两段提升管催化裂解-催化裂化柴油深度加氢回炼耦合工艺的过程集成与参数优化

加强环烷基重油深加工具有极其重要的工业和经济意义。以环烷基秦皇岛原油减压蜡油馏分（350~500 ℃）为原料,提出了两段提升管催化裂解与催化裂化柴油（LCO）深度加氢处理耦合的DHTMP新工艺。基于中试试验数据,对以生产低碳烯烃和轻质芳烃为目的产物的DHTMP工艺进行了模拟和优化,得到了优化的操作参数。采用优化的操作参数,即一段和二段提升管反应器出口温度分别为520 ℃和540 ℃,DHTMP工艺得到汽油和液化气产率之和超过83%。此外,DHTMP工艺的经济性良好,对于加工能力2.0 Mt/a装置,其财务净现值为2.16×10⁹元,内部收益率为21.57%。碳排放分析结果表明,创造每百万元生产总值,DHTMP工艺排放二氧化碳70.08 t。     

FCC干气在ZSM-5分子筛中吸附的分子模拟及热力学分析

应用巨正则蒙特卡罗（GCMC）模拟方法研究了干气中的氢气、氮气、甲烷、乙烷和乙烯5种主要组分在ZSM-5分子筛中的吸附行为,得到了0~1 000 kPa压力范围内,温度分别为298 K和823 K下的纯组分吸附时的吸附等温线和吸附质分布。结果表明：与其它组分相比,乙烯在ZSM-5中的吸附量最大,在298 K、10 kPa下饱和吸附量达到3.05 mol/kg;各组分优先吸附在分子筛的直线型孔道中。由热力学计算结果可知,吸附过程中各组分的ΔG0（标准吸附吉布斯自由能变）<0,ΔH0（标准吸附焓变）<0,且ΔS0（标准吸附熵变）<0,表明模拟条件下的吸附是一个自发、放热且有序度增加的过程,低温有利于吸附,并且乙烯在ZSM-5分子筛上最容易吸附。对混合气吸附性质计算的结果表明,组分之间存在竞争吸附,竞争能力受温度影响,并且乙烯吸附不再占优势。在总压500 kPa下,298 K和823 K时竞争吸附能力最强的组分分别是甲烷和乙烷,与乙烯的吸附量之比分别为1.5:1和2.3:1。     

减压渣油中氮化物的结构表征及其与焦化蜡油中氮化物的对比分析

In this study, the heteroatom classes and molecular structures of nitrogen compounds in vacuum residue arecharacterized by the electrospray ionization （ESI） Fourier transform ion cyclotron resonance mass spectrometry （FT-ICRMS） combined with the Fourier transform infrared （FT-IR） spectroscopy. The results demonstrate that three basic nitrogencompounds, N1 （in which a molecule contains one nitrogen atom, similarly hereinafter）, N1O1 and N2, are identified bytheir positive-ion mass spectra, and three non-basic nitrogen compounds, N1, N1O1, and N1S1, are characterized by theirnegative-ion mass spectra. Among these nitrogen compounds, the N1 class species are the most predominant. Combinedwith the data of ESI FT-ICR MS and FT-IR, the basic N1 class species are likely alkyl quinolines, naphthenic quinolines,acridines, benzonacridines, while the abundant non-basic N1 class species are derivatives of benzocarbazole. In comparisonwith CGO, the N1 basic nitrogen compounds in VR exhibit a higher average degree of condensation and have much longeralkyl side chains.     

催化裂化干气组分在沸石Y上吸附的分子模拟

Adsorption of catalytic cracking dry gas components, hydrogen (H2), nitrogen (N2), methane (CH4), ethane (C2H6) and ethylene (C2H4) in zeolite Y was studied by performing the Grant Canonical Monte Carlo (GCMC) simulations at 298 and 823K and a pressure range up to 10MPa. Simulation results were analyzed using Langmuir model and it presented fitting of dry gas components adsorption suggesting monolayer adsorption. C2H4 presented most single adsorption amount, which reached 7.63mol/kg at 298K under 200kPa. Thermodynamic parameters of Gibbs free energy change, enthalpy change and entropy change were analyzed based on adsorption equilibrium constant obtained from the GCMC simulations. The results suggested that it was more favorable for C2H4 to adsorb in zeolite Y. Adsorption molecules were in ordered arrangement in zeolite, and C2H4 exhibited more orderly arrangement than other components. Additionally, it was found that there was a competition between dry gas components for mixture adsorption, supercages were prior adsorption space. The competition was favorable to CH4 and C2H6, and competitive power was affected by temperature.     

我国典型中间基原油炼化一体化加工方案的技术经济分析与生命周期评价

炼化一体化（IRPUs）已成为石化工业可持续发展的必然选择。选择这样的配置可以提高石油资源的利用效率。然而，将经济和环境影响纳入IRPUs模型仍然是一个巨大的挑战。本文在Aspen HYSYSTM平台上建立了TEA-GHG-OPWM（面向全厂的技术经济分析和温室气体排放模型）模型，计算了减压渣油加氢裂化（VRHCRU）和减压渣油脱硫（VRDS-RFCC）两种方案的能耗、技术经济性和温室气体排放。此外，还开发了一种新的加工途径VGOHDT-HTMP-DC（减压蜡油加氢处理-加氢与TMP耦合工艺-延迟焦化），以期在千万元产值的基础上寻求提高经济效益和减少温室气体排放的方法。结果表明，VRHCRU比VRDS-RFCC（817.03 tCO2 eq·TMYOV-1·h-1）和VGOHDT-HTMP-DC（721.96 t CO2 eq·TMYOV-1·h-1）具有更高的能耗和温室气体排放量（877.11 t CO2 eq·TMYOV-1·h-1）。VGOHDT-HTMP-DC工艺的原料消耗、氢气消耗、能耗和温室气体排放最低，表明VGOHDT-HTMP-DC具有良好的经济性和环保性。     

受免疫原理启发的Web攻击检测方法

随着Internet应用的不断深入,Web服务器成为了黑客的主要攻击目标。为克服传统误用入侵检测系统无法识别未知Web攻击和异常入侵检测系统误报率高等缺陷,受生物免疫系统启发,该文提出了一种基于免疫原理的Web攻击检测方法。给出了自体、非自体、抗原、抗体基因库、免疫细胞等的数学定义,描述了免疫学习算法。对比实验结果表明该方法较传统的基于神经网络和ID3算法的Web攻击检测技术能有效检测未知Web攻击,具有检测率和分类率高、误报率低和实时高效等特点,是检测Web攻击的一种有效新途径。