委内瑞拉重油悬浮床加氢裂化尾油循环工艺研究
发布时间：2018-07-22 10:36
【摘要】：重油悬浮床加氢工艺具有产品质量好和轻油收率高等显著特点,单程通过反应中尾油收率过高会制约工艺的经济性,尾油循环反应是在相对缓和条件下进行,在保证装置长周期运转同时有效降低尾油收率。然而,目前对悬浮床加氢裂化尾油循环工艺的研究还不够系统深入,不能够为该工艺的推广提供有效的指导和理论支持。本论文以委内瑞拉常压渣油为原料,在高压釜中考察了工艺条件对重油悬浮床加氢裂化反应的影响;在较缓和的反应条件下进行不同馏程尾油循环反应可行性研究,并考察了反应条件对尾油循环反应的影响;采用~1H-NMR、FT-IR、XRD等手段研究了加氢尾油循环反应过程中沥青质与甲苯不溶物的组成结构变化规律。研究结果表明,委内瑞拉常渣悬浮床加氢裂化反应适宜的工艺条件为:反应温度435℃、反应压力12MPa、催化剂添加量150μg·g-1、钼镍金属质量配比3:2、硫化剂添加量300μg·g-1、助剂添加量200μg·g-1。采用大于500℃的尾油循环,反应过程中的生焦量持续增加,不适合循环反应长周期操作;而采用大于400℃的尾油和大于350℃的尾油循环时,在循环超过4次后,反应过程中的沥青质含量与生焦量逐渐趋于恒定。在合适的循环尾油馏程和缓和的操作条件下,降低尾油外甩比例能提高反应产物中轻质馏分油的收率。通过循环反应过程中沥青质与甲苯不溶物结构组成的变化规律的研究,可知尾油循环反应一定次数后,反应生焦量和焦炭形态基本不变。沥青质分子发生加氢开环、烷基侧链断裂反应,在裂解了芳香片层外围环结构和烷基长侧链后,以芳香环系连接短烷基侧链的稳定结构形式存在,并未随着循环反应次数的增加而生成缩合度更高沥青质分子,从而有利于控制尾油循环过程中沥青质缩合生焦。
[Abstract]:The process of heavy oil suspension bed hydrogenation is characterized by good quality of product and high yield of light oil. High yield of tail oil in one way through reaction will restrict the economy of process. The reaction of tail oil cycle is carried out under relatively mild conditions, which can ensure the long cycle operation of the device and reduce the yield of tail oil effectively. However, the hydrocracking of the suspension bed is currently used. The study on the process of tail oil circulation is not enough to provide effective guidance and theoretical support for the promotion of the process. In this paper, the effect of process conditions on the hydrocracking reaction of heavy oil suspension bed was investigated in a autoclave of Venezuela, and the different distillation range tail oil was carried out under the mild reaction conditions. The feasibility study of cyclic reaction and the effect of reaction conditions on the reaction of tail oil cycle were investigated. The composition and structure of asphaltenes and toluene insoluble compounds in the hydrogenation tail oil cycle were studied by means of ~1H-NMR, FT-IR and XRD. The results showed that the suitable technological conditions for the hydrocracking reaction of the suspended bed of Venezuela were shown. The reaction temperature is 435, the reaction pressure is 12MPa, the amount of catalyst is 150 mu g. G-1, the mass ratio of molybdenum and nickel metal is 3:2, the dosage of vulcanizing agent is 300 mu g. G-1, the additive amount is 200 mu g. G-1., the tail oil is more than 500 centigrade, the coking amount in the reaction process is continuously increased, and the long cycle operation is not suitable for the cycle reaction; and the tail oil is more than 400 centigrade. The asphaltene content and the coke content in the reaction process gradually tend to be constant when the tail oil cycle is over 350 degrees centigrade, and the amount of asphaltene and coke in the reaction process gradually tend to be constant. The reduction of the proportion of the tail oil to the light fraction in the reaction products can increase the yield of the light distillate oil in the reaction products. The study of the change law of the structure composition of insoluble compounds shows that the reaction coke rate and the coke form are basically unchanged after the reaction of the tail oil cycle for a certain number of times. The asphaltene molecule occurs hydrogenation ring, alkyl side chain fracture reaction, after splitting the outer ring structure and the long side chain of the aromatic lamellar, the stable junction of the short alkyl side chain is connected with the aromatic ring. The existence of the structure does not produce a higher condensation degree of asphaltene molecules with the increase of the number of cyclic reactions, which is beneficial to the control of the coking of asphaltene condensation during the cycle of the tail oil.
【学位授予单位】：中国石油大学(华东)
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TE624
本文编号：2137161
[Abstract]:The process of heavy oil suspension bed hydrogenation is characterized by good quality of product and high yield of light oil. High yield of tail oil in one way through reaction will restrict the economy of process. The reaction of tail oil cycle is carried out under relatively mild conditions, which can ensure the long cycle operation of the device and reduce the yield of tail oil effectively. However, the hydrocracking of the suspension bed is currently used. The study on the process of tail oil circulation is not enough to provide effective guidance and theoretical support for the promotion of the process. In this paper, the effect of process conditions on the hydrocracking reaction of heavy oil suspension bed was investigated in a autoclave of Venezuela, and the different distillation range tail oil was carried out under the mild reaction conditions. The feasibility study of cyclic reaction and the effect of reaction conditions on the reaction of tail oil cycle were investigated. The composition and structure of asphaltenes and toluene insoluble compounds in the hydrogenation tail oil cycle were studied by means of ~1H-NMR, FT-IR and XRD. The results showed that the suitable technological conditions for the hydrocracking reaction of the suspended bed of Venezuela were shown. The reaction temperature is 435, the reaction pressure is 12MPa, the amount of catalyst is 150 mu g. G-1, the mass ratio of molybdenum and nickel metal is 3:2, the dosage of vulcanizing agent is 300 mu g. G-1, the additive amount is 200 mu g. G-1., the tail oil is more than 500 centigrade, the coking amount in the reaction process is continuously increased, and the long cycle operation is not suitable for the cycle reaction; and the tail oil is more than 400 centigrade. The asphaltene content and the coke content in the reaction process gradually tend to be constant when the tail oil cycle is over 350 degrees centigrade, and the amount of asphaltene and coke in the reaction process gradually tend to be constant. The reduction of the proportion of the tail oil to the light fraction in the reaction products can increase the yield of the light distillate oil in the reaction products. The study of the change law of the structure composition of insoluble compounds shows that the reaction coke rate and the coke form are basically unchanged after the reaction of the tail oil cycle for a certain number of times. The asphaltene molecule occurs hydrogenation ring, alkyl side chain fracture reaction, after splitting the outer ring structure and the long side chain of the aromatic lamellar, the stable junction of the short alkyl side chain is connected with the aromatic ring. The existence of the structure does not produce a higher condensation degree of asphaltene molecules with the increase of the number of cyclic reactions, which is beneficial to the control of the coking of asphaltene condensation during the cycle of the tail oil.
【学位授予单位】：中国石油大学(华东)
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TE624
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