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。     

傅里叶变换离子回旋共振质谱仪表征伊朗减压渣油中的钒卟啉

采用索氏抽提结合固相萃取(SPE)技术对伊朗减压渣油中的钒卟啉化合物进行了分离,并且使用具有超高分辨率的大气压光致电离傅里叶变换离子回旋共振质谱仪(APPI FT ICR MS)对伊朗减压渣油中的钒卟啉进行了鉴定。结果表明,SPE分离技术能够实现索氏抽提抽出物中镍卟啉、钒卟啉的有效分离,并使钒卟啉得到富集;乙腈为索氏抽提溶剂时,缺氢数(Z)范围为－28～－46、碳数分布范围为25～55的共10类钒卟啉得到了鉴定;伊朗减压渣油中的钒卟啉以脱氧叶红初卟啉（DPEP）型为主,其次为初卟啉（ETIO）型。采用样品预处理技术与APPI FT ICR MS的结合,有效鉴定了伊朗减压渣油中的钒卟啉。     

Quantitative Analysis Using Fourier Transform Ion Cyclotron Resonance Mass Spectrometry and Correlation between Mass Spectrometry Data and Sulfur Content of Crude Oils

Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS) has become a powerful tool for analyzing the detailed composition of petroleum samples. However, the correlation between the numerous peaks obtained by FT-ICR MS and bulk properties of petroleum samples is still a challenge. In this study, the internal standard method was applied for the quantitative analysis of four straight-run vacuum gas oils(VGO) by atmospheric pressure photoionization(APPI) FT-ICR MS. The heteroatom class distribution of these VGO samples turned to be different when the concentration changed. Linear relationship between the normalized abundance and the concentration of VGO samples was identified for the total aromatic compounds, aromatic hydrocarbons, S1 and N1 species. The differences of the response factors were also discussed. The sulfur contents of a series of crude oils were proved to be linear with the FT-ICR MS data calibrated by the response factor of S1 species. This study demonstrated the feasibility of the internal standard method in quantitative analysis with APPI FT-ICR MS, and the bulk properties of petroleum samples could be correlated directly with the FT-ICR MS data.     

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.     

苏丹Dar原油及其馏分油石油酸组成分析

The Dar crude oil produced in Sudan was distilled into several fractions. The heteroatom class species in crude and its fractions were characterized by the negative-ion ESI FT-ICR MS. The major emphasis was put upon the study on the O2 class species (petroleum carboxylic acids). The test results revealed that aliphatic acids and monocyclic naphthenic acids accounted for a large proportion in petroleum carboxylic acids of the Dar crude. The relative abundance of aliphatic acids and monocyclic naphthenic acids decreased with an increasing boiling point of fractions. Meanwhile, the relative abundance of bicyclic and tricyclic naphthenic acids increased at first and then decreased, whereas the relative abundance of petroleum carboxylic acids with higher double-bond equivalence (DBE) values increased. The high abundance of aliphatic acids in the Dar crude and its fractions covered the carbon numbers in a range of 16 to 18 which had important geochemical signifi- cance. The O2 class species were distributed in a broad range of DBE values and carbon numbers with increasing boiling points of fractions.     

不同基属FCC油浆中芳烃结构组成分析

为实现催化裂化(FCC)油浆的高附加值利用,研究了不同油浆窄馏分中芳烃的结构和组成变化。以中间基属和石蜡基属FCC油浆的抽出油为原料,采用实沸点减压蒸馏切割得到7个窄馏分,以改进的Brown-Ladner(B-L)法和全二维气相色谱/飞行时间质谱为表征手段,考察了2种油浆各窄馏分中芳烃的结构组成变化。结果表明：中间基属的青岛炼化催化裂化油浆(QD-FCC油浆)以3~5环芳烃为主,而石蜡基属的兰州炼化催化裂化油浆(LZ-FCC油浆)以2~4环芳烃为主,石蜡基属LZ-FCC油浆的总饱和碳及环烷碳分率大于中间基属QD-FCC油浆。2种油浆中三环芳烃主要是渺位缩合的菲类和氢化苯并蒽类化合物;四环芳烃以渺位缩合的苯并蒽类化合物为主,且含有部分迫位缩合的芘类化合物;五环芳烃以迫位缩合的苯并芘类化合物为主,石蜡基属LZ-FCC油浆中的五环芳烃含量远远小于中间基属QD-FCC油浆。     

比较几种髙酸原油及其柴油、蜡油馏分的石油酸组成

Three high-acidity crudes,Dar,SZ36-1,and QHD326,were separated through distillation into several fractions,including diesel distillates,and VGOs.Samples were characterized by negative-ion ESI FT-ICR MS.The O 2 class species (petroleum carboxylic acids),which have a close relationship with corrosion of equipment caused by high-acidity crudes,were put in the focus of attention and were discussed in this paper.Monocyclic,bicyclic,and tricyclic naphthenic acids are the main types of petroleum carboxylic acids in naphthenic-base crudes (SZ36-1 and QHD326).But the main types of petroleum carboxylic acids in paraffinic-base crude (Dar) are aliphatic acids and monocyclic naphthenic acids.The O 2 class species in SZ36-1 and QHD326 are distributed in a wider range and have bigger DBE value (double-bond equivalence value) and carbon number than Dar.Bicyclic naphthenic acids have the highest proportion among petroleum carboxylic acids in diesel distillates,but monocyclic and tricyclic naphthenic acids also occupy a high proportion.Particularly,aliphatic acids in the diesel distillate of Dar still have high proportion among petroleum carboxylic acids.The distribution of petroleum carboxylic acids in VGO is basically identical.The bicyclic naphthenic acids assume the first place (about 25 m%),while the monocyclic and tricyclic naphthenic acids take the next place.The comparison of petroleum carboxylic acids in diesel distillates and VGOs has revealed that the molecules of carboxylic acids in VGOs are not only bigger but also more complicated.     

催化裂化待生剂积炭结构组成的多重表征

 了解催化裂化待生剂上焦炭的结构成分和结焦位置对深入认识催化裂化反应机理和指导催化剂研发具有重要意义。以加工减压渣油和减压瓦斯油混合原料的催化裂化工业待生剂为例,通过萃取、溶解催化剂骨架等手段将焦炭分离,同时结合元素分析、热重分析、红外光谱、色 质联用、核磁共振、N₂吸附等多种表征手段,对催化裂化待生剂上的焦炭含量、结构成分和结焦位置进行综合分析。结果表明,该催化裂化待生剂上焦炭质量分数约为1.9%,包含可溶于二氯甲烷等有机溶剂的轻质组分和不溶于有机溶剂的重质组分。轻质组分主要由饱和烷烃和轻度聚合的芳香烃组成,质量分数约为27%;重质组分主要为稠环芳烃,质量分数约为73%。焦炭主要存在于待生剂的中孔和大孔中。此结果说明,在工业催化裂化装置中存在通过调整汽提工艺参数进一步降低焦炭产量,从而提高汽油/柴油产率的可能性。     

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.     

离子淌度飞行时间质谱表征减压蜡油加氢脱氮过程中氮化物的变化

用配备了电喷雾电离源(ESI)的离子淌度飞行时间质谱(IMS-TOF MS),对不同温度下加氢的大庆减三线蜡油(VGO)中的碱性氮化物和中性氮化物进行了表征,探讨了加氢脱氮过程中氮化物的转化机理。氮元素分析结果表明,反应温度更高的加氢产物脱氮程度更深,大庆VGO的中性氮含量高于碱性氮,经过轻度脱氮处理后会出现中性氮含量低于碱性氮的情况,但深度脱氮后2种氮化物的含量相当。质谱表征结果显示：加氢前大庆VGO的中性氮化物以苯并咔唑和二苯并咔唑类化合物为主,碱性氮化物以吡啶类化合物为主。在脱氮程度较浅的大庆VGO样品里,中性氮化物的含量有所下降,还出现了环胺类碱性氮化物,这部分环胺类化合物在深度脱氮的大庆VGO样品中明显减少,说明中性氮化物经加氢后先生成了环胺类碱性氮化物,再进一步被加氢去除。研究结果表明,无论是中性氮化物还是碱性氮化物,不饱和度更高以及侧链更短、更少的氮化物都更容易被加氢去除。     

FCC原料加氢预处理对催化柴油中硫、氮化合物分布的影响

分别采用气相色谱-脉冲火焰光度检测器（GC-PFPD）及气相色谱-氮化学发光检测器（GC-NCD）对催化裂化柴油中的硫化物和氮化物类型进行了分析,考察了加氢预处理的反应温度对FCC柴油中的硫化物、氮化物的转化规律的影响。结果表明：FCC柴油中的硫化物主要为BTs和DBTs,氮化物主要以非碱性的含氮化合物为主,吲哚类和咔唑类约占总氮含量的98%;加氢预处理后的FCC柴油中的硫化物以BTs为主,4- MDBT 和4, 6- DMDBT含量很少;随着加氢预处理温度的提高,FCC柴油氮化物中的咔唑类逐渐减少,主要以吲哚类为主。     

气相色谱-飞行时间质谱表征馏分油芳烃分子组成的馏程分布

建立了气相色谱-飞行时间质谱表征馏分油芳烃分子组成馏程分布的分析方法。以不同环数芳烃标样的"沸点-色谱保留时间"关系曲线为芳烃试样色谱图馏分切割的依据,利用此方法表征了试样Y中芳烃的分子组成、平均相对分子质量和平均结构的馏程分布。实验结果表明,各馏分段中芳烃的平均相对分子质量与此馏分段的温度呈良好的线性关系,相关系数为0.995 4,可由此预测芳烃试样在任意馏分段的平均相对分子质量;在相同馏分段中,芳烃不饱和度越高,平均碳数和平均相对分子质量越小,侧链碳率越低。该方法开拓了分子水平表征石油及其产品的新思路。