Determination of polar compounds in Rundle shale oil

The acidic and basic components of three distillate fractions (light, middle and heavy) of shale oil from the Rundle (Queensland, Australia) deposit were selectively extracted. Capillary gas chromatography/mass spectrometry was used to identify individual polar components. The major nitrogen-containing polar compounds in the light fraction were alkyl-substituted pyridines, and substituted quinolines were more abundant in the middle and heavy fractions. Significant quantities of pyrrole derivatives were also identified. Small quantities of anilines and benzoquinolines made up the remainder of the bases. The oxygen-containing compounds were mainly phenolic in nature; alkyl-substituted phenols were the major components, but significant quantities of naphthols and traces of fluorenols were identified.     

煤直接液化粗油提质加工工艺研究现状

分析对比了煤直接液化油的汽油和柴油馏分与石油基汽油和柴油馏分杂原子含量和族组分的差异,指出煤直接液化油中氮和芳烃含量高,需要经过苛刻的加工改质,才能作为车用内燃机燃料使用。介绍了煤液化粗油提质加工的研究现状,讨论了油品加氢催化剂和不同馏分产物的加氢提质工艺,展望了该工艺的发展趋势。     

Comparison of hydrogenated shale oils with standard jet fuels

The characteristics of jet fuels obtained from typical U.S. shale oils (Geokinetics, Occidental, Paraho and Tosco II) were compared with standard petroleum jet fuels in order to study the possibility of using these shale oils as a substitute. The shale oil fractions distilling below 343°C were catalytically hydroprocessed at low, medium and high severities and fractionated to the jet fuel range (121–300°C). The hydroprocessed products and jet fuels were compared for composition and physical properties. High severity hydroprocessing of shale oils decreased the nitrogen, sulfur, olefin and aromatic content while increasing the hydrogen content. The nitrogen content in shale oil jet fuels was considerably higher even after the high severity treatment. The aromatic content, except in Paraho shale oil, was relatively higher and the hydrogen content was slightly lower. Sulfur and olefin contents were lower at all severities. The physical properties and heat of combustion, except the high freezing point of shale oil jet fuels, were comparable to those of standard petroleum jet fuels.     

微波场中低变质煤与油页岩的热解

采用微波加热技术对低变质煤与油页岩的共热解特性进行探讨,研究了不同配比混合物的热解产物产率及成分,并通过气相色谱-质谱(GC-MS)联用技术对液体产物的成分进行了分析.结果表明:微波热解过程中,适当配入低变质煤可提高焦油产率,增加热解气中可燃气体CO,CH4及H2的含量;微波热解共混物所得焦油成分主要是烃类(约50%～80%),其中烷烃和芳香烃居多(约40%～50%左右),其次是少量的以苯酚类为主的含氧化合物,而并未检测出含氮化合物,这一组成有利于焦油的进一步加氢处理.     

中低温煤焦油蒸馏过程中金属元素的迁移规律

以中低温煤焦油轻油和重油为实验原料,采用常压蒸馏获得170~200℃、200~240℃、240~270℃、270~300℃、300~320℃、320~340℃、340~360℃和360~390℃煤焦油馏分油;利用配有油品加氧制冷进样系统的ICP-OES测定了21种微量元素在馏分油中的含量,考察了不同馏分油中元素的分布情况。研究表明：在原煤焦油中,未发现Ag、Mg、Mo、Na、Ni、Fe、Mn、Cr及Ti元素,含量较高的元素有Sn、P、Al、Pb、Si,其中Sn元素在轻油和重油中的含量分别为11.78μg/g和14.04μg/g;在所有馏分油中,未发现Al、Mo、Fe、Mn、Cr及Ti元素,含量比较高的元素有Si、Sn、Na、Zn、Pb,特别是Si、Na、Sn、Zn、Ni、Pb及B元素可以有效富集于馏分油中。可能的原因是Ca、Fe、Mg、Al等金属以不同的盐类形态存在,在煤焦油脱水及<170℃蒸馏过程中,这些金属盐类会被部分带出,导致其在馏分油中的含量未富集或未检出;通过关联金属元素在馏分油中的分布与其组成的关系,馏分油中元素的分布可能与酚类化合物、杂环化合物和蒸馏温度等相关。酚类化合物及杂环化合物可能与Ag、B、Cu、Mo、Sn、Na、Zn、Ca、Pb等金属形成络合物或卟啉配合物,蒸馏温度一方面可以破坏Sn、Cd、Pb、Zn、Cu、Ca、Pb等元素在馏分油中的结合力,另一方面也可以促进这些元素与馏分油中的含氧、含氮等化合物更好地发生化合反应,进而影响金属元素在馏分油中的含量分布。     

劣质混合馏分油加氢改质生产清洁柴油

以环烷基原油生产的直馏柴油、催化柴油与焦化汽柴油的混合馏分油为原料,在200 mL串联固定床加氢装置上进行加氢改质试验,重点考察劣质含酸高氮馏分油加氢改质后能否满足GB 19147-2009车用柴油质量要求.结果表明,混合馏分油氮含量高,十六烷值低,采用目前传统的加氢精制技术与加氢改质技术进行加氢处理,柴油产品难以满足...     

神府煤液化油石脑油馏分重整生产芳烃的研究

由于煤液化油石脑油馏分(200℃)中芳烃潜含量较高,利用煤液化油石脑油馏分为原料,进行加氢精制,将原料中的硫氮含量降至1 mg/kg左右,满足重整进料要求,然后在小型固定床连续反应器上进行加氢重整生产芳烃试验。着重考察重整反应前、后族组成的变化及主要芳烃化合物的产率。结果表明,加氢重整过程中发生正构烷烃异构化反应;环烷烃主要发生脱氢芳构化反应转化为芳香烃;煤液化油石脑油馏分适宜进行催化重整,C_1~C_4烃气产率6.03%,氢气产率3.60%;重整后,芳烃含量达83.20%,其中C_6~C_8芳烃含量61.03%,是提取BTX的良好原料。石脑油的馏程对芳烃的组成和产率有一定影响,适宜的馏程为60~160℃。     

焦化轻蜡油掺炼加氢柴油试验研究

通过实沸点蒸馏仪对加氢柴油进行精密分离,得到不同馏程温度段的窄馏分油,分析了不同窄馏分油的收率分布与烃类组成分布,分析结果表明：随着馏程温度升高,窄馏分油收率逐渐降低,加氢柴油中的链烷烃主要富集在馏程温度点高的窄馏分中,环烷烃与芳烃主要富集在馏程温度低的窄馏分中。焦化轻蜡油回炼加氢柴油窄馏分油后,加氢裂化产物65~175 ℃馏分收率增加,>175 ℃馏分收率均降低。由于窄馏分油中的烃类组成不同,所得加氢裂化产物性质有所差异。掺炼富含环烷烃与芳烃的窄馏分油所得65~175 ℃馏分芳潜值最高,掺炼链烷烃窄馏分油所得>175 ℃馏分的十六烷值指数最高。     

离子液体脱氮-加氢精制处理高氮焦化汽柴油的研究

采用离子液体对高含氮焦化汽柴油进行脱氮预处理,确定了处理过程适宜脱氮预处理条件,并对预脱氮后焦化汽柴油进行加氢精制工艺评价。结果表明,离子液体预脱氮处理适宜条件为：剂油质量比1∶100,反应温度50 ℃,搅拌时间30 min,沉降时间1.0 h,此条件下,焦化汽柴油的碱氮脱除率为94.9％,且离子液体具有较好的重复使用性。在相同条件下,经预脱氮处理后的柴油与未处理柴油相比,加氢生成油中硫、氮和芳烃含量明显降低,尤其是氮含量低,氮化物的含量高低对催化剂的加氢精制性能有影响。采用离子液体脱氮-加氢精制可深度脱除焦化汽柴油中硫化物与氮化物,降低芳烃含量,改善产品质量,达到生产低硫和低芳烃清洁燃料的目的。
     

Method for determining the olefinic content of the saturated and aromatic fraction of petroleum distillates by hydroboration

This study was prompted by a perceived need for a reliable method for determining olefin content in petroleum distillate fractions. An improved analytical method for the determination of olefin content in naphtha and higher boiling distillate fractions is described. The procedure comprises quantitative addition of diborane that specifically converts the olefins in the saturated and aromatic portion of the petroleum to alcohols. The reaction mixture is chromatographed on alumina, and alcohols are eluted with dichloromethane. The procedure was applied to two hydrocarbon mixtures of 20 saturated, olefinic and aromatic hydrocarbons in the investigated boiling range. Naphtha (ibp–200 °C) and light gas oil (200–350 °C) fractions from the Lloydminster oil were also analysed. Results are compared with the standard FIA method, and a method utilizing both the FIA and proton magnetic resonance spectrometry.     

Nitrogen distribution in the products from the hydrothermal liquefaction of Chlorella sp. and Spirulina sp.

The high contents of nitrogen-containing organic compounds in biocrude obtained from hydrothermal liquefaction of microalgae are one of the most concerned issues on the applications and environment. In the project, Chlorella sp. and Spirulina sp. were selected as raw materials to investigate the influence of different reaction conditions (i.e., reaction temperature, residence time, solid loading rate) on the distribution of nitrogen in the oil phase and aqueous phase. Three main forms of nitrogen-containing organic compounds including nitrogen-heterocyclic compounds, amide, and amine were detected in biocrudes. The contents of nitrogen-heterocyclic compounds decreased with temperature while amide kept increasing. The effect of residence time on the components of nitrogen-containing organic compounds was similar with that of temperature. However, the influence of solid loading rate was insignificant. Moreover, it was also found that the differences of amino acids in the protein components in the two microalgae might affect the nitrogen distribution in products. For example, nitrogen in basic amino acids of Spirulina sp. preferred to go into the aqueous phase comparing with the nitrogen in neutral amino acids of Chlorella sp. In summary, a brief reaction map was proposed to describe the nitrogen pathway during microalgae hydrothermal liquefaction.     

Upgrading of middle distillate fractions of a syncrude from Athabasca oil sands

Current processes for upgrading bitumen from Athabasca oil sands produce synthetic crudes which are high in aromatics and deficient in hydrogen. As a consequence, middle distillate fractions derived from these syncrudes produce diesel fuels of low cetane number and jet fuels which are hydrogen deficient. Results obtained from bench-scale hydrotreating experiments indicate that quality fuels may be produced from Athabasca syncrudes. Middle distillate fractions from this source were subjected to high-severity hydroprocessing in a continuous-flow reactor unit using conventional hydrotreating catalysts which were pre-sulphided by a mixture of $\text{H}{}_2\text{H}{}_2\text{S}$. Aromatic hydrogenation at high temperatures and pressures was affected by the approach to thermodynamic equilibrium, however, at lower temperatures, in some cases virtually 100% saturation was achieved and treated fractions were found to meet cetane number and jet fuel smoke point requirements. Data treatment in the present study includes a model for the hydrogenation kinetics and correlations between aromatic carbon and fuel combustion properties.     

页岩油馏分油非加氢脱氮技术研究

将抚顺页岩油减压蒸馏得到200～250℃馏分油,采用SH/T0162-92和C2BE30003.861的标准,滴定页岩油馏分油中碱性含氮化合物含量,用预处理后树脂D001cc、树脂D72和树脂D61在室温下进行模拟平推流树脂脱氮,树脂D001cc和树脂D72的碱氮脱除率达95%以上.在模拟全混合树脂脱氮条件下,树脂D7...     

生物质裂解油催化裂解精制

在HZSM-5催化剂存在的条件下，生物质裂解油在固定床反应器内进行了催化裂解. 实验研究了精制生物油的产率受温度、催化剂粒度、质量空速、溶剂诸因素的影响程度. 在较佳的反应条件下，即质量空速3.7 h-1、温度380℃时，获得了较高的精制生物油产率(44.68%). 产物分析表明，精制油中的含氧化合物如有机酸、酯、醇、酮、醛的含量大大降低，而不含氧的芳香族碳氢化合物和多环芳香碳氢化合物含量有所增加.     

加氢裂化变压器油提质探索及工业应用

中国石油化工股份有限公司金陵分公司加氢裂化装置运行至末期,产品变压器油中多环芳烃含量增加且颜色较深,造成销售困难;本文介绍了利用NJBMZDA-II催化剂针对加氢裂化变压器油开展的产品提质试验情况,结果表明在反应温度150℃、空速为3.0 h~(-1)、压力为3.0 MPa、氢油体积比500∶1的条件下,原料中总芳烃含量降低了13%,其中稠环芳烃含量降低为0.6%,产品赛氏比色提高了7个单位;利用公司尾油异构化装置工业应用情况表明,在空速2.68 h~(-1)、反应温度178℃、反应压力2.95 MPa、氢油体积比305∶1工况下,变压器油稠环芳烃含量、油品色泽等指标都能达到产品指标。     

Nitrogen compound distributions in hydrotreated shale oil products from commercial-scale refining

The distributions of nitrogen compounds in crude and hydrotreated shale oil products have been determined. About 11600 m³ (73000 bbl) of Paraho retorted shale oil were hydrotreated by The Standard Oil Company of Ohio at their Toledo refinery. A hydrotreated whole product, a jet fuel, a diesel fuel, and a residuum were produced and individually separated into compound-type fractions by adsorption chromatography. The nitrogen compound types in these fractions were characterized by i.r. spectroscopy, differential potentiometric titration, and high-resolution m.s. The distributions of nitrogen compound types and nitrogen base types in the hydrotreated products are compared with those in the Paraho retorted shale oil feedstock used in the hydroprocessing. The nitrogen compound types that were readily hydrodenitrogenated during commercial-scale refining are similar to nitrogen compound types removed during one-pass, bench-scale hydroprocessing.     

洗油初蒸馏塔的新工艺流程模拟研究

通过Aspen Plus软件,对某焦化厂提出的洗油初蒸馏塔新工艺方案进行流程模拟。模拟结果显示:随着塔顶萘油采出量的增加,C-甲基萘油中萘含量迅速下降,β-甲基萘含量先增加后下降,α-甲基萘增加;通过调整塔顶萘油采出量,可以解决C-甲基萘油中萘含量高的问题,但β-甲基萘含量会下降;增加回流量,对C-甲基萘油中各组分影响不明显。如果改变采出塔板为第12块,则β-甲基萘质量分数能保持在70%左右,α-甲基萘质量分数在18%左右。     

印尼油砂沥青组成及化学结构分析

利用FTIR和¹³C NMR对印尼油砂沥青中的脂肪烃结构、芳香烃结构、含氧官能团以及碳骨架进行研究,并就印尼油砂样品中较高的硫含量进行XPS分析。结果表明：4个印尼油砂样品沥青中脂肪碳含量均占到了70%左右,脂肪烃主要由亚甲基构成,甲基与次甲基次之,样品中有大量的烷基侧链。FTIR无法准确分辨芳香烃部分的苯环取代结构,通过¹³C NMR发现芳香烃中质子化芳碳的含量较高,桥头芳碳与侧枝芳碳为主要非质子化芳碳,由带质子化芳碳的比例大小可以推断样品芳香环上的取代度为2～4。样品含氧官能团部分以C－O形式存在于醇和醚中,部分以羧基形式存在。样品中硫主要为有机硫,芳香族硫化物含量最高,其次为脂肪族硫化物,存在一定比例亚砜。无机硫以黄铁矿硫与硫酸盐硫形式存在,由于油砂表面被有机质包裹,无机物裸露较少,XPS没有测得硫酸盐硫,黄铁矿硫的检测值也偏低。     

焦化蜡油脱碱氮技术研究进展

我国焦化蜡油具有碱性氮化物含量高的显著特点,作为催化裂化、加氢裂化的掺兑原料时,极易造成催化剂中毒,对装置的正常运行与产品分布造成不利影响。本文介绍了我国焦化蜡油的主要性质以及所含碱性氮化物对催化剂的作用机理,并对焦化蜡油加氢精制、酸处理脱氮、溶剂精制、吸附精制、络合精制等脱碱氮技术进行了综述。     

Hydroprocessing peculiarities of Fischer–Tropsch syncrude

When catalysts developed for crude oil hydroprocessing are used for syncrude, there are syncrude-specific peculiarities to consider. These relate to differences in the nature and abundance of heteroatoms, olefins, metal species, waxes and aqueous products. Some important aspects are (a) heat release during naphtha and distillate hydroprocessing is very high, but wax hydrocracking is almost isothermal; (b) syncrude is sulphur-free and the use of sulphided base-metal hydroprocessing catalysts require the addition of sulphur-containing compounds to the syncrude; (c) oxygenates strongly adsorb on some catalytic surfaces to affect catalytic behaviour; (d) carbonyl–carboxylic acid interconversion and water produced by hydrodeoxygenation (HDO) may result in catalyst degradation by acid and hydrothermal attack; (e) carboxylic acids in syncrude result in equipment corrosion and catalyst leaching; (f) metal carboxylates are the main metal-containing species in syncrude and are not removed by hydrodemetallation (HDM) catalysis, but by thermal decomposition.