神东煤与煤液化残渣共热解研究

为实现煤液化残渣的资源化利用,采用神东煤与液化残渣进行共热解试验,研究了神东煤粒度、残渣粒度、残渣比例对热解产物分布及热解半焦强度的影响,建立了热解半焦强度测试方法。结果表明,共热解后焦油干基收率随着液化残渣加入量的增多而增大,液化残渣的加入对焦油的生成有正协同作用。1 mm液化残渣添加量由10%增加到30%,3~6 mm神东煤共热解半焦转鼓强度增大29.3%,易碎性F值降低22.8%;同样条件下,液化残渣添加量对3~6 mm神东煤共热解半焦转鼓强度的影响更大,1 mm的液化残渣添加量对神东煤共热解半焦易碎性F值影响更大,3 mm神东煤和1 mm的液化残渣共热解半焦转鼓强度小,易碎性F值高,因此热解过程原料煤应当设置粒度下限。     

煤油共炼残渣掺配水煤浆气化评价研究

将延长石油集团煤油共炼残渣与煤掺配制备水煤浆进行高温气化处理。结果表明,在分散剂的作用下,残渣的掺配量可达到水煤浆总重的5%,水煤浆成浆性良好,气化性能优良,对气化工艺、设备及后续工艺无不良影响,能够实现对残渣的资源化利用及无害化处理。     

煤油共炼残渣掺配水煤浆气化评价研究

将延长石油集团煤油共炼残渣与煤掺配制备水煤浆进行高温气化处理。结果表明,在分散剂的作用下,残渣的掺配量可达到水煤浆总重的5%,水煤浆成浆性良好,气化性能优良,对气化工艺、设备及后续工艺无不良影响,能够实现对残渣的资源化利用及无害化处理。     

煤油共炼残渣资源化处理技术研究

对延长石油集团煤油共炼装置产生的共炼残渣进行原料特性分析,并对其理化性质及危害性进行了评价。基于煤油共炼残渣的特性,提出了煤油共炼残渣与多元料浆气化技术相结合,实现煤油共炼残渣的资源化高效清洁利用的思路,并详细介绍了技术路线和研究情况。多元料浆气化技术能使煤油共炼残渣中的有机物在高温下得到有效分解,实现污染物消减;能使无机物在熔融条件下与原料煤的灰渣形成安全稳定的玻璃化产物,有利于最终的处置利用。结果表明将煤油共炼残渣作为部分原料进行多元料浆气化反应,能够实现对残渣的资源化处理,气化指标良好。     

HRI煤油共炼技术

0 前言美国碳氢化合物研究公司(HRI)是专门从事石油重油深加工和煤炭直接液化技术开发的研究机构。1974年开始煤油共炼初期试验研究,用微型高压釜、高压釜和25kg/d 小型连续试验装置进行了原料筛选和技术经济初步可行性研究。1985年开发出两段煤油共炼工艺,从此得到美国电力研究院、安大略-俄亥俄合成燃料等公司的资助,制订了三年研究和技术发     

煤直接液化残渣与神东煤共热解特性研究

实验选用500 g级基于热重系统热解装置研究了神华液化残渣与神东煤共热解特性.结果表明,在反应器侧壁温度为200～600℃区间内,同一时刻,随着液化残渣配比的增加,热解胶质层比例增加,热解过程中传热加剧,煤样中心温度逐渐升高;液化残渣配比为20％时,煤样中心温度最高.液化残渣配比由0％增加至25％时,热解总失重量逐渐减...     

甘蔗渣与褐煤共热解半焦的特性

利用自制的干馏装置进行褐煤与甘蔗渣的低温共热解实验,并探究甘蔗渣的添加量对热解产物产率及半焦品质的影响。研究结果表明,在甘蔗渣掺混比为20%时,产物产率的实验值与理论值偏差达到最大,此时焦油产率的实验值比理论值高出9.61%;FTIR检测表明半焦中主要含有-OH、C=C和C=O官能团,且甘蔗渣的添加能促进半焦中苯类化合物转化为其他类低分子化合物;SEM检测表明褐煤与甘蔗渣共热解半焦比煤样单独热解半焦孔隙发达;BET分析表明甘蔗渣与褐煤的相互作用不仅能提高共热解半焦比表面积,而且能改善孔径分布,使共热解半焦孔径有减小的趋势。半焦吸附重金属离子实验表明未经任何处理的煤半焦及甘蔗渣半焦对铅离子去除率分别达到78.42%和87.80%。     

煤油共炼的研究进展

煤油共炼技术不但可以有效利用石油资源,而且可将价格低廉的煤炭资源转化成油,实现煤炭资源清洁利用。简述了煤油共炼工艺、原料及催化剂,并论述了煤油共炼后残油的处理。     

油煤共炼残渣成分分析及危害性评价

通过组分分析、工业分析、元素分析、有害物质分析、腐蚀性、浸出毒性、易燃易爆性、挥发分、热失重等分析,对油煤共炼装置产生残渣进行了成分解析并对其理化性质及危害性进行了研究。结果表明,残渣空气干燥基灰分7.27%,发热量40 462 k J/kg,闭口闪点337℃,哈氏可磨系数60,油煤共炼的含油率约65%,固含量约8%。主要危害源为石油烃类物质污染,油煤共炼残渣具有较高的资源化利用价值。     

煤热解半焦物化特性表征研究进展

论述总结了煤热解半焦的各种物化特性表征方法研究进展,重点阐述了煤热解半焦的化学成分组成表征、结构特征表征、其它物化特性表征等研究方法,为各种煤热解半焦的利用研究提供参考。最后对煤热解半焦物化特性表征方法的研究方向提出了建议。     

油泥焦与褐煤共燃特性及动力学

采用热重分析法研究了不同升温速率下油泥焦、褐煤及其混合物燃烧特性,并利用Kissinger-Akahira-Sunose（KAS）、Flynn-Wall-Ozawa（FWO）和Friedma（FR）等方法计算其燃烧动力学参数。结果表明,油泥焦燃烧主要是固定碳燃烧过程,而褐煤燃烧是挥发分和少量固定碳连续燃烧的过程。褐煤比油泥焦具有更好的燃烧特性,平均活化能更低。油泥焦和褐煤共燃过程中存在明显的协同促进作用,当混合燃料中褐煤占比为75%时协同促进效应达到最强。通过比较KAS、FWO和FR的结果发现,FR法能够更好地体现反应变化的趋势,而KAS法和FWO法的结果具有较高的准确性。通过比较油泥焦和褐煤共燃动力学参数的理论计算值与实验计算值发现,利用热重分析预测混合燃料的燃烧性质具有较高的可靠性,对油泥焦与褐煤共燃技术的应用具有重要的指导作用。     

生物质与煤共热解研究现状

综述了近年来国内外煤与生物质共热解的研究现状。当生物质与煤共热解过程中存在协同反应时,能够将生物质中的氢有效地转移到煤热解过程中,改善煤热解过程中产物的性质,提高煤的热解效率。后续对生物质与煤共热解的研究可以考虑适当的方法,如添加合适的催化剂等来促进协同反应的发生。     

Evaporation of pyrolysis oil: Product distribution and residue char analysis

The evaporation of pyrolysis oil was studied at varying heating rates (～1–10⁶°C/min) with surrounding temperatures up to 850°C. A total product distribution (gas, vapor, and char) was measured using two atomizers with different droplet sizes. It was shown that with very high heating rates (～10⁶°C/min) the amount of char was significantly lowered (～8%, carbon basis) compared to the maximum amount, which was produced at low heating rates using a TGA (～30%, carbon basis; heating rate 1°C/min). The char formation takes place in the 100–350°C liquid temperature range due to polymerization reactions of compounds in the pyrolysis oil. All pyrolysis oil fractions (whole oil, pyrolytic lignin, glucose and aqueous rich/lean phase) showed charring behavior. The pyrolysis oil chars age when subjected to elevated temperatures (≥700°C), show similar reactivity toward combustion and steam gasification compared with chars produced during fast pyrolysis of solid biomass. However, the structure is totally different where the pyrolysis oil char is very light and fluffy. To use the produced char in conversion processes (energy or syngas production), it will have to be anchored to a carrier. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

低阶煤与浒苔低温共热解过程分析及动力学

采用自行设计低温干馏装置对不同配比的低阶煤（LRC）和浒苔（EN）进行低温干馏实验,发现在浒苔配入量为30%时,焦油的产率达到最大值11.39%,比煤单独热解提高了28.61%,比理论加权值提高了8.87%。对低阶煤、浒苔及浒苔配入量为30%的混合样进行热重分析,发现低阶煤与浒苔共热解时在240～750℃段存在明显的协同效应,且其相对最大值达18.5%。动力学分析表明,混合热解时活化能与指前因子之间存在补偿效应,两者混合使反应活性增大,反应速率降低,协同作用主要表现在使共热解反应活性增大。     

A review on co-pyrolysis of coal and oil shale to produce coke

It has become the top priority for coking industry to rationally use and enlarge coking coal resources because of the shortage of the resources. This review focuses on the potential utilization of oil shale (OS) as a feedstock for coal-blending coking, in which the initial and basic step is pyrolysis. However, OS has a high ash content. If such OS is directly used for coal-blending coking, the coke product will not meet market demand. Therefore, this review firstly summarizes separation and beneficiation techniques for organic matter in OS, and provides an overview on coal and OS pyrolysis through several viewpoints (e.g., pyrolysis process, phenomena, and products). Then the exploratory studies on co-pyrolysis of coal with OS, including co-pyrolysis phenomena and process mechanism, are discussed. Finally, co-pyrolysis of different ranks of coals with OS in terms of coal-blending coking, where further research deserves to be performed, is suggested.     

生物油蒸馏残渣与废弃塑料催化共热解协同作用的研究

利用热重分析仪和两段式固定床研究了生物油蒸馏残渣(DR)与废弃塑料(MS)的共热解特性,探索了DR与MS混合比、无催化、原位催化及异位催化对产物分布及液相产物化学组分的影响,以及共热解产物的相对选择性与协同作用。结果表明：随着混合比的增加,液相产率呈现增长趋势;相比于无催化,原位催化、异位催化下液相产物中芳烃相对含量增高、含氧化合物相对含量降低。在原位催化下,DR与MS在脂肪族化合物与含氧化合物上表现出的协同作用与异位催化、无催化相反。对于单环芳烃,DR与MS的协同作用参数值大小关系为：无催化>异位催化>原位催化;对于脂肪烃,在DR∶MS=1∶1时,无催化、原位与异位催化下的协同作用参数最大,分别为-20.7%、25.2%、-41.2%;对于脂环烃,在DR∶MS=2∶1时,无催化、原位与异位催化下的协同作用参数最大,分别为184.2%、132.5%、50.0%;对于多环芳烃,DR与MS在不同催化方式下均表现为负协同作用。     

催化裂化（FCC）油浆作煤直接液化溶剂的研究进展

煤制油工艺等煤炭清洁高效转化技术是能源化工领域的研究热点,溶解性好、提供/传递氢能力强且热稳定性高,其溶剂选择、使用是影响煤制油工艺经济运行的关键。本文以煤液化溶剂作用为基础,通过对液化自身产物、废塑料及FCC油浆等煤直接液化溶剂的组成、性质及作用效果的综合评述,指出煤、溶剂、氢气间的混合并非理想混合,与煤H/C适宜、极性相近的溶剂在共处理过程表现出良好的协同作用,液化过程的转化率、轻质产物选择性明显提高。分析表明,协同作用的大小取决于煤、溶剂的组成、性质匹配。煤-重质烃共处理工艺利用富芳烃油浆溶解性好、提供/传递氢能力强的特点强化了煤热解加氢反应的进行,同时煤加氢液化产生的多孔残煤具有吸附性强的特点,有助于重质烃改质,使共处理转化率显著提高、轻质产物选择性增大。最后指出,煤-重质烃共处理的协同作用为改善煤、中质/重质芳烃的综合利用提供了可能。     

Formation mechanism of solid product produced from co-pyrolysis of Pingdingshan lean coal with organic matter in Huadian oil shale

A mixture of Pingdingshan lean coal and acid-treated Huadian oil shale was co-pyrolyzed in a drop-tube fixed-bed reactor in the temperature range of 300℃–450℃.To reveal the formation mechanism of the solid co-pyrolysis product,changes in some physicochemical properties were investigated,using analysis by X-ray diffraction,X-ray photoelectron spectroscopy,scanning electron microscopy,pore analysis,thermogravimetry,and electron spin resonance.X-ray diffraction showed that the lattice plane spacing for the co-pyrolyzed mixture decreased from 0.357 nm to 0.346 nm and the average stacking height increased from 1.509 nm to 1.980 nm in the temperature range of 300°C–450°C,suggesting that pyrolysis treatment increased its degree of metamorphism.The amount of oxygen-containing functional groups and pore volume decreased with increasing temperature.Thermogravimetry and electron spin resonance results showed that synergistic effects occurred during the co-pyrolysis process.A formation mechanism for the solid product was proposed.Hydrogen-rich radicals generated from the pyrolysis of the oil shale were trapped by hydrogen-poor macromolecular radicals of the intermediate metaplast produced from coal pyrolysis,thereby increasing the yield of solid product.     

高碱低阶煤热解及热解半焦研究进展

我国碱金属、碱土金属(AAEM)含量高的低阶煤储量丰富。高碱含量造成锅炉受热面结渣沾污及气化炉结块腐蚀等难题,低阶煤内水高、氧含量高、挥发分高、发热量低以及易氧化自燃等特性为其储、运、用带来极大的难题。热解可生产优质燃料和高附加值化工原料,也是燃烧、气化、直接液化等过程的起始阶段和/或伴随反应,煤在热解阶段发生的反应、经历的变化,对煤转化利用的效率和清洁程度起重要、甚至决定性作用。笔者对煤热解与热解半焦研究及进展进行综述性评价,着重探讨煤中AAEM对热解过程及半焦的影响。结果表明,热解研究装置模拟的工况与现代煤化工过程中煤热解所处环境相差甚远,半焦样的代表性不强使热解研究成果的指导意义不大;对煤中不同赋存形态AAEM的分离方法有待完善,还需筛选、尝试新的萃取试剂;基本掌握了煤热解过程中AAEM的变迁行为,但尚缺乏控制煤中AAEM危害的有效方法。高碱低阶煤的安全高效洁净转化利用技术仍待突破。     

Study on pyrolysis of oil sludge with microalgae residue additive

The pyrolysis of oil sludge (OS) with microalgae residue (MR) additive was conducted with a TGA and a tube furnace. The pyrolysis process of OS with the MR additive can be divided into three stages: 1) water evaporation, 2) the release of light groups of hydrocarbon compounds, the cracking of heavy groups, and carbon decomposition, and 3) minerals decomposition. With the MR addition ratio increasing, the yield of oil and gas increased, and oil to gas ratio increased during OS pyrolysis. The MR addition improved the quality of pyrolysis oil and gas from OS pyrolysis. The proportion of light oil increased from 38 % with a 5 % MR addition ratio to 45 % with a 30 % addition ratio. Major components of pyrolysis gas included H₂, CO, CO₂, and C_xH_y. With the increase of the MR blending ratio, CO and CO₂ contents increased, while H₂ and C_xH_y contents decreased. Adding MR favoured the transformation of heavy hydrocarbons (C₆₊), resulting in a high content of light hydrocarbons. This work can help promote massive synergistic treatment of OS and microalgae biomass.