煤直接液化制取喷气燃料原料油的组成分析

以国产煤液化油为原料,通过实沸点蒸馏,切割同喷气燃料馏分范围一致的航空煤油馏分;对切得的航空煤油馏分进行了理化性能、烃类组成分布、碳数分布及部分单体烃含量检测.结果表明,煤液化航空煤油馏分的部分指标不符合喷气燃料规范要求,不能直接用作喷气燃料,但它又具有高密度、高闪点、低冰点等突出优点.煤液化航空煤油馏分含有大量的环烷烃、四氢萘和茚满衍生物以及烷基苯酚类化合物.煤直接液化合成煤油馏分所具有的高密度、高闪点、低冰点以及富含环烷烃和氢化芳烃的特点,使其凸显高性能喷气燃料的特征,因此作为未来开发高性能喷气燃料的原液具有良好的发展前景.     

加氢催化裂化柴油关键组分催化裂化的反应特性研究

以四氢萘、茚满、十氢萘和3-乙基甲苯4种加氢催化裂化柴油（LCO）关键组分作为模型化合物,采用小型固定流化床（ACE）装置和Y分子筛催化剂进行了系统的催化裂化反应性能研究。结果表明：在两种转化深度下,模型化合物均表现出其特有的反应特性,四氢萘以发生氢转移反应为主,茚满更倾向于烷基化/烷基转移和脱氢-缩合生成C₉+重芳烃,十氢萘虽具有较高的开环-裂化反应选择性,但芳烃产物选择性较低,3-乙基甲苯轻质化效率主要受到异构化反应的影响;高转化深度更有利于模型化合物转化生成轻质芳烃苯、甲苯、乙苯和二甲苯（合称BTEX）,四氢萘、茚满、十氢萘和3-乙基甲苯催化裂化反应的BTEX选择性分别为22.65%,19.66%,15.70%,34.36%;四氢萘和茚满容易发生连续的α位C—C键断裂生成苯,十氢萘由于存在两个叔碳正离子更倾向于生成二甲苯,3-乙基甲苯具有较高的甲苯和乙苯选择性。     

金属与分子筛含量对预加氢1-甲基萘的加氢裂化催化剂的影响

考察了加氢裂化催化剂中HY分子筛与金属负载量对其催化1-甲基萘精制油样加氢裂化反应产物的影响。结果表明,在酸性较强的催化剂上甲基四氢萘类反应主要是单分子反应机理,通过异构开环路径生成较大量单环芳烃,同时有一定量BTX化合物生成。HY分子筛质量分数的增加可提高催化剂中中强B酸中心数量,提高四氢萘类异构开环转化成断侧链单环芳烃的选择性;增加催化剂的金属负载量对四氢萘类生成多环烷烃及单环烷烃有利。     

加氢裂化产品分子组成特点及其随转化深度的变化规律研究

采用气相色谱/质谱（GC/MS）及气相色谱/场电离-飞行时间质谱（GC/FI-TOF MS）对加氢裂化全馏分产品进行表征分析,考察了全馏分产品的分子组成特点,并对其分子组成随反应深度的变化规律进行探讨。结果表明：全馏分产品中正构烷烃主要分布在C18～C40的较高碳数范围内;随转化深度的增加,异构烷烃含量大幅度增加,正构烷烃含量整体变化较小,原料中链烷烃的含量及组成直接影响尾油馏分产品BMCI值及低温流动性;在全馏分产品的环烷烃化合物中,C5～C13范围内一环环烷烃含量最高,侧链碳数大于7的一至三环环烷烃更易发生断侧链反应,趋向于转化为侧链碳数更低的环烷烃化合物;芳烃化合物主要分布在小于350 ℃馏分中,主要以烷基苯、茚满及萘满的形式存在,较少以无侧链取代苯的形式存在。     

多环芳烃指纹参数在催化裂化过程中的应用

采用气相色谱-质谱法分析1-甲基萘/戊基苯、四氢萘两种反应体系的烷基萘含量,发现α位和β位烷基萘质量分数随着反应转化率的升高而增加,而且不同取代位烷基萘质量分数之比（烷基萘参数）可以反映反应体系转化率的高低。进一步研究发现,不同体系的烷基萘反应机理相同,并且烷基萘产物分布受到分子筛孔道的限制。提取5种不同减压馏分油反应后的液体产物中烷基萘、烷基菲的含量信息,发现烷基萘参数与油品转化率的线性关系较好,而烷基菲参数与油品转化率的线性关系较差,因此烷基萘参数更适合作为反映减压馏分油转化率高低的指标。     

云南先锋褐煤液化轻质油的分析

采用双球计量管法将云南先锋褐煤液化轻质油(简称褐煤液化轻质油)萃取分离为酸性组分、碱性组分和中性组分;用经典柱色谱法对中性组分进行族组成分离,分离为饱和烃、芳烃和极性化合物3种组分;通过气相色谱-质谱联用仪分析了酸性组分、碱性组分和芳烃的组成。实验结果表明,褐煤液化轻质油中酸性组分、碱性组分和中性组分的质量分数分别为23.46%,0.68%,75.86%;酸性组分主要为苯酚及其烷基衍生物,其中苯酚、甲酚和二甲酚的质量分数分别为16 11%,33.55%,14.44%;碱性组分以烷基吡啶为主,三甲基吡啶的质量分数为23.41%;中性组分以芳烃为主,芳烃中单环芳烃最多,双环芳烃其次,质量分数分别为37.91%,28.69%。     

基于高温裂解仪的氢化芳烃热裂解研究

以顺式十氢萘、反式十氢萘、四氢萘、茚满等为氢化芳烃模型化合物,利用高温裂解仪与气相色谱串联装置快速评价了不同结构氢化芳烃的热裂解性能,研究了其热裂解行为。结果表明：热裂解时,十氢萘以开环裂解反应为主,反应温度升高时,其开环裂解反应选择性降低,脱氢反应和氢转移反应增强,反应物原子利用变得不合理;受苯环大π键影响,四氢萘和茚满环烷环上C—H键的键能较低,其脱氢能力与氢转移能力较强,产物以芳烃为主;氢饱和度高的氢化芳烃是生产低碳烯烃的优质原料,含苯环的芳香基氢化芳烃是生产苯、甲苯、二甲苯(BTX)的优质原料。     

氢油体积比对柴油加氢烃类碳数分布的影响

以不同氢油体积比下加氢前后的柴油为研究对象,在对其进行烃类组成分析的基础上,借助气相色谱-场电离飞行时间质谱(GC-FI TOF MS),对加氢反应前后的柴油进行烃类碳数分布组成分析。结果表明:烃类组成分析可以反映柴油加氢前后1环、2环等环烷烃,以及烷基苯等芳烃的组成变化;氢油体积比超过500∶1后,精制柴油的烃类组成无明显变化,可用于指导工艺条件的初步优化;而GC-FI TOF MS的分析结果可以定量化地反映不同氢油体积比对柴油加氢精制过程中烃类碳数分布组成的影响,如氢油体积比由500∶1继续提高时,精制柴油中不同碳数下单环芳烃等烃类组成的变化趋于平缓;集中分布的低碳数多环芳烃通过逐环的加氢反应,转化为低碳数的单环芳烃、2环和3环环烷烃,如原料柴油中C_(10)~C_(15)萘类加氢转化为精制柴油中C_(10)~C_(15)茚满/四氢萘和C_(11)~C_(15)2环环烷烃等反应。     

NiMo加氢催化剂上1-甲基萘的饱和反应规律

 以NiMo/Al₂O₃为催化剂,1-甲基萘作为加氢反应的模型化合物,在高压加氢微反装置上考察了不同温度、压力下的反应规律,并利用Material studio模拟计算得出加氢反应过程中的反应自由能(ΔG),得到了1-甲基萘加氢饱和的热力学反应网络和双环芳烃部分加氢生成甲基四氢萘较优的工艺条件。结果表明,在温度360℃、氢分压4.0 MPa下,1-甲基萘加氢饱和生成甲基四氢萘的选择性高达98.3%以上;适当增加氢分压对1-甲基萘加氢生成四氢萘类有利,而过高压力和温度会降低生成四氢萘类的选择性;热力学反应网络表明,生成四氢萘类的反应自由能要远低于进一步生成十氢萘的自由能,同时加氢优先发生在无烷基取代的芳环上,在压力为3.0~4.5 MPa、温度为330~370℃条件下,产物中5-甲基四氢萘与1-甲基四氢萘的质量分数比均接近2。     

轻汽油芳构化工艺条件优化

以催化裂化轻汽油为原料,采用大连理工大学开发的SHY-DL催化剂在200 mL多功能固定床试验装置上进行了芳构化反应工艺条件的优化及长周期稳定运行试验。结果表明:随着反应温度升高,烯烃转化率,干气和液化石油气(LPG)收率,C_5～205℃馏分中芳烃质量分数均增加,C_(≥5)液体收率下降;随着反应压力增大,C_5～205℃馏分中芳烃质量分数和C_(≥5)液体收率减小;随着质量空速提高,烯烃转化率和C_5～205℃馏分中芳烃质量分数降低,而C_(≥5)液体收率则增加;在反应温度为380℃,反应压力为1.6 MPa,质量空速为3.0 h~(-1)的最佳工艺条件下,运行1 500 h后,C_(≥5)液体收率大于50%,C_5～205℃馏分中芳烃质量分数高于40%。     

柴油馏分碳数分布的预测研究

收集一定数量的柴油馏分样品，利用标准方法分别测定其基本物性、烃类组成信息和详细的碳数分布信息，建立起对应的数据库。对于一个待测柴油样本，首先根据其物性数据和烃类组成信息在库中找出与之距离最近的6个样本，然后利用这几个样本的信息，结合过采样技术在待测样本周围生成大量的虚拟样本，最后根据KNR算法进行回归计算，选择与待测样本最相似的4个虚拟样本，将这些样本的碳数分布组成信息进行线性加权加和，以此作为待测样本的预测值。将该方法应用于直馏柴油碳数分布的预测模型，柴油的硫含量、氮含量、酸值以及11个烃类（分别为链烷烃、单环烷烃、双环烷烃、三环烷烃、烷基苯、茚满/四氢萘、茚类、萘类、苊类、苊烯类和三环芳烃）的组成信息作为模型的输入特征，计算结果表明，这种模型能同时计算出直馏柴油中312项碳数集总的含量，计算速度快，准确度高，模型维护简单，具有一定的应用价值。     

AN EVALUATION OF OIL PRODUCED FROM ASPHALT RID (UTAH) TAB SAND AS A FEEDSTOCK FOR THE PRODUCTION OF ASPHALT AND TURBINE FUELS

In this article an evaluation is made of the potential end uses of an oil produced from Asphalt Ridge tar sand by wet forward combustion. The oil is evaluated with respect to its potential to produce a specification-grade asphalt and aviation turbine fuels. To accomplish this the oil was vacuum distilled to produce a distillate and a residue. The distillation residue meets all of the ASTM D 3381 Table 1 specification tests for an AC-10 asphalt. However, the viscosity at 135°C (275°F) is low when compared with the more stringent D 3381 Table 2 requirements. This indicates that the residue has a higher temperature susceptibility than allowed for by Table 2. The residue also has an unusually low aging index. This indicates that it may not set properly. However, it may also mean that it may be resistant to rapid age hardening. The results from successive freeze-thaw cycling indicate that the residue, when coated on appropriate aggregates, is comparable to or better than some petroleum asphalts coated on the same aggregates. Freeze-thaw cycling to failure is an indirect measure of the resistance of an asphalt-aggregate mixture to moisture-induced loss of strength

The distillate of the thermally-produced oil which represents about 50 wt % of the whole oil was also evaluated as a feedstock for the production of transportation fuels. The chemical and physical properties of the distillate are improved with respect to those of the original bitumen and the thermally-produced oil. Combined gas chromatographic/mass spectral analysis of the neutral fraction from the distillate indicates it is composed of predominantly aromatic structures. The aromatic structures are primarily of the 2- and 3-     

APPLICATION OF NORMAL AND DERIVATIVE ULTRAVIOLET ABSORPTION SPECTROSCOPY FOR THK DETERMINATION OF AROMATIC HYDROCARBONS IN GAS OILS

Ultraviolet absorption spectroscopy, has an immense potential for characterization of aromatic hydrocarbons in distillate petroleum fractions. The second derivative ultraviolet spectroscopy has improved the understanding of complex aromatic structures, such as polynuclear aromatics, which are present in gas oil fractions. Normal and second derivative ultraviolet spectroscopy of gas oils and their separated fractions are discussed in detail and conclusions are drawn regarding mono-di-and polynuclear aromatics in various gas oils.     

AN EVALUATION OF OIL PRODUCED FROM ASPHALT RID (UTAH) TAB SAND AS A FEEDSTOCK FOR THE PRODUCTION OF ASPHALT AND TURBINE FUELS

Abstract

In this article an evaluation is made of the potential end uses of an oil produced from Asphalt Ridge tar sand by wet forward combustion. The oil is evaluated with respect to its potential to produce a specification-grade asphalt and aviation turbine fuels. To accomplish this the oil was vacuum distilled to produce a distillate and a residue. The distillation residue meets all of the ASTM D 3381 Table 1 specification tests for an AC-10 asphalt. However, the viscosity at 135°C (275°F) is low when compared with the more stringent D 3381 Table 2 requirements. This indicates that the residue has a higher temperature susceptibility than allowed for by Table 2. The residue also has an unusually low aging index. This indicates that it may not set properly. However, it may also mean that it may be resistant to rapid age hardening. The results from successive freeze-thaw cycling indicate that the residue, when coated on appropriate aggregates, is comparable to or better than some petroleum asphalts coated on the same aggregates. Freeze-thaw cycling to failure is an indirect measure of the resistance of an asphalt-aggregate mixture to moisture-induced loss of strength

The distillate of the thermally-produced oil which represents about 50 wt % of the whole oil was also evaluated as a feedstock for the production of transportation fuels. The chemical and physical properties of the distillate are improved with respect to those of the original bitumen and the thermally-produced oil. Combined gas chromatographic/mass spectral analysis of the neutral fraction from the distillate indicates it is composed of predominantly aromatic structures. The aromatic structures are primarily of the 2- and 3-     

气相色谱-飞行时间质谱联用仪测定柴油烃类分子组成的馏程分布

利用气相色谱-飞行时间质谱联用仪（GC-TOFMS）建立了测定柴油烃类分子组成的馏程分布的方法,可以得到柴油样品中各种类型烃类在不同馏程段的碳数分布与平均相对分子质量。利用所建方法研究了柴油中各种类型烃类平均分子结构随馏程的变化情况,发现柴油不同馏程段的平均相对分子质量与其芳烃含量和烃类异构化程度有关：芳烃含量越低、烃类异构化程度越高,该馏程段的平均相对分子质量越高。考察了柴油加氢精制前后烃类分子组成的馏程分布变化情况,柴油经加氢精制后,饱和烃的馏程分布基本不变,只是含量有所增加,芳烃的馏程分布在低馏分段没有变化,在高馏分段含量下降,导致产物的平均相对分子质量在高馏分段高于原料的平均相对分子质量。     

2-甲基四氢呋喃的回收工艺研究

在制备三苯基硅烷时需使用大量的2-甲基四氢呋喃作溶剂,而三苯基硅烷中并不含有2-甲基四氢呋喃。因此,从经济性、环境保护等方面考虑,对2-甲基四氢呋喃进行回收、精制和再利用是完全必要的。通过蒸馏和使用分子筛对2-甲基四氢呋喃进行回收、精制,使回收得到的2-甲基四氢呋喃能够达到再利用,特别是能满足制备格氏试剂的要求。采用2种方案进行实验。方案1：一次蒸馏→分子筛除水→二次蒸馏;方案2：一次蒸馏→二次蒸馏→分子筛除水。方案1的2-甲基四氢呋喃最终收率为85．93％,纯度为99．4295％;方案2的2-甲基四氢呋喃最终收率为84．91％,纯度为96．0629％。因此,溶剂2-甲基四氢呋喃的回收应采用一次蒸馏→分子筛除水→二次蒸馏的方案。     

DISTILLATION CHARACTERISTICS AND COMPOSITIONAL ANALYSIS OF ARABIAN LIGHT STRAIGHT RUN NAPHTHA

Straight run naphtha is a basic constituent of refined petroteum products. It consists mainly of aliphatic hydrocarbons along with small amounts of naphthenic and aromatic hydrocarbons. It has a wide boiling range between 95°F and 410°F. Currently, its main utilization is as gasoline blend, however, naphtha is a potential feedstock for the production of various petrochemicals. Continuous catalytic reforming of naphtha can produce aromatic compounds in amounts up to 70% of the reformat. Nevertheless, the catalytic reforming process is usually associated with various limitations that may be related to the wide-ranging composition of naphtha. In this study straight run naphtha derived from Arabian Light crude oil was fractionated, and the hydrocarbon composition of its different distillation cuts was determined. The results indicate that, straight run naphtha can be split into two main fractions. A light fraction boiling between ambient temperature and 225°F, consists mainly of C₇^(-) and a medium heavy fraction boiling between 225°F and 335°F, consists mainly of C₇⁽⁺⁾. Detailed distillation characteristics, along with compositional analysis of SRN seems to be useful for diversifying its processing technologies, and upgrading currently applied processing practices to yield various high-value products and petrochemicals feed stocks.     

The composition of aromatic destruction products of Domanic shale kerogen after aquathermolysis

In this article we studied a sample of Domanic rock with high kerogen content obtained from Volga-Ural oil and gas basin. A laboratory modeling of the catagenesis process was carried out in order to establish the transformation mechanism of organic matter. The composition of liquid products resulting from kerogen pyrolysis was investigated. The kerogen fragments fall in aromatic hydrocarbons fraction. Alkyltoluenes also exist in saturated hydrocarbon fractions due to alkyl substitutes. The thermal influence changes the ratios of relative content of ortho-, para- and meta-isomers. Heavy aromatic hydrocarbons content increases by increasing temperature and kerogen macroelements ratio changed under thermal effect that is an indicator for maturation process of organic matter.     

炼油厂恶臭污染源综合监测与评价 Ⅱ. 污染源分级与排放评估

 系统地监测和评价了某典型炼油厂各类储罐排放气、污水处理场逸散气及氧化脱硫醇尾气等主要恶臭污染源,估算了臭气浓度和总烃、苯系物、臭味排放量。结果表明：上述恶臭污染源非甲烷烃、苯、甲苯和二甲苯、硫化氢、甲硫醇、乙硫醇和二甲二硫等污染物均有不同程度的超标,浓度超标比排放量超标严重;污染物和污染源按排放量可各分为三类,一类的恶臭污染物为硫化氢,其臭味排放贡献约占67.9％;二类恶臭污染物为甲硫醇、乙硫醇、异丙硫醇、二甲二硫、甲乙二硫和二乙二硫,臭味排放贡献合计约占31.8％;三类恶臭污染物为苯系物,臭味排放贡献合计仅占0.3%。一类的恶臭污染源为酸性水罐废气,其臭味排放贡献约为57.1％;二类恶臭污染源为污水处理场、高温蜡油罐和污油罐废气,臭味排放贡献合计约占37.3％;三类恶臭污染源为碱渣罐、冷焦水罐、油品中间罐和氧化脱硫醇废气,臭味排放贡献合计约占5.6％。主要恶臭污染源总烃和苯系物排放总量分别约为261 kg/h和23.8 kg/h,其中污水处理场、酸性水罐及氧化脱硫醇合计约占总烃排放量的三分之二,污水处理场和冷焦水罐合计约占苯系物排放量的三分之二。     

DISTILLATION CHARACTERISTICS AND COMPOSITIONAL ANALYSIS OF ARABIAN LIGHT STRAIGHT RUN NAPHTHA

ABSTRACT

Straight run naphtha is a basic constituent of refined petroteum products. It consists mainly of aliphatic hydrocarbons along with small amounts of naphthenic and aromatic hydrocarbons. It has a wide boiling range between 95°F and 410°F. Currently, its main utilization is as gasoline blend, however, naphtha is a potential feedstock for the production of various petrochemicals. Continuous catalytic reforming of naphtha can produce aromatic compounds in amounts up to 70% of the reformat. Nevertheless, the catalytic reforming process is usually associated with various limitations that may be related to the wide-ranging composition of naphtha. In this study straight run naphtha derived from Arabian Light crude oil was fractionated, and the hydrocarbon composition of its different distillation cuts was determined. The results indicate that, straight run naphtha can be split into two main fractions. A light fraction boiling between ambient temperature and 225°F, consists mainly of C₇ ^(?) and a medium heavy fraction boiling between 225°F and 335°F, consists mainly of C₇ ⁽⁺⁾. Detailed distillation characteristics, along with compositional analysis of SRN seems to be useful for diversifying its processing technologies, and upgrading currently applied processing practices to yield various high-value products and petrochemicals feed stocks.