拔头油和油田轻烃与石脑油共裂解技术优化研究

在KBR公司的BSPA乙烯裂解评价试验装置上,分别对拔头油、油田轻烃与石脑油单独裂解工艺进行优化试验研究。在此基础上,对拔头油和油田轻烃分别与石脑油按不同比例掺混共裂解技术进行优化试验研究。研究发现,拔头油与石脑油掺混共裂解时,拔头油掺入量不低于40%、尽量≥70%,掺混共裂解协同效应才能充分发挥。油田轻烃与石脑油适合分储分裂,如果必须与石脑油掺混共裂解,油田轻烃的掺入量应≥40%。将研究结果应用于工业乙烯裂解装置,取得了较好的工业应用效果。     

油田轻烃、拔头油、石脑油的共裂解及单独裂解技术分析

在蒸汽热裂解制乙烯实验室装置上,分别进行了石脑油、拔头油和油田轻烃的单独裂解和共裂解性能试验,得到适宜的裂解操作条件和掺混比例。拔头油和油田轻烃均为优质的裂解原料,提高裂解温度对其有利,且单独裂解性能优于与石脑油的共裂解性能,宜采用单独裂解的方式;石脑油的裂解性能较差,增大水油质量比对其单独裂解有利,且也不宜采用共裂解的方式来生产乙烯。     

广州乙烯裂解原料方案优化的探讨

对广州乙烯裂解原料的选择问题进行了探讨，针对广石化的惭烯原料资源，对直馏石脑油，直馏柴油，重整拔头油，焦化汽油，焦化柴油的乙烯理解解性能的进行比较，提出了广州乙烯应优先选用重整拔头油及加氢精制后的焦化汽油和焦化柴油作乙烯理解解原料。     

广州乙烯裂解原料的选择

对广州乙烯裂解原料的选择问题进行了探讨,并针对广石化的乙烯原料资源,对直馏离油、直馏柴油、重整拔头油、经汽油、经柴油的乙烯裂解性能进行比较。提出广州乙烯应优选选用重整拔头油及加氢精制后的焦化汽油和经柴油作乙烯裂解原料。     

抚顺乙烯联合装置改扩建的总体设想

1 原料优化的设想 抚顺乙烯装置原设计裂解原料中轻烃、拔头油占85.5％,石脑油仅占14.5％。而实际生产中,原料的结构有重大变化,1994年上半年石脑油占90％,轻烃仅占10％,乙烯收率只有29.78％。主要的原因是,所用原料为炼厂的焦化加氢石脑油,单程乙烯收率仅     

裂解原料卸车系统节能降耗技术改造

中国石油天然气股份有限公司兰州石化分公司乙烯厂原料罐区承担着兰州石化公司炼化一体化项目中优质裂解原料(轻烃/拔头油)的输转和外部采购的轻烃/拔头油、油田液化气等轻质裂解原料的卸车、储存和输转。由于优质裂解原料在卸车过程中损失率偏高、存在运输安全隐患和环保排放的压力,故对原有卸车系统进行行了技术改造,增加了余压回收系统、改变了利用氮气压力卸车模式,实现了卸车过程中物料损耗大幅度降低、杜绝无序排放,经济效益和社会效益显著提高。     

拔头油热裂解制乙烯反应动力学模型及模拟

针对拔头油热裂解的反应动力学进行了研究,结合前人经验构造一个新的分子反应动力学模型,并将新模型应用于针对石化研究院的拔头油热裂解制乙烯标定实验的模拟,模拟结果与实验结果相符合,新模型能较好地反映实验室热裂解过程。为进一步研究工业拔头油热裂解的分子反应动力学模型提供了基础,能更好地对拔头油热裂解过程实现数值模拟。     

四川石化裂解原料优化方案的研究

中国石油四川石化公司800 kt/a乙烯装置依托10 000 kt/a炼油项目而建,采用美国SW公司专利技术。充分利用炼化一体化企业内部原料互供的优势,通过裂解一次加工产生的石脑油、拔头油等,以及二次加工产生的重整精制油、加氢裂化石脑油、液化气等,生产乙烯、丙烯、丁二烯等主要化工产品。原设计进料有加氢裂化尾油、轻重石脑油及轻烃。因炼油负荷及原油的变化,造成作为乙烯装置主要原料的石脑油品质变差,严重影响装置乙烯收率。从加工效益上看,评价及优化裂解原料,对装置提高产品收率具有重要意义。     

乙烯原料的调研及建议

国内乙烯原料的供应主要依靠油田和炼油厂。其种类有油田轻烃、轻柴油、减压柴油、石脑油、抽余油、拔头油、液态烃等。实际情况是装置尚未投产,原料的供应即发生了变化。国内的原料情况:一是原料不足;二是原油的直馏油收率低。大庆油的汽油收率仅为8～     

原料变重后的瓶颈现象分析及改进措施

抚顺乙烯装置以丙烷、丁烷馏分、重整液化气、重整拔头油为主要原料,以直馏石脑油、焦化加氢石脑油为补充。投产后,由于原料供应波动,石脑油成为主要裂解原料。原料构成变重,给装置操作带来一系列变化。     

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.     

Synergistic effect in low temperature co-pyrolysis of sugarcane bagasse and lignite

Sugarcane bagasse was co-pyrolyzed with lignite in a fixed bed reactor to investigate the possible interaction during co-pyrolysis. GC-MS revealed that the concentration of phenols and aliphatic compounds in the tar increased with the addition of sugarcane bagasse, while the content of aromatic compounds had the contradictory tendency. The phenol content in co-pyrolyzed tar reached 20.35%, which increased by 142.26% compared with the calculated values. The sugarcane bagasse decomposition peak partly overlapped with lignite pyrolysis peak from TG-DTG curves, which meant more interaction between lignite and sugarcane bagasse during the pyrolysis process. The difference between the experimental and calculated values of pyrolysis products yield, tar components, DTG values and kinetics analysis indicated the synergetic effect between lignite and sugarcane bagasse.     

神木烟煤与桦甸油页岩的共热解特性

采用热重分析仪和固定床反应器研究了神木烟煤和桦甸油页岩的混合共热解特性及协同作用机制. 结果表明,神木煤与桦甸油页岩混合共热解的失重率高于计算值,表明二者在热解和挥发分逸出过程中存在相互作用,促进了挥发分释放,减少了半焦生成. 煤与油页岩的协同作用可增加热解油收率、降低半焦和水收率. 油页岩与煤质量比为1:1时,所得油收率最高,为9.84%,比计算值提高8.8%. 共热解有助于提高轻质油含量和收率,油页岩与煤质量比为1:4时,轻质油含量超过80%,收率约为7.5%,比计算值分别提高了8%和11.2%,表明添加少量油页岩可明显提高热解油品质. 共热解过程中油页岩产生的富氢组分及自由基能抑制煤热解产生的芳香族化合物的聚合反应,促进芳烃向产物油转化,提高热解油的收率和品质.     

煤与稻壳共热解热重分析及动力学

利用热重分析仪对长焰煤和稻壳分别单独及按不同掺混比例进行热质量损失实验研究。通过比较煤与稻壳共热解热质量损失曲线和计算得到的理论曲线发现,添加稻壳对共热解过程有促进作用,在不同的稻壳掺混比例下,共热解过程质量损失率和最大质量损失速率均较理论值有不同程度的增大,推测稻壳掺混对共热解存在促进作用,促进作用与稻壳掺混比例不成线性关系。对煤与稻壳及共热解过程进行动力学分析,获得了反应活化能和频率因子,分析计算热解动力学参数表明共热解过程存在动力学补偿效应。     

哈萨克斯坦原油蒸馏及裂解性能评价

对哈萨克斯坦原油进行了简单分析,并进行了实沸点蒸馏评价.对蒸馏所得的石脑油馏分和轻柴油馏分进行了裂解性能评价.结果表明哈萨克斯坦原油属含硫中间基原油,拔出率一般,石脑油与轻柴油馏分的乙烯收率也不太高,裂解性能一般.     

Co-pyrolysis of pine cone with synthetic polymers

Biomass from pine cone (Pinus pinea L.) was co-pyrolyzed with synthetic polymers (PE, PP and PS) in order to investigate the effect of biomass and plastic nature on the product yields and quality of pyrolysis oils and chars. The pyrolysis temperature was of 500 °C and it was selected based on results from thermogravimetric analysis of the studied samples. Co-pyrolysis products namely gases, aqueous and tar fraction coming from biomass, oils from synthetic polymers and residual char were collected and analyzed. Due to the synergistic effect in the pyrolysis of the biomass/polymer mixtures, higher amounts of liquid products were obtained compared to theoretical ones. To investigate the effect of biomass content on the co-pyrolysis, the co-pyrolysis of pure cellulose as model natural polymer for biomass with polymer mixture was also carried out. In the presence of cellulose, degradation reaction leading to more gas formation and less char yield was more advanced than in the case of co-pyrolysis with pine cone. Co-pyrolysis gave polar oxygenated compounds distributed between tar and aqueous phase and hydrocarbon oils with composition depending on the type of synthetic polyolefin. Co-pyrolysis chars had higher calorific values compared to pyrolysis of biomass alone.     

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.     

Pyrolysis and co-pyrolysis of Laminaria japonica and polypropylene over mesoporous Al-SBA-15 catalyst

The catalytic co-pyrolysis of a seaweed biomass, Laminaria japonica, and a typical polymer material, polypropylene, was studied for the first time. A mesoporous material Al-SBA-15 was used as a catalyst. Pyrolysis experiments were conducted using a fixed-bed reactor and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). BET surface area, N₂ adsorption-desorption isotherms, and NH₃ temperature programmed desorption were measured to examine the catalyst characteristics. When only L. japonica was pyrolyzed, catalytic reforming slightly increased the gas yield and decreased the oil yield. The H₂O content in bio-oil was increased by catalytic reforming from 42.03 to 50.32 wt% due to the dehydration reaction occurring on the acid sites inside the large pores of Al-SBA-15. Acids, oxygenates, mono-aromatics, poly aromatic hydrocarbons, and phenolics were the main components of the bio-oil obtained from the pyrolysis of L. japonica. Upon catalytic reforming over Al-SBA-15, the main oxygenate species 1,4-anhydro-d-galactitol and 1,5-anhydro-d-manitol were completely removed. When L. japonica was co-pyrolyzed with polypropylene, the H₂O content in bio-oil was decreased dramatically (8.93 wt% in the case of catalytic co-pyrolysis), contributing to the improvement of the oil quality. A huge increase in the content of gasoline-range and diesel-range hydrocarbons in bio-oil was the most remarkable change that resulted from the co-pyrolysis with polypropylene, suggesting its potential as a transport fuel. The content of mono-aromatics with high economic value was also increased significantly by catalytic co-pyrolysis.     

Co-pyrolysis of soybean soapstock with iron slag/aluminum scrap,and characterization and analysis of their products

Soybean soapstock(SS) is one of the main solid wastes produced in the refinery of edible oil processing. In this study, the co-pyrolysis of SS with iron slag(IS) and aluminum scrap(AS) was carried out in a tubular furnace. The gas, liquid and solid products were characterized and the char yield decreased with increasing IS/AS ratio. IS and AS can improve the gas yield, and when the ratio of SS/IS was 1:0.25, the total pyrolysis gas and hydrogen contents were significantly increased. The content ...     

热解条件对西湾煤与秸秆流化床加压共热解的影响

在流化床加压热解装置中考察温度、压力、气氛和生物质掺混比等条件对西湾煤与秸秆共热解特性的影响,结果表明:在600℃,0.3 MPa,100%N₂气氛条件下,随着生物质掺混比增加,共热解油产率先增加后降低,实验值均大于计算值;当生物质掺混比为30%(质量分数)时,共热解油的实验值达到最大(16.90%),高于计算值(13.05%);热解压力由常压升至1.0 MPa时,受高氢分压作用下较多的氢分子参与自由基的加氢饱和作用,共热解油产率先增加后降低,在0.3 MPa时共热解油产率达到最大(17.90%);100%(体积分数,下同)N₂,100%CO₂和50%CO₂+50%H₂气氛下的共热解油产率分别为16.73%,16.55%和16.07%;与焦油相比,共热解油的密度变化不大,在元素中碳的质量分数由79.32%降低至71.80%,硫的质量分数由0.60%降低至0.31%,n(H)/n(C)增加;共热解油中脂肪烃、芳香烃和含氧化合物的质量分数降低,酚类组分的质量分数增加,三环及以上的多环产物裂解为小分子化合物,油品质量得到改善。