溶剂萃取法分离沙特中质原油VGO及其硫分布规律

以不同水含量的糠醛和N-甲基吡咯烷酮作萃取溶剂,沙中原油减压馏分油经3段萃取被分离为重芳烃相、中芳烃相、轻芳烃相和饱和烃相4个亚组分,采用气相色谱-质谱联用、傅里叶变换离子回旋共振质谱等方法分析了亚组分中烃类组成和硫化物的分布,考察了萃取分离过程各烃类的分离效率和芳烃萃取选择性。结果表明,3段萃取分离出的重芳烃相、中芳烃相和轻芳烃相中芳烃质量分数分别在89.6%~95.6%、80.8%~91.0%和63.9%~77.7%,表明糠醛和NMP是适于分离减压馏分油中芳烃的溶剂;芳烃环数增加,分子极性提高,溶剂对其溶解能力增强,极性较强的三环及以上芳烃主要存在于重芳烃相和中芳烃相;不同水含量的糠醛和NMP对芳烃,尤其是对三环及以上芳烃的分离效率高于饱和烃;水含量增加,溶剂的萃取分离效率降低,但对芳烃的萃取选择性β值提高;NMP对芳烃的萃取选择性高于糠醛。三环及以上噻吩类硫化物主要存在于重芳烃相和中芳烃相中,单、双环噻吩类硫化物基本均匀分布于各亚组分中。     

苯与重芳烃烷基转移BHAT-01催化剂的工业应用

介绍了新型BHAT-01催化剂在中国石油辽阳石化分公司芳烃联合装置甲苯歧化单元的工业应用情况。工业应用结果表明,该催化剂能以苯和重芳烃为原料生产甲苯和C_8芳烃,具有原料转化率高、甲苯及C_8芳烃收率高的特点,其标定结果为:在反应温度360℃、高压气液分离器压力2.7 MPa、重时空速1.8 h~(-1)、氢油摩尔比7.5的条件下,苯平均转化率为35.99%,重芳烃平均转化率为74.26%,甲苯和C_8芳烃的平均总收率为96.34%;该催化剂也能按照目前工业上的甲苯歧化与烷基转移工艺进行生产,其标定结果为:在反应温度355℃、高压气液分离器压力2.7 MPa、重时空速2.0h~(-1)、氢油摩尔比5.7的条件下,甲苯和重芳烃的平均转化率为47.22%,苯和C_8芳烃的平均总收率为94.98%,其性能优于现有工业催化剂。     

甲苯歧化制取苯和二甲苯

(一)前言在石油馏份重整和热裂化过程中,可以得到大量苯、甲苯、二甲苯和 C_9等芳烃原料,其中苯和二甲苯现在已是化学工业的基础原料,而大量甲苯和 C_9芳烃尚未得到充分利用。根据不同沸程石油馏分和加工方法,甲苯和 C_9芳烃的含量,一般占芳烃总重量的40—     

苯对甲苯歧化与烷基转移反应的影响

研究了原料中苯含量对甲苯歧化与烷基转移反应的影响。随着原料中苯含量的增加 ,甲苯歧化反应受到明显抑制 ,同时发生苯和C9芳烃之间的烷基转移反应 ,C9芳烃转化率和C8芳烃选择性明显升高 ,有利于歧化装置多产C8芳烃。     

甲苯歧化与三甲苯烷基转移反应体系的化学平衡

对甲苯歧化与三甲苯烷基转移反应体系中反应的化学平衡常数进行了详细计算,并对不同温度、不同进料组成下的平衡组成进行了分析。结果表明,随温度升高,甲苯与三甲苯的芳烃平衡转化率降低,二甲苯的平衡组成亦降低;降低进料中甲苯和三甲苯的摩尔比,甲苯和三甲苯的总芳烃平衡转化率降低,而二甲苯的平衡组成明显上升。比较了β沸石催化剂上此体系在不同空速和温度下的化学反应产物组成与平衡组成,升高温度有利于缩小化学反应与平衡的差距。     

苯/甲苯与甲醇/合成气在ZSM-5体系下烷基化对比

为调配BTX芳烃比例,进行了苯/甲苯的转化率以及各产物选择性的研究,对比了苯与甲醇/合成气、甲苯与甲醇三类反应。当对比合成气/甲醇作为甲基化试剂与苯反应时,苯的转化率分别为36.81%/39.98%,生成各芳烃选择性相差不大,但合成气生成水的选择性远高于甲醇;此外与合成气相比,甲醇的转化率更高。当甲醇作为甲基化试剂与苯/甲苯反应时,在与芳烃、甲醇、氢气相关的性能指标相差不大,说明甲醇作为甲基化试剂对苯/甲苯的反应性能大致相同。本文为以后甲基化试剂的选择提供了依据。     

芳烃抽提装置甲苯收率低原因分析

针对中国石油天然气股份有限公司独山子石化分公司0.6 Mt/a芳烃抽提装置甲苯收率低的情况,定性与定量分析了甲苯产品中非芳烃组分。分析表明甲苯产品中含有3种C8环烷烃共沸物影响其纯度,这3种C8环烷烃分别为反1-甲基-2-乙基环戊烷、反1,2-二甲基环己烷和反1,3-二甲基环己烷,这3种非芳烃与甲苯共沸使甲苯塔顶甲苯纯度与收率难以兼得。分析了该装置2013年和2015年两次标定及生产跟踪数据,包括苯、甲苯损失最小时的条件分析、类两苯抽提数据分析、抽提油中非芳烃对甲苯质量收率的影响。结果表明,装置在类两苯抽提时能有效解决三苯抽提中存在的产品质量与收率不达标问题,要解决甲苯收率偏低的问题需在优化抽提进料组成及提升抽提塔抽提效果。     

甲苯的利用

<正> 一、前言在不同来源的芳烃原料中,都含有一定数量的甲苯。在重整法生产的芳烃原料中,甲苯含量高于苯,在煤液化法或煤气化气合成的芳烃原料中甲苯产率更高。在今后数年内,甲苯生产能力将随着苯产量的增长而相应增长,很可能接近苯的水平(例如美国从1978年到1985年,甲苯产量将增长15％,产量约1.5百万加仑)。自从1939年临氢重整法用于工业生产取得     

上海石化院开发甲苯岐化和烷基转移催化剂已用于九套装置

上海石化研究院完成的“甲苯与重质芳烃歧化与烷基转移成套技术及催化剂”，已成功应用于齐鲁石化、扬子石化等9套芳烃装置，其芳烃处理量占国内总处理量的90％。     

甲苯选择性歧化与传统歧化组合工艺研究

针对甲苯选择性歧化工艺能生产含高浓度对二甲苯的混合二甲苯、但不能处理C9A的特点 ,提出在芳烃联合装置中将甲苯选择性歧化和传统歧化组合在一起的组合工艺。以PRO/Ⅱ流程模拟软件为工具 ,研究了甲苯 /C9芳烃在两个歧化单元中的质量比对产品产量和装置处理规模的影响。研究表明 ,随分配到选择性单元甲苯量的增加 ,芳烃联合装置对二甲苯的产量下降 ,苯产量增加 ,各单元处理规模下降 ;该组合工艺是芳烃联合装置扩能改造的较好方法     

石脑油脱芳烃-FCC汽油耦联脱硫的实验研究

根据酸-碱相互作用理论,对石脑油脱芳烃-FCC汽油耦联脱硫工艺进行实验研究。在无水AlCl3与石脑油质量比为0.06、反应温度为70 ℃、反应时间为60 min、络合脱芳烃助剂L与石脑油质量比为0.011的条件下,石脑油的芳烃质量分数可以从8.15%降至0.46%,脱芳烃率为94.36%。将石脑油络合脱芳烃生成的芳烃络合物MTS-1作为FCC汽油的络合脱硫剂,在反应温度为35 ℃、反应时间为3 min、剂油质量比为0.05的条件下,FCC汽油中的硫化物与络合物中的芳烃发生络合置换,脱硫率为72.24%,汽油质量收率为99.81%,汽油硫质量分数从526 μg/g降至146 μg/g,达到国Ⅲ排放标准对车用汽油硫含量的要求。     

The Improvement of the Quality of Raffinate Obtained from Solvent Extraction of Lubricating Oils

Abstract

Vacuum distillates of an Egyptian crude oil were subjected to solvent extraction process applying N-methyl-2-pyrrolidone (NMP) and furfural as dearomatization solvents. The study shows that the extraction solvent together with the temperature and solvent-to-oil ratio have a significant effect on the yield and quality of produced lubricating oils. The optimum temperature for extracting light waxy distillates with NMP is 55°C at the solvent-to-feed ratio 2:1. These conditions are appropriate to remove the major portion of aromatics from the raffinate. The apparent activation energy (Ea), enthalpy (ΔH*), entropy (ΔS*), and free energy of activation (ΔG*) were calculated for the solvent dearomatization process.     

TWO-DIMENSIONAL SOLUBILITY PARAMETER MAPPING OF HEAVY OILS

ABSTRACT

The solubility and insolubility of heavy oils and their fractions in dilute mixtures with various solvents were used to characterize heavy oil interactions. A two-dimensional solubility parameter, developed for the selection of solvents for organic polymers, was found to group all the solvents for each heavy oil fraction in polygon areas when the complexing solubility parameter component was plotted against the field force solubility parameter component. All fractions of Cold Lake vacuum residua, except for the saturate fraction, form concentric solubility areas. Therefore, in going in the direction of decreasing aromaticity from coke to asphaltenes to resins to aromatics, all solvents for the previous fraction in the series are also solvents for all subsequent fractions in the series. As a result, asphaltenes can be precipitated, but not extracted, from heavy oils. This is attributed to the interaction among polynuclear aromatics being the dominate interaction in petroleum that causes insolubility in hydrocarbon liquids. However, the paraffinic chains on the same petroleum molecules limit their solubility in highly complexing liquids. In contrast, even vacuum gas oils from the Exxon Donor Solvent coal liquefaction process are insoluble in aromatic liquids but soluble in moderately complexing liquids because of hydrogen bonding, resulting from oxygen functionality. Hydrotreating of these coal derived vacuum. gas oils reduces their oxygen functionality and increases their solubility areas so that they become compatible with petroleum liquids.     

TWO-DIMENSIONAL SOLUBILITY PARAMETER MAPPING OF HEAVY OILS

The solubility and insolubility of heavy oils and their fractions in dilute mixtures with various solvents were used to characterize heavy oil interactions. A two-dimensional solubility parameter, developed for the selection of solvents for organic polymers, was found to group all the solvents for each heavy oil fraction in polygon areas when the complexing solubility parameter component was plotted against the field force solubility parameter component. All fractions of Cold Lake vacuum residua, except for the saturate fraction, form concentric solubility areas. Therefore, in going in the direction of decreasing aromaticity from coke to asphaltenes to resins to aromatics, all solvents for the previous fraction in the series are also solvents for all subsequent fractions in the series. As a result, asphaltenes can be precipitated, but not extracted, from heavy oils. This is attributed to the interaction among polynuclear aromatics being the dominate interaction in petroleum that causes insolubility in hydrocarbon liquids. However, the paraffinic chains on the same petroleum molecules limit their solubility in highly complexing liquids. In contrast, even vacuum gas oils from the Exxon Donor Solvent coal liquefaction process are insoluble in aromatic liquids but soluble in moderately complexing liquids because of hydrogen bonding, resulting from oxygen functionality. Hydrotreating of these coal derived vacuum. gas oils reduces their oxygen functionality and increases their solubility areas so that they become compatible with petroleum liquids.     

催化裂化轻循环油萃取脱芳烃的溶剂选择

通过分析催化裂化轻循环油（LCO）中烃类的组成筛选合适的模型化合物,考察了溶剂对LCO中芳烃组分的萃取分离效果,探讨了溶剂萃取性能与溶剂物性参数之间的关系。结果表明: 溶剂对芳烃的选择性系数从大到小的顺序为环丁砜＞二甲亚砜＞糠醛＞N,N-二甲基甲酰胺（DMF）＞N-甲基吡咯烷酮＞N,N-二甲基乙酰胺;溶剂的偶极矩和介电常数与LCO中烃类的这两个参数要有足够大的差异才能有效分离LCO中的芳烃;溶剂对芳烃的选择性系数可与其溶解度参数进行关联,对于与芳烃色散力参数δD相近的溶剂,其极性力δP越大,对芳烃的选择性系数越大;在40 ℃、剂油质量比1:1的条件下,DMF单次萃取LCO得到的抽出油中芳烃质量分数仅为87.2%,而环丁砜单次萃取时为97.3%;通过向DMF中引入助溶剂提高δP,在相同条件下萃取得到的抽出油中芳烃质量分数可达96.5%,抽出油收率为29.9%,萃取性能优于单一溶剂。     

溶剂效应对络合反应法脱除模拟柴油中氮化物的影响

考察溶剂对络合反应法脱除石油中氮化物效果的影响。选择一系列具有代表性的金属盐络合剂与模型化合物进行络合反应,结合气相色谱-质谱（GC-MS）分析结果,研究不同金属盐在不同反应溶剂中对氮化物的络合脱除效果。结果表明:溶剂效应会显著影响部分盐络合反应脱除氮化物的效果,乙醇有利于金属盐的溶解和金属离子的解离,因此Fe2(SO4)3,ZnSO4,CuSO4,NiSO4,PdCl2在乙醇体系中能较好地络合脱除碱性氮化物;甲苯和乙醇能促进CuCl2金属离子解离,使得CuCl2在甲苯和乙醇中比在二氯甲烷中络合脱除碱性氮化物的效果好;溶剂效应对ZnCl2络合脱除碱性氮化物效果的影响不显著;FeCl3在乙醇体系中络合脱除碱性氮化物时伴随有显著的副反应,副产物有氯代芳烃和聚合物。     

Clarified Oil from Fluid Catalytic Cracking as an Additional Source of Group II Base Oil Components

Abstract

Clarified oil (CLO) from a commercial fluid catalytic cracking unit was subjected to solvent extraction followed by solvent dewaxing and adsorption chromatography to analyze its various components for different end-use applications. The clarified oil was first solvent extracted using N-methyl pyrrolidone (NMP) to produce paraffinic rich raffinate (68.9 wt% yield). The raffinate thus obtained was dewaxed using methyl isobutyl ketone (MIBK) to get an oil of pour point 0°C. This dewaxed oil was then subjected to adsorption chromatography to determine group II base oil potential through yield v/s viscosity index (VI) curve. The results revealed that clarified oil has an actual potential of around 27.1 wt% of group II base oil components, suggesting that clarified oil can be used as an additional source of feed for production of group II base oil. This article also describes the potential of other components in clarified oil such as slack wax (24.2 wt%), aromatics (31.1 wt%), and low VI oil (17.6 wt%).     

焦化蜡油预处理及综合利用的技术措施

焦化蜡油是延迟焦化工艺过程中产生的一种产品,由于其碱性氮化物、稠环芳烃、胶质含量高,使其加工利用受到限制,需要进行预处理。介绍了焦化蜡油的性质,综述了焦化蜡油预处理及综合利用的技术措施,包括加氢精制、溶剂精制、络合脱氮、氧化处理等预处理方法,经过预处理可作为催化裂化或加氢裂化原料,经溶剂抽提可回收芳烃等,对焦化蜡油的综合利用前景进行了展望。     

芳烃联合装置生产技术进展及成套技术开发

概述了以生产BTX芳烃为目标的现代芳烃联合装置的主要工艺单元结构及其作用,介绍了催化重整、芳烃抽提或抽提蒸馏、甲苯歧化及烷基转移、二甲苯异构化、对二甲苯吸附分离各单元技术的最新进展,以及中国石油化工股份有限公司(简称中国石化)相关技术的研究开发和应用情况。中国石化采用自主研发的芳烃成套技术,在中国石化海南炼油化工有限公司建成1套60万t/a对二甲苯的芳烃联合装置,2013年底投产成功并已完成考核标定,结果表明各项工艺指标均达到设计要求,能耗明显降低,成套技术可靠、先进。