【摘要】：重油懸浮床加氫工藝具有產(chǎn)品質(zhì)量好和輕油收率高等顯著特點(diǎn),單程通過反應(yīng)中尾油收率過高會(huì)制約工藝的經(jīng)濟(jì)性,尾油循環(huán)反應(yīng)是在相對緩和條件下進(jìn)行,在保證裝置長周期運(yùn)轉(zhuǎn)同時(shí)有效降低尾油收率。然而,目前對懸浮床加氫裂化尾油循環(huán)工藝的研究還不夠系統(tǒng)深入,不能夠?yàn)樵摴に嚨耐茝V提供有效的指導(dǎo)和理論支持。本論文以委內(nèi)瑞拉常壓渣油為原料,在高壓釜中考察了工藝條件對重油懸浮床加氫裂化反應(yīng)的影響;在較緩和的反應(yīng)條件下進(jìn)行不同餾程尾油循環(huán)反應(yīng)可行性研究,并考察了反應(yīng)條件對尾油循環(huán)反應(yīng)的影響;采用~1H-NMR、FT-IR、XRD等手段研究了加氫尾油循環(huán)反應(yīng)過程中瀝青質(zhì)與甲苯不溶物的組成結(jié)構(gòu)變化規(guī)律。研究結(jié)果表明,委內(nèi)瑞拉常渣懸浮床加氫裂化反應(yīng)適宜的工藝條件為:反應(yīng)溫度435℃、反應(yīng)壓力12MPa、催化劑添加量150μg·g-1、鉬鎳金屬質(zhì)量配比3:2、硫化劑添加量300μg·g-1、助劑添加量200μg·g-1。采用大于500℃的尾油循環(huán),反應(yīng)過程中的生焦量持續(xù)增加,不適合循環(huán)反應(yīng)長周期操作;而采用大于400℃的尾油和大于350℃的尾油循環(huán)時(shí),在循環(huán)超過4次后,反應(yīng)過程中的瀝青質(zhì)含量與生焦量逐漸趨于恒定。在合適的循環(huán)尾油餾程和緩和的操作條件下,降低尾油外甩比例能提高反應(yīng)產(chǎn)物中輕質(zhì)餾分油的收率。通過循環(huán)反應(yīng)過程中瀝青質(zhì)與甲苯不溶物結(jié)構(gòu)組成的變化規(guī)律的研究,可知尾油循環(huán)反應(yīng)一定次數(shù)后,反應(yīng)生焦量和焦炭形態(tài)基本不變。瀝青質(zhì)分子發(fā)生加氫開環(huán)、烷基側(cè)鏈斷裂反應(yīng),在裂解了芳香片層外圍環(huán)結(jié)構(gòu)和烷基長側(cè)鏈后,以芳香環(huán)系連接短烷基側(cè)鏈的穩(wěn)定結(jié)構(gòu)形式存在,并未隨著循環(huán)反應(yīng)次數(shù)的增加而生成縮合度更高瀝青質(zhì)分子,從而有利于控制尾油循環(huán)過程中瀝青質(zhì)縮合生焦。
[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.
【學(xué)位授予單位】：中國石油大學(xué)(華東)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TE624

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