轮古高硫渣油中类型硫的分布

对轮古渣油进行了系统的分离、分析,考察了硫在组分中的分布规律.针对轻、重组分不同的特点,分别采用选择性氧化结合色谱分离和溶剂抽提分离的方法,测定了亚组分中的硫醚硫和噻吩硫,从而完善了渣油体系类型硫的测定方法.在此基础上,进一步研究了渣油及组分中类型硫的分布.结果表明,轮古渣油中硫在各组分中的分布并非单调增加,而是呈双峰形分布,主要集中在芳香分和沥青质中.轮占渣油中的硫约有18.24%为可氧化的硫醚硫,约有81.76%为噻吩硫.随组分变重,轮古渣油组分中的总硫增加,硫醚硫在组分中所占比例变小,而噻吩硫的比率越来越大.硫醚硫主要分布在芳香分中,在重组分中分布相对均匀;噻吩硫分布规律同总硫一致,主要集中于芳香分和沥青质中.     

塔河常压渣油及其亚组分的非等温热转化反应性能研究

采用热重分析法对塔河常压渣油(THAR)及其亚组分的热转化反应性能进行了考察;在Sharp微分法基础上,采用分段动力学拟合,获得了渣油及其亚组分热转化速率峰值、速率峰值处的反应温度、转化率和剧烈裂解温度区间等动力学基本数据以及各亚组分的生焦性能。结果表明：各亚组分生焦率由低到高依次为饱和分＜芳香分＜胶质＜沥青质,沥青质是焦炭的主要来源;四组分按组成加权后的生焦率较THAR生焦率高4.21百分点,表明THAR亚组分混合物共焦化有利于抑制各亚组分的生焦;饱和分可促进其它亚组分生焦,而芳香分和胶质可抑制沥青质生焦,且芳香分的抑焦性能更强;在热转化反应过程中,裂化反应活性由高到低的顺序为饱和分＞芳香分＞胶质＞沥青质,各亚组分在低温段和高温段的活化能由低到高的顺序均为饱和分＜芳香分＜胶质＜沥青质,表明胶质和沥青质大分子的热转化过程需要提供较多的能量。     

热重法考察渣油及其亚组分的焦化性能

以热重法考察锦州石化渣油及其亚组分的焦化性能，并揭示了渣油各亚组分间的焦化特理化学作用。结果表明，四组分焦化生焦率从大到不的顺序和沥青质，胶质，芳香分，饱和分，渣油的生焦率介于芳香分和胶质之间。焦化过程中表观热裂化反应活性顺序为饱和分＞芳香分＞胶质＞沥青质，而实际热裂化热裂化的剧烈程度的顺序相反。饱和分可促进其它亚组分生焦，而芳香分可抑制胶质，沥青质生焦，渣油按四组分组成物理加权后的生焦率大于该渣的生焦率。还探讨了渣油及其亚组分在焦化过程中的动力学特征。     

两种中东减压渣油非等温热转化反应的热重法研究

采用热重法对科威特减渣、沙特减渣及其四组分的非等温热转化反应进行了研究,获得了减压渣油及亚组分热转化行为的基本特征。结果表明：渣油中的饱和分、芳香分对胶质、沥青质热转化反应活性具有促进作用,沥青质、胶质的热稳定性明显高于饱和分及芳香分。渣油及其四组分的热裂化反应可划分为两个温度区间,每一温区都服从一级动力学反应,两温区活化能差别较大,各温度区间内不同组分的活化能也不相同。     

孤岛减压渣油加氢处理过程中硫类型的变化

孤岛减压渣油加氢脱硫后所得残渣油（〉５００℃）的化学组成与原料渣油明显不同，饱和分、轻芳烃、中芳烃显著增加，饱和分与芳烃占８３％，而原料渣油中这两个组分仅占４１％。加氢残渣油的硫含量远低于原料的硫含量，残余硫主要集中在重胶质和沥青质中，且主要是硫醚硫，其中脂硫醚硫约占一半，说明在高压加氢条件，渣油中噻吩类化合物的主要脱硫途径是先加氢生成相应的硫醚，然后进一步氢解脱硫。     

稠油水热裂解反应中有机硫化合物的转化研究

在不同的温度下 ,对辽河稠油进行室内实验 ,研究有机硫化合物在稠油水热裂解反应中的转化规律。反应 36h后 ,两种油样中的总硫含量分别由 0 .5 2 7% (ω ,下同 )和 0 .4 7%降至 2 0 0℃时的 0 .396 %、0 .383% ,2 2 0℃时的 0 .378%、0 .372 %和 2 4 0℃时的 0 .36 7%、0 .36 4%。硫醚硫的裂解率和噻吩硫的生成率随反应时间的延长和反应温度的升高而增大 ,反应初期转化率随时间增长较快 ,后期逐渐减缓。硫醚中的C -S键容易断裂 ,生成H2 S气体。部分环硫醚和芳香硫醚转化成少量噻吩类物质 ,新生成的噻吩硫主要来源于稠油中胶质、沥青质等大分子物质的解聚。     

氧化深度对减压渣油组分及其硫分布的影响

用双氧水对中海油惠州炼油分公司减压渣油(ZHVR)进行氧化处理,以傅里叶变换红外光谱(FT-IR)和X射线光电子能谱(XPS)分析氧化前后硫化物形态,以渣油四组分分析方法测定了氧化剂添加量对氧化前后渣油中饱和分、芳香分、胶质和沥青质4种组分含量及其硫分布的影响.结果表明:ZHVR中的硫化物以硫醚和噻吩类为主,氧化处理后...     

常压渣油热反应过程中胶体的稳定性

利用质量分数电导率方法研究了中东和克拉玛依常压渣油在热反应过程中胶体的稳定性。结果表明，随着反应时间的增长，在热反应生焦诱导期内，渣油的胶体稳定性迅速下降；开始生焦后，胶体稳定性缓慢下降。从中东常压渣油的SARA四组分的数均相对分子质量、碳氢元素组成、平均芳碳率等方面探讨了中东常压渣油在热反应过程中胶体稳定性下降的原因。结果表明，在热反应中，由于裂解和缩聚反应的共同作用，使渣油的沥青质和饱和分含量上升，芳香分含量下降，胶质含量变化不大；随着热反应的进行，四组分的数均相对分子质量均呈下降趋势，导致了渣油胶体稳定性的下降并发生生焦反应。     

胜利减压渣油胶质热反应生焦特性的研究

以胜利减压渣油中的饱和分、芳香分和胶质为原料，通过其热反应行为的考察，表明在本反应条件下，饱和分不转化成沥青质和甲苯不溶物；仅有少量芳香分转化成沥青质和甲苯不溶物；在热反应中沥青质和甲苯不溶物的生成主要来自胶质的缩合反应。还比较了饱和分、芳香分和胶质的裂解与缩合性能。研究表明，纯胶质的热反庆体系，其胶溶沥青质的能力很强；原生胶质经热反应后所生成的次生胶质和次生沥青质与减压渣油中的原生胶质和原生沥青     

重质稠油供氢剂减粘裂化试验研究

以反应釜为热反应装置,对重质稠油在两种不同的供氢剂A、B下的热反应性能进行了多方面考察。实验结果表明,在搀兑一定比例供氢剂的条件下,重质稠油热反应产物小于350℃馏分油收率有了大幅度提高,其残渣油粘度随反应温度的升高呈先降后升的趋势。对反应产物残渣油4个组分考察的结果表明,随着反应温度的升高,饱和分、芳香分、胶质的总含量呈下降趋势,沥青质的含量呈上升趋势。     

An Active Carbon Catalyst Prevents Coke Formation from Asphaltenes during the Hydrocracking of Vacuum Residue

Active carbons were prepared by the steam activation of a brown coal char. The active carbon with mesopores showed greater adsorption selectivity for asphaltenes. The active carbon was effective at suppressing coke formation, even with the high hydrocracking conversion of vacuum residue. The analysis of the change in the composition of saturates, aromatics, resins, and asphaltenes in the cracked residue with conversion demonstrated the ability of active carbon to restrict the transformation of asphaltenes to coke. The active carbon that was richer in mesopores was presumably more effective at providing adsorption sites for the hydrocarbon free-radicals generated initially during thermal cracking to prevent them from coupling and polycondensing.     

STRUCTURAL CHARACTERIZATION OF ARABIAN HEAVY CRUDE OIL RESIDUE

The residue (370°C+) from Arabian Heavy Crude Oil was separated into four fractions, asphaltenes, resins, aromatcis and saturates. The four fractions were found to be free of artifacts and analytically significant in themselves. Each fraction was further characterized by elemental analysis, infrared spectroscopy, n.m.r. spectroscopy and mass spectroscopy. The aromatics are the major constituent of the residue and the ratio of asphaltenes, resins, aromatics and saturates is about 2:3:8:3. The strucutral characterization study led to the conclusion that asphaltene fraction is maximum hydrogen deficient followed by resins, aromatics and saturates thus suggesting larger degree of ring condensation in the structure of asphaltenes than resins and aromatics.     

STRUCTURAL CHARACTERIZATION OF ARABIAN HEAVY CRUDE OIL RESIDUE

ABSTRACT

The residue (370°C+) from Arabian Heavy Crude Oil was separated into four fractions, asphaltenes, resins, aromatcis and saturates. The four fractions were found to be free of artifacts and analytically significant in themselves. Each fraction was further characterized by elemental analysis, infrared spectroscopy, n.m.r. spectroscopy and mass spectroscopy. The aromatics are the major constituent of the residue and the ratio of asphaltenes, resins, aromatics and saturates is about 2:3:8:3. The strucutral characterization study led to the conclusion that asphaltene fraction is maximum hydrogen deficient followed by resins, aromatics and saturates thus suggesting larger degree of ring condensation in the structure of asphaltenes than resins and aromatics.     

An Active Carbon Catalyst Prevents Coke Formation from Asphaltenes during the Hydrocracking of Vacuum Residue

Abstract

Active carbons were prepared by the steam activation of a brown coal char. The active carbon with mesopores showed greater adsorption selectivity for asphaltenes. The active carbon was effective at suppressing coke formation, even with the high hydrocracking conversion of vacuum residue. The analysis of the change in the composition of saturates, aromatics, resins, and asphaltenes in the cracked residue with conversion demonstrated the ability of active carbon to restrict the transformation of asphaltenes to coke. The active carbon that was richer in mesopores was presumably more effective at providing adsorption sites for the hydrocarbon free-radicals generated initially during thermal cracking to prevent them from coupling and polycondensing.     

减压渣油及其四组分在接触剂上的裂化反应规律

以减压渣油为原料,采用热解色谱和热重-质谱,考察了减压渣油及其四组分(饱和分、芳香分、胶质和沥青质)在惰性接触剂L HBK和酸性接触剂C上的裂化反应.结果表明:四组分在有孔无酸剂L HBK上裂化程度由强到弱的顺序为胶质、沥青质、芳香分、饱和分,在有孔有酸剂C上裂化程度由强到弱的顺序为饱和分、芳香分、胶质≈沥青质.四组分...     

Removing of resins from crude oils

Crude oil contains four chemical group classes, namely saturates, aromatics, resins, and asphaltenes (SARA fractions). Resins fraction of crude oil comprises polar molecules often containing heteroatoms such as nitrogen, oxygen, or sulfur. Resin is a heavier fraction than aromatics and saturates. Resins are composed of fused aromatic rings with branched paraffin and polar compounds. The resin fraction is soluble in light alkanes such as pentane and heptane, but insoluble in liquid propane. The resins are adsorbed on a solid such as alumina, clay, or silica, and subsequently recovered by use of a more polar solvent and the oils (aromatics and saturates) remain in solution. The resins often coprecipitate with the asphaltenes in controlled propane deasphalting procedures. The composition of the resins can vary considerably and is dependent on the kind of precipitating liquid and on the temperature of the liquid system. The resins are adsorbed on a solid such as alumina, clay, or silica, and subsequently recovered by use of a more polar solvent and the oils (aromatics and saturates) remain in solution.