催化裂化油浆及其窄馏分芳烃组成分析

大庆、大港和沙特催化裂化油浆经减压蒸馏和超临界萃取分馏，分离出一系列窄馏分。用液相色谱分离其中的芳香烃，质谱法分析原料及窄馏分的芳烃组成，以研究不同类芳烃在不同窄馏分中的变化规律。结果表明，四环芳烃是催化裂化油浆芳烃的主要组分，三环、五环芳烃在不同窄馏分中相对含量变化较大     

沥青质的热转化

研究了从阿大巴斯卡沥青分离出的沥青质馏分的焦化过程,发现,从烃类中分离出的沥青质生焦的最初阶段生成挥发性烃类碎片和非挥发性产物(杂原子物系)。一般认为的石油沥青质系多核芳烃组成的大分子这样一个结构模型不能很好地解释沥青质生焦机理的细节。     

FCC催化剂上积炭组成及形态分析

采用二氯甲烷超声波萃取,结合 GC-MS 分离并分析了 FCC 待生剂外表面和孔内可溶性积炭的组成,采用透射电镜结合能量损失谱（TEM-EELS）和¹³C CP NMR 对 FCC 待生剂上不可溶性积炭的形态进行了分析。结果表明,在 FCC 待生剂外表面提取的可溶物主要是二环和三环芳烃,而在催化剂孔道内的则是二元环到七元环的多环芳烃;不可溶性积炭为无定型结构,且含有一些高度缩合的稠环芳烃。     

FCC油浆精制前后焦化蜡油产物的组成和结构分析

运用GC-FID/MS和NMR从分子水平表征FCC油浆加氢精制前后焦化蜡油产物的详细组成和结构。对其中121种芳烃单体化合物进行分子识别,基本实现该焦化蜡油中多环芳烃、氢化多环芳烃、噻吩和咔唑以及这些化合物的烷基取代物的定量,并考察了油浆精制前后焦化蜡油的结构及其变化。结果表明,尽管FCC油浆加氢精制前后焦化蜡油产物的烃族组成相近,但化合物组成和结构有较大变化。FCC油浆精制后再焦化,蜡油产物中无取代母核多环芳烃加氢转化及缩合减少,烷基桥链的多芳核结构裂化减少,硫、氮杂原子芳香化合物被较多地脱除,C₁和C₂取代芳烃、单环芳烃以及环烷芳烃含量增加,说明加氢精制对FCC油浆延迟焦化过程有利,其焦化蜡油产物的组成和结构得到改善。     

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。     

多级错流萃取分离糠醛抽出油中烃类组分

针对烃类组成复杂多样的糠醛抽出油(FEO),分别选取糠醛、二甲基亚砜(DMSO)、N-甲基吡咯烷酮(NMP)为溶剂,研究三级错流萃取分离FEO中不同烃组分的分离规律。采用气相色谱-质谱联用、傅里叶变换离子回旋共振质谱等手段分析了萃取抽出油、抽余油的组成信息,并计算萃取平衡分配系数、萃取选择性与抽余油收率。结果表明：DMSO萃取后抽余油中多环芳烃含量显著降低,糠醛与烃组分形成的“连续体”被破坏,促使糠醛对芳烃的萃取选择性显著增大;多种溶剂组合的三级错流萃取能有效分离FEO中的烃类组分,可将不同环数的芳烃分别富集在不同萃取级;相同的芳核结构,短侧链的芳烃更易溶解于极性溶剂中;三级萃取对杂环化合物的选择性明显高于纯碳氢芳烃化合物。     

新型稠环芳烃萃取剂的研究开发

中国石油化工股份有限公司九江分公司催化裂化重油抽提工艺以糠醛为萃取剂分离催化油浆或回炼油中稠环芳烃,但因糠醛在酸性物质存在以及一定的温度下,易与稠环芳烃起缩合反应,造成设备结焦。现开发新型稠环芳烃萃取剂来替代糠醛,对于完善和改进催化裂化重油抽提工艺,具有重要意义。新型稠环萃取剂在抽提效果、溶剂损失、经济效益均优于糠醛。     

现代化工分离技术讲座

<正>第八章 富勒烯的分离纯化5 用超临界流体萃取分离富勒烯 因为富勒烯在普通有机溶剂中的溶解度很低,即便用甲苯、CS2、二氯苯等良溶剂萃取,也只能从富勒烯烟灰中得到含C60、C70和一些高富勒烯的混合物,而且还需要将溶剂蒸发掉,才能分离出萃取物。近年来用超临界CO2流体,萃取、分离富勒烯,取得了以下进展。因为CO2的溶剂强度很低,它与组成富勒烯分子的五元环、六元环的π     

沥青质临氢热裂化转化规律初步研究

运用APPI+结合FT-ICR MS、XPS等方法分析塔河沥青质结构。以塔河减压渣油为原料研究沥青质在临氢热裂化转化规律。结果表明,沥青质临氢热裂化过程中的裂化反应以热裂化为主,催化剂可以抑制沥青质的缩合反应,并对沥青质中芳环结构加氢以促进其转化。在合适的条件下,塔河减压渣油沥青质转化率可以达到85.8%,裂化率达到78.2%。次生沥青质的转化是沥青质转化的关键,次生沥青质中最难转化的是稠环芳烃结构和氮稠环结构,其转化难度按从难到易的顺序为HC(芳烃结构)、N1(含1个氮原子的芳香性氮化物结构)、N2(含2个氮原子的芳香性氮化物结构)。含硫结构以及含有2种或多于2种杂原子的沥青质结构的转化率较高。加氢反应是沥青质轻质化的关键。     

催化裂化油浆的分离与化工利用

采用减压蒸馏与超临界流体萃取分馏相结合的方法,将大庆、大港和沙特重油催化裂化分离出催化剂后的油浆切割成窄馏分,研究表明,油浆窄馏分中除含芳烃外,还有相当数量的饱和分,两者之和在90％以上,饱和分中环烷烃是主要成分,蒸馏馏分中主要是三环、四环芳烃、萃取馏分芳香分中主要是五环及更重的芳烃,各窄馏分的平均结构是带短侧链的环烷稠环芳烃,油浆的蒸馏馏分可直接作为橡胶软化剂;大庆油浆超临界萃取分馏馏分可制备中间相沥青炭纤维。     

高温煤焦油制备针状焦工艺及机理研究

通过溶剂稀释在110℃热过滤脱除高温煤焦油中的喹啉不溶物（QI）；再经过减压蒸馏将溶剂及煤焦油中的轻组分去除，得到软化点适中、QI 质量分数为0.548%的净化沥青。进一步通过温和加氢工艺，将沥青中的 QI 质量分数降低至0.087%；加氢沥青经过500℃延迟焦化、1 000℃高温煅烧获得针状焦制品。与日本三菱公司产品相比较，针状焦性能指标相当。机理研究表明：煤焦油沥青催化加氢是不饱和烃加氢和脱硫、脱氮的过程，加氢后体系的H/C原子比提高，N、S元素含量降低；焦化反应中，芳烃会经过脱氢、环化、芳构化重组形成相对分子质量大、热力学稳定的多核稠环芳烃化合物，继而形成平面圆盘状的缩合多核稠环芳烃化合物，由于空间表面能会卷曲生成中间相复球，进而融并成平行排列的中间相体系，在气流作用下形成“针状”结构，固化、焦化后获得针状焦。     

煤液化油模型分子结构的研究

对神华煤在连续液化装置的加氢液化油(试样1#)和实验室获得的液化油(试样2#)进行了模型分子结构的研究。通过元素分析、平均相对分子质量的测定、核磁共振谱图和傅里叶变换红外光谱的分析,得到了两种液化油的平均分子结构式和相关的结构参数,并利用这些参数推测了模型分子的结构。实验结果表明,试样1#和试样2#的平均相对分子质量分别为228,299;平均分子式分别为C17H23N0.1S0.006O0.02和C23H21N0.02S0.002O0.1;试样1#的模型分子结构以含一个芳香环的部分氢化芳烃为主体;试样2#主要以含3~4个芳香环的缩合芳烃为结构单元;两种试样芳香环上均存在取代基,但取代基的碳数不一样,且存在少量氮和氧形成杂环。     

CGO关键组分结构分析及其对FCC反应性能的影响

 以大港CGO 400～425 ℃窄馏分为研究对象,采用盐酸+糠醛分级抽提的方法富集其中的碱性氮化物及稠环芳烃,采用GC-MS对抽出物进行结构分析,并比较了抽提前后油样的FCC反应性能。结果表明,盐酸抽出相中的碱性氮化物主要是氮杂菲系和氮杂芘系,其中以苯并喹啉系及二苯并喹啉系含量最多;这类化合物与催化剂活性中心结合,使催化剂活性下降。糠醛再抽提抽出相中的稠环芳烃包括荧蒽、苯基萘、菲蒽系、芘系及苯并芘系,其中3～4环的稠环芳烃所占比例最大;这类化合物在催化剂表面缩合生焦,降低了CGO的FCC反应性能。盐酸及糠醛抽余油的FCC反应性能均得到了改善,但糠醛抽余油的改善程度不及盐酸抽余油;碱性氮化物对CGO FCC反应性能的影响比稠环芳烃大。     

煤衍生油和低阶煤在固体酸催化剂条件下共处理产物特性

高温煤焦油是一种劣质煤衍生重油，和低阶煤进行加氢共处理是实现其高效利用的重要途径。对煤和煤焦油在固体酸催化剂条件下加氢共处理的产物进行蒸馏特性、元素、族组成和GC-MS分析。结果表明：小于230 ℃馏分收率较高，为35.14%；C、N元素含量随着沸点升高依次上升，H、O元素含量、H/C原子比随沸点升高依次下降。随着各馏分沸点的升高，饱和烃和一环化合物含量逐渐下降，二环、三环化合物含量呈先增大后减小趋势，其中二环化合物在230～300  ℃馏分达到最大值，三环化合物在300～350  ℃馏分达到最大值，小于230  ℃馏分和230～300  ℃馏分中所含烃类化合物主要为由1～3环的芳香结构组成的结构单元和脂肪结构的桥键组成，也有含量很少的带杂原子的芳香环结构。     

STRUCTURAL CHARACTERIZATION OF AROMATIC FRACTIONS OF SOME TYPICAL SOLVENT REFINED COALS USING MASS SPECTROMETRIC TECHNIQUES

Three aromatic fractions from two typical Chinese solvent-refined coals (one, FS2, derived from bituminous-sapropelitic cannel coal, and the other two, DT2A and DT2B, derived from a bituminous, weakly caking coal) were characterized for their chemical composition and molecular weight distribution using field ionization (FI) and field desorption (FD) mass spectrometric techniques. Some characteristic components derived from the chemical ionization technique were subjected to further fragmentation analyses using tandem mass spectrometry.

The FS2 fraction is composed of 3-5 ring condensed aromatics of cata configuration with abundant naphthenic groups fused with an aromatic cluster. The most abundant component -- cyclopentachrysene -- is resolved at M/Z 268, which may possibly be the product of aroir.atization of hopanes existing in the source material during dia- and catagenesis. Sample DT2A contains polycyclic aromatic hydrocarbons with a higher degree of aromatic condensation and 3-5 ring clusters. The concentration of C-4 substituted phenanthrene was especially high, indicating the probable presence of retene derived from triterpanic acid in the land plantresins during geological conversion of coal. The second aromatic fraction, DT2B, is differentiated from DT2A mainly by the aromatic ring number (6-9 rings for DT2B) and degree of aromatic condensation (mainly cata configuration). The suitability for producing advanced carbon materials of the three samples studied is discussed.     

STRUCTURAL CHARACTERIZATION OF AROMATIC FRACTIONS OF SOME TYPICAL SOLVENT REFINED COALS USING MASS SPECTROMETRIC TECHNIQUES

ABSTRACT

ABSTRACT

Three aromatic fractions from two typical Chinese solvent-refined coals (one, FS2, derived from bituminous-sapropelitic cannel coal, and the other two, DT2A and DT2B, derived from a bituminous, weakly caking coal) were characterized for their chemical composition and molecular weight distribution using field ionization (FI) and field desorption (FD) mass spectrometric techniques. Some characteristic components derived from the chemical ionization technique were subjected to further fragmentation analyses using tandem mass spectrometry.

The FS2 fraction is composed of 3-5 ring condensed aromatics of cata configuration with abundant naphthenic groups fused with an aromatic cluster. The most abundant component -- cyclopentachrysene -- is resolved at M/Z 268, which may possibly be the product of aroir.atization of hopanes existing in the source material during dia- and catagenesis. Sample DT2A contains polycyclic aromatic hydrocarbons with a higher degree of aromatic condensation and 3-5 ring clusters. The concentration of C-4 substituted phenanthrene was especially high, indicating the probable presence of retene derived from triterpanic acid in the land plantresins during geological conversion of coal. The second aromatic fraction, DT2B, is differentiated from DT2A mainly by the aromatic ring number (6-9 rings for DT2B) and degree of aromatic condensation (mainly cata configuration). The suitability for producing advanced carbon materials of the three samples studied is discussed.     

Structural Description of Polyaromatic Nucleus in Residue

The proton nuclear magnetic resonance spectroscopy （1H-NMR）, the synchronous fluorescence spectrometry （SFS） and the ruthenium ions catalyzed oxidation （RICO） method were used to determine the chemical structure of polyaromatic nucleus in Oman residue fractions. The results of 1H-NMR analyses showed that the average numbers of aromatic rings in the aromatics, resins and asphaltenes units were 3.2, 5.6 and 8.2, respectively. SFS was used to investigate the distribution of aromatic rings in residue fractions, the main distribution range of aromatic rings in aromatics, resins and asphaltenes were 3 4 rings, 3--5 rings and more than 5 rings, respectively. The aromatic network in residue fractions was oxidized to produce numerous carboxylic acids. The types and content of benzenepolycarboxylic acids, such as phthalic acid, benzenetricarboxylic acids, benzenetetracarboxylic acids, benzenepentacarboxylic acid and benzenehexacarboxylic acid disclosed the condensed types of aromatic nuclei in the core. The biphenyl fraction （BIPH）, the cata-condensed fraction （CATA）, the peri-condensed fraction （PERI） and the condensed index （BCI） were calculated based on the benzenepolycarboxylic acids formed. The results implied that there was less biphenyl type structures in all residue fractions. The aromatics fraction was almost composed of the cata-condensed type system, and the asphaltenes fraction was wholly composed of the peri-condensed type system, while in the resins fraction co-existed the two types, herein the peri-con- densed type was predominant over the cata-condensed type. Based on the analytical results obtained in the study, the components --aromatics, resins and asphaltenes -- were given the likely structural models.     

煤焦油中甲苯不溶物的性质和组成分析

利用元素分析、扫描电子显微镜、X射线光电子能谱、红外光谱等手段对煤焦油中甲苯不溶物（TIM）的组成、结构进行了分析表征。结果表明,97%的甲苯不溶物颗粒粒径在21.06 μm以下,其形状不规则,稳定分布在煤焦油中。该物主要由有机物组成,O含量较高,金属元素中Ca、Na、Mg、Fe含量较高。其有机成分主要是稠环芳烃类物质,无机成分大部分是煤粉、煤灰、碳质和矿物质颗粒等。甲苯不溶物固体表面C、O元素总摩尔分数为91.56%,C主要以碳氢化合物和酚类 、醚类化合物的形式存在,O主要以酚羟基和醚氧键的形式存在。     

中低温煤焦油的加氢处理工艺研究

以中低温煤焦油为原料,先进行高压釜模拟悬浮床加氢预处理,再进行固定床加氢处理,对所得液体产物进行分析。结果表明:中低温煤焦油经悬浮床加氢预处理后,轻质化程度显著提高,再经固定床加氢处理后,所得汽油馏分中C_6～C_9芳烃质量分数达到32.72%,芳烃潜含量为66.15%,适于生产芳烃或用作高辛烷值汽油调和组分;柴油馏分中总芳烃、单环芳烃和双环芳烃质量分数分别为90.9%,46.9%,36.9%,适于进一步加氢改质最大化生产化工原料。     

Structural Changes of Sub-fractions in Residue Hydrotreating Products by Ruthenium Catalyzed Oxidation

Abstract

Structure of aromatics, resins, and asphaltenes in petroleum residue was undertaken by using ruthenium ion catalyzed oxidation. The distribution of alkyl side chains and bridges connected to aromatic rings was quantified, and the condensed type of aromatic rings was deduced. The structural changes of fractions in residue during hydrotreating were discussed. The results showed that fractions have abundant alkyl side chains (C₁–C₂₇), mainly n-alkyl side chains, attached to aromatic carbons, and polymethylene bridges connected to at least two aromatic ring systems are also present. The molar concentrations of these alkyl groups are declined as the increase of chain length. Cata-condensed, peri-condensed, and biphenyl-type aromatic unit structures coexist in fractions, while the proportion of biphenyl type structure is relatively small. The aromatic structure of aromatics is mostly cata-condensed, while for resins the proportion of cata-condensed and peri-condensed type aromatic structures is comparable, and structure of asphaltene is mostly peri-condensed. The chemical structure of fractions in residue changed due to the increase of hydrotreating degree. The enrichment of large aromatic units made asphaltene have more aromatic structures and higher condensed degree.