窑街油页岩热解特性及产物分析

采用铝甑低温干馏和TG-DTG、FT-IR、GC、GC-MS等分析手段研究了窑街油页岩（YJOS）的热解特性及其热解产物页岩油、半焦和干馏气的组成。结果表明,YJOS的最佳热解温度约为510℃,油页岩中的无机质组分一方面对有机质的热解起着催化剂的作用,降低了热解初始温度,同时也因为其与有机质的紧密结合阻碍了热解产物的顺利逸出;半焦中的脂肪烃几乎完全消失,有机质的缩合度和芳香度增加;干馏气的主要可燃成分是H2和CH4,其次是C2H6、CO和C2H4,干馏气的平均相对分子质量约为20.4,平均比热容约为51.9 J/(mol?℃),平均热值约为40.13MJ/ Nm3;页岩油的密度为0.938g/mL,其中饱和烃和芳烃的质量分数分别为35.91%和26.51%,同时还含有较多的含氧、氮、硫等杂原子的有机化合物。     

油页岩与褐煤地下共气化模型试验

为了打开劣质能源资源的利用途径,进行了油页岩和褐煤热解干馏以及地下共气化试验。热解时,两者均在400℃开始有大量气体析出,在500℃~600℃达到最大,析出气以氢气和甲烷为主,并含微量的C2和C3的烷烯烃等;地下共气化时,气化剂从空气到富氧空气能够使煤气的有效组分含量大幅提升,但气化剂φ(O2)在30%～50%变化时,得到的煤气的有效组分含量并没有太大差异,因此以φ(O2)为40%的富氧气化时的煤气组分较为经济,此时煤气中有效组分体积分数约为40.79%,热值约5300kJ/m3,沿气化通道方向,页岩层先后出现气体析出峰值,页岩层析出气体中烷烯烃组分的体积分数C2>C3>C4,且其均在1%以下;经历高温燃烧气化后,黄褐色、致密的油页岩变成疏松、分层开裂明显的岩块。     

油页岩原位注蒸汽开采油气中试与多模式原位热采技术的适用性分析

油页岩是中国储量巨大的重要战略资源,也是国际公认的重要非常规石油资源。对油页岩进行地下原位干馏是目前实现其大规模工业开发的唯一可行技术方案。太原理工大学于2010年获得油页岩原位注蒸汽开采油气技术（MTI）的发明专利授权。基于MTI技术原理,对大尺寸油页岩试件实施原位注蒸汽开采油气的中试实验,并对多模式油页岩原位干馏技术的适用性进行分析。研究结果表明：①在实施油页岩原位多井水力压裂连通过程中,最高注水压力仅为地应力的41%,裂缝起裂扩展压力低。②蒸汽对流传热方式具备很高的传热效率,有机质热解迅速,蒸汽携带油气快速从生产井产出。同时,通过选择开启或关闭井组钻孔阀门的方式,实时调整蒸汽的流量和流向,灵活控制油页岩目标加热热解区域,实现了蒸汽的科学调配。③在油页岩原位注蒸汽正常运行过程中,蒸汽的注入压力仅约为自重应力的1/4,蒸汽锅炉长期低负载运行。④油页岩原位热解引发的地面沉降量很小,对地质环境危害小。⑤注汽热解区采出的含油率高达95%以上,总体原油采收率达到67.3%,充分证明利用MTI技术原位注蒸汽热解油页岩可达到较高的原油采收率。⑥所得油页岩油中轻质油品的占比达到72.51%;H₂在热解气体中的比例占据绝对优势,体积含量高达68.87%。⑦注蒸汽热解区的顶、底板油页岩层热解不充分,裂隙发育不明显,成为良好的防渗隔热层。⑧MTI技术与其他油页岩原位热采技术相比,其在技术流程和经济性方面具有明显优势,具备广阔的商业开发应用前景。     

AIR OXIDATION OF EASTERN OIL SHALES OF KENTUCKY. II. THE EFFECTS OF AMBIENT AUTOXIDATION

Ambient air oxidation leads to lower Fischer assay oil yields and often lower process yields from retorting of eastern oil shales. Slight changes in the kerogen and mineral matter of the oil shale and in its pyrolysis products, both liquid and gaseous, were evident following autoxidation. Experimental observations suggest that the hydrogen deficiency of eastern kerogen, as compared to western kerogen, makes its synfuel potential (by Fischer assay) a more sensitive function of the degree of oxidation.

A better yield of oil from oxidized eastern oil shale could be obtained by dissolving away sulfates and other water soluble oxidized materials prior to retorting. The air oxidation of pyrite was demonstrated by SEH, and addition of iron(II) sulfate was shown to reduce assay oil yields. Such observations suggest that combusted shale may not always be a suitable heat transfer agent for atmospheric pressure retorting applications.     

AIR OXIDATION OF EASTERN OIL SHALES OF KENTUCKY. II. THE EFFECTS OF AMBIENT AUTOXIDATION

ABSTRACT

Ambient air oxidation leads to lower Fischer assay oil yields and often lower process yields from retorting of eastern oil shales. Slight changes in the kerogen and mineral matter of the oil shale and in its pyrolysis products, both liquid and gaseous, were evident following autoxidation. Experimental observations suggest that the hydrogen deficiency of eastern kerogen, as compared to western kerogen, makes its synfuel potential (by Fischer assay) a more sensitive function of the degree of oxidation.

A better yield of oil from oxidized eastern oil shale could be obtained by dissolving away sulfates and other water soluble oxidized materials prior to retorting. The air oxidation of pyrite was demonstrated by SEH, and addition of iron(II) sulfate was shown to reduce assay oil yields. Such observations suggest that combusted shale may not always be a suitable heat transfer agent for atmospheric pressure retorting applications.     

COMPARATIVE STUDY BETWEEN THE KINETICS OF RETORTING OF OHIO ANO COLORADO SHALE

ABSTRACT

A comparative study between the kinetics of oil generation from Ohio and Colorado shales has been done. To facilitate comparison and to eliminate systematic errors, the same retorting system was used to study the kinetics of both Ohio and Colorado shales. Temperatures ranging to 923° K and nitrogen and carbon dioxide as sweep gases were used for this study. Both the isothermal and non-isothermal retorting techniques were employed for the kinetic measurement and the results obtained compared favorably with each other. The pyrolysis of Ohio shale was also found to comply with first order kinetics within the limits of experimental error. The study gave an apparent activation energy of 149.1 ± 2.8 KJ/mol for Ohio shale (25 cm³/kg) and 182.5 ± 3.5 KJ/mol for Colorado shale (110 cm³/kg).     

油页岩固体热载体综合利用系统工艺模拟

结合循环流化床锅炉构建了一套油页岩固体热载体综合利用系统,以锅炉产生的高温循环灰为油页岩干馏提供热量,并集成燃气-蒸气联合循环和常规蒸气轮机发电机组实现油-电联产。利用Aspen Plus软件对所构建的系统进行建模,结合公朗头矿区油页岩样品的物性数据,计算系统的物流参数和发电功率,并探讨了循环灰温度和油页岩干馏比例对系统的影响。结果表明,提高循环灰温度将降低系统的灰岩比,同时有利于提高系统的发电功率,但系统总发电效率会有所下降;增大油页岩干馏比例能提高页岩油的产能,系统能效呈上升趋势,同时也增加了燃气-蒸气联合循环机组的发电功率,但系统总发电功率却急剧下降。     

小颗粒页岩流化干馏工艺及其影响因素

以桦甸小颗粒页岩尾矿为原料,在流化干馏装置上进行热解实验。结果表明,页岩尾矿最佳热解反应条件为:粒径5 mm左右,加热速率6～10℃/min,干馏终温500℃。在此条件下,油页岩热解收率可达90%。     

微波干馏方法是开发页岩油的有效手段

目前在国内外的油页岩开发技术中,利用微波对油页岩进行干馏的方法逐渐受到了重视,微波干馏法已应用于油页岩原位开采技术当中。为考察微波干馏与常规干馏这两种方法对页岩油产品品质的影响,以我国桦甸、抚顺、农安、达连河4个地区的油页岩为研究对象,通过元素分析、模拟蒸馏、催化加氢等手段,对比分析了上述两种干馏方式的加工效果。结果发现：微波干馏法所得产物中油含量略低,而气体损失量相对略高,水及半焦产量也低于常规干馏法;但微波干馏页岩油比常规干馏页岩油烃类含量更高,而硫、氮含量低,同时轻组分含量更高,加氢效果也较理想。结论认为：微波干馏法加工的油页岩产品性质较优,该方法是油页岩开发的有效手段。     

大庆柳树河油页岩特点及干馏工艺选择

大庆柳树河盆地油页岩资源丰富，分布比较稳定。研究了该盆地油页岩含油率、热值、水分、热稳定性、强度等特性，针对该地区油页岩 “三高一低”（高含油、高含水、高热值和低强度）的特点，采用自主研制的2 kg级别室内干馏装置对油页岩进行全面室内评价，同时自主研发了新型小颗粒固体热载体干馏工艺，提出对大庆柳树河油页岩可采用小颗粒固体热载体干馏工艺技术。     

石油馏份蒸汽裂解结焦动力学

在可连续测量石油烃水蒸汽热裂解结焦速度的流动积分反应装置上,研究了石脑油和轻柴油结焦速度与温度、烃分压和动力学裂解深度的关系,小试与工业炉的结焦过程,给出了结焦模型。结果表明,同小试一样,工业炉的结焦反应也为反应控制。结焦反应的活化能随原料的芳烃指数增大而变小。结焦速度与结焦母体随裂解深度的变化表明,在低裂解深度下,原料和焦油中的芳烃是主要结焦母体,在高裂解深度下,二次反应生成的“缩聚物”是主要结焦母体。     

不同介质条件下油页岩热解的初步研究

利用高压釜热解实验装置,对采自民和盆地的油页岩进行全岩、全岩加去离子水和全岩加碱性饱和KCl溶液等3个系列的热解实验研究,并对这3个系列生成的页岩气和页岩油进行对比分析。结果表明：介质的加入有利于液态物的产出,跟油页岩直接加热相比,去离子水的加入使得页岩油的平均产率从83.66 mg/g提高到210.15 mg/g,但是抑制页岩气的生成;而碱性饱和KCl溶液的加入对页岩油和页岩气都有贡献,使得页岩油平均产率从83.66 mg/g提高到186.16 mg/g,页岩气平均产率从7.56 mL/g增大到9.08 mL/g。     

油页岩干馏工艺热载体特性研究

气体热载体干馏工艺是最成熟的油页岩炼油技术.热载体的利用方式、设计思路,决定着整个系统是否高效运转、节能安全.抚顺干馏技术经过近10 a发展,推出了4代不同干馏工艺,新建成并运行4套年产高于3×104 t/a页岩油的生产装置,形成了1整套的工艺设计理论和独特的热载体运用方法.文中总结了3个方面的热载体特性,阐述干馏工艺...     

0.12t/d油页岩干馏炉预热过程中温度分布特性

油页岩干馏炉启动升温过程中,其炉内的温度分布特性对油页岩的预热具有显著影响。干馏炉内气体在固体物料间的空隙内流动十分复杂,难以实现模拟研究。试验结果表明,空炉与填料时水平截面的温度分布变化基本相似,可通过空炉时的温度分布特性来进行近似分析。在进气量12 m3/s、进气比1的工况下,采用LES和RNS模型分别对空炉下干馏段和布气装置的升温过程进行数值模拟,分析干馏段和布气装置内温度及流速的变化。结果表明,布气方式决定炉内不同区域油页岩发生热解的顺序,率先发生热解的油页岩吸热减少,该位置温度加速上升,加剧炉内温度分布不均;加权平均数公式能更加准确反映截面温度不均性;炉内温度分布主要由不同区域的喷嘴加热功率与该区域的流场特性共同作用形成。     

COMPARATIVE STUDY BETWEEN THE KINETICS OF RETORTING OF OHIO ANO COLORADO SHALE

A comparative study between the kinetics of oil generation from Ohio and Colorado shales has been done. To facilitate comparison and to eliminate systematic errors, the same retorting system was used to study the kinetics of both Ohio and Colorado shales. Temperatures ranging to 923° K and nitrogen and carbon dioxide as sweep gases were used for this study. Both the isothermal and non-isothermal retorting techniques were employed for the kinetic measurement and the results obtained compared favorably with each other. The pyrolysis of Ohio shale was also found to comply with first order kinetics within the limits of experimental error. The study gave an apparent activation energy of 149.1 ± 2.8 KJ/mol for Ohio shale (25 cm³/kg) and 182.5 ± 3.5 KJ/mol for Colorado shale (110  cm³/kg).     

EMPIRICAL APPROACH FOR THE DIAGNOSTIC ANALYSIS OF CHEMICALLY RELATED OIL YIELD LOSSES DURING THE RETORTING OF OIL SHALE

The analysis of chemically related oil yield losses during the retorting of oil shale is important for understanding the chemistry of a process, supplying data for modeling efforts and process control of a production facility. Previously developed gas chromatographic correlations for evaluating oil yield losses were duplicated using combined gas chromatograph/mass spectrometric data. Evaluation of these results through calculation of local oil yields indicated that they were higher than expected when compared to material balance oil yields.

A new correlation was developed to estimate the fraction of oil lost by cracking plus combustion. The approach to the new correlation was based on selection of steranes and pentacyclic triterpanes as the species in shale oil which would undergo cracking and combustion to yield selected aromatic compounds. Evaluation of the results from this correlation for determination of local oil yields was found to produce acceptable results.

The two approaches for estimating the fraction of oil lost by cracking plus combustion are compared. The differences appear to be that the earlier approach is dependent upon severe cracking and combustion conditions. The new approach for determining the fraction of oil lost by cracking plus combustion appears to be applicable to a wider range of process conditions and therefore is more useful in research.     

利用原位电法加热技术开发油页岩的物理原理及数值分析

针对目前国内传统地面干馏油页岩技术的缺点,并结合油页岩自身特性,介绍了一种新的油页岩开发技术--原位电法加热开发技术(ICP).该技术可以解决传统油页岩开发技术在开发过程中高成本、高污染的难题.对油页岩高温热解失重及热破裂特征进行的分析结果表明:在350～500℃时,油页岩具有集中热解的特性,失重质量约占总质量的15%.高温热解后的油页岩会产生大量的孔隙、裂隙,从根本上提高了油页岩的渗透性,孔隙和裂隙的形成为应用ICP技术开采中油气的产出创造了条件.基于ICP开发技术的原理,建立了考虑化学反应热的能量守恒方程,并采用三维有限元法,对油页岩ICP原位电法加热开发过程进行了数值分析,获得了开发过程中温度场随时间的变化规律及地下油页岩热解范围,并计算了ICP技术在小规模开发过程中油气的产量.     

EMPIRICAL APPROACH FOR THE DIAGNOSTIC ANALYSIS OF CHEMICALLY RELATED OIL YIELD LOSSES DURING THE RETORTING OF OIL SHALE

ABSTRACT

The analysis of chemically related oil yield losses during the retorting of oil shale is important for understanding the chemistry of a process, supplying data for modeling efforts and process control of a production facility. Previously developed gas chromatographic correlations for evaluating oil yield losses were duplicated using combined gas chromatograph/mass spectrometric data. Evaluation of these results through calculation of local oil yields indicated that they were higher than expected when compared to material balance oil yields.

A new correlation was developed to estimate the fraction of oil lost by cracking plus combustion. The approach to the new correlation was based on selection of steranes and pentacyclic triterpanes as the species in shale oil which would undergo cracking and combustion to yield selected aromatic compounds. Evaluation of the results from this correlation for determination of local oil yields was found to produce acceptable results.

The two approaches for estimating the fraction of oil lost by cracking plus combustion are compared. The differences appear to be that the earlier approach is dependent upon severe cracking and combustion conditions. The new approach for determining the fraction of oil lost by cracking plus combustion appears to be applicable to a wider range of process conditions and therefore is more useful in research.     

Reaction behavior of oil sand in fluidized-bed pyrolysis

The reaction behavior of oil sand from Inner Mongolia（China） were studied in a fluidizedbed pyrolysis process,and a comparative study was conducted on the properties of the liquid products obtained through fluidized-bed pyrolysis of oil sand and the native bitumen obtained by solvent extraction.The results indicated that the fluidized-bed pyrolysis,a feasible carbon rejection process,can be used to upgrade oil sand.The reaction temperature and time were found to be the key operating parameters affecting the product distribution and yields in fluidized-bed pyrolysis of oil sand.The optimal temperature was 490℃ and the most suitable reaction time was 5 min.Under these operation conditions,the maximum yield of liquid product was 80wt%.In addition,the pyrolysis kinetics of oil sand at different heating rates of 5,10,20 and 30℃/min was investigated using a thermogravimetric analyzer（TGA）.     

废弃印刷线路板热解油的分析

在固定床实验装置上进行 FR4型印刷线路板的热解,利用气相色谱-质谱、傅里叶变换红外光谱分析了热解油的组成,用氧弹式量热仪测定了热解油各馏分的热值,并初步探讨了溴化环氧树脂的热解机理。实验结果表明,FR4型印刷线路板热解产物中热解油的质量分数为18.23%。热解油由轻质馏分、重质馏分和石油蜡组成。轻质馏分中包括少量水和轻质油。轻质油的主要组分为苯酚、4-乙基苯酚、3-(1-甲基乙基)-苯酚、5-甲基-乙基苯,其他组分主要为烷基取代的苯和苯酚,还含有丙酮及少量其他含氧有机物(苯甲醚和苯并呋喃等),轻质油中溴含量较低。重质馏分和石油蜡所含官能团与轻质油基本相同。轻质油和重质馏分的低位热值分别为27 183 kJ/kg 和29 240 kJ/kg。溴化环氧树脂的热解反应存在 CH_2-O,C-C,CH-OH,C-Br 键的断裂。