Selective removal of nitrogen compounds from shale oil

A solid extraction process for selectively removing nitrogen from alternative refinery feedstock has been developed. It has been demonstrated that solid CuCl₂ · xH₂O can reduce the nitrogen content of shale oils to acceptable levels for some refineries. In a simple single-stage process, the nitrogen content was reduced by more than 85% to levels below 0.2 wt%. The solid extraction process was remarkably selective and produced high oil recovery yields corresponding to ≈98% of the theoretical limit. Experiments with model systems have shown complete selectivity for the nitrogen compounds and have demonstrated that the entire bulk of the solid is involved in the extraction process. Many other solids have been shown to be effective, namely transition metal halides, nitrates, sulphates, acetates, fluoroborates, and phosphates.     

Nickel-containing catalysts for hydroprocessing of aromatic oils

A series of nickel-containing catalysts was prepared by a sequence of impregnation and calcining steps using a γ-alumina support. The calcined catalysts were reduced in a flow of hydrogen and mixtures of hydrogen with hydrogen sulfide. Both the calcining temperature and nickel loading strongly influenced the hydrogenation activity. The changes in surface species which resulted from some of the preparation steps were identified by spectroscopy. The catalysts containing nickel without molybdenum were quickly poisoned by sulfur, but a certa in sulfur tolerance was achieved by a two-step impregnation and calcining procedure. Improved hydrogenation activity and high hydrogenation vs. hydrocracking selectivity of nickel—molybdenum catalysts were obtained with relatively low loading of molybdenum and high loading of nickel. A three-step impregnation and calcining procedure appeared to produce the most effective catalysts.     

Structural changes in catalytic hydroprocessing of syncrude coker gas oil

A method of Structural Group Analysis (SGA) was used to characterize feed and liquid products from catalytic hydroprocessing using a commercial Ni-Mo catalyst. Comparison of the structural profiles revealed significant changes in the concentration of various structural groups. SGA is a promising tool for investigating chemical changes in complex reacting systems.     

植物油加氢制备高十六烷值柴油组分研究进展

介绍了植物油加氢制备柴油的主要化学反应、工艺方法以及该项技术的工业化状况,分析了植物油直接加氢、先加氢后异构、直接脱羧工艺以及植物油与矿物柴油掺炼工艺的特点,阐述了各工艺采用的催化剂类型、工艺条件以及产品属性。指出了该领域存在的问题和研究方向。     

油页岩地下转化工艺技术

当前对油页岩的利用存在成本高和对环境污染大的问题。Shell公司研发的油页岩地下转化工艺技术,通过现场试验具有成本低、对环境污染小和效率高的特点,具有极大的商业推广价值。     

中国油页岩综合利用研究及工业前景

中国油页岩资源较丰富(预测资源量约为7199.37亿t),并有超过50a的开发利用经验,全球油页岩开发已有近200a历史,开采和综合利用技术日趋成熟和完善。因此,中国应加大油页岩的勘探开发力度和综合利用研究。目前中国已经在辽宁、吉林、广东等省开展了油页岩的综合利用。     

油页岩开发利用技术研发进展

近几年,油页岩利用技术的发展引起了广泛关注,世界上许多公司研发了先进的工艺。新技术取得的进展包括用水量减少、CO2减排、能源利用效率提高,以及对地下水和周围环境的保护。本文按地表处理和原位处理技术分别介绍了目前正在研发的新型油页岩利用技术,并详细论述了欧美几家公司的工艺流程及研发进展,同时对各种新技术的优缺点进行了评价。     

干馏温度对油页岩半焦着火的影响

基于石油价格的增长和环保要求的日益提高,提出了油页岩资源的炼油、发电、供热、建材的综合利用方案,其中油页岩半焦干馏温度是该方案的一个关键参数。采用热分析方法研究干馏温度对半焦着火方式影响的实验,结果表明:随着干馏温度的升高,油页岩半焦的着火方式将由均相着火转变为多相着火;干馏温度500℃不仅有利于炼制页岩油,从燃烧角度来说,该温度所制取的半焦着火温度低且着火方式为均相着火,因此也有利于锅炉的燃烧。     

油页岩颗粒的热解模型

以实验为依据,分析了油页岩的热解机理及特性,并充分考虑了油页岩中挥发分在整个热解过程的作用,在此基础上建立了与油页岩固有热解特性相适应的热解模型。在能量方程中考虑了油页岩挥发分的热解反应吸热量及其挥发分的释放对油页岩固体颗粒质量的影响,并根据油页岩的热解特性,采用分阶段模型来描述油页岩的热解过程,以减小一步本征动力学方程带来的较大误差,还对模型进行了实验验证。     

Kinetics of oil generation from oil shale from Liaoning province of China

The intrinsic kinetics of oil generation from 0.124 dm³ kg^?1 Chinese oil shale were determined by a non-isothermal method. Overall first-order kinetics satisfactorily represented the mechanism of kerogen decomposition. The kinetic parameters were determined as 142.8 kJ mol^?1 and 7.495 × 10⁶ s^?1 for activation energy and pre-exponential factor, respectively.     

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.     

Rapid pyrolysis of brown coal and oil shale

A brown coal, peat and oil shale were subjected to a rapid pyrolysis process and medium-heat-value gases together with tar were collected. The char residue was of high activity and suitable for gasification to create a two-stage gasification system. The coal-tar is used for manufacturing liquid fuels and chemicals.     

Determination of shale oil yields by petrographic analysis

Rundle-type oil shales from five Australian deposits (Rundle, Stuart, Condor, Byfield and Duaringa) contain abundant lamellar alginite that is easily recognized using fluorescence microscopy. Shale oil yield, as determined by modified Fischer assay, is directly related to the volume per cent of alginite in the parent shales for each of the above deposits. Data provided show that interdeposit estimates of shale oil yield, based on alginite content, are more reliable than estimates based on specific gravity of the parent shales. Application of petrographic techniques should provide rapid assessment of the shale oil yield for other deposits with Rundle-type oil shale. The method requires initial calibration of alginite content, in a limited number of samples, with Fischer assays.     

中国油页岩成矿特征分析

中国油页岩资源丰富,陆相、湖泊海相以及海陆交互相都有油页岩沉积,而陆相沉积最为普遍。油页岩资源丰富的盆地主要有松辽、鄂尔多斯、准噶尔3个盆地,共占全国油页岩资源储量的76．8％以上,主要赋存于新生代地层中。油页岩产出状态多样,以薄层状为主,多为褐黑色,有机质类型属于Ⅰ-Ⅱ型干酪根。含油率大于5％的页岩油资源占67．64％,表明中国油页岩品质中等偏好。     

小颗粒油页岩及半焦CFB锅炉燃烧适应性研究

油页岩经低温干馏可以得到页岩油,因生产工艺限制,干馏炉无法使用粒径12 mm以下的油页岩,同时会产生大量副产品(页岩半焦)。为提高副产品的利用能力,实现资源利用最大化。通过在1 MW_(th)CFB燃烧试验台对小颗粒页岩及页岩半焦进行试烧试验,研究小颗粒页岩及页岩半焦的理化特性、着火特性、燃尽特性、结焦特性。试验结果表明,控制床温在720~850℃内,由油页岩小颗粒和半焦掺混而成的设计燃料在试验台采用CFB方式能够稳定燃烧,试验各工况灰渣含碳量均低于1.81%,试验燃料较易燃尽。CFB锅炉适合油页岩小颗粒与半焦掺烧利用,且燃烧效率高,燃烧稳定性较好。     

Studies of the batch hydrotreatment of Rundle shale oil

Studies of the batch hydrotreatment of shale oil from the Rundle (Queensland, Australia) deposit were carried out, and the suitabilities of three commercial catalysts based on Ni-Mo, Co-Mo and Ni-W were evaluated in terms of nitrogen removal and hydrocracking ability. All catalyst systems were effective for olefin saturation and removal of labile N and O compounds (nitriles and ketones). Both the Ni-Mo and Co-Mo systems removed significant amounts of pyridines and quinolines, but failed to convert the less basic pyrrolic material. The Ni-Mo system gave the most satisfactory performance in this area. The Ni-W catalyst behaved poorly. Only limited hydrocracking was observed, and this was confined to cracking of n-paraffins and alkyl side chains of aromatics. Polyaromatic structures were not cracked.     

Chemical depolymerization of oil shale

The chemical structure of the organic matter from Krassava oil shale has been investigated by means of chemical degradation with metallic sodium in liquid ammonia and with phenol in the presence p-toluenesulphonic acid. The former reaction yielded 20 wt% of pyridine-soluble material and the latter ≈ 65 wt%. Extensive depolymerization of the oil shale was achieved by a combination of both methods in which case the solubility of the organic matter was increased to 85–95 wt%. The characterization of soluble and insoluble products by pyrolysis g.c. and elemental analysis indicated that aliphatic chains were prevalent in the organic matter of the Krassava oil shale.     

Pyrolysis with partial combustion of oil shale fines in a spouted bed

Pyrolysis with partial combustion of oil shale fines from the Irati Formation in Brazil has been investigated in a 30 cm diameter spouted bed reactor. Experiments were carried out at atmospheric pressure and temperatures between 450 and 600°C. The oi] shale particle size was less than 6.35 mm. Spouting gas temperatures ranged from 20 to 565°C. Three inlet gas pipe diameters and two spouted bed heights were studied. Operation of the process was found to be stable over a wide range of test conditions. Results are presented for oil and gas quality, efficiency of retorting and overall performance of the plant.     

Thermogravimetry and decomposition kinetics of British Kimmeridge Clay oil shale

The characteristics of volatile matter evolution and the kinetics of thermal decomposition of British Kimmeridge Clay oil shale have been examined by thermogravimetry. TG has provided an alternative to the Fischer assay for shale grade estimation. The following relation has been derived relating TG % volatiles yield to the shale gravimetric oil yield: oil yield (g kg^?1) = (TG volatiles, % × 5.82) ? 28.1 ± 14.5 g kg^?1. A relationship has also been established for volumetric oil yield estimation: oil yield (cm³ kg^?1) = (TG volatiles, % × 4.97) – 5.43. TG is considered to give a satisfactory estimation of shale oil yield except in certain circumstances. It is found to be less reliable for low yield shales producing <≈40 cm³ kg^?1 of oil (≈10 gal ton^?1) where oil content of the TG volatiles is low: volumetric yield estimation accuracy is affected by variations in shale oil specific gravity. First order rate constants, k = 4.82 × 10^?5s^?1 (346.3 cm³ kg^?1shale) and k = 6.78 × 10^?5s^?1 (44.6cm³ kg^?1shale) have been obtained for the devolatilization of two Kimmeridge oil shales at 280 °C using isothermal TG. Using published pre-exponential frequency factors, an activation energy of ≈57.9 kJ mol^?1 is calculated for the decomposition. Preliminary kinetic studies using temperature programmed TG suggest at least a two stage process in the thermal decomposition, with two maxima in the volatiles evolution rate at ≈450 and 325 °C being obtained for some samples. Use of published pre-exponential frequency factors gives activation energies of ≈212 and 43 kJ mol^?1 for these two stages in the decomposition.     

Pyrolysis of model compounds on spent oil shales, minerals and charcoal: Implications for shale oil composition

Aliphatic compounds (alkanes, alkenes, alkanoic acids, ketones, alcohols and amines) were passed through beds of spent oil shales (Condor brown, Condor carbonaceous, Julia Creek), minerals (quartz, calcite, K-feldspar, pyrite, kaolinite) and charcoal at temperatures of 300–600 °C and the products were analysed by g.c.m.s. All the materials catalysed isomerization, aromatization and cracking to varying degrees: non-clay minerals < kaolinite ≈ spent oil shales < charcoal. Products included branched alkanes, isomeric alkenes, nitriles, ketones and alkyl-substituted benzenes, naphthalenes, pyridines, phenols, thiophenes and pyrroles. These compounds occur in shale oils and may be derived from secondary reactions of aliphatic products arising from kerogen cracking.