页岩油反应吸附脱除含氮化合物的研究  

Study on the Removal of Nitrogen-Containing Compounds by Reaction Adsorption of Shale Oil

作　　者：唐津莲 袁起民 李泽坤 龚剑洪 TANG Jinlian;YUAN Qimin;LI Zekun;GONG Jianhong(SINOPEC Research Institute of Petroleum Processing Co.,Ltd.,Beijing 100083,China)

机构地区：[1]中石化石油化工科学研究院有限公司,北京100083

出　　处：《石油学报(石油加工)》2025年第2期425-432,共8页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：“十四五”国家重点研发计划项目(2022YFB3805402)基金资助。

摘　　要：采用小型固定流化床装置,以稀土超稳Y分子筛为活性组分的吸附剂,对氮质量分数0.94%的抚顺页岩油在吸附温度360~500℃、吸附剂/页岩油质量比(简称剂/油质量比)0.68~5.24、质量空速3.5~22.5 h^(-1)条件下进行水蒸气流化非临氢吸附脱氮,考察吸附反应条件对页岩油脱除含氮化合物的影响。结果表明:总液体收率为95.33%~98.02%,吸附脱氮率14.13%~30.54%,脱碱氮率27%~40%,且随着吸附温度降低、剂/油质量比增加和质量空速减小,脱氮率提高;页岩油中碱性氮化物占总氮量的2/3,其碱性越强且吸附温度越低越容易脱除,脱除率由低到高依次为:吡啶<喹啉<吖啶<苯基吖啶<萘基吖啶;页岩油中非碱性含氮化合物主要是吡咯、吲哚和含NO的衍生物,仅在高温下发生侧链断裂反应,相对较难脱除。与水蒸气和N 2非临氢流化吸附相比,在H 2氛围下对页岩油临氢流化吸附的脱氮率和脱硫率更高,分别达到58.47%与39.25%;适宜反应条件为吸附温度450℃左右、压力不高于125 kPa。A case of Fushun shale oil with a nitrogen mass fraction of 0.94%is studied.Using the adsorbent with molecular sieve REUSY as active component,non-hydrogen adsorption denitrification of Fuhshun shale oil under water vapour fluidization was performed on a small fixed fluidized bed(FFB)under the conditions of adsorption temperature 360—500℃,adsorbent/shale oil mass ratio(adsorbent/oil mass ratio)0.68—5.24 and mass hourly space velocity(MHSV)3.5—22.5 h^(-1),aiming to investigate the effect of adsorption reaction conditions on the removal of nitrogen-containing compounds from shale oil.The results show that the total liquid yield,the adsorption denitrification rate and the alkaline nitrogen removal rate are within the range of 95.33%to 98.02%,14.13%to 30.54%,and 27%to 40%,respectively,and the nitrogen removal rate increases with the decreasing of adsorption temperature and MHSV,and the increasing of adsorbent/oil mass ratio.Alkaline nitrogen compounds in shale oil accounts for 2/3 of the total nitrogen;the stronger the alkalinity and the lower the adsorption temperature,the more easily the nitrogen compounds can be removed,with a removal rate ranking from low to high as follows:pyridine<quinoline<acridine<phenyl acridine<naphthalene acridine.The non-alkaline nitrogen compounds in the shale oil,mainly including pyrrole,indole and NO-containing derivatives,undergo side chain breakage reaction only at high temperature,which is relatively difficult to be removed.Compared with the adsorption of steam and N 2 by non-hydrofluidization reaction,the removal rates of nitrogen and sulphur from shale oil are higher when adsorbed by hydrofluidization reaction under H 2 atmosphere,reaching 58.47%and 39.25%,respectively.The suitable reaction conditions are an adsorption temperature of approximately 450℃and a pressure not exceeding 125 kPa.

关 键 词：页岩油 吸附剂 反应吸附 脱氮 碱性氮化物 脱硫 

分 类 号：TE624[石油与天然气工程—油气加工工程]