Characterization of Nitrogen Compounds in Vacuum Residue and Their Structure Comparison with Coker Gas Oil

In this study, the heteroatom classes and molecular structures of nitrogen compounds in vacuum residue are characterized by the electrospray ionization(ESI) Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS) combined with the Fourier transform infrared(FT-IR) spectroscopy. The results demonstrate that three basic nitrogen compounds, N1(in which a molecule contains one nitrogen atom, similarly hereinafter), N1O1 and N2, are identified by their positive-ion mass spectra, and three non-basic nitrogen compounds, N1, N1O1, and N1S1, are characterized by their negative-ion mass spectra. Among these nitrogen compounds, the N1 class species are the most predominant. Combined with 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 comparison with CGO, the N1 basic nitrogen compounds in VR exhibit a higher average degree of condensation and have much longer alkyl side chains.     

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.     

反应条件对渣油加氢产物中碱性氮化物的影响

利用间歇式固定床反应器对大连混合渣油进行催化加氢反应,研究氢分压和剂油比对加氢液体产物中碱性氮化物分布及类型的影响;利用电喷雾傅里叶变换离子回旋共振质谱（ESI FT-ICR MS）对原料油及产物中的碱性氮化物进行表征。结果表明：反应前后渣油中N1（含1个N原子）类的碱性化合物占绝大比例,N1S1（含1个N、1个S原子）和O1（含1个O原子）类化合物的比例次之,其它类型的相对丰度均较低;随氢分压的增大,产物中大部分碱性氮化物类别的丰度有所下降,同时发生了加氢断侧链致使N1类化合物分子的碳数减少,分子尺寸变小;随剂油质量比的增大,杂原子的相对丰度减弱,分子饱和度减小,N1类化合物的等效双键数（DBE）分布没有显著变化（DBE为9~18）;但加氢反应的断链使得分子碳数明显变小为C20~C34;反应后产物中杂原子明显减少。     

神木低温煤焦油中含氧化合物的分析与鉴定

采用酸碱分离和萃取色谱分离方法将陕西神木地区低温煤焦油分离为酸性组分、碱性组分和5个中性组分。采用气相色谱-质谱(GC-MS)和负离子电喷雾傅里叶变换离子回旋共振质谱(ESI FT-ICR MS)鉴定了神木低温煤焦油酸性组分、中性组分4和中性组分5中含氧化合物的组成与分布。结果表明,神木低温煤焦油酸性组分中含氧化合物主要包括苯酚、茚满酚、萘酚、联苯酚、芴酚、菲酚类化合物;中性组分4和中性组分5中含氧化合物主要包括C₁₀-C₂₉脂肪酮和少量芳香酮。神木低温煤焦油中含氧化合物主要有O₁、O₂、O₃、O₄、O₅、O₆类化合物,其中O₂类化合物相对丰度最高。     

渣油加氢反应过程中芳香性化合物转化规律

在中型试验装置上考察了仪长渣油和沙轻渣油加氢反应性能差异,采用傅里叶离子回旋共振质谱分析方法,深入分析了沿反应器物流方向渣油中芳香性化合物加氢转化规律。结果表明,仪长加氢生成油中含有较高含量N1类化合物（含有1个氮原子的烃类,以下类推）,其中存在较高比例DBE值（化合物分子等效双键数目）大于15的化合物,是其脱残炭率相对较低的主要原因。仪长渣油中CH类、S1类和N1类化合物的平均碳数和平均DBE值均略高于沙轻渣油,随加氢深度增加,两类渣油CH类和S1类化合物逐渐向低碳数和低DBE值方向移动,N1类化合物的变化并不明显。经过加氢脱残炭剂后,沙轻渣油S1类化合物中高碳数和高DBE值的化合物大部分转化,而仪长渣油N1类化合物中出现了少量原料中不存在的高碳数和高DBE值的化合物。     

Characterization of Basic Nitrogen Aromatic Species Obtained during Fluid Catalytic Cracking by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

The basic-nitrogen aromatic compounds in feedstocks and liquid products from the micro-reactor and soluble components of coke obtained during fluid catalytic cracking (FCC) process were analyzed by the micro-electrospray ionization (ESI) 9.4T Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) with an average mass resolving power of 300 000 at a mass range of 100-1 200. The analytical results revealed that the coker gas oil (CGO) contained a higher abundance of basic-nitrogen aromatic compounds with the type of -5N to -9N compared with those in deasphalted oil (DAO) and mixed FCC feedstock. After catalytic cracking, the abundance of lowly condensed basic-nitrogen aromatic compounds was much less than those of highly condensed aromatics in the liquid products, with the carbon number mainly ranging from 6 to 25 and the average carbon number of the side-chains equating to 1-5. On the contrary, with respect to the soluble components of coke, the abundance of lowly condensed basic-nitrogen aromatic compounds was more than those of highly condensed aromatics, and the carbon number ranged from 12 to 30, which was much smaller than that of the mixed FCC feedstock but slightly larger than that of the cracked liquid products. These results have provided some fundamental information on FCC process.     

中东常压渣油加氢处理过程中含硫化合物的分子转化规律

对重质油加氢原料和生成油进行甲基衍生化反应,使含硫化合物具有极性,然后用正离子模式下电喷雾 傅里叶变换离子回旋共振质谱(FT ICR MS)进行检测;结合油样的物化性质,讨论在固定床重油加氢反应过程中含硫化合物的分子转化规律。结果表明,甲基衍生化结合FT ICR MS手段能够成功地用于杂原子化合物尤其是含硫化合物的分析。重质油加氢处理过程中,无论是S1类还是S2类化合物,优先进行的都是双键的加氢饱和,而且S2类化合物脱除率更高;随着加氢深度的增加,低不饱和度含硫化合物的脱硫作用和烷基侧链的断侧链作用更加明显。     

The transformation of basic nitrogen compounds in coker gas oil during catalytic cracking

Two narrow fractions distilled from Liaohe coker gas oil were used for the research. The distribution of basic nitrogen compounds in feedstocks and their liquid products were characterized by ESI FT-ICR MS. The results showed that N1 class species were the most predominant in both feedstocks and products. The catalytic cracking progress reduced the relative abundance of all class species, except for the N1 and N1S1 class species. Although the N1 class species had longer side chains and higher condensation in the heavier feedstock, the distribution of N1 class species became similar in the two liquid products.     

催化剂对渣油悬浮床加氢产物氮分布的影响

以塔河稠油常压渣油为原料,进行悬浮床加氢裂化反应,用非水溶液滴定法测定各产物中的碱性氮含量,用舟进样化学发光法测定产物中的总氮含量;考察了催化剂种类、催化剂含量对产物氮分布的影响。实验结果表明,在相同反应条件下,碱性氮和总氮含量都随馏分变重而增加,碱性氮含量增加缓慢,总氮含量急剧增加;催化剂为环烷酸铁时,对于产物中的同一馏分,其中的碱性氮和总氮含量比催化剂为二烷基二硫代氨基甲酸钼时的低;对于同一催化剂,随催化剂含量的增加,汽油馏分和柴油馏分中的碱性氮和总氮含量先增加后降低,而尾油中的碱性氮和总氮含量逐渐降低;蜡油馏分及尾油中的碱性氮与总氮的质量比约为0.300-0.390,且不随催化剂含量的改变而改变。     

车用废润滑油中酸性组分的高分辨质谱分析

车用新鲜及废润滑油样品的傅里叶变换红外光谱(FT-IR)表明,两者中均存在羧基及羟基官能团,即存在酸性组分。利用具有超高分辨率的负离子电喷雾-傅里叶变换离子回旋共振质谱仪(negative-ion ESI FT-ICR MS)分析了车用新鲜及废润滑油中酸性化合物的组成及分布。结果表明,从新鲜润滑油中鉴定出的酸性化合物主要为O3、O1及O2类,而从废润滑油中鉴定出的酸性化合物则主要为O3、O2、O4及O1类。经对比分析可知,新鲜润滑油中的酸性化合物在废润滑油中均存在,其种类及所占比例基本未发生变化,但绝对含量不同;废润滑油中新产生的O3、O2及O1类酸性化合物种类较多,但其所占比例较小;车用新鲜与废润滑油中酸性组分的显著差异在于后者中产生了前者所没有的O4类化合物,且所占比例较大。     

Molecular Characterization of Hydrotreated Atmospheric Residue Derived from Arabian Heavy Crude by GC FI/FD TOF MS and APPI FT-ICR MS

High resolution mass spectrometry in combination with distillation and SARA fractionation provides us an opportunity for in-depth understanding about the hydrotreating process at the molecular level. In this study, the atmospheric residue derived from Arabian heavy crude and its hydrotreated products were initially subjected to distillation and SARA fractionation. The saturates were characterized by GC FI/FD TOF MS. The aromatics and resins were characterized by APPI FT-ICR MS. Compositional changes of different compounds (paraffins, naphthenes, aromatic hydrocarbons, and heteroatomic compounds) contained in different distillates (vacuum gas oil, vacuum residue) were obtained. More detailed knowledge about the hydrotreating process was achieved.     

吉林常压渣油在提升管内催化裂解的反应规律

在XTL-5小型提升管催化裂化实验装置上,以吉林常压渣油为原料,进行了催化裂解多产丙烯的实验,考察了反应温度、停留时间、催化剂类型对丙烯收率的影响。实验结果表明,提高反应温度、适宜的停留时间和采用多产丙LTB-2烯催化剂均可提高丙烯的收率,其中适宜的反应条件是反应温度530℃、停留时间1.4s左右。采用LTB-2催化剂,在第一段提升管反应温度530℃、m(LTB-2催化剂)∶m(常压渣油)(剂油比)为6.70、停留时间1.36s,第二段提升管反应温度530℃、剂油比7.21、停留时间1.8s左右的操作条件下,进行两段提升管催化裂解多产丙烯(TMP)工艺的模拟实验。模拟实验结果表明,TMP工艺可使丙烯收率达到22.67%,同时兼顾汽油、柴油的生产。     

委内瑞拉常压渣油悬浮床加氢裂化尾油循环反应实验研究

以委内瑞拉常压渣油为原料,分别采用3种加氢裂化反应产物（＞500℃馏分、＞400℃馏分、＞350℃馏分）作为循环尾油,在高压釜中进行了425℃、14 MPa下的悬浮床加氢裂化尾油循环反应研究,考察了循环尾油馏程以及尾油外甩比对循环反应体系生焦量、沥青质含量和液体产物分布的影响,并采用SEM、1H NMR测定了焦炭形貌 和沥青质结构参数,以探索重油悬浮床加氢裂化尾油循环工艺的可行性。结果表明,相对于一次通过反应,尾油循环反应能有效提高原料转化率;采用＞500℃馏分作为循环尾油时,体系生焦量随循环反应次数的增加而持续增加,而采用＞400℃馏分或＞350℃馏分作为循环尾油时,循环反应4次后,体系生焦量、焦炭形貌、液体产物分布、沥青质含量和结构均基本保持不变。说明当选择合适馏分作为悬浮床加氢裂化循环尾油时,重油悬浮床加氢裂化尾油循环工艺可行。此外,当反应温度和压力一定时,降低循环尾油的初馏点或减小外甩尾油比可提高原料的转化率,同时会使新鲜原料空速降低。因此,为保证较高的新鲜原料空速和转化率,必须采用合适的循环尾油馏程和尾油外甩比。     

煤直接液化重油胶质和沥青质中杂原子化合物的分子表征

采用傅里叶变换离子回旋共振质谱(FT-ICR MS)研究沸点大于360℃的煤直接液化重油中胶质、沥青质的组成,通过在分子水平上对杂原子化合物进行表征分析胶质、沥青质中杂原子类型、碳数分布和等效双键(DBE)。结果表明,煤直接液化重油中胶质及沥青质中杂原子化合物的分子组成十分复杂,采用正离子电喷雾结合高分辨傅里叶变换离子回旋共振质谱鉴定出了N₁、N₁O₁、N₂、N₂O₂、N₂S₁ 5类不同分子组成的碱性氮化物和S₁、S₂ 2种含硫化合物;采用负离子电喷雾鉴定出了N₁、N₁O₁、N₁O₂、N₂、N₂O₁、N₂O₂ 6类非碱性氮化物和O₁、O₂、O₃、O₄、O₅、O₆、O₁S₁、O₂S₁、O₃S₁、O₄S₁ 10类含氧化合物,其中碱性氮化物相对丰度较高的是N₁类化合物,含硫化合物相对丰度较高的是S₁类化合物,非碱性氮化物相对丰度最高的是N₁O₂类化合物,含氧化合物相对丰度最高的是O₂类化合物。根据各类化合物的DBE和碳数分布,获得了煤直接液化重油中胶质、沥青质分子组成的重要信息。碱性N₁类化合物主要母核结构是吡啶和喹啉为中心官能团的化合物,非碱性N₁类化合物主要母核结构是苯并咔唑,S₁类化合物主要以高缩合、长侧链的稠环含硫芳烃为主,O₂类化合物主要母核结构是菲二酚及蒽二酚。     

青海原油分子组成特征及其常压渣油含氮化合物加氢转化规律

利用气相色谱和高分辨质谱等手段分析了格尔木炼油厂的青海原油、常压渣油及渣油加氢产物的分子组成,发现青海原油中的硫、氮化合物具有特殊的分子组成,解释了该原油生产的催化裂化汽油中硫含量异常偏高及其常压渣油加氢脱氮率低的化学机理：含硫化合物富含噻吩结构单元,催化裂化过程中小分子噻吩在汽油中实现富集;氮化物烷基侧链较长,形成较强的空间屏蔽,抑制了加氢过程中氮的脱除。常压渣油加氢实验结果表明：高温裂化反应有利于提高常压渣油中氮元素的脱除率;常压渣油加氢过程中具有高缩合度的小分子含氮化合物被优先脱除,缩合度高的大分子氮化物发生芳环加氢反应形成部分饱和的中性氮化物,但芳环加氢反应仅发生在与中性氮化物氮原子未直接共轭的芳环上。     

辽河减压渣油中金属铁的赋存与分布特征

考察了辽河减渣在吸附分离、酸性溶液萃取和沥青质轻度降解过程中金属铁的分布和转移情况。结果表明，辽河减渣中有近90％的铁富集在胶质和沥青质中，部分铁以侧链较短的环烷酸盐或酚盐形式存在，部分铁连接在沥青质分子的侧链上，或是被包裹在沥青质大分子中。     

A Study on the Process Conditions of Removing Basic Nitrogen Compounds from Gasoline

The methods of hydrochloric acid extraction, liquid-solid adsorption, and complexation were used to remove basic nitrogen compounds from gasoline, and the efficiencies of three removal methods were studied. The experimental results show that the optimum range of the concentration of hydrochloric acid is 0.05 ∼ 1.0 mol L^-1, and the optimum extraction time is 20 min for hydrochloric acid extraction method. The efficiency of removal of basic nitrogen compounds reaches its top when the ratio of liquid to solid is controlled at 5:1, and that the optimum range of concentration of complexing agent is 15 ∼ 20 wt% for complexation. Under the conditions mentioned above, all the removal yields of basic nitrogen of these three present methods can exceed 90%.     

辽河双南油田原油中性氮化合物的分布与运移特征研究

利用含氮化合物定量分离分析技术,研究了双南油田原油中中性氮化合物的分布、组成与浓度变化。分析结果表明原油中烷基咔唑系列呈现富和贫C-1位烷基取代2种模式,这与辽河盆地西部凹陷沙河街组烃源岩中烷基咔唑系列较好的可比性。依据原油甾萜烷成熟度参数、含氮化合物浓度和运移参数的变化特征,结合区域地质背景认为清水凹陷是双南油田的主要油源区。油气的运移方向是从双201井向双110-1井和双202井推进。     

渤海湾盆地济阳坳陷樊页1井页岩油与临近页岩中含氮化合物组成特征

采用负离子电喷雾（ESI）—傅里叶变换离子回旋共振质谱（FT-ICR MS）,分析了渤海湾盆地济阳坳陷樊页1井页岩油和临近页岩油产层的两种不同岩相的岩心抽提物组成,重点研究其中吡咯类含氮化合物分子组成的差异。页岩油和岩心抽提物杂原子化合物以N₁类为主。对比高分辨质谱图全貌和指纹细节、3个样品中N₁类化合物的等效双键数及碳数分布以及N₁类化合物的平均分子量,均揭示页岩油中吡咯类氮化物组成与相邻层位的纹层状页岩抽提物组成类似,而与块状页岩抽提物中该类化合物组成差异较大。电喷雾—高分辨质谱具有超高的分辨率,能有效分析不同类型样品中杂原子化合物的精细分子组成差异,可为陆相页岩油近源示踪研究提供借鉴。