EFFECT OF ATTAPULGITE CLAY ON THE COMPOSITION OF JET FUELS

To identify the chemistry of polar molecules affecting the stability of jet fuels, spent Attapulgite clays collected from the top, middle and the bottom of the clay treater, were analyzed. The GC/MS analysis allowed for the selective desorption of polar organic molecules. At the low temperature range of 50–200°C, the GC/MS analysis showed desorption of C₉–C₁₆ hydrocarbons which are typical jet fuel molecules. At the higher temperature range of 50–400°C, the GC/MS analysis of spent clays showed desorption of water, amines, pyridines, quinolines, thiophenes, sulfides, thiols and alkylbenzenes. At the high temperature range of 50–600°C, the GC/MS analysis showed desorption of water, phenols, pyridines, quinolines, alkylbenzenes and other unidentified N compounds. No desorption of S compounds was observed above 400°C. Desorption of water above 200°C indicated that the water molecules were held inside the crystalline structure of the clay. The Attapulgite clay was found to be effective in adsorbing a wide range of polar molecules from jet fuel. Desorption of pyridines, quinolines and alkylbenzenes below and above 400°C indicated that their chemistry was different and required different energy to desorb from the clay. The high adsorbent capacity clays capable of adsorbing different chemistry polar molecules are required to assure stability of jet fuels.     

SURFACE ACTIVE PROPERTIES OF CLAY TREATED JET FUELS

The effect of water contamination in jet fuels on the adsorbent capacity of Attapulgite clay to adsorb and retain N compounds was studied. The effluent jet fuel showed the presence of N molecules indicating that the clay, contaminated with water, does not retain N compounds. The GC/MS analysis of spent clay indicated that only quinolines were adsorbed and retained on the clay. The interfacial tension (IFT) values measured at the jet fuel/water interface were found to increase with a decrease in basic N content of clay treated jet fuels. Quinolines and pyridines present in jet fuel are surface active and adsorb on the Attapulgite clay, however, in the presence of water some N molecules adsorb at the jet fuel/water interface. Since pyridines were not found on the spent clay, the results indicate that the pyridines adsorb at the jet fuel/water interface. The tendency of pyridines to adsorb at the jet fuel/water interface will lead to their poor retention on the clay. The presence of N compounds and water contamination in jet fuel might lead to inefficient operation of clay treaters. The jet fuels having the IFT value below 40 mN/m were found to contain basic N molecules and have poor stability. The clay treated jet fuels having the IFT values in the range of 42.6–46.2 mN/m were found to have a good stability. The use of IFT measurements at the jet fuel/water interface provides an opportunity to better monitor the efficiency of clay treatment and the quality of jet fuels.     

SURFACE ACTIVE PROPERTIES OF CLAY TREATED JET FUELS

The effect of water contamination in jet fuels on the adsorbent capacity of Attapulgite clay to adsorb and retain N compounds was studied. The effluent jet fuel showed the presence of N molecules indicating that the clay, contaminated with water, does not retain N compounds. The GC/MS analysis of spent clay indicated that only quinolines were adsorbed and retained on the clay. The interfacial tension (IFT) values measured at the jet fuel/water interface were found to increase with a decrease in basic N content of clay treated jet fuels. Quinolines and pyridines present in jet fuel are surface active and adsorb on the Attapulgite clay, however, in the presence of water some N molecules adsorb at the jet fuel/water interface. Since pyridines were not found on the spent clay, the results indicate that the pyridines adsorb at the jet fuel/water interface. The tendency of pyridines to adsorb at the jet fuel/water interface will lead to their poor retention on the clay. The presence of N compounds and water contamination in jet fuel might lead to inefficient operation of clay treaters. The jet fuels having the IFT value below 40 mN/m were found to contain basic N molecules and have poor stability. The clay treated jet fuels having the IFT values in the range of 42.6-46.2 mN/m were found to have a good stability. The use of IFT measurements at the jet fuel/water interface provides an opportunity to better monitor the efficiency of clay treatment and the quality of jet fuels.     

喷气燃料组成对润滑性影响的实验研究

考察了加氢喷气燃料主体烃组分对燃料润滑性的影响。根据喷气燃料的组成,选择代表喷气燃料不同组分的纯化合物,建立简单的模拟系统,研究其对喷气燃料润滑性的贡献。结果表明,碳数相同的烃组分中润滑性以芳烃最好,其次为烯烃、环烷烃,链烷烃最差。将四氢萘、二甲苯和1-癸烯按比例加入到加氢喷气燃料基础油中,四氢萘对燃料润滑性的改善优于1-癸烯和二甲苯;对燃料润滑性起主要作用的是在加氢喷气燃料中含量很少的四氢萘和烯烃,含量多的二甲苯对喷气燃料润滑性的影响很小。     

EFFECT OF CLAYS AND ADSORBENTS ON THE NITROGEN CONTENT AND THE STABILITY OF JET FUELS

The effect of composition, surface area and pH of different clays and alumina adsorbents on the stability of jet fuel was studied. The stability of jet fuel was tested following the ASTMD 3241 procedure. Under the batch adsorption conditions, clays and adsorbents were not effective in adsorbing polar molecules and improving the stability of jet fuels. Under the column adsorption conditions, the effectiveness of clays and adsorbents in improving the stability of jet fuel was found to vary. Clays having a high surface area and an acidic pH were found to be more effective in adsorbing polar molecules and improving the stability of jet fuel. High surface area alumina adsorbents were found effective in adsorbing basic nitrogen molecules and improving the stability of jet fuel despite having a basic pH. The basic type nitrogen compounds, pyridines and quinolines, were found to affect the stability of jet fuel. The initial effluent jet fuel passed through fresh clays was found to have no N compounds and a good stability. However, the analysis of effluent jet fuel showed a gradual increase in N content reaching the level of N content in untreated jet fuel. The effluent jet fuel reaching 9-10 ppm of N content failed the stability test indicating that clays need to adsorb and retain N compounds. The adsorbent capacity of different clays was studied but no significant difference in retaining N molecules was observed.     

EFFECT OF CLAYS AND ADSORBENTS ON THE NITROGEN CONTENT AND THE STABILITY OF JET FUELS

The effect of composition, surface area and pH of different clays and alumina adsorbents on the stability of jet fuel was studied. The stability of jet fuel was tested following the ASTMD 3241 procedure. Under the batch adsorption conditions, clays and adsorbents were not effective in adsorbing polar molecules and improving the stability of jet fuels. Under the column adsorption conditions, the effectiveness of clays and adsorbents in improving the stability of jet fuel was found to vary. Clays having a high surface area and an acidic pH were found to be more effective in adsorbing polar molecules and improving the stability of jet fuel. High surface area alumina adsorbents were found effective in adsorbing basic nitrogen molecules and improving the stability of jet fuel despite having a basic pH. The basic type nitrogen compounds, pyridines and quinolines, were found to affect the stability of jet fuel. The initial effluent jet fuel passed through fresh clays was found to have no N compounds and a good stability. However, the analysis of effluent jet fuel showed a gradual increase in N content reaching the level of N content in untreated jet fuel. The effluent jet fuel reaching 9–10 ppm of N content failed the stability test indicating that clays need to adsorb and retain N compounds. The adsorbent capacity of different clays was studied but no significant difference in retaining N molecules was observed.     

植物油加氢转化制喷气燃料

随着石油资源日益枯竭、CO2减排压力日益增加和航空业需求日益增强,发展生物喷气燃料技术是实现我国航空领域绿色可持续发展的必然要求.在生物喷气燃料生产技术中,植物油加氢转化制喷气燃料路线技术相对较成熟,工艺路线短,成本低,受到了广泛的关注.介绍了喷气燃料的有关规格要求以及植物油的组成和特性,详细论述了这一路线的主要反应过...     

盆地形成演化对粘土矿物组成和分布的影响

物源、古气候、沉积环境和成岩作用是控制含油气盆地内泥岩粘土矿物分布特征的4个主要因素,这4个因素均与盆地形成的大地构造背景和构造发育史密切相关.我国东、西部含油气盆地的大地构造背景、形成机制和构造发育史明显不同,文中研究了这些因素对泥岩粘土矿物分布特征的影响.     

溶解氧对喷气燃料润滑性能的影响

利用球柱润滑性试验机和ＲＪＹ－２型溶解氧测定仪，研究了溶解氧对喷气燃料润滑性的影响。研究结果表明，给喷气燃料通入氮气可迅速降低其中溶解氧，在充氮气条件下，６种试样溶解氧含量比充空气时，平均下降３０．５μｇ／ｇ，磨痕直径比充空气时平均减小了０．０４８ｍｍ，表明降低喷气燃料中溶解氧含量有利于改善其润滑性能。     

影响喷气燃料与橡胶相容性的因素

采用几种具有不同初始物理性能及不同丙烯腈含量、不同硫化剂和硫化程度的丁腈橡胶，考察了其配方和物理性能对采用不同工艺条件生产的喷气燃料的相容性。结果表明，喷气燃料与橡胶的相容性不仅与喷气燃料的加工工艺有关，而且与橡胶的组成及其制备工艺有关。采用非加氢工艺生产的喷气燃料与橡胶的相容性好于采用加氢工艺(特别是加氢裂化工艺)生产的喷气燃料。橡胶材料的初始力学性能的好坏并不完全决定其与喷气燃料相容性的好坏，橡胶材料的耐过氧化物侵蚀能力才是影响相容性好坏的主要因素。橡胶的组成和其制备工艺决定了橡胶在喷气燃料中萃取物的数量和组成，不同萃取物的综合作用给相容性带来不同程度的影响。用硫作硫化剂的橡胶虽然原始强度低于用过氧化物作硫化剂的橡胶，但前者与喷气燃料的相容性却远好于后者。     

取消喷气燃料中33号添加剂的研究

喷气燃料３３号添加剂，用作防止镍基合金火焰筒的烧蚀。长期使用中发现，它对喷气燃料的润滑性、安全性和安定性有不良影响。经过不加３３号添加剂喷气燃料的发动机长期台架试车、外场长期定点定机飞行试验考察、到寿命发动机返厂拆检，以及对航空发动机机型与其火焰筒结构和材质改进方面的调研，认为在保证飞行安全的条件下，可以取消喷气燃料３３号添加剂，这有利于提高喷气燃料质量和环境保护，并具有较好的经济和社会效益。     

凹凸棒黏土脱色剂对FCC汽油脱色的实验研究

 以甘肃临泽凹凸棒黏土为载体,加入硝酸铁活性剂制备成汽油脱色剂,对精制前FCC汽油进行脱色。通过正交实验考察了制备凹凸棒黏土脱色剂时的酸度、焙烧温度、活性剂加入量以及对FCC汽油脱色时采用的脱色剂用量和脱色时间对脱色效果的影响。结果表明,采用以焙烧温度600℃、硫酸质量分数6%、活性剂质量分数4%制备的凹凸棒黏土脱色剂,在脱色剂用量16g、脱色时间80min、汽油/脱色剂剂质量比为5的条件下,能够使FCC汽油的一次脱色率达到96.94%;当油/剂质量比为25时,脱色率达到80.06%。     

喷气燃料中溶解水含量变化规律研究

水含量是喷气燃料质量检测的一项重要性能指标。针对环境温度、湿度、储存时间、防冰剂含量等因素对喷气燃料中溶解水含量的影响,采用微量水分测定仪研究了不同条件下喷气燃料中溶解水含量的变化规律,确立了变化规律模型,建立了溶解水含量数据库,为进一步准确、高效测定喷气燃料中的水含量提供了参考依据。     

EFFECT OF PRECIPITATION TEMPERATURE ON THE COMPOSITION OF N-HEPTANE ASPHALTENES

Petroleum asphaltenes were separated from Boscan and Kuwait crude oils by n-heptane at constant temperatures ranging from -2 to 80 ° C. A decreased yield with increase in temperature was observed. The precipitated material was characterized using infrared spectroscopic functional group analysis, HPLC-size exclusion chromatography, vapor pressure osmometry, and elemental analysis. The change in vanadium porphyrin content was estimated for Boscan using UV-Vis. With elevated temperature the asphaltenes are more aromatic (lower H/C) and have higher apparent molecular weight, whereas the pattern of changes in functional groups and heteroatoms (NSO) are more complex and apparently dependent on the crude oil. Porphyrins and low molecular weight types were seen to stay in solution at increased temperature, and a specific extraction of these takes place above 40 ° C. Asphaltene solubility is seen to approximate the Flory-Huggins theory as small molecules go into solution before large molecules. Several other mechanisms may, however, be involved in the phase separation. The molecular size distribution curves obtained by HPLC-SEC were found to explain the trends found in the molecular weights by VPO.     

生物柴油对低硫柴油润滑性的增进作用

用菜籽油、大豆油以及芸香籽油制备了多种脂肪酸低碳醇酯即生物柴油，用高频往复试验机法（HFRR）考察了生物柴油对低硫柴油润滑性的增进作用。研究结果表明，生物柴油对低硫柴油润滑性有增进作用，但添加质量分数在0．2％以下时效果不明显；柴油组分不同，对生物柴油的感受性也不同：对于馏分较重、粘度较大的柴油，生物柴油的添加量只需超过2．0％其润滑性就能满足标准要求（磨斑直径不大于460／μm）；而对于馏分较轻、粘度较小的柴油，需添加4．0％～5．0％才能使其润滑性满足要求；生物柴油的烷氧基链长对其润滑性没有明显影响，而甘油单酸酯或游离脂肪酸等杂质能够显著提高其润滑性；以不同植物油为原料制备的生物柴油在较低的添加比例下对低硫柴油的润滑性没有明显的不同，超过2．0％以后略有差别。     

凹凸棒黏土脱色剂对FCC汽油的脱色

以甘肃临泽凹凸棒黏土为载体,加入硝酸铁活性剂制备成汽油脱色剂,对精制前FCC汽油进行脱色。通过正交实验考察了制备凹凸棒黏土脱色剂时的酸度、焙烧温度、活性剂加入量以及对FCC汽油脱色时采用的脱色剂用量和脱色时间对脱色效果的影响。结果表明,采用以焙烧温度600℃、硫酸质量分数6%、活性剂质量分数4%制备的凹凸棒黏土脱色剂,在脱色剂用量16g、脱色时间80min、汽油/脱色剂剂质量比为5的条件下,能够使FCC汽油的一次脱色率达到96.94%;当油/剂质量比为25时,脱色率达到80.06%。     

柴油及组分的润滑性研究

对12个柴油样品的润滑性进行了分析.结果表明,柴油润滑性普遍较差,WS1.4≥460μm,且润滑性与硫含量、总芳烃含量、粘度等性质没有良好的对应关系.通过色谱柱分离等方式解析润滑组分,表明柴油润滑性关键组分是酸性杂环化合物;润滑性好的柴油,其酸度也较大;含氮极性化合物是良好的吸附润滑组分.     

EFFECT OF IRON CATALYST ON THE COMPOSITION OF OIL FROM COAL LIQUEFACTION

ABSTRACT

The effect of two iron catalysts, red mud and CGS S-G, as well as C0-Mo/AI₂O3 and Ni-Mo/Al₂03 commercial catalysts on the composition of oil derived from the liquefaction of Japanese subbituminous coal have been investigated comparatively by conventional autoclave experiments at 440 and 450^°C under initial hydrogen pressure of 85kg/cm² G with tetralin to coal weight ratio of 3. From the results obtained at 450^°C, total conversion and the yield of gas revealed almost same level with four catalysts, but the oil product from molybdenum catalysts showed higher yield than that from iron catalysts. CGS S-G catalyst also showed higher yield of oil product than red mud catalyst. Reaction behavior of two iron catalysts were also tested by solvent recycle mode experiments.     

EFFECT OF IRON CATALYST ON THE COMPOSITION OF OIL FROM COAL LIQUEFACTION

The effect of two iron catalysts, red mud and CGS S-G, as well as C0-Mo/AI₂O3 and Ni-Mo/Al₂03 commercial catalysts on the composition of oil derived from the liquefaction of Japanese subbituminous coal have been investigated comparatively by conventional autoclave experiments at 440 and 450^°C under initial hydrogen pressure of 85kg/cm² G with tetralin to coal weight ratio of 3. From the results obtained at 450^°C, total conversion and the yield of gas revealed almost same level with four catalysts, but the oil product from molybdenum catalysts showed higher yield than that from iron catalysts. CGS S-G catalyst also showed higher yield of oil product than red mud catalyst. Reaction behavior of two iron catalysts were also tested by solvent recycle mode experiments.     

EFFECT OF PRECIPITATION TEMPERATURE ON THE COMPOSITION OF N-HEPTANE ASPHALTENES Part 2

ABSTRACT

Petroleum asphaltenes precipitated by n-heptane at temperatures between ambient and 80^°C from two crude oils have been characterized regarding hydrocarbon structures using ¹H and ¹³C nmr, and fluorescence spectroscopy. This indicates a very complex and apparently very small change in structural features except for a molecular weight increase as more material stays in solution at elevated temperature. Aromaticity increase and apparently alkyl chains diminish. The latter trend is however affected by the structural equation used. According to the fluorescence spectroscopy the content of large and complex chromophores increases but a significant effect of the presence of porphyrins on the spectra is also observed. The data is analyzed in combination with previous characterizations of the same asphaltenes presented in the first part of this work (Andersen, 1994). This indicates that as smaller molecules are extracted at elevated temperature the precipitated asphaltenes tend to associate more. This implys that these small molecules block association sites which therefore become available for further association at elevated temperature. For Boscan part of the smaller easy to extract porphyrins may have this behavior.