国内油页岩加工工艺及展望

结合国内油页岩资源现状,分析了国内油页岩干馏加工的方法,以及未来油页岩加工的发展趋势。各种油页岩性质不同,需要选择合适的加工工艺。开发油页岩干馏制油成套技术与装备是我国油页岩加工行业的发展方向。     

油页岩地面干馏技术研究

近年来,随着国际石油供求矛盾的不断突出和石油价格的居高不下,油页岩资源逐渐引起了众多科研人员的青睐.油页岩是一种重要的非常规油气资源.世界油页岩分布范围广,储量十分丰富,其探明可采储量如果折算成页岩油,数倍于世界原油的探明储量.页岩油作为石油的一种理想替代品,进行油页岩制油技术的研究不仅蕴含巨大的商业利益和经济价值,对国家安全和能源战略也具有十分重要的意义.油页岩制取页岩油的技术可分为地面干馏技术和原位开采技术.地面干馏技术的工艺和设备发展比较成熟,也是目前制取页岩油最主要的途径.根据颗粒粒度的大小又可分为块状干馏技术和小颗粒干馏技术.着重介绍的块状油页岩干馏技术有抚顺炉技术、Kiviter技术和Petrosix技术,小颗粒干馏技术有Tosco-Ⅱ技术、ATP 工艺和Enefit-280工艺等.最后指出了油页岩地面干馏技术的发展趋势.     

Modular methanol manufacturing from shale gas: Techno‐economic and environmental analyses of conventional large‐scale production versus small‐scale distributed,modular processing

This article presents comparative techno‐economic and environmental analyses of four representative shale gas monetization options, namely, conventional shale gas processing, large‐scale methanol manufacturing, modular methanol manufacturing with shale gas supplied by pipelines, and modular methanol manufacturing with consideration of plant relocation. We first present shale gas supply models for the four gas monetization options. Next, the process designs for shale gas processing and methanol manufacturing from shale gas are described. We develop detailed process simulation models for shale gas processing and methanol manufacturing with different scales using raw shale gas extracted from the Marcellus, Eagle Ford, and Bakken shale plays. On this basis, techno‐economic analyses and environmental impact analyses are conducted for the four shale gas monetization options to systematically compare their economic and environmental performances based on the same conditions. The results show that modular methanol manufacturing is more economically competitive than conventional shale gas processing, although it leads to higher environmental impacts. Besides, modular methanol manufacturing is better than large‐scale methanol manufacturing for raw shale gas produced from distributed, remote wells from both economic and environmental perspectives. © 2017 American Institute of Chemical Engineers AIChE J, 64: 495–510, 2018     

Separation of kerogen from green river oil shale

The complex analysis of the chemical composition and technological properties of oil shale from the Green River formation was carried out. The technical characteristics and granulometric composition of test samples and the element compositions of the mineral and organic matters of shale rocks were determined. The structure of organomineral aggregates formed upon the crushing of shale rocks was studied by electron microscopy. Based on the experimental data, a procedure was developed for the separation of kerogen from the oil shale by physicochemical processing.     

Environmental problems of oil shale processing industry

Main environmental problems of the full oil shale processing cycle including mining, heat treatment, and direct combustion of oil shale in power plants are considered. Possible lines of utilization of both the mineral matter remaining after shale preparation and ash residues after shale processing are elucidated.     

页岩气压裂返排液回用处理技术研究与应用

在页岩气的开发过程中,对页岩气压裂返排液进行无害化处理具有一定的难度。主要分析了页岩气压裂排液中影响回用的主要成分,根据实验对比研究了影响压裂排液回用的主要原因,同时也介绍了页岩气压裂返排液回用所用的处理技术和利用这种处理技术组成的装置应用。     

页岩灰对油页岩低温干馏产物的影响

分别介绍了油页岩低温干馏试验、油页岩与页岩灰掺混的干馏试验,结果表明,其他条件相同时,页岩灰与油页岩以4:1比例掺混时,油页岩干馏所产页岩油(凝点10℃,密度0.898 2g/cm3)与油页岩不掺混页岩灰干馏所得页岩油(凝点26℃,密度0.909 6g/cm3)相比,页岩油品质有所提升,有助于后续加工。     

抚顺页岩油加工方案初步研究

介绍了世界上页岩油的各种加工方法,从工程设计的角度出发,研究了抚顺页岩油加工精制的工艺路线和工艺方法,提出了以煤制氢作为氢源的加氢精制工艺流程。     

世界油页岩资源的开发利用现状

油页岩是一种非常规能源,世界储量巨大,作为石油的补充能源,开发前景广阔.油页岩在隔绝空气条件下加热至500℃左右,会热解生成页岩油,经加工处理后可以制得汽油、柴油等油品.油页岩也可直接燃烧,产生蒸气、发电,目前利用油页岩燃烧发电的国家有爱沙尼亚、中国、德国等.本文介绍了世界主要油页岩国家的油页岩储量和加工利用情况,目前世界上利用油页岩干馏制取页岩油的国家主要有3个,中国(产量80万吨)、爱沙尼亚(产量50万吨)和巴西(18万吨),其他国家略有生产.中国页岩油产量一直居世界首位,目前有将近10座油页岩干馏厂投入运行,其中抚顺矿业集团年产页岩油35万吨,全国居首,该公司引进的日处理颗粒油页岩量6000t的ATP干馏工艺,目前已经在调试中阶段性运转,并逐渐延长连续运转时间,山东龙口等其他地方的油页岩加工利用也取得很大进展.美国目前没有进行油页岩干馏炼制页岩油的工业化生产,但有多所大学、公司和研究所已经对油页岩进行了长期的地上和地下干馏工艺的研究和开发.文中还介绍了国内外油页岩干馏的3种主要炉型,分别为块状页岩气体热载体干馏炉、颗粒页岩固体热载体干馏炉和粉末页岩流化干馏炉,并对比了不同国家的干馏炉型的优缺点.     

The prediction of clay contents in oil shale using DRIFTS and TGA data facilitated by multivariate calibration

The prediction of clay content in oil shale is important for the optimisation of oil shale processing conditions and process feasibility. The multivariate calibration technique of partial least squares regression (PLSR) was implemented in order to predict clay content in oil shale samples taken from the Stuart oil shale deposit, Queensland, Australia. The calibration data used were the diffuse reflectance infrared Fourier transformed spectroscopy (DRIFTS) spectra of 34 oil shale samples. DRIFTS data from another set of 20 oil shale samples were used for model validation. The data pre-processing includes the use of derivatives facilitated by the Savitsky-Golay nine-points’ method. A four components model was constructed and it showed a root mean square error of calibration (RMSEC) of 4.79% and a root mean square error of prediction (RMSEP) of 4.35%. TGA data sets were also used to construct a calibration model, which produced less accurate results than DRIFTS. DRIFTS, when combined with multivariate calibration, provided an accurate in situ method of evaluating clay content in oil shale. Clay content measured using XRD was used as a reference.     

油页岩固体热载体流化干馏炼油工艺中试研究

介绍了以依兰粉末页岩作原料的页岩流化干流中试装置概况及试验流程,并对试验结果进行了分析。中试结果表明,中试装置页岩油产率为铝甑干馏法的90.15%,经冷凝回收系统及油泥处理后获得的页岩油收率为铝甑的82%;固体热载体流化干馏工艺所产页岩油较轻,337℃以前馏分大于80%。     

基于灵敏度分析的页岩气净化流程的模拟与优化

原料气中酸性气体与水等杂质的脱除净化是页岩气下游加工与利用的基础。应用化工流程模拟软件对页岩气脱酸与脱水流程进行模拟,旨为气体净化工业的实践提供理论与技术指导。在脱酸流程模拟中,采用灵敏度分析的方法讨论并优化了吸收剂再生进料位置、再生塔回流比等参数对脱酸流程的影响。脱水流程模拟中,提出了页岩气水含量与水露点的关联方法,为脱水标准的选取提供依据;采用汽提法解决了高浓度吸收剂的再生问题,使流程能够满足更高的脱水要求。     

Attrition and abrasion models for oil shale process modelling

As oil shale is processed, fine particles, much smaller than the original shale, are created. This process is called attrition or, more accurately, abrasion. In this paper, models of abrasion are presented for oil shale processed in several unit operations. Two of these unit operations, a fluidized bed and a lift pipe, are used in the Lawrence Livermore National Laboratory hot recycle solid (HRS) process being developed for the above-ground processing of oil shale. Abrasion occurs so commonly in the handling and processing of paniculate materials that numerous studies have been conducted to characterize the phenomenon and to attempt to minimize it. In the review of the literature, materials which have been studied for attrition potential are examined, as are the specific unit operations for which either experimental or modelling studies have been conducted. Several papers are discussed in which attrition in fluidized beds or lift pipes is addressed. In this paper, empirical models are derived for the processes occurring in the HRS process from the experimental studies conducted on oil shale. The derived models are presented, as are comparisons with experimental results.     

Sorptional properties of fuel shale and spent shale

The sorptional properties of fuel shales and spent shales in removing organic compounds (petroleum and its derivatives) from water are studied. The basic benefit of spent shale as a sorbent is that it is available at no expense as the processing waste of fuel shale. After sorption, the fuel shale or spent shale saturated with petroleum or its derivatives may expediently be used as a fuel, on account of their high calorific value.     

中国油页岩加工业新的发展机遇

从科学发展观的角度,论述了油页岩加工业在我国能源结构中的独特位置与发展优势,在我国已有的生产实践的基础上,总结了国内外油页岩加工业在加工工艺、环境保护以及副产品回收等方面积累的经验和未来的发展要求,以使我国拥有的丰富的油页岩资源能够得以充分的综合利用.     

Current trends in the pyrolysis of oil shale: A review

The review surveys recent publications on the pyrolysis of oil shale. The effect of process parameters on the composition and properties of the resulting products and problems related to the further thermal processing of shale oils are considered.     

页岩气储层体积压裂改造体积影响因素分析

体积压裂技术的发展是页岩气储层成功开发的巨大推动力。在北美的页岩气藏的开发中体积压裂技术已经取得了显著的成果。其本质上属于水里压裂期间,增大自然形成的缝隙以及使硬度较小的岩石出现剪切滑移,得到自然与人力两种环境下纵横密布的裂缝网络结构,以此扩大处理体积,获得更多的原始产量与采收成果。在不同缝网参数角度,对页岩气储层体积压裂改造体积的影响因素进行分析。     

Data-driven distributionally robust optimization of shale gas supply chains under uncertainty

This article aims to leverage the big data in shale gas industry for better decision making in optimal design and operations of shale gas supply chains under uncertainty. We propose a two-stage distributionally robust optimization model, where uncertainties associated with both the upstream shale well estimated ultimate recovery and downstream market demand are simultaneously considered. In this model, decisions are classified into first-stage design decisions, which are related to drilling schedule, pipeline installment, and processing plant construction, as well as second-stage operational decisions associated with shale gas production, processing, transportation, and distribution. A data-driven approach is applied to construct the ambiguity set based on principal component analysis and first-order deviation functions. By taking advantage of affine decision rules, a tractable mixed-integer linear programming formulation can be obtained. The applicability of the proposed modeling framework is demonstrated through a small-scale illustrative example and a case study of Marcellus shale gas supply chain. Comparisons with alternative optimization models, including the deterministic and stochastic programming counterparts, are investigated as well. © 2018 American Institute of Chemical Engineers AIChE J, 65: 947–963, 2019     

Oxidative pyrolysis of oil shale in tubular flow reactors with external heating

This article discusses the possibilities of the multipurpose use of oil shale based on the methods of their thermal processing. The main current concepts of oxidative pyrolysis processes are considered. A facility for the oxidative pyrolysis of powdered oil shale in tubular reactors of the gas-suspension type with external heat supply to the reaction zone is described.     

Environmental data from bench-scale pressurized fluidized-bed hydroretorting of Eastern oil shales

As part of a three year programme to develop the pressurized fluidized-bed hydroretorting (PFH) process for Eastern oil shales, tests were conducted in laboratory-scale batch and continuous units as well as a bench-scale unit (45 kg h⁻¹) to generate a data base for six Eastern shales. Data were collected during PFH processing of raw Alabama and Indiana shales and a beneficiated Indiana shale for environmental mitigation analyses. The data generated include trace element analyses of the raw feeds and spent shales, product oils and sour waters. The sulphur compounds present in the product gas and trace components in the sour water were also determined. In addition, the leaching characteristics of the feed and residue solids were determined. The data obtained were used to evaluate the environmental impact of a shale processing plant based on the PFH process. This paper presents the environmental data obtained from bench-scale tests conducted during the programme.