Results of mathematical modeling of oil shale retorting in an aboveground,internal combustion retort

The one-dimensional mathematical model developed at the Lawrence Livermore National Laboratory to simulate the detailed chemical reaction kinetics involved in modified in-situ retorting of oil shale has been applied to simulate aboveground retorting in a moving, packed-bed retort. Application of the model to simulate such a retort was made for the internal combustion mode of operation, using typical operating conditions of the Paraho semiworks retort. Comparison with the semiworks experimental data revealed the general accuracy of the model in calculating retort temperature profiles, oil yield, off-gas composition, and outlet shale composition. The model was also applied to a hypothetical set of commercial-scale conditions in order to identify key operating or design parameters. These parameter studies predicted that the oil yield and the overall process performance could be markedly improved by increasing the recycle gas flux, decreasing the inlet-air flux, and relocating the inlet-air distributors. A process flowsheet was developed for the complete retorting system.     

油页岩炼制过程技术经济分析

我国油页岩资源储量大, 开发油页岩可以缓解我国石油短缺问题。但迄今少有研究对现有的油页岩炼制的能量利用情况和经济效益进行系统量化分析。本文以油页岩典型炼制工艺:抚顺炉工艺和瓦斯全循环炉工艺为案例, 对两种工艺建模和模拟, 根据模拟结果分析两种工艺物流和(火用)流情况, 分析单元中质量损失和(火用)损失的组成和主要因素。基于物流和能流对两种工艺进行经济性能分析。结果表明:以油页岩处理量为418t/h为基准规模, 抚顺炉工艺的(火用)损失比瓦斯全循环炉工艺的(火用)损失高出19.5%;经济方面, 瓦斯全循环炉工艺投资费用为16.9亿元, 较抚顺炉工艺的投资费用高5.1亿元, 但是瓦斯全循环炉工艺多生产5.4t/h页岩油和84.8MW电力, 所以其投资利润率为18.6%, 较后者提高了10个百分点。     

Fluidized bed steam retorting of Kentucky oil shale

A three-inch (7.6-cm) diameter fluidized bed reactor has been used at the Kentucky Center for Energy Research Laboratory (KCERL), operated by the Institute for Mining and Minerals Research (IMMR), to investigate the fluidized bed retorting characteristics of Kentucky oil shales. Because steam has been indicated to be a reactive pyrolysis gas for both Eastern and Western U.S. oil shales by many, a main objective of the fluidized bed investigation was to determine the effects of steam as a fluidizing medium. This was accomplished by comparing the yields and compositions of the products from steam and N₂ retorting under otherwise equivalent fluidized bed conditions. Oil yields obtained from steam fluidization were approximately 2% greater than oil yields obtained from N₂ retorting. Steam retorting released significantly more pyritic sulfur from the shale, providing evidence that reduced hydrogen scavenging from the kerogen for H₂S production was a possible mechanism for the increased oil production. Steam fluidization resulted in increased oil collection efficiency, and represented the most significant difference between the steam and nitrogen systems. Liquid product quality was similar for both steam and N₂ fluidization and the oils were more aromatic, more viscous, higher in density, higher in nitrogen content, and lower in volatility than Fischer Assay oil derived from the same shale.     

回转式油页岩干馏炉测温技术研究进展

介绍了油页岩低温干馏制油气的过程和工艺,阐明了干馏是一个复杂的物理传热和化学热解的过程,是整个页岩炼油中最关键的工艺,并介绍了目前国际上关于低温干馏反应炉的技术,其中包括Galoter技术、ToscoⅡ技术、LR技术以及ATP技术。分析了在油页岩反应炉中温度对产油率的影响,表明温度对整个反应炉的重要性,并进一步分析了温度对干馏所造成影响的原因,重点阐述了温度测量的重要性与技术方法。对回转式油页岩干馏炉的测温现状进行了综述,总结了目前常用的一些回转炉测温方法,针对回转式油页岩反应炉目前存在的问题,提出了在温度控制、系统检测、红外测温等方面的改进措施。     

Modelling of oil shale pyrolysis in a fluid-bed retort

Pyrolysis of large oil shale particles in an isothermal fluid bed retort is theoretically studied in this paper. The governing equations describing diffusion and chemical reaction inside shale particles are solved analytically by using a finite Sturm—Liouville integral transform technique. The analysis gives not only the final distribution of products but also the dynamic response of these species from the onset of operation. Based on the information of the final product distribution (yield) and the dynamic response, the model solutions give guidance in choosing a proper temperature to operate the fluid bed retort for a given size of oil shale particle.     

Composition and kinetics of oil generation from non-isothermal oil shale retorting

Oil shale retorting has been carried out under non-isothermal conditions between 623 and 773 K and at different pressures(78 and 765 kPa). The shale oil is separated into five individual components: polar, weak polar, saturates, aromatics and olefin, using a comprehensive analytical procedure. The effects of retorting pressure and heating rate have been studied. The oil yield under high pressure (765 kPa) is ≈10% less than the oil yield under ambient pressure (78 kPa). Much of this reduced yield can be accounted for by the reduced amount of polar component formed at high pressure. Heating rates of 1.67 × 10^?2, 6.67 × 10^?2and 8.33 × 10^?2Ks^?1 have been used; a higher heating rate causes a delay in the appearance of the oil. A simplified kinetic scheme is proposed which includes the distribution of liquid products and pressure effects. The activation energies and frequency factors of generation reactions for total oil and individual components have been obtained.     

气体热载体干馏炉内布气方式对油页岩干馏特性的影响

为研究炉内油页岩的干馏特性及炉内的温度分布,自行搭建处理量为5 kg/h的循环瓦斯热载体干馏试验装置,试验结果表明炉内布气方式对页岩的干馏特性具有很大影响。在边壁进气与中心管进气体积比为8∶4时油收率达到最大值,且炉内温度分布最均匀,单位时间内的放热量最大;不同的布气方式导致干馏层内气体冲刷页岩颗粒程度的不同,使得炉内油页岩的传热特性存在差异,炉内温度分布与放热量不同,最终油收率也不同。边壁进气在炉体内部的传热效果优于中心进气。温度分布越均匀,油收率越高;该布气方式依然存在局限,需要进一步研究。     

煤系共伴生油页岩热解残渣利用技术

油页岩残渣是油页岩热解过程中排放的固体废物,约占油页岩的80%~90%。中国油页岩残渣利用率较低,残渣堆积量日益增多,后续问题十分突出。煤系油页岩残渣的资源化利用成为油页岩热解提油产业发展的瓶颈。介绍了油页岩热解加工利用现状及其残渣在废水处理和废气吸附方面的应用,分析了当前页岩热解残渣利用过程中存在利用方式单一的问题,并结合油页岩热解残渣结构和组成的特殊性,提出了油页岩残渣用作环保材料如吸附剂的发展方向。     

中国油页岩干馏技术现状与发展趋势

中国油页岩资源丰富,换算成页岩油储量高达476亿吨.目前中国页岩油生产企业仍然采用以抚顺炉为主的干馏技术,该技术成熟稳定,但油收率不高.本文介绍了目前国内已投产运行和即将工业化的干馏技术以及曾经投入生产、后因多种原因停产的干馏技术.分析表明,我国油页岩产业正处于技术快速发展和产业成长阶段:为显著提高油收率,针对抚顺炉的改进技术已有一些进展,自主研发的成大气体热载体干馏工艺已经开始商业化运行,我国自主知识产权的固体热载体干馏技术出现.但依然存在诸多问题:国内干馏炉单炉处理量小、油收率偏低、半焦无法利用等问题亟需解决,国内固体热载体干馏自主技术依然处于试验阶段,引进国外先进的干馏技术尚没有实质性进展,国内页岩油回收技术亟待改进,油洗技术亟需完善和推广.     

油页岩气体热载体干馏炉内干馏特性研究

文章利用自行设计搭建的处理量120 kg/d的瓦斯全循环气体热载体干馏炉,通过试验的方法,研究新型气体热载体干馏炉在干馏过程中的一些运行参数和产生的页岩油的一些特性,对现有干馏工艺的改进具有指导意义。试验通过改变油页岩颗粒的粒径,进而改变物料之间的空隙率、空隙结构和进气流量,来研究不同粒径的样品对干馏特性和干馏产物的影响。结果表明:油页岩颗粒的粒径不同,物料之间的空隙率和干馏炉的进气流量不同,导致炉内传热传质的不同,不同粒径的油页岩干馏油收率不同,粒径为20—25 mm的页岩油收率最高。由于气体热载体流量不同,干馏炉内传热传质情况和冷却器的工作负荷也不相同,因此不同粒径的页岩干馏之后,在4个收油点所收到的页岩油质量分数也不相同。     

布气方式对油页岩干馏炉内温度分布的影响

为研发新型气体热载体干馏技术,自主搭建了气体热载体干馏炉试验台。对不同进气方式下的炉内温度分布进行了试验研究。通过采集干馏炉内温度数据,得到炉内沿半径方向和高度方向上温度分布。分析了中心管和边壁同时进气的特点,并与中心管单独进气时进行了对比,研究了联合进气时的温升特性。试验结果表明:中心管单独进气时靠近边壁处存在滞留层,温度较低,与炉内中心处温差较大。采用中心管联合边壁进气可以较大程度改善滞留层温度较低的问题。联合进气时,炉内沿高度方向上升温速率有所不同。试验结果将为进一步研发和改进油页岩气体热载体干馏炉布气方式提供参考和依据。     

Analysis of a retort oil from an Israeli shale by gas chromatography-mass spectrometry-selected ion monitoring

The oil from an Israeli shale was fractionated by solvent extraction and silica gel column chromatography. The straight-chain pentane and benzene soluble materials were analysed by the gas chromatography-mass spectrometry-selected ion monitoring method. By monitoring specific fragment ions with representative $\text{m}\text{z}$ values, information was obtained of the chemical structures of the fractions.     

油页岩含氧低温载气干馏过程实验

油页岩干馏生产页岩油是油页岩的主要加工利用方式。为降低油页岩干馏所需热载气温度,以延长载气预热器使用寿命并实现节能操作,本文向热载气中掺入一定比例氧气,对含氧低温载气情况下的油页岩干馏过程进行了研究。测定了油页岩在含氧气体氛围中热解时的反应器床层升温特性,对气液相产物组成进行了分析并与无氧干馏产物进行了比较。结果表明,含氧低温载气干馏过程能够通过载气中的氧气与油页岩反应产生的热量使油页岩达到其干馏所需要的温度,页岩油收率及其成分与无氧高温载气干馏过程接近、而轻组分含量更高,并且含有更多的具有O—H键和C==O键官能团的化合物。本文研究结果为油页岩干馏生产页岩油提供了一种新的技术方法,具有较好的工业应用前景。     

A mathematical model for the retorting of a large block of oil shale: effect of the internal temperature gradient

A mathematical model which incorporates the intrinsic kinetics of the decomposition of kerogen and carbonate minerals and the internal as well as external heat-transfer effects has been developed. This rigorous model is compared with the uniform-temperature model. The results indicate that at a heating rate of 1 °C/min and a mass velocity of gas of 0.0179 $\text{kg}\text{m}{}^2$ s, the uniform-temperature model gives about 10% error in the extent of conversion for particles of 6 cm in radius. As the particle size increases, the error becomes greater. Also, at higher heating rates or mass velocities the error is larger for the same particle size. The new model has been applied to the results of thermogravimetric experiments published in the literature. The comparison shows that the rigorous model describes the retorting of oil shale more accurately than the shrinking-core model or the uniform-temperature model.     

基于Aspen Plus的桦甸式油页岩干馏工艺系统模拟

引言油页岩是一种富含有机质、具有微细层理、可燃烧的细粒沉积岩,油页岩作为能源资源,既可以干馏炼油也可以燃烧发电。油页岩储量丰富,截至2005年底,37个国家油页岩探明总储量折算     

Enhancement of oil recovery in the combustion retorting of oil shale by the addition of coal

The effect of coal addition in the combustion retorting of oil shale has been studied for various flow rates of air and grades of oil shale. The results indicate that oil yield is increased with coal addition, for example, by as much as 40% with 4 wt.% of coal in the retorting of 0.059 dm³/kg (14 gallons per short ton) oil shale. The distance between the combustion and the retorting zone is separated farther with the addition of coal. This makes it possible to operate the combustion retorting process at an increased rate without an increased oil loss. It is thus possible to increase the oil yield as well as the rate of retorting with a relatively small addition of solid fuel.     

干馏条件对油页岩半焦孔隙结构的影响

油页岩干馏过程中发生挥发分物质的析出,导致颗粒的孔隙结构发生重大的变化,进而会对油页岩半焦的燃烧反应、成灰等特性产生重要的影响。利用扫描电镜、氮气吸附/脱附法对不同干馏温度、不同干馏时间下制备得到的桦甸油页岩半焦进行了孔隙分析,并与前人针对相同样品的油页岩半焦燃烧特性实验研究进行了对照分析。结果表明,在实验范围内,随干馏温度增加,受热解二次反应产生的焦炭对孔隙堵塞的影响,油页岩半焦孔隙比表面积和比容积先增加后减小;随干馏时间增加,伴随着小孔之间的合并,油页岩半焦孔隙比表面积先增加后减小,比容积单调增加。     

油页岩低温干馏过程的Aspen Plus模拟

利用Aspen Plus系统流程模拟软件模拟油页岩的低温干馏,并按照含油率测定实验工况来设置系统流程,以探讨将Aspen Plus应用于油页岩热解领域的可行性。针对吉林地区桦甸一矿4层和二矿11层的油页岩试样进行模拟,并将所得的含油率、含水率、半焦产率、干馏气体产率及半焦中各元素含量等模拟数据与实验值进行对比分析,模拟结果与实测值间的误差均控制在合理范围之内。对比结果表明,系统流程的建模及物性参数设置是正确合理的,可为后期构建完整的油页岩综合利用系统提供参考。     

油页岩干馏技术影响因素及工业发展展望

对油页岩资源的分布及储量情况、油页岩干馏过程及其影响因素、国内外的油页岩干馏技术及其工业发展现状进行了介绍,并对油页岩干馏工业进行了展望。