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.     

小颗粒油页岩炉内阻力研究

我国油页岩矿藏多为中、贫矿资源,干馏后页岩半焦中的热值低,不适合国际现有的固体热载体干馏工艺,但采取气体热载体工艺,又遇到干馏炉干馏强度低,运行成本高的问题,其难点在于很难设计出单元工艺尺寸内对应的工艺运行条件。本文研究干馏炉内料层阻力与对应的工艺条件的关系,并得出数学模型,使新工艺、新炉型的设计得以优化,减少投资、节省时间。     

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.     

油页岩与固体热载体在回转干馏炉内混合特性的冷态实验

实验研究了回转干馏炉内非等粒径油页岩与固体热载体颗粒群的混合行为,以回转干馏炉出口油页岩质量分数的样本变异系数作为混合指数。对2种填充率、2种抄板形式、2种倾角在5种转速的不同工况下出口的混合指数进行计算,对比分析了混合指数的变化趋势及不同影响因素的混合机理,得出20%填充率采用直角抄板在倾角为3.24°时混合度优于其它对应工况,以对流混合为主。     

基于Aspen Plus抚顺式油页岩干馏工艺数值模拟

在Aspen Plus平台上建立了抚顺式油页岩干馏工艺模型,利用Aspen Plus的灵敏分析模块研究了抚顺炉气化段温度对产气组分的影响、空气/水蒸汽质量流率比值对产气组分和产气热值的影响,以及干馏段温度对收油率的影响,模拟结果与实际数据吻合良好。结果表明,抚顺炉气化段温度在650～750℃反应最为剧烈,生成的气体量收益最好。随着空气/水蒸汽质量流率比的逐渐增加,CH4和CO2量逐渐减少,CO、H2和N2量逐渐增加,热值也随之降低。干馏段温度在550℃时,收油率达到6.85%,可作为干馏炉热解段的最佳运行温度。     

油页岩气体热载体干馏过程模拟

运用Aspen Plus软件,将油页岩定义为常规物流、非常规物流和常规惰性固体物流的混合物流,结合油母质热解机理、总包一级热解动力学模型,建立了油页岩气体热载体干馏炉模型。在干馏炉正常运行温度下,对油页岩中有机质及其热解产物页岩油、热解气体、半焦等物质的质量进行了计算和分析,并对不同温度下有机质及其热解产物的质量进行了计算和分析。模拟结果与干馏炉设计运行参数符合较好,能方便的对不同温度下热解产物的质量进行预测。     

煤固体热载体流化干馏实验研究

在实验室小型煤—固体热载体流化干馏装置上,以半焦为热载体,氮气为流化载气,对神木煤做了热解特性评价实验,考察了反应温度、反应时间及热载体/煤质量比对热解产物产率的影响;结果表明,神木煤流化干馏最佳操作条件为:反应温度550℃,反应时间6 min,热载体/煤质量比为2∶1;在最佳操作条件下,油收率为12.51%,比铝甑含油率高35%。     

中心进气式油页岩干馏炉的冷态模拟优化

油页岩气体热载体干馏炉稳态运行过程中,炉内的流程分布对油页岩干馏具有显著影响。干馏段流程分布情况越均匀对油页岩的干馏越有利。本文对自行设计的某种四层布气的干馏炉干馏段进行CFD冷态模拟,并分析了该结构形式干馏炉的优缺点,对相应缺点进行了改进。结果表明:此类四层中心进气的干馏炉总体上可以提供较好的气体热载体充满度及热载体的流程分布。将入口形式改造为带十字导叶的入口形式对干馏炉内流程分布有积极影响。此种结构下炉膛局部区域存在气体充满度欠缺问题。保证整体进气量不变的前提下,在特定位置增加边壁进气配合中心进气可以较好地填补干馏段的热载体缺口。改进后的干馏炉干馏段气体热载体分布均匀情况更为理想。     

低阶煤无热载体快速热解炉工艺试验研究

为实现煤炭热解分质梯级利用,提出了低阶煤无热载体粉煤快速热解炉工艺,以印尼褐煤为研究对象,对无热载体粉煤快速热解工艺所产焦油、热解气、半焦等进行分析,验证低阶煤无热载体热解炉工艺的技术可行性。结果表明,试验煤种经低阶煤无热载体粉煤快速热解炉工艺处理后热解焦油产率达11.84%、热解气产率14.08%,半焦产率64.97%,其中焦油产率比格金干馏试验提高了1.49%,半焦发热量较原煤提高了2.63 MJ/kg,热解气有效气体含量达80%以上。表明该低阶煤无热载体粉煤快速热解炉工艺具有热解温度可区域精确控制、热解速度快、焦油产率高、产品品质好等优点。     

国内油页岩干馏炼油技术发展现状

描述了中国油页岩的主要分布区域和储量;阐述了国内油页岩资源加工利用技术现状.主要介绍了茂名方炉、茂名圆炉、抚顺炉、神木三江SJ-Ⅳ型直方炉等几种油页岩块岩干馏炉型,以及DG干馏技术、油页岩流化床干馏及脱碳技术、茂名流化干馏技术等几种小颗粒油页岩干馏技术.指出了油页岩加工利用技术的发展趋势,对我国油页岩工业的发展提出了建议.     

COMPARISON OF METHODS OF ANALYSIS OF GYPSUM1

The different analytical methods proposed for the evaluation of gypsum have been subjected to an experimental test. A combination method, consisting of a fusion with KHCO₃ and determination of CaO by KMnO₄ titration, the SO₃ by Andrews method of titration of BaCrO₄ has been found to give very reliable results with the least consumption of time.     

氢气纯度分析方法准确性的探讨

ONACCURACYOFANALYSISOFOFHYDROGEN1前言我公司目前应用的氢气纯度分析方法有两种,一种是爆炸反应法,另一种是焦性没食子酸吸收法。几年来,人们对两种分析方法的准确性曾有过褒贬不一的评论。这里我们也谈谈自己粗浅的观点。2爆炸法测定氢气纯度一定量的氢气样品与适量的空气之均匀混合物因反应后生成液体水而引起气体体积减少,减少的体积等于参加反应气体体积之和。其中l／3为氧气,2／3为氢气。根据氢气取样量和反应前后混气体体积之差,以及氢气在反应中的体积比例关系,可计算出样品的氢气纯度。计算公式式中：A一混…     

HEASUREHENT OF INSTANTANEOUS RATES OF LOSS OF VOIATILE COMPOUNDS DURING DRYING OF DROPS

A novel technique serves to monitor instantaneous rates of loss of a volatile solute from a suspended drop during drying. A highly sensitive electron capture detector is used to monitor concentrations of SF6 released into a flowing gas stream from a suspended, drying drop. Simultaneously, the appearance and morphological development of the drop are monitored with a video camera. This provides the wherewithal of relating instantaneous rates of loss of the volatile solute to particular events during the development of particle morphology.

Initial experiments have been carried out with drops of aqueous solutions of glucose, sucrose, maltodextrin and coffee extract. The results clearly display the onset of the volatiles-retentive selective diffusion phenomenon. There is also substantial loss of the volatile component later in the drying process, when the drops undergo repeated ex ansion, bursting and cratering due to the formation of internaf bubbles. These experiments appear to be the first quantitative demonstration of major losses accompanying changes in drop morphology.     

SEDIMENTATION OF BINARY MIXTURES OF PARTICLES OF UNEQUAL DENSITIES AND OF DIFFERENT SIZES

A model is developed for the sedimentation from a suspension of two particle species of unequal densities and of different sizes. The composition and the thickness of various layers in the sediments are predicted using graphical and analytical methods. The model predictions were in excellent agreement with experimental results, when the particle size ratio was ≥ 108. When size ratio of the particles was 2.60 and 4.31 the agreement occurred in about 50 percent of the cases.     

茶多酚提取方法进展

本文综述了国内外现有茶多酚提取方法的现状以及近期的研究进展，并对其优缺点进行了评价。这将有助于中低档茶的综合利用和茶多酚的进一步开发应用。     

ANALYSIS OF RECENT MEASUREMENTS OF THE VISCOSITY OF GLASSES

Viscosity of Simple Soda-Silicate 500° to 1400°C Comparison of the results given by English with those of Washburn, Shelton and Libman, indicates a discrepancy in the absolute values of log₁₀ viscosity amounting to 0.6, those of Washburn et al., being relatively too high. If correction for this is made, the isothermal curves of log₁₀ viscosity as a function of soda content are smooth up to 50% Na₂O, showing no inflection. The observations as a function of temperature T are all represented within accidental error by an equation of the type where all three constants vary regularly with the composition. Change of Viscosity of Glass (6SiO₂, 2Na₂O) due to Molecular Substitution of CaO, MgO and Al₂O₃ for Na₂O The effect is clearly brought out by plotting (from the results of English) the change of log₁₀η due to the substitution as a function of temperature. The curves each show a sharp bend at a temperature between 840° and 1050°C, which is designated the aggregation temperature T_a. If we divide these curves by the corresponding percentage substituted, we get curves for each oxide which are straight and parallel below the aggregation temperatures, the slopes (increase of change of log₁₀η per 100°C) being −0.056 (CaO), −0.055 (MgO), −0.018 (A1₂O₃) per per cent oxide substituted. For substitution of 1/2 molecule the slopes are −0.325 (CaO), −0.23 (MgO) and −0.18 (Al₂O₃) per 100°. At the aggregation temperature the change of log₁₀η per per cent is a minimum, 0.03 to 0.06 for CaO, 0.12 for MgO, 0.07 for Al₂O₃. Evidence of Aggregation in Glasses, from viscosity Measurements The sharp bends in the plots of change of log₁₀η due to substitution of an oxide for Na₂O, suggest the beginning of molecular aggregation at these temperatures. These aggregation temperatures are close to the devitrification temperatures, but the effect on the viscosity curves cannot be due to actual devitrification since it does not change with time. Taking the aggregation temperatures as equal to devitrification temperatures, additional isotherms are roughly sketched into the equilibrium triangle of the system Na₂O-CaO-SiO₂. Change of Viscosity of Glass (4SiO₂, 2Na₂O) due to of Substitution of B₂O₃ for SiO₂ The change of log₁₀η (from the results of English) is plotted as a function of temperature, and also the change of log₁₀η per per cent B₂O₃. The curves are more complex than for the substitution for Na₂O.     

环氧树脂羟基值测定方法的研究

利用乙酸酐、吡啶和浓硫酸混合的乙酰化试剂测定环氧树脂中羟基值含量的方法具有操作简便、滴定终点明显和分析结果误差小等优点。     

骑式摩托车油箱喷涂工艺的改进

面对日益激烈的市场竞争,摩托车油箱外观质量越来越成为影响销售的因素之一。文章介绍了改进工艺后的油箱涂装,该涂装体系提高了油箱外观的丰满度,降低了油箱涂装的生产成本。     

用两个形状指数表征粉煤灰颗粒形貌的研究

引用两个形状指数表征颗粒形状的概念,即先将颗粒形状近似为椭圆,再将椭圆图像分离:以圆为基准的颗粒宏观形状指数δ;以光滑椭圆为基准的颗粒轮廓凹凸度,即微观形状指数ζ。分析和发展了近似椭圆模型。并运用图像分析仪对粉煤灰、水泥样品进行实验。结果表明,粉煤灰颗粒的两个形状指数δ和ζ都大于水泥颗粒。证明粉煤灰颗粒的球形度、表面光滑度优于水泥,而且,随着粒径增大,δ和ζ呈下降趋势,表明磨制颗粒越粗。(?)粒形状越不规则。文中还运用近似椭圆模型再现了颗粒的模拟图像。     

典型煤碳燃烧特性研究和数值模拟

本文以三种典型煤的碳燃烧为研究对象，分别采用简单一维沉降燃烧方式和等温加热燃烧方式，实验研究了煤在快速加热条件下，其碳的初期和中，后期燃烧过程。以实验为基础，建立了煤的碳燃烧模型，变工况数值模拟了煤的碳燃烧过程，揭示了煤不同条件下的单颗粒碳燃烧特性。