High resolution capillary gas chromatographic hydrocarbon-type analysis of naphtha and gasoline

A slightly modified, commercially available high resolution capillary gas chromatograph and a PC-based data processing system running proprietary software (“PONA”) have been employed in the development of a system for petroleum type analysis which would be equivalent or superior to the FIA (fluorescent indicator adsorption) method in terms of ease of use and the speed, variety, and accuracy of the analytical data produced. The system is capable of performing identification and quantitation of most of the individual components in a complex gasoline sample consisting of more than 230 components and can report weight percentage and/or volume percentage for each component as well as types by carbon number (e.g., isoparaffins, normal paraffins, olefins, naphthenes, aromatic compounds) within a ca. 70 minute analysis cycle. Precolumn sulfonation to trap olefins and aromatic compounds has been used as an complementary technique to the basic mass spectrometric identification of components of interest. The estimation of correction factors for weight percentage (or volume percentage) calculation are also discussed. Comparisons are made between this system and others, and the results indicate that the proposed method supersedes the conventional method employing FIA.     

A History of Fischer-Tropsch Wax Upgrading at BP—— from Catalyst Screening Studies to Full Scale Demonstration in Alaska

Conversion of Fischer-Tropsch wax into high quality synthetic crude or finished transportation fuels such as premium diesel has been studied over the past 15 years within BP. Catalyst screening and selection was carried out in dedicated micro-reactors and pilot plants, whose designs are critical to the performance selection. Variation in catalyst composition and defining the gas to oil feed ratios with the operating temperature are a few of the parameters studied. Product selection and maximizing diesel yield combined with stability (catalyst life) were the ultimate drivers. The selected catalyst was then tested under commercial conditions in a dedicated 300 barrel per day demonstration plant. The products were also tested in engines to assess their combustion characteristics.     

中温热解焦油重馏分悬浮床加氢裂化的研究

以中温热解煤焦油为原料,对其性质进行了分析,其中,350℃重质馏分中胶质含量30.88%,沥青质含量37.27%,四氢呋喃不溶物3.36%,属于常规固定床加氢裂化难以直接处理的馏分。合成了一种Mo系超分散催化剂,采用FT-IR、XPS、XRD、SEM和TEM等对催化剂进行了表征,催化剂中含有Mo=O和Mo-S特征结构,活性金属的硫化率为84.34%,在体系中具有优良的分散性,在反应体系内原位分解为超分散MoS_2颗粒;在0.25 t/d连续装置上进行了热解重油悬浮床加氢裂化实验研究,考察了反应条件对产物分布情况和结焦率的影响,得出适宜的反应条件为19 MPa,440℃,催化剂的添加量为300 mg/kg;此条件下石脑油收率24.47%,柴油馏分收率49.71%,结焦率1.32%。     

中国催化重整技术进展

催化重整是将石脑油转化为高辛烷值汽油、芳烃,并副产大量氢气的过程,催化重整技术的进步关系到石油炼制与石油化工行业技术的战略安全与竞争力,因此受到极大重视.本文从催化材料、催化反应活性中心及反应机理、催化重整工艺、催化重整反应和再生动力学、关键设备、工程控制技术等方面阐述了我国在理论研究、工业开发及工业应用方面取得的技术进步和成果,对未来的技术进步途径进行了分析与展望.     

黏合剂对其ZSM-5分子筛成型物裂解石脑油的影响

为考察成型时,黏合剂性能对ZSM-5分子筛的影响,对同一分子筛用六种不同黏合剂捏合,挤条成型,进行SEM、NH₃-TPD和N₂物理吸附表征。结果表明,六个成型物在形貌和BET比表面积均无明显差异,二次孔数量明显比分子筛原粉增加。所用纯硅溶胶黏合剂的成型物,其NH₃-TPD酸量、微孔体积和微孔比表面积低于其分子筛原粉。所用含铝黏合剂的成型物,其NH₃-TPD酸量、微孔体积和微孔比表面积变化不明显,BJH累积孔体积明显增加。在固定床反应器中于600 ℃裂解石脑油。发现,纯硅溶胶黏合剂成型物的乙烯+丙烯收率明显低于含铝黏合剂。     

废轮胎热解石脑油馏分的组成分析

研究了废轮胎在回转窑中试反应器中进行中温段(450 ℃～650 ℃)热解所得产物油中石脑油馏分(i.b.p.～200 ℃)的品质。对原始热解油进行实沸点蒸馏,石脑油馏分的收率随热解温度的升高而明显增加,在600 ℃取得最大值40.48%,之后又有所下降。采用GC和GC-MS对石脑油馏分的组成进行了分析。结果表明,热解石脑油具有很强的芳香性,而且芳烃含量随热解温度的升高而持续增加,热解温度在550 ℃以上的石脑油中的芳香烃含量超过80%。轻质单环芳烃苯、甲苯、乙苯和二甲苯等为其中的主要芳烃。热解石脑油中的脂肪烃多为不饱和烃。     

Characterization of sixty alkenes in a cat-cracked gasoline naphtha by gas chromatography

Summary The alkene-rich petrol fraction from refinery fluid catalytic cracking (FCC) has been characterized by GC and GC-MS. Quantitative proportions and retention data of 52 acyclic and 11 cyclic C₅–C₇ alkenes are given. Relative retentions are reported for methylsilicone and aluminium oxide stationary phases as methylene units (MU). Applications of mass spectra, single-ion GC-MS monitoring and retention data for identifications are demonstrated.     

FCC汽油二次裂化增产丙烯过程中主要影响因素的研究

利用提升管中试实验装置,研究了催化汽油二次裂化制丙烯过程中热裂化、氢转移反应的特点和影响因素,给出了不同反应条件对丙烯选择性的影响,考察了丙烯选择性最大点处热裂化反应、氢转移反应的变化。研究结果表明,采用适当的反应温度和剂油比以及缩短反应时间能有效抑制热裂化反应和氢转移反应的发生,提高丙烯的选择性。     

油剂混合区的工艺条件对催化裂化汽油改质的影响

利用连续式小型提升管催化裂化实验装置研究了原料预热温度、再生剂温度、油剂混合区温度和剂油比等油剂混合区的工艺条件对催化裂化汽油改质的影响规律。结果表明,降低再生剂温度、油剂混合区温度和剂油比均可以降低干气和焦炭的产率,同时也对催化裂化汽油改质的效果产生了影响。其中,再生剂温度对干气和焦炭产率影响最大;剂油比对催化裂化汽油改质的效果影响显著。降低再生剂温度、剂油比和油剂混合区温度一定程度上降低了烯烃转化率、异构烷烃增加率和芳烃增加率。提高原料预热温度可以一定程度上增加烯烃转化率、异构烷烃增加率和芳烃增加率。催化裂化汽油改质油剂混合区的最佳工艺条件为维持一定的反应温度和剂油比,并尽可能降低再生剂温度和提高原料预热温度。     

Application of multivariate techniques for optimization of direct method for determination of lead in naphtha and petroleum condensate by electrothermal atomic absorption spectrometry

A direct method is proposed for the determination of lead in naphtha and petroleum condensate by electrothermal atomic absorption spectrometry (ET AAS) using palladium as a permanent modifier. The procedure includes the dilution of 3 mL of sample (naphtha or petroleum condensate) to a final volume of 10 mL with xylene, and direct injection of 30 μL of this solution into the graphite furnace. The optimization of the instrumental conditions was performed using multivariate techniques. Firstly, a 2³ full factorial design was performed for preliminary evaluation of the factors: pyrolysis time, pyrolysis temperature and atomization temperature. This experiment showed that in the studied levels only the factors pyrolysis time and atomization temperature were significant. Then, a 3² full factorial design was performed for the determination of the critical conditions of these variables. The method allows the determination of lead using the standard calibration technique with a calibration curve from 2.6 to 30 μg L⁻¹ (correlation coefficient higher than 0.998). A limit of detection (3σ) of 0.8 μg L⁻¹ and a characteristic mass of 35 pg were obtained in the presence of palladium as modifier. The precision expressed as relative standard deviation (RSD) was 1.5 and 0.8% for lead concentrations of 3.0 and 30 μg L⁻¹ (n = 10). Recovery studies demonstrate that lead can be determined in naphtha and petroleum condensate using calibration with organic standard solutions. This method was applied for the determination of lead in three petroleum condensate and two naphtha samples. The concentrations found for the petroleum condensate was between 2.7 and 5.7 μg L⁻¹, while the naphtha samples did not contain any detectable lead.