直馏VGO中芳烃的分子组成特点

采用傅里叶变换离子回旋共振质谱分析了大庆、胜利、辽河和塔河4种VGO的芳烃化合物类型和碳数分布,并对分离得到的芳烃组分进行钌离子催化氧化实验来考察其侧链形态和长度。结果表明,各VGO芳烃主要由Z值为-6~-40的分子组成,在15~50的碳数范围内呈单峰连续分布,不同类型芳烃化合物在各VGO中的相对含量存在差异。芳烃分子的侧链形态主要是碳数小于25的正构烷基,异构烷基的量较少;大庆、胜利VGO芳烃分子中碳数大于9的长正构烷基较多,而塔河、辽河VGO芳烃分子中碳数小于9的短正构烷基较多。VGO中芳烃分子大多数以芳环上有多个正构烷基的形态存在,少量为单取代或有异构取代基。     

钌离子催化氧化法研究胜利减压渣组分的化学结构

利用对芳香碳有高选择性转化能力的钌离子催化氧化法研究了胜利减压渣油中芳香分、胶持和沥青质３种组分的化学结构。定量测定了与芳香核相连的正构烷基侧链和连接两个芳香核的正构基桥的分布。结果表明，该渣油的３种组分都含有Ｃ１－Ｃ３３的正构烷基侧链和Ｃ２－Ｃ２２的正构烷基桥。正构烷基侧链的摩尔浓度随其碳数的增加而下降。相对来说，沥青质含有较多的〈Ｃ１０的侧链而〉Ｃ１６的侧链较少。正构烷基桥的浓度按沥青质、胶质     

钌离子催化氧化法研究胜利减压渣油组分的化学结构

利用对芳香碳有高选择性转化能力的钌离子催化氧化法研究了胜利减压渣油中芳香分、胶质和庚烷沥青质３种组分的化学结构。定量测定了与芳香核相连的正构烷基侧链和连接两个芳香核的正构烷基桥的分布。结果表明，该渣油的３种组分都含有Ｃ１～Ｃ３３的正构烷基侧链和Ｃ２～Ｃ２２的正构烷基桥。正构烷基侧链的摩尔浓度随其碳数的增加而下降。相对来说，沥青质含有较多的＜Ｃ１０的侧链而＞Ｃ１６的侧链较少。正构烷基桥的浓度按沥青质、胶质、芳香分顺序下降。在３种组分的水相氧化产物中都检测出从邻苯二甲酸到苯六甲酸的一系列苯多甲酸，表明胜利减压渣油中的芳香分、胶质和沥青质都含有缩合程度较高的芳香环系结构。对不同结构苯多甲酸的定量分析表明，沥青质以迫位缩合芳香环系结构为主，芳香分以渺位缩合芳香环系结构为主，胶质介于两者之间。     

减压渣油中胶状沥青状物质的化学结构研究

利用对芳香碳有高选择性转化能力的钌离子催化氧化法研究了减压渣油中轻、中、重胶质和戊烷沥青质的化学结构,定量了与芳香环相连的正构烷基侧链和桥链的分布,并了芳香环系的缩合型式,结果表明,这些石油重质组分中均存在碳数为Ｃ１￣Ｃ３０的与芳香 相连的正构烷基侧链,其摩尔浓度随链长的增加而下降,也存在由正构烷基桥连接的至少具有两个芳香环系的芳香性分子,在芳香结构中存在着渺位缩合,迫位缩合以联苯型结构,其中联苯     

沙中原油减压馏分油的分离及表征

采用溶剂脱蜡法和溶剂萃取法将沙中原油的减压馏分油分离为正构烷烃相、轻芳烃-饱和烃相、中芳烃相和重芳烃相等亚组分,采用气相色谱、气相色谱-质谱联用、固体核磁共振等方法分析了减压馏分油及其亚组分的基本性质、烃类组成和结构参数,同时考察了上述分离过程中各组分的分离百分率。结果表明：溶剂脱蜡法和溶剂萃取法分别分离减压馏分油中链烷烃和多环芳烃的选择性及分离效率均较高;采用溶剂脱蜡法得到的正构烷烃相中链烷烃含量在88.3％～95.2％之间,其碳数呈正态分布,链烷烃分离百分率在24.4%~36.8%之间,约是环烷烃分离百分率的12倍;采用两段溶剂萃取法得到的重芳烃相和中芳烃相具有随着馏分油变重CA降低,CN,CP,RA,RN增加,平均分子式中S和N原子数增加的规律,重芳烃相和中芳烃相中芳烃含量分别为85.4%~88.8%和73.2％～78.5％,三环及以上芳烃的分离百分率在72.8%~75.5%之间,分别是链烷烃和环烷烃分离百分率的5~8倍和4~5倍。     

烷基芳烃裂化反应性能及生成苯的反应路径

以甲苯、异丙苯、正戊基苯和苯基环己烷为模型化合物,研究了烷基芳烃在酸性催化剂上的裂化反应性能及生成苯的化学反应路径。结果表明,甲苯很难发生裂化反应,苯的生成主要来自甲苯歧化反应;当烷基苯取代基碳原子数在3以上时,烷基苯裂化反应性能随着烷基侧链碳原子数的增加而增加,烷基侧链含有叔碳原子则更易裂化,苯的生成主要来自脱烷基反应;随着烷基苯取代基碳原子数的增多,烷基芳烃的侧链裂化反应选择性增强,可利用此反应特性控制反应路径,达到降低汽油苯含量的目的。     

钌离子催化氧化法研究沥青质经加氢处理后的变化

 利用钌离子催化氧化方法研究了渣油中沥青质的化学结构，定量测定了与沥青质芳香核相连的烷基侧链和烷基桥链的分布，推断了沥青质中芳香环系的缩合形式，讨论了沥青质组分在加氢处理过程中的结构变化规律。结果表明，渣油组分中都存在C1～C27的烷基侧链，并且主要是正构烷基侧链，也存在与两个芳香核相连接的C2～C16烷基桥链，它们的浓度随链长增加而下降。沥青质的氧化产物中检测出从邻苯二甲酸到苯六甲酸的一系列苯多甲酸。沥青质芳香核结构中存在着渺位缩合、迫位缩合和联苯结构，其中联苯结构较少。沥青质可以看作纯粹的迫位缩合。随着加氢处理深度的增加，沥青质组分的化学结构发生变化，芳香结构较大的芳香核在沥青质中富集，使得沥青质组分中的芳香结构逐渐增多，芳香核缩合程度逐渐增加。     

新型柱色谱分离法在塔河减压馏分油分离中的应用

为了有效分离重油中的各种烃类组分,开发了以负载银离子的填料为固定相的新型柱色谱分离方法。将塔河减压馏分油分离为饱和烃、轻芳烃、中芳烃、重芳烃和胶质等组分,并采用气相色谱-质谱联用(GCMS)、气相色谱-场电离-飞行时间质谱(GC-FI-TOF MS)分析了塔河减压馏分油各组分的烃类组成和碳数分布。该方法提高了分离效率,将单次分离时间缩短至4~5h;消除了固定相上银离子流失对组分造成的污染,实现了芳烃组分的进一步分离富集,轻芳烃组分中的单环芳烃质量分数为74.3%,中芳烃组分中的双环芳烃质量分数为37.1%,重芳烃组分中的三环以上芳烃质量分数为65.9%。     

中/低温煤焦油减压馏分油的组分分离与鉴定

通过减压蒸馏切取中/低温煤焦油减压馏分油（360~480 ℃）,设计柱色谱层析分离对比实验,通过比较柱色谱收率、组分冲洗难易程度及淋洗切割点清晰度,确定了以硅胶为吸附剂,正庚烷可溶质为柱色谱原料,以石油醚、甲苯、甲苯-乙醇、乙醇为冲洗剂的柱层析方法,将煤焦油减压馏分油分离为四个组分,并通过NMR、元素分析及相对分子质量测定等手段对各组分进行分析鉴定。结果表明：该馏分油中饱和分、芳香分、极性组分和C7-沥青质含量分别为13.28%,35.10%,33.15%,18.21%,其中链烷烃占6.00%,环烷烃占7.25%,芳香烃占35.13%。极性组分和C7-沥青质芳碳率高,二者均为以稠环芳烃为主体并配以少量短侧链的大分子,是造成煤焦油轻质化难度大的主要因素。     

全二维气相色谱-飞行时间质谱法分析表征重馏分油中多环芳烃化合物

建立全二维气相色谱-飞行时间质谱分析方法,利用该方法对重馏分油中多环芳烃进行详细表征,通过标准化合物的保留时间、质谱图和NIST谱库定性和半定量分析重馏分油中的多环芳烃和烷基取代多环芳烃,并研究结构和烷基取代基对多环芳烃加氢转化的影响。结果表明,不同结构、不同烷基取代位置和不同烷基取代数量的多环芳烃的加氢转化率有很大区别。全二维气相色谱-飞行时间质谱具有高分辨能力和高灵敏度,是分析表征复杂样品中目标化合物的强有力工具,将在石油的分子水平表征领域发挥重要的作用     

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.     

Structural Studies on Residual Fuel Oil Asphaltenes by RICO Method

Structural characterization of asphaltenes isolated from Saudi Arabian heavy and medium crude oils was undertaken by using ruthenium ion catalyzed oxidation (RICO) method. The RICO method was capable to convert aromatic carbons selectively into carbon dioxide and carboxylic acids and esters group while leaving aliphatic and naphthenic structures of asphaltenes essentially unaffected. Detailed analyses of RICO products of both Arab heavy and Arab medium asphaltenes were conducted using FT-IR, ¹³C-NMR, IC, GPC, and GC-MS techniques. These analyses indicate that the aqueous phase fraction (water-soluble products) obtained from RICO reaction of asphaltenes consists of aliphatic dicarboxylic acids and aromatic poly carboxylic acids with longer alkyl chains. The ¹³C-NMR and GC-MS analyses of organic phase products of asphaltenes indicate that this fraction contains large amount of aliphatic carboxylic acids with longer alkyl groups. The oxidation products of both Arab heavy and Arab medium asphaltenes were found to be dominated by a homologous series of straight chain monocarboxylic acids suggesting that the normal alkyl chains are major and important constituents of the chemical structure of both asphaltenes.     

Structural Studies on Residual Fuel Oil Asphaltenes by RICO Method

Abstract

Structural characterization of asphaltenes isolated from Saudi Arabian heavy and medium crude oils was undertaken by using ruthenium ion catalyzed oxidation (RICO) method. The RICO method was capable to convert aromatic carbons selectively into carbon dioxide and carboxylic acids and esters group while leaving aliphatic and naphthenic structures of asphaltenes essentially unaffected. Detailed analyses of RICO products of both Arab heavy and Arab medium asphaltenes were conducted using FT-IR, ¹³C-NMR, IC, GPC, and GC-MS techniques. These analyses indicate that the aqueous phase fraction (water-soluble products) obtained from RICO reaction of asphaltenes consists of aliphatic dicarboxylic acids and aromatic poly carboxylic acids with longer alkyl chains. The ¹³C-NMR and GC-MS analyses of organic phase products of asphaltenes indicate that this fraction contains large amount of aliphatic carboxylic acids with longer alkyl groups. The oxidation products of both Arab heavy and Arab medium asphaltenes were found to be dominated by a homologous series of straight chain monocarboxylic acids suggesting that the normal alkyl chains are major and important constituents of the chemical structure of both asphaltenes.     

CHANGES IN THE COMPOSITION AND PROPERTIES OF THE VACUUM RESIDUES AS A RESULT OF VISBREAKING

Two vacuum residues of heavy petroleum blends and residues of the products of their visbreaking, on a commercial unit, were investigated by means of column chromatography, cryoscopic analysis, elemental analysis, NMR spectroscopy, etc. An increase in the contents of asphaltenes and saturated, increase in asphaltenes/polar components ratio, and decrease in the aromatics contents during visbreaking were observed for both kinds of feed. The N/C ratio increased, the S/C ratio did not change significantly. Most of the nickel and vanadium were concentrated in the asphaltenes and aromatics. The length of the paraffinic chains of the saturated decreases during visbreaking from about 50 to 30 carbon atoms. The number of carbon atoms per alkyl chain and the number of naphthenic rings in the average molecule of the aromatics decreased, whereas the number of aromatic rings increased. About 2/3 of the total aromatic carbon in the aromatics are non-bridged. The average asphaltenes molecule contains about 36-38 aromatic rings (mostly condensed), 5-7 naphthenic rings and 12-16 alkyl substituents having relatively short (n = 5-6) chains. Two contrary processes, relating asphaltenes, take place during visbreaking: 1) cracking of asphaltenes, which results in a decrease in their content and molecular weight, decrease in the number of the side chains and their length, and increase in asphaltenes aromaticity; 2) asphaltenes formation from the polar components of the feed. The resulting process may be expressed both in a decrease and in an increase in the asphaltenes content. Reactions of condensation of the asphaltenes precursors (resins, etc.) prevail for the light stocks. For heavier stocks, cracking of the asphaltenes plays a more significant role, and the increase in asphaltenes content takes place mainly due to concentrating them in the visbreaking residue as a result of the distillation of the visbroken product.     

CHANGES IN THE COMPOSITION AND PROPERTIES OF THE VACUUM RESIDUES AS A RESULT OF VISBREAKING

ABSTRACT

Two vacuum residues of heavy petroleum blends and residues of the products of their visbreaking, on a commercial unit, were investigated by means of column chromatography, cryoscopic analysis, elemental analysis, NMR spectroscopy, etc. An increase in the contents of asphaltenes and saturated, increase in asphaltenes/polar components ratio, and decrease in the aromatics contents during visbreaking were observed for both kinds of feed. The N/C ratio increased, the S/C ratio did not change significantly. Most of the nickel and vanadium were concentrated in the asphaltenes and aromatics. The length of the paraffinic chains of the saturated decreases during visbreaking from about 50 to 30 carbon atoms. The number of carbon atoms per alkyl chain and the number of naphthenic rings in the average molecule of the aromatics decreased, whereas the number of aromatic rings increased. About 2/3 of the total aromatic carbon in the aromatics are non-bridged. The average asphaltenes molecule contains about 36-38 aromatic rings (mostly condensed), 5-7 naphthenic rings and 12-16 alkyl substituents having relatively short (n = 5-6) chains. Two contrary processes, relating asphaltenes, take place during visbreaking: 1) cracking of asphaltenes, which results in a decrease in their content and molecular weight, decrease in the number of the side chains and their length, and increase in asphaltenes aromaticity; 2) asphaltenes formation from the polar components of the feed. The resulting process may be expressed both in a decrease and in an increase in the asphaltenes content. Reactions of condensation of the asphaltenes precursors (resins, etc.) prevail for the light stocks. For heavier stocks, cracking of the asphaltenes plays a more significant role, and the increase in asphaltenes content takes place mainly due to concentrating them in the visbreaking residue as a result of the distillation of the visbroken product.     

聚α—烯烃烷基侧链结构对降凝效果和适应性的影响

以皂蜡（含油量＜5％）裂解的聚α-烯烃为原料,考察了烷基侧链平均碳原子数不同的聚α-烯烃降凝剂在不同性质基础油中的降凝效果以及烷基侧链碳原子数分布不同的聚α-烯烃降凝剂在不同性质基础油中的适应性,工业实验结果表明：选择碳原子数分布在C7－C20的宽馏分聚α-烯烃为原料,所得的聚α-烯烃降凝剂烷基侧链平均碳原子数在11．3左右时,可使各种不同性质的轻质基础油的凝固点降低25－32℃,烷基侧链平均碳原子数在11．7左右时,可使中间基不同性质的重质基础油的凝固点降低15－20℃,使石蜡基不同性质的重质基础油的凝固点降低10－15℃。     

STRUCTURAL CHARACTERIZATION OF GUDAO ASPHALTENE BY RUTHENIUM ION CATALYZED OXIDATION

ABSTRACT

Structural characterization of Gudao asphaltene was undertaken by using ruthenium ion catalyzed oxidation (RICO ) which is capable of converting aromatic carbons selectivety to carbon dioxide and/or carboxyUc groups while leaving aliphatic and alicyclic structures essentially unaffected. The oxidation products were dominated by a homologous series of straight chain monocarboxyfic acids ( C₂ -C₃₅) indicating that normal alkyl chains are important constituents of the asphaltene. A series of α,ω; -dicarboxylic acids (C₄ - C₂₆) were also detected and determined, confirming the presence of poh/methylenc mokties linking two aromatic units. Relative high yields of benzenepenta- and hexacarboxyhc acids fonned in the RICO of Gudao asphaltene clearly indicate that substantia] aromatic structures of this asphaltene are peri-condensed.     

催化裂化汽油中芳烃在酸性催化剂上反应规律的研究

在提升管中型催化裂化装置上,采用MLC-500催化剂,分别以全馏分和重馏分汽油为原料研究在催化转化过程中,汽油中的芳烃在不同反应温度下的转化规律.结果表明,以全馏分汽油为原料,反应温度较低时,主要发生芳环的烷基化反应;在较高温度下,芳环的烷基化反应和芳环上侧链的裂化反应都比较明显.以重馏分汽油为原料,在实验温度范围内主要发生芳环上侧链的裂化反应,随着反应温度的提高,裂化向含有较少碳数的芳烃转移.