,需在长的停留时间下才能发生,但该反应的发生不利于脱氢反应,进而导致芳构化途径的变化。该研究为正己烷芳构化多产芳烃并兼产小分子烷烃提供了理论依据。     

双咪唑环离子液体的制备及其正己烷异构化性能

设计合成了3种分别含甲基、乙基和丁基取代基的双咪唑环离子液体前驱体M₁、M₂和M₃,并对其进行核磁共振(¹H NMR和¹³C NMR)、高分辨质谱(ESI-MS)和同步热分析(TG/DTG/DSC)等表征。基于前驱体M₁、M₂和M₃合成了一系列双咪唑环离子液体催化剂AlCl₃/M₁、AlCl₃/M₂和AlCl₃/M₃,利用紫外-可见光谱(UV-visible)和乙腈红外(CAN-IR)表征方法对其酸性进行了研究。在此基础上研究取代基对正己烷异构化性能的影响并优化其反应工艺条件。结果表明：乙基为取代基的双咪唑环离子液体所合成的催化剂AlCl₃/M₂具有较多的BrÖnsted酸和Lewis酸位,有助于异构化反应的进行;在AlCl₃与前驱体M₂中Cl^-的摩尔比为2.1∶1、反应温度30 ℃、反应时间10 h和剂/油质量比1∶1的最佳工艺条件下,正己烷转化率为74.52%,异己烷选择性和收率分别为29.51%和21.99%。     

应用因子分析方法识别热液蚀变作用类型

结合薄片鉴定资料和测井响应特征分析表明,位于准噶尔盆地乌尔禾地区夏子街组的部分井区发育热液成因的蚀变地层。根据常规测井资料与薄片鉴定资料的对比分析,以蚀变作用导致的测井响应变化规律为依据,建立了以因子分析技术为手段的热液蚀变作用识别方法,该方法能够有效识别不同热液蚀变作用类型,其中岩性界面处与高自然伽马对应性较好,蚀变砂砾岩的底部为铀质富集的主要部位,为进一步研究热液蚀变作用的分布模式奠定了基础。     

Hydroisomerization of n-Hexane Using Unloaded and Low-Platinum-Loaded H-ZSM-5 and H-MOR Catalysts

Abstract

The applicability for investing and comparing two zeolites (H-ZSM-5 and H-MOR) as supports for low-platinum (less expensive) catalysts used principally for hydroisomerization of n-paraffins in light petroleum naphtha is investigated using n-hexane as a model n-paraffin feed at temperatures of 250°C–500°C in a flow-type reactor with a hydrogen flow of 20 cm³ min^?1 at atmospheric pressure. H-ZSM-5 zeolite acquires higher density of strong acid sites, which are still somewhat weaker than the respective sites in H-MOR. These milder sites in H-ZSM-5 zeolite enhanced hydroisomerization and dehydrocyclization but suppressed hydrocracking after incorporating 0.15% Pt. Hydrochlorination (HCl) and hydrofluorination (HF) of 0.15% Pt/H-ZSM-5 were carried out to modify its acidity and Pt dispersion with the goal of maximizing n-hexane hydroisomerization. The HCl treatment seems to have significantly approached the requirement for optimum catalytic bifunctionality, whereas HF treatment appears mostly deteriorative.     

High Yields of LPG Via n-Hexane Hydrocracking Using Unloaded Acidic Zeolite Catalysts

This work includes investigating the hydrocracking of n-hexane, as a low-octane naphtha component to high-octane gaseous motor fuel (LPG) in a pulse flow atmospheric microreactor using untreated and steam-treated H-MOR, H-BEA, or H-ZSM-5 zeolite catalysts. All zeolites were metal-free and their bifunctionality depended only on the Brønsted zeolitic acid sites. The temperature programmed desorption analysis was performed to compare the weak and strong acid sites in the current catalysts. The catalytic activities of the catalysts were found to correlate well with their acid strengths. The most active catalyst was St-H-MOR, which acquired the strongest acid sites and highest densities. On this catalyst, 92.1% LPG was produced at 350°C, whereas on the un-steamed one (H-MOR), the LPG yield amounted to 88.0% at the same temperature. Maximum LPG production on H-BEA acquired 84.6% at 400°C, whereas on St-H-BEA, it acquired a close yield (85.7%). Zeolites H-ZSM-5 and St-H-ZSM-5 acquire very low catalytic activities mainly due to their narrow pore structure, as well as due to their partial pore filling by Al debris in case of St-H-ZSM-5.     

Linkage of Aromatic Ring Structures in Saturates,Aromatics, Resins and Asphaltenes Fractions of Vacuum Residues Determined by Collision-Induced Dissociation Technology

The linkage of aromatic ring structures in vacuum residues was important for the refining process. The Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS) combined with collision-induced dissociation(CID) is a powerful method to characterize the molecular structure of petroleum fractions. In this work, model compounds with different aromatic ring structures were measured by CID FT-ICR MS. The cracking of the parent ions and the generated fragment ions were able to distinguish different linkage of the model compounds. Then, vacuum residues were separated into saturates, aromatics, resins and asphaltenes fractions(SARA), and each fraction was characterized by CID technology. According to the experimental results, the aromatic rings in saturates and aromatics fractions were mainly of the island-type structures, while the aromatic rings in resins and asphaltenes fractions had a significant amount of archipelago-type structures.     

用经三氯化铝改性的1-烷基-3-甲基咪唑溴盐离子液体催化烷基化脱除芳烃中微量烯烃的研究

Removal of trace olefins from aromatic liquids had been investigated in the presence of various ionic liquids like 1-ethyl-3-methylimidazolium bromochloroaluminate(EMIMBr-AlCl3),1-butyl-3-methylimidazolium bromochloroaluminate(BMIMBr-AlCl3),1-hexyl-3-methylimidazolium bromochloroaluminate(HMIMBr-AlCl3),and 1-octyl-3-methylimidazolium bromochloroaluminate(OMIMBr-AlCl3).It was found that the longer the alkyl chain of ionic liquid cations was,the higher the olefins conversion would be.OMIMBr-AlCl3(with 0.67 mo...     

全二维气相色谱-高分辨飞行时间质谱分析LCO中芳烃化合物

采用全二维气相色谱 高分辨飞行时间质谱(GC×GC/HR-TOF MS)对催化裂化轻循环油(LCO)中的芳烃化合物进行详细表征。通过质谱图解析、沸点信息和标准物质保留时间对比,结合仪器高分辨率的优势,确定LCO中的主要芳烃类型及结构。对相同Z值、但类型不同的芳烃在总离子流色谱图中的峰面积进行归一化计算,结合SH/T 0606-2005法测定结果,得到不同类型芳烃在LCO中的含量。结果表明：LCO中除含有Z值为-6的烷基苯类、Z值为-12的萘类和Z值为-18的菲类和蒽类化合物外,还含有Z值为-8的芳烃包含茚满类和四氢萘类化合物,以茚满类为主;Z值为-10的芳烃主要为茚类,含有少量的二环烷基苯类;Z值为-14的芳烃包含联苯类、苊类和二苯并呋喃类化合物,以苊类为主;Z值为-16的芳烃主要为芴类,不含苊烯类化合物。该方法可以提供更为详细的芳烃类型和单体化合物的分子组成信息。     

用高分辨率地震资料研究舞阳凹陷地震相

以高分辨率地震资料为基础,从地震层序划分、地震相类型及特征分析入手,对舞阳凹陷地震相进行了系统研究,指出了凹陷内主要发育与冲积扇、扇三角洲和三角洲沉积相对应的地震相类型,剖面上具体表现为九种类型。展示了各层序地震相平面分布特征。     

碰撞诱导解离技术研究减压渣油四组分中芳环结构的连接方式

The linkage of aromatic ring structures in vacuum residues was important for the refining process. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) combined with collision-induced dissociation (CID) was a powerful method to characterize the molecular structures. In this work, model compounds with different aromatic ring structures were measured by CID FT-ICR MS. The cracking of the parent ions and the generated fragment ions were able to distinguish different linkage of the model compounds. Then, vacuum residues were separated into saturates, aromatics, resins and asphaltenes fractions (SARA), and each fraction was characterized by CID technology. According to the experiment results, the aromatic rings in saturates and aromatics fractions were mainly island-type structures, while the aromatic rings in resins and asphaltenes fractions had a significant amount of archipelago-type structures.     

芳烃联合装置生产技术进展及成套技术开发

概述了以生产BTX芳烃为目标的现代芳烃联合装置的主要工艺单元结构及其作用,介绍了催化重整、芳烃抽提或抽提蒸馏、甲苯歧化及烷基转移、二甲苯异构化、对二甲苯吸附分离各单元技术的最新进展,以及中国石油化工股份有限公司(简称中国石化)相关技术的研究开发和应用情况。中国石化采用自主研发的芳烃成套技术,在中国石化海南炼油化工有限公司建成1套60万t/a对二甲苯的芳烃联合装置,2013年底投产成功并已完成考核标定,结果表明各项工艺指标均达到设计要求,能耗明显降低,成套技术可靠、先进。     

利用谱蓝化和有色反演分辨薄煤层

基于模型反演在实际应用中,存在反演结果过度模型化、反演可能扩展到地震频带以外以及估计的子波不准确导致反演误差较大等不足,谱蓝化和有色反演可有效白化地震子波,在地震带宽内改善频谱,提高地震分辨率,同时确保谱蓝化后的地震数据保持地下地层的真实反射系数。设计优化了谱蓝化和有色反演技术流程并将其应用在煤层气勘探三维地震资料中,有效地提高了反演波阻抗体对薄煤层的分辨能力。同时,反演结果被用于辅助精细构造解释薄煤层,纠正了单纯利用地震原始数据体解释层位出现的错误。     

芳烃抽提法优化乙烯联合装置的裂解原料

根据裂解和结焦反应理论,分析了石脑油裂解反应中芳烃结焦过程的规律,研究了石脑油族组成与乙烯收率的关系,选择了用于计算乙烯联合工艺装置综合能耗的统一基准。在石脑油中烷烃和环烷烃含量相同或相近的条件下,降低石脑油的芳烃含量可提高乙烯收率并减少结焦。在不增加工艺装置和设备的前提下,提出了优化裂解原料的前抽提乙烯联合装置工艺流程(简称前抽提流程),即先将石脑油送芳烃抽提装置分离出芳烃,再将抽余石脑油送裂解炉生产乙烯。选择低能耗芳烃抽提技术,可使前抽提流程总能耗低于常规乙烯联合装置工艺流程的总能耗。     

正己烷和乙酸乙酯间歇共沸精馏分离共沸剂的研究

正己烷和乙酸乙酯形成最低共沸物,采用间歇共沸精馏方法分离回收时,共沸剂的选择和用量直接影响实验效果。研究了正己烷-乙酸乙酯共沸物系间歇共沸精馏法分离适宜的共沸剂,并从理论上和实验中考察了共沸剂与原料适宜的配比。实验结果表明,丙酮为合适的共沸剂,当丙酮和正己烷的质量比为1.15时,正己烷和乙酸乙酯的收率最高,分别达75.15%和73.89%。通过实验绘制了正己烷-乙酸乙酯-丙酮三元物系的剩余曲线,确定了正己烷-乙酸乙酯共沸物系分离步骤:共沸精馏塔中馏出丙酮和正己烷的共沸物和高纯度的乙酸乙酯;萃取塔中用水萃取丙酮和正己烷的混合物得到较纯的正己烷;萃取后的丙酮水溶液由共沸剂精馏回收塔回收丙酮。     

一种典型曲线拟合分析新方法──无因次压力与时间比法

提出了一种新的适用于均质无限大油藏具有井筒储存和表皮效应影响的压力不稳定试井分析方法，即无因次压力与时间比典型曲线拟合法。该方法首先求出无因次压力pwD，然后以PwD／（tD／CD）及1－PwD／（tD／CD）为纵坐标，tD／CD为横坐标，CDe2s为参数绘制半对数及双对数图版，即PTR典型曲线，放大了早、中、晚期曲线特征，使数据拟合更精确。在已知Cs值时，只需水平移动即可实现拟合，减少了图版拟合的多解性；若不知Cs值，通过调整Cs值进行拟合分析。本方法较适合于机抽井液面恢复分析。     

旋转环梁楔块式液压升降装置设计

为降低投资风险,海上边际油田开发要求采油平台具备可移动、自安装功能。为此,研发了一种新型的旋转环梁楔块式液压升降装置。该装置由上挟桩器、下挟桩器、锁桩器、升降油缸、回转油缸、固桩筒和桩腿组成,通过升降油缸的伸缩运动实现平台的升降,通过回转油缸的伸缩运动实现与桩腿的锁紧和解锁。该装置具有安全可靠、造价经济、技术国产化、可拆卸重复使用等特点。     

利用地球化学方法进行油藏表征

地球化学用于油藏表征具有成本低、耗时短、精度高等多种优势。根据不同储层流动单元中储层流体的宏观组成和微观组成的差异性可直接判断油藏流体连通性,羊二庄油田羊二断块庄产层连通性判识证明了原油气相色谱指纹法的适用性。根据气相色谱指纹技术对板桥油田板834—1井的单层产能变化监测表明该技术不仅能对合采井进行单层产量贡献计算,还能对合采井进行动态监测,研究产能贡献变化趋势。利用原油中生物标志的相对含量与原油粘度的相关性．预测了冷43断块区的储集油粘度。并与地质条件相符合,为稠油开发方案的制订提供了定量依据。结合具体地质背景,油藏地球化学表征可为油田勘探开发方案的制订提供定量的科学依据。     

叠加法静校正

叠加法静校正方法,是采用叠加原理,充分利用地震数据中的折射波信息、反射波信息以及目前使用的较强的地震数据交互处理系统,分别求取炮点和检波点的相对静校正值,以消除不同波长静校正对地震数据的影响,提高地震数据处理分辨率。就该方法的原理、实现过程以及运用效果加以介绍。     

BaX分子筛吸附C8芳烃作用机理

采用正则系综蒙特卡洛方法模拟等量4种C₈芳烃分子分别在SiFAU和BaX分子筛上的吸附行为,并结合量子化学计算和波函数分析,基于分子筛组成和结构、C₈芳烃分子结构和电子分布特征进行吸附机理研究。蒙特卡洛模拟结果表明：4种C₈芳烃分子的密度分布主要在分子筛超笼内,吸附能分布近似为正态分布,吸附状态多样化;SiFAU上吸附位随机且范围广,但对二甲苯无选择性;BaX上吸附位集中在超笼内的Ba附近,平均吸附热由高到低的顺序为对二甲苯、乙苯、邻二甲苯、间二甲苯,与BaX分子筛对C₈芳烃吸附选择性的实验结果顺序一致。波函数分析结果表明,4种C₈芳烃分子静电势分布相似,芳环区域静电势为负,静电势极小值点偏离于取代基方向。考虑乙苯侧链柔顺性,将C₈芳烃分子的负静电势面积与其在BaX分子筛上的平均吸附能进行关联,阐明电子分布特征对吸附性能的影响。