轻质原油注空气低温氧化反应动力学研究

采用室内静态反应釜实验,研究了三种不同类型的原油静态氧化反应特性,通过阿雷尼厄斯方程的分析方法,并对该模型进行了改进。结果发现,随着油藏含水饱和度的上升,饱和度零阶反应速率的假设已不再适用,地层水的存在对反应动力学参数有较大影响,原油芳香烃含量大小对反应速率有较大影响。A、B、C三种油样的饱和度指数n分别为0.276 5,0.297 9,0.218 8,该数值可以综合反映原油中各组分含量对低温氧化反应效果的影响;并且C原油参与低温氧化反应的持续时间长,氧化耗氧效果好,惰性气体CO2的转化率也较高,适宜于进行注空气开发。     

轻质油品光催化氧化脱硫研究进展

近年来，光催化氧化已成为光化学领域和环保领域中的研究热点之一。综述了采用光催化氧化脱除轻质油品中含硫化合物的研究方法以及应用情况，提出了脱硫过程存在的问题，展望了光催化氧化脱硫的发展前景。     

轻质油品氧化脱硫技术进展

介绍了国内外轻质油品氧化脱硫技术的研究进展情况，分析了选择性氧化脱硫、超声波氧化脱硫、光催化氧化脱硫、等离子体液相氧化脱硫等技术的优缺点，展望了氧化脱硫技术应用前景。     

轻质燃料油的氧化脱硫研究

研究了H2O2以及促氧剂AC和TFAC对汽油中硫醇的氧化脱除效果。实验结果表明，H2O2可能有效的将汽油中硫醇氧化并且添加促氧剂能明显改善H2O2的作用效果。同时，工艺条件结果表明，较低反应温度，较短反应时间以及高剂油比对硫醇的氧化脱除反应有利。     

重质原油的腐蚀与防护

重质原油的腐蚀是炼油工业目前急需解决的重要实际问题。本文首先对原油中的腐蚀介质及其腐蚀类型进行了说明,概述了目前世界上采用的各种原油腐蚀表征手段和方法,尤其是电喷雾傅立叶变换离子回旋共振高分辨质谱技术(ESI-FTICR MS)的使用,可以从分子元素水平上表征石油组成。最后分析了原油腐蚀的基本机理,综述并对比了各种防腐措施和方法。     

两级臭氧深度催化氧化高酸重质原油废水的研究

针对高酸重质原油废水的特点,提出了两级臭氧深度催化氧化的处理工艺.采用自主研发的催化剂和设计的试验装置对某炼油企业高酸重质原油废水的MBR出水进行了处理,并对影响因素进行了研究.结果表明,在最佳运行条件下,经该工艺处理后的出水COD和氨氮均达到《城市污水再生利用工业用水水质》(GB/T 19923-2005)中的敞开式...     

重质原油电脱盐污水深度处理中试研究

重质原油电脱盐污水生化性差、油含量高,采用双膜法对其进行深度处理时对预处理工艺要求高,同时膜过滤产生的浓水的处理也是后续处理的一大难题.中试采用自主研发的催化氧化工艺对浓水进行处理试验.结果表明:活性炭过滤+纤维束过滤或臭氧催化氧化预处理工艺均满足膜对污染物的控制要求;双膜系统运行稳定,浓水处理后达到国家一级排放标准,...     

苯甲醚和苯乙醚氧化特性及其产物

设计了跟踪测定苯甲醚、苯乙醚与氧气加热氧化反应过程的小型压力容器试验装置(MCPVT),得到了它们的压力-时间、温度-时间的变化规律。用碘量法测定了两种醚氧化过程中过氧化物的生成,采用气相色谱-质谱联用仪(GC-MS)分析了氧化产物。结果表明,苯甲醚、苯乙醚在195℃时会发生明显的放热氧化反应。两种醚生成过氧化物最高浓度时的温度均为160℃。苯甲醚在反应温度≤200℃时,氧化产物为甲酸苯酯、邻甲氧基苯酚;反应温度≥210℃时,氧化产物变得复杂,主要有酚、醇、醛、酸和酯等。苯乙醚在反应温度≤150℃,氧化产物为乙醛、苯酚、乙酸苯酯、邻乙氧基苯酚;反应温度≥160℃时,氧化产物有二十多种,主要有乙醛、乙酸、苯酚、乙酸苯酯、邻乙氧基苯酚等。     

苯甲醚和苯乙醚氧化特性及其产物

设计了跟踪测定苯甲醚、苯乙醚与氧气加热氧化反应过程的小型压力容器试验装置(MCPVT),得到了它们的压力-时间、温度-时间的变化规律。用碘量法测定了两种醚氧化过程中过氧化物的生成,采用气相色谱-质谱联用仪(GC-MS)分析了氧化产物。结果表明,苯甲醚、苯乙醚在195℃时会发生明显的放热氧化反应。两种醚生成过氧化物最高浓度时的温度均为160℃。苯甲醚在反应温度≤200℃时,氧化产物为甲酸苯酯、邻甲氧基苯酚;反应温度≥210℃时,氧化产物变得复杂,主要有酚、醇、醛、酸和酯等。苯乙醚在反应温度≤150℃,氧化产物为乙醛、苯酚、乙酸苯酯、邻乙氧基苯酚;反应温度≥160℃时,氧化产物有二十多种,主要有乙醛、乙酸、苯酚、乙酸苯酯、邻乙氧基苯酚等。     

重质原油电脱盐污水深度处理新工艺应用

重质原油电脱盐污水由于具有生化性差、油含量高、来水COD波动大等特点,对其有效回收利用一直以来是业内的一个难题。传统处理工艺一般是经过除油、浮选、生化处理后直接排放。浙江某炼厂将原本直接排放的生产废水进一步进行双膜预处理及臭氧催化氧化深度处理,在有效回收水资源的同时,实现减排COD的目标。     

Phase behavior analysis of heavy oil containing asphaltene

A thermodynamic asphaltene precipitation model was developed based on the model of Nghiem et al. using the Peng-Robinson equation of state (PR EOS). This model calculates the amount of asphaltene precipitation based on changes in temperature and pressure. The effects of asphaltene precipitation on rock properties were investigated by observing changes in porosity and permeability. In this model, phase equilibrium was achieved by repeatedly reducing the amount of the asphaltene component, in contrast to the model of Qin et al. using the secant method. The results of this model were compared with experimental data of measured precipitation, based on changes in pressure, and agreed more closely than the model of Qin et al. Our results also confirmed that the maximum precipitation of asphaltene occurred at the bubble-point pressure. Thus, using the model, we verified that the precipitation pattern of asphaltene depended on temperature and pressure, and it is expected that changing patterns in reservoir productivity can be analyzed using asphaltene precipitation in heavy oil-containing asphaltene.     

地层原油及其族组分的氧化反应特性研究

为了考察油藏注空气过程中地层原油的氧化反应规律,采用柱层析方法将地层原油组分分离为饱和烃、芳香烃、胶质和沥青质。采用热重和差示扫描量热仪,研究了原油和其不同族组分的氧化反应特性。结果表明,中原油田该区块原油差示扫描量热曲线第一放热区间峰值热流高于第二放热区间峰值热流,饱和烃和芳香烃的第一放热区间的峰值高于第二放热区间峰值,胶质和沥青质的第二放热区间峰值高于第一放热区间峰值,原油中饱和烃和芳香烃的含量较高时,有利于轻质油藏注空气过程中原油自燃现象的发生。原油的族组成对原油的氧化特性有决定性影响。     

稠油低温氧化动力学实验与模型研究

注空气辅助蒸汽吞吐/蒸汽驱是稠油开发的一新工艺。针对典型稠油油样,进行了稠油-空气的低温氧化(LTO)动力学实验,研究了温度(100～150℃)和压力(8～17 MPa)对稠油-空气氧化特性的影响。基于Arrhenius方程,确定了反应的活化能、频率因子,并给出了反应焓,建立了稠油-空气低温氧化的动力学模型,为稠油油藏注空气数值模拟提供了理论基础。低温氧化实验结果表明,稠油具有很好的低温氧化活性,氧化反应速率与温度、氧气分压、原油的性质有关。在实验的温度范围内,氧化反应能有效消耗氧气,产生大量CO2。     

Demetallization of heavy oil through pyrolysis: A reaction kinetics analysis

By tracking the transfer of vanadium and nickel in pyrolysis products, a seven-lump reaction kinetic model for pyrolysis-based demetallization of heavy oil was established. During pyrolysis, the demetallization of heavy oil is achieved by condensing metal-rich resins and asphaltenes to coke. The condensation of oil components originally contained in heavy oil differs greatly in reaction behavior, having the activation energy between 167 and 361 kJ/mol. As the pyrolysis progresses, the newly formed heavy components show a condensation behavior close to that of the light components. Limited by high activation energy and low initial fraction, the condensation of asphaltenes to coke and the resulting removal of metals contained in asphaltenes are hindered. Meanwhile, the condensation of light components has a major contribution to coke formation. An increase in reaction temperature accelerates the demetallization, but hardly changes the yield and component distribution of liquid products at the same metal removal rate.     

Coking behavior and catalyst deactivation for catalytic pyrolysis of heavy oil

For the catalytic pyrolysis of heavy oil on catalyst CEP-1, coking behavior was investigated in a confined fluidized bed reactor. Coke content on the spent catalyst decreases with the increase of H/C mol ratio of feeds and catalyst-to-oil weight ratio, while it increases with the enhancement of reaction temperature. An empirical model is proposed to predict the coke content based on feed properties and operating conditions. The predicted coke content is close to the experimental data. The relationship between micro-activity index of catalysts and coke content is studied. A coking deactivation model for pyrolyzing catalysts is established, and then model parameters are determined by the least square regression analysis. According to the deactivation model, the variations of relative activity of catalysts with both residence time of catalysts and catalyst-to-oil weight ratio are predicted.     

Interfacial tension behavior and ESR properties of asphaltenes derived from heavy oil

Asphaltenes extracted from Lloydminster heavy oil (from Saskatchewan, Canada) were separated by sequential elution solvent chromatography (SESC) using ten different organic solvents. The fractions so obtained were dissolved in toluene and then examined for their interfacial tension (IFT) behavior against 0.1 wt.% sodium hydroxide solution. It was found that only about 40% (by weight) of the original asphaltenes contained species which were capable of lowering IFT against the alkaline solution. Multi-functional phenolic and other polar compounds were considered to be the components most likely responsible for the observed interfacial activity. Electron spin resonance measurements showed that the individual fractions contained varying concentrations of free radicals and VO²⁺ ions. However, no direct correlation between the content of either of these two species and the interfacial tension could be detected.     

Kinetic modeling of the hydrotreatment of light cycle oil and heavy gas oil using the structural contributions approach

The kinetics of the hydrodesulfurization of light cycle oil (LCO) and heavy gas oil (HGO) over a CoMo/Al₂O₃ catalyst were investigated in a perfectly mixed flow reactor with stationary basket of the Robinson-Mahoney type at temperatures of 330, 310 and 290 °C, H₂/HC molar ratios of 2.8, 3.6 and 7.2 and a pressure of 65 bar. Hougen-Watson type rate equations were derived for the conversion of dibenzothiophene, substituted (di)benzothiophene and their products. To avoid having to deal with a huge number of model parameters, a methodology based upon structural contributions was applied. In the absence of own kinetic data on key components a number of kinetic and adsorption parameters were taken from published work on a very similar catalyst. For a given value of H₂/HC only a small number of experiments was required to determine the value of the very complex denominators DEN_σ and DEN_τ appearing in the rate equations for the hydrodesulfurization of LCO and of HGO and of their evolution with the conversion of the feedstock. With the rate equations constructed in this way the calculated total conversion of DBT, its conversion into biphenyl and into cyclohexylbenzene were in excellent agreement with the experimental values.     

重油生产低碳烯烃等化工品技术研究进展

当前国内炼油产能过剩,化工品如低碳烯烃及苯-甲苯-二甲苯混合物（BTX）等存在缺口,因此应推动炼油向石化的生产转变,化解过剩产能同时提高化工品供给。我国原油馏分偏重且原油重质化劣质化趋势不可逆转,因此利用重油生产低碳烯烃等化工品成为技术关键。本文介绍了重油生产低碳烯烃的催化裂解单项技术典型工艺,包括重油深度催化裂解（DCC）、催化热裂解（CPP）及重油裂解制烯烃（HCC）工艺,认为催化裂解技术的发展在于催化剂的改性与反应器型式的革新优化,下行床反应器前景更为广阔。同时,本文也介绍了从重油或原油通过加氢裂化联合催化裂解、蒸汽裂解及芳烃装置一体化生产化工品的几种国内外工艺技术及工程项目。在单项技术无法取得明显突破之前,炼化一体化生产化工品具有集约化、高效化、灵活性高及经济效益好等优势。一体化技术的重点在于重油（渣油）的深度转化,可通过渣油的加氢裂化工艺来实现。     

金属盐和油层矿物存在下的稠油水热裂解反应动力学

根据金属盐和油层矿物存在下的稠油水热裂解反应实验结果,建立包括气体、饱和烃、芳香烃、胶质和沥青质在内的五集总动力学模型,并求取模型中的反应速率常数和活化能.计算结果表明,胶质作为主要反应中心,是气体、芳香烃和饱和烃等轻组分含量增长的主要来源.沥青质主要转化成胶质,裂化产物较少.实验数据与计算结果较吻合,所提出的五集总动力学模型可用来描述金属盐和油层矿物存在下的稠油水热裂解反应规律.