煤直接液化油加氢提质RCHU技术的工业应用

介绍中国石化石油化工科学研究院开发的煤直接液化油加氢提质RCHU技术在全球首套百万吨级煤直接液化油加氢提质装置的工业应用及标定情况。结果表明：装置石脑油产品硫质量分数低于0.5μg/g，芳烃潜含量达68%左右；柴油产品密度（20℃）为0.842~0.855 g/cm3，硫质量分数低于0.5μg/g，产品质量达到设计要求；催化剂经过两次再生，累计运行近9年后仍保持较好的反应性能，稳定性好，取得良好的应用效果。     

石脑油加氢精制催化剂LY-2010的工业应用

开发了一种石脑油加氢精制催化剂LY-2010,以中国石油兰州石化公司直馏石脑油为原料,在360mL绝热评价装置上对LY-2010与国内参比剂进行了对比评价。结果表明,在重整预加氢反应器入口温度较使用参比剂时低10℃的条件下,LY-2010催化剂的加氢性能依然略优于参比剂。LY-2010催化剂在中国石油辽阳石化公司1.4 Mt/a连续重整装置首次工业应用,一次开车成功,在入口温度274℃、反应压力2.2 MPa、体积空速5.0h-1的条件下,加氢石脑油产品硫、氮质量分数均小于0.5μg/g,完全满足重整装置进料指标的要求。     

加氢汽油博士试验不通过的原因及解决方案

催化裂化汽油加氢后,在硫质量分数降低到10g/μg以下的同时,其硫醇硫质量分数甚至降低到5g/μg以下,但仍会引起博士试验经常不通过的问题。以某炼油厂的日常博士试验检测数据为依据,分析了加氢汽油博士试验不通过的原因,并提出相应的解决方案。加氢汽油博士试验不通过的主要原因在于催化裂化汽油加氢后新生成了微量的大分子硫醇。解决方案为:在执行满足国Ⅴ、国Ⅵ排放标准要求的汽油时取消对汽油产品的博士试验检测;加大无硫汽油组分与加氢汽油组分的调合比例;对加氢汽油进行氧化脱臭等。     

Thermodynamic analysis of reaction pathways and equilibrium yields for catalytic pyrolysis of naphtha

The chain length and hydrocarbon type significantly affect the production of light olefins during the catalytic pyrolysis of naphtha. Herein, for a better catalyst design and operation parameters optimization, the reaction pathways and equilibrium yields for the catalytic pyrolysis of C_5–8 n/iso/cyclo-paraffins were analyzed thermodynamically. The results revealed that the thermodynamically favorable reaction pathways for n/iso-paraffins and cyclo-paraffins were the protolytic and hydrogen transfer cracking pathways, respectively. However, the formation of light paraffin severely limits the maximum selectivity toward light olefins. The dehydrogenation cracking pathway of n/iso-paraffins and the protolytic cracking pathway of cyclo-paraffins demonstrated significantly improved selectivity for light olefins. The results are thus useful as a direction for future catalyst improvements, facilitating superior reaction pathways to enhance light olefins. In addition, the equilibrium yield of light olefins increased with increasing the chain length, and the introduction of cyclo-paraffin inhibits the formation of light olefins. High temperatures and low pressures favor the formation of ethylene, and moderate temperatures and low pressures favor the formation of propylene. n-Hexane and cyclohexane mixtures gave maximum ethylene and propylene yield of approximately 49.90% and 55.77%, respectively. This work provides theoretical guidance for the development of superior catalysts and the selection of proper operation parameters for the catalytic pyrolysis of C_5–8 n/iso/cyclo-paraffins from a thermodynamic point of view.     

基于分子矩阵预测石脑油分子水平组成

针对石脑油的组成特点,对分子同系物(MTHS)矩阵进行简化,以C_3~C_(12)的正构烷烃、异构烷烃、环烷烃和芳烃构成的分子矩阵来表示石脑油的分子水平组成;建立了通过工业中常用的石脑油物性数据(如蒸馏曲线、密度)等计算石脑油分子水平组成的方法。以各项物理性质的实测值与预测值的残差平方和构建目标函数,并在原模型的基础上加以有效的约束,进行优化求解,得到石脑油分子水平组成数据。选择两组已知组成的石脑油作为样本,由Aspen Plus模拟软件计算其蒸馏曲线、密度等整体性质,根据上述方法对两组样本进行计算。两组样本的预测结果与真实组成的对比表明,该方法可用来预测石脑油分子水平组成,且准确度较原模型有提升。     

生产国V汽油的RSDS-III技术开发

The 3rd generation catalytic cracking naphtha selective hydrodesulfurization(RSDS-III) technology developed by RIPP included the catalysts selective adjusting(RSAT) technology, the development of new catalysts and optimized process conditions. The pilot plant test results showed that the RSDS-III technology could be adapted to different feedstocks. The sulfur content dropped from 600 μg/g and 631 μg/g to 7 μg/g and 9 μg/g, respectively, by RSDS-III technology when feed A and feed B were processed to meet China national V gasoline standard, with the RON loss of products equating to 0.9 units and 1.0 unit, respectively. While the feed C with a medium sulfur content was processed according to the full-range naphtha hydrotreating technology, the sulfur content dropped from 357 μg/g in the feed to 10 μg/g in gasoline, with the RON loss of product decreased by only 0.6 units. Thanks to the high HDS activity and good selectivity of RSDS-III technology, the ultra-low-sulfur gasoline meeting China V standard could be produced by the RSDS-III technology with little RON loss.     

独山子焦化汽油单独加氢试验评价研究

采用一种加氢催化剂,以中国石油独山子石化分公司(独山子石化)焦化汽油为原料,开展焦化汽油单独加氢生产乙烯裂解原料石脑油的可行性试验研究,通过对反应温度、体积空速、氢油比的考察,确定了适宜条件:单独加氢时,温度290~295℃,体积空速为2.0~2.5 h~(-1),氢油比300,压力2.5 MPa;稀释后焦化汽油单独加氢时,温度280℃,体积空速为2.0~2.5 h~(-1),氢油比300,压力2.5 MPa,产品性质均能达到石脑油质量要求。由于催化剂易结焦,装置稳定运行受限,因此,该催化剂不适合双烯值较高的焦化汽油单独加氢,独山子石化焦化汽油也不适合单独加氢,掺炼更为适合。     

应用BCM模拟软件对石脑油裂解炉进行价值优化

应用BCM模拟软件分析了SRT-Ⅳ(HS)型石脑油裂解炉的操作条件(炉管出口温度(COT)、进料量、稀释蒸汽与原料的质量比(稀释比))对裂解产物总价值的影响,同时研究了裂解产物价格波动对裂解产物总价值的影响。计算结果表明,石脑油裂解产物总价值分别随COT的升高和稀释比的增大出现局部极大值,并与进料量呈线性关系;当裂解产物价格发生变化时,裂解产物总价值及其达到最大时对应的COT也随之变化;当某一裂解产物的价格高于其他裂解产物价格两个数量级时,该裂解产物的收率与裂解产物总价值的变化规律相同。石脑油裂解炉的裂解产物总价值优化结果与裂解产物收率优化结果存在差异,应用BCM模拟软件对工业裂解炉实施价值优化,有利于提高工业裂解炉裂解产物的总价值。     

辽河油田石脑油中有机氯化物的形态鉴定及脱除

 采用GC-ECD气相色谱法对石脑油中的有机氯化物进行定性定量分析,并根据其形态结构选择适宜的吸附剂进行吸附脱氯,探索吸附剂吸附脱氯的适宜条件。结果表明,石脑油中的有机氯化物主要为氯仿、四氯化碳、四氯乙烷和二氯苯,其质量浓度分别为0.16、0.02、3.32和4.52 mg/L。制备的吸附剂N适用于石脑油吸附脱氯,其适宜的吸附条件为吸附温度40℃、吸附时间3 h、剂油质量比(m(Adsorbent)/m(Oil))为0.1。在此条件下石脑油中有机氯质量浓度从2.70 mg/L降至0.68 mg/L。吸附剂M对脱后石脑油进行再次吸附后,其氯质量浓度可以减少到0.47 mg/L,达到石脑油工业生产的要求。