粉末页岩流化干馏中试试验

介绍了以粉末页岩作为原料的流化干馏中试装置概况及试验流程,并对试验过程中产生的页岩油与块状页岩干馏页岩油进行了对比。结果表明,粉末页岩流化干馏工艺所产的页岩油较轻,其主要原因是粉末页岩流化干馏采用固体热载体干馏技术,并且原料粒径较小,可以达到较快的加热速率,挥发物逸出较快,从而影响页岩油的性质。     

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%。     

页岩灰在油页岩固体热载体流态化干馏中催化作用试验分析

通过对油页岩固体热载体流态化干馏中试装置所产页岩油与某气体热载体所产页岩油对比分析,页岩灰在固体热载体干馏中具有一定的催化作用,并通过实验室验证该催化作用的存在。     

轮胎胶粒及低温热解产物特性研究

为掌握废轮胎的低温无催化热解特性,本文作者对轮胎胶粒及其热解产物进行了研究,铝甑干馏实验研究表明500℃的干馏热解过程,能够实现轮胎胶粒充分热解,热解产生的油和半焦炭黑占原料比为90.7%;通过500℃干馏热解实验及固体半焦的铝甑干馏和工业分析表明,500℃温度条件能较好地实现轮胎胶粒充分干馏热解;但干馏加热时间较长,建议考虑强化热解炉换热工艺的措施。从热解油分析结果可知,其中含微量的灰分、沥青质等成分,在工业设计时应考虑避免油气回收时堵管等现象发生。     

新疆塔城地区油砂的实验室研究

对塔城地区的油砂样品进行实验室铝甑干馏试验研究,分析其含油率,并且使用甲苯抽提法测试油砂样中的沥青含量,为工业化应用提供基础技术数据。     

褐煤和油页岩固体热载体新法干馏试验研究

在实验室建成了10kg/h的固体热载体新法干馏连续实验装置。在此装置上进行了粉末状的桦甸和茂名油页岩、平庄、黄县、先锋、昌宁和罗茨等褐煤试验研究。油页岩干馏温度为500℃,采油率达到西德实验水平,是铝甑试验值的90～94％,油质轻,煤气热值为18～20MJ/m~3。页岩灰渣中含固定碳低。褐煤低温干馏温度为500～600℃,每吨干煤的煤气产率为200～250m~3,煤气热值为15～20MJ/m~3。焦油产率为80～100kg,半焦产率为450～600kg,用低灰分褐煤可生产优质半焦,反应性好,燃点低并有多种用途。新法干馏工艺流程简单,不用氧气、常压生产、单元设备生产能力化、热效率高、投资省及生产费用低。     

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。     

油页岩干馏的冷凝回收系统研究现状与发展趋势

随着世界石油需求量不断上升,页岩油作为石油替代资源越来越受到重视,其中油页岩干馏技术中的冷凝回收系统直接影响产品的质量、能耗和环保问题,是干馏技术中的重要环节。本文介绍了几种国内外已应用的页岩油冷凝回收水洗和油洗工艺。水洗工艺主要介绍了抚顺炉工艺,茂名流化干馏炉工艺,Petrosix炉工艺和Lurgi炉工艺。油洗工艺主要介绍了Galoter炉工艺和ToscoⅡ法油洗工艺。对上述两种工艺从装置和工艺先进性进行对比得到如下结论：水洗工艺成熟,但存在工艺落后、能耗大、循环水量大等缺点。油洗工艺先进,能有效回收高温荒煤气的热量,但目前国内该方面的技术还不成熟,需要深入研究。     

油页岩干馏炉提高油产率技术方案的研究

介绍了油页岩资源的基本情况及抚顺式干馏工艺的特点,对影响抚顺式干馏炉页岩油产率的因素进行了分析,并针对影响因素进行了改变干馏机理、确定最佳工况参数的半工业化试验。试验证明,对抚顺式干馏炉可通过改变工艺配量的方式,使其达到最佳工作状态,从而保证干馏炉得到较高的页岩油产率。     

蓄热式外燃油母页岩低温干馏新工艺研究

世界上油页岩储量巨大。油页岩干馏可以生产类似于石油的页岩油,利用油页岩生产页岩油可以缓解石油短缺的问题。目前,我国页岩油的年产量居世界首位,但这种干馏工艺也存在一些弊端:产油率低,产油率仅为60.9%-65%,国外页岩油产率可达90%。因此,有必要对传统油页岩干馏工艺进行优化,提高油页岩的出油率。     

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。     

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.     

Method for determining the kinetics of cracking and coking of shale oil vapours in fluidized beds

The secondary cracking and coking of oil vapours produced from oil shale retorting have been previously shown to depend upon the nature and temperature of the substrate over which these reactions occur. To realistically examine the kinetics of these reactions during fluidized bed retorting, an apparatus has been developed which permits shale oil vapours generated in one fluidized bed to pass over selected substrates in a second fluidized bed. Substrates can be fed as a batch or continuously. In the batch mode, the substrate is heated to reaction temperature and is then exposed to shale oil vapours for a chosen period of time. Carbon deposition onto the solid is monitored in real-time by combusting the pyrolysis products and measuring the oxides of combustion with an on-line mass spectrometer. The extent of carbon uptake is also determined by elemental analysis of the substrate following reaction. These two methods of analysis were shown to correspond well under all the conditions investigated. In the continuous mode, substantial amounts of product oil can be collected so the effects of cracking may be evaluated. The rates of carbon deposition onto processed shales and pure minerals have been measured.     

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。     

油页岩循环流化床燃烧室密相区物料颗粒与燃烧特性

在 65t/h油页岩循环流化床锅炉上进行了燃烧室密相区物料特性与燃烧特性的工业试验。得到了极具片状结构特点的油页岩颗粒特性 ,经燃烧破碎磨损后的密相区床料和循环物料的颗粒特性与燃烧特性及相应的锅炉运行参数。试验结果对油页岩循环流化床锅炉的放大设计与运行调节具有一定的参考价值。同时为进一步建立油页岩循环流化床燃烧室密相区的流动、燃烧、传热、磨损、扬析与夹带模型奠定了基础。     

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.     

油页岩矿物质催化半焦燃烧特性及机理

利用微型流化床反应分析仪（MFBRA）研究了油页岩矿物质催化半焦燃烧特性，重点考察了半焦内部矿物质和外部页岩灰床料对半焦燃烧的催化作用，揭示了流化床反应器中半焦燃烧过程和机理。结果表明：内部矿物质和外部床料对半焦燃烧均具有明显催化作用，而两者共同催化效果最为显著。矿物质中CaO和Fe₂O₃对半焦燃烧具有催化活性，CaO催化作用强于Fe₂O₃。油页岩半焦燃烧反应活化能在60.41~78.97 kJ/mol之间，矿物质的催化作用会明显降低反应活化能。流化床反应器中，矿物质对半焦燃烧的催化作用主要表现在四个反应，即：挥发分裂解和燃烧、半焦表面炭燃烧、半焦内部炭燃烧以及一氧化碳燃烧。     

Characteristics and mechanism of catalytic effect of inner minerals on combustion of oil shale coke

The micro fluidized bed reaction analyzer (MFBRA) was used to study the combustion characteristics of oil shale mineral catalytic semi-coke. This study compared the effect of minerals inside char and bed material (oil shale ash) outside char on char combustion, and the process and mechanism of char combustion in the fluidized bed were further revealed. Both of minerals inside char and bed material outside char had a marked catalysis for char combustion and their combined catalysis was most notable. It is found that the CaO and Fe₂O₃ were the major active components in oil shale minerals for catalytic combustion of char, and the catalysis of CaO was stronger than that of Fe₂O₃. The activation energy of char combustion ranged from 60.41 kJ/mol to 78.97 kJ/mol, and it would significantly decrease with presence of the catalysis by minerals in oil shale. For char combustion in a fluidized bed, the contribution of minerals to catalytic combustion was mainly reflected in four reactions, such as volatiles cracking and combustion, surface carbon combustion, internal carbon combustion and CO combustion.     

小颗粒油页岩热裂解制取页岩油试验研究

针对中国小颗粒油页岩的利用现状,在实验室条件下,利用自行研制的流化床热裂解装置进行了小颗粒油页岩制取页岩油的试验研究,通过正交试验优化出了热裂解制取页岩油的最优工艺参数。实验结果表明,在最优工艺条件下,产油率在5%左右。因此流化床热裂解技术是一种有效的小颗粒油页岩加工制油的新方法。