乙醇-氨法化学萃取精制直馏柴油研究

以兰州石化公司提供的直馏柴油为原料，考察了乙醇－氨法萃取精制直馏柴油的最佳实验室操作条件，并首次将聚结过滤法和溶剂部分循环再生法应用于醇－氨法萃取精制直馏柴油研究。试验结果表明，在评选的最佳实验室操作条件下采用聚结过滤法处理氨精制油，消除了溶剂损耗，溶剂回收率从89．26％提高到99．82％以上，采用溶剂部分循环再生方法，使溶剂再生负荷和再生能耗下降50％，克服了现有醇－氨法的缺点，精制柴油质量完全满足产品指标要求。     

柴油低温流动性改进剂的研制及性能评价Ⅱ.柴油低温流动性改进剂组分之间的协同效应

研究评价了本课题组合成的低温流动性改进剂蜡晶分散剂M分别与乙烯 -醋酸乙烯酯共聚物、聚甲基丙烯酸高级酯之间的协同效应。结果表明 :M组分与乙烯 -醋酸乙烯酯共聚物复配使用时表现出了良好的协同效应 ,M和乙烯 -醋酸乙烯酯聚合物以及聚甲基丙烯酸高级酯组成的三元复配体系的协同效应更强 ,M具有助降冷滤作用。研究结果还表明 ,协同作用取决于M组分的分子结构 ,其中烃基链的长短具有重要影响。     

Isothermal soot oxidation experiments with intermediate gas change in a Perkin-Elmer TGA6

Two isothermal soot oxidation protocols were tested in a Perkin-Elmer TGA6: (1) the sample was heated under N₂ and then the reaction gas was introduced and (2) the sample was introduced after the empty furnace was heated under the reaction gas. The first protocol is common in soot oxidation studies, it gives a measure of the volatiles and is easier to handle, but as it is shown the determined reaction rate may be falsified by the O₂ concentration. Using gas analysis it was found that ∼2000 s are necessary for the complete gas change in the instrument. An instrument specific correction function involving the O₂ concentration and reaction order n with respect to O₂ was developed which allowed the correlation of the rates measured with both protocols.     

过渡金属-铈基复合氧化物的制备与碳烟燃烧催化性能

采用溶胶凝胶法制备了不同过渡金属TM(Fe,Co,Ni,Mn)-Ce复合氧化物,并经800℃水热处理20 h后得到老化样品。利用XRD,BET对样品结构进行了表征,并采用CO-TPR和TPO分别考察了样品的还原性能和碳烟催化燃烧活性。结果表明,复合氧化物通过过渡金属和铈离子的变价和协同作用,有效地提高了催化剂的碳烟燃烧催化活性。在催化剂-碳烟松散接触条件和含NO+O2气氛下,由于催化剂表面氧的活化和硝酸盐分解释放的NO2,Co-Ce和Mn-Ce具有良好的碳烟燃烧活性。催化剂-碳烟紧密接触和含O2气氛中的活性则与催化剂的比表面积成正比关系,并受活性氧释放能力的影响。     

反应气氛中二氧化硫存在下La_(0.8)K_(0.2)Mn_(0.95)Cu_(0.05)O_3催化剂对碳烟的氧化

利用La0.8K0.2Mn0.95Cu0.05O3氧化模拟碳烟,考察预硫化处理及程序升温氧化中SO2对催化剂性能的影响。采用H2-TPR,FTIR和XPS等方法对催化剂性能进行了表征。XPS表明催化剂在0.02%SO2气氛中400℃下进行4 h的预硫化后OI(O2-)转化为OII(O-),催化剂活性增加;TPO反应中低浓度SO2(0.01%)促进了催化剂的活性,可能是较高温度下高活性K的存在,有效阻止了硫酸盐的生成及积累,对O-的消耗减少。催化剂在0.02%SO2气氛中300℃下预硫化超过1 h以后活性明显降低,预硫化1.5 h后催化剂表面的O2-几乎消耗完全,O-大大减少,二者都转化为O(O2-);可能是较低温度下硫酸盐逐渐积累,加快了O2-的消耗,导致可用的氧源枯竭,催化剂活性降低。     

异辛酸稀土型柴油清净剂的合成和应用研究

对异辛酸镧的合成工艺进行了系统的研究,研究表明异辛酸镧的最佳合成条件为:反应温度80℃,反应时间20 min,皂化率为80%,在此条件下稀土的转化率可达99.98%。通过模拟台架试验和柴油发动机尾气排放试验,考察了其对柴油发动机各部件沉积物的清净效果和改善柴油发动机有害排放情况。模拟台架试验表明,在柴油中添加300×10-4%异辛酸镧清净剂后,柴油发动机低温部件积炭的产生量降低74.8%,同时形成一种彩色膜,可有效阻止沉积物的生成;柴油发动机尾气排放试验表明它可将尾气中CO的排放量降低49.4%,同时NOx的排放量也降低34.2%。     

Sulfur-Selective Desulfurization of Dibenzothiophene and Diesel Oil by Newly Isolated Rhodococcus erythropolis NCC-1

A dibenzothiophene （DBT）-desulfurizing bacteria strain was isolated from oil-contaminated soils and identified as Rhodococcus erythropolis NCC-1. Strain NCC-1 was found to convert DBT to hydroxybiphenyl （2-HBP） via the 4S pathway and also be able to use organic sulfur compounds other than DBT as a sole sulfur source. The strain could desulfurize 4,6-dimethyldibenzothiophene （4,6-DMDBT）, which is one of the most recalcitrant dibenzothiophene derivatives to hydrodesulfurization. When two type of oils, a model oil [n-hexadecane （n-C16） containing DBT] and a hydrodesulfurized diesel oil with various organic sulfur compounds, were treated with Rhodococcus erythropolis NCC-1 cells, the total sulfur content significantly decreased, from 150 to 20 mg/L for n-C16 and from 554 to 274 mg/L for diesel oil. The newly isolated strain NCC-1 is considered to have good potential for application in the biodesulfurization of fossil fuels.     

Poly-Acrylic Acid Derivatives as Diesel Flow Improver for Paraffin-Based Daqing Diesel

Since the diesel products from paraffin-based Daqing crude oil showed low sensitivity to certain commercial diesel pour point depressant (PPDs) that resulted from the high content of paraffin, certain poly-acrylic acid derivatives (PADE) with -COOR, -COOH, -CONHR, and -COO-NH3 R groups by molecular design on the mechanics of diesel; PPDs were synthesized and evaluated as cold flow improver for Daqing 0# diesel in this paper. The pure PADE was superior to the commercial PPDs and displayed a substantial ability of wax crystals dispersion. There was a synergistic effect among the PADE and T1804 and secondary amine. The synergism clearly improved the low temperature performance of Daqing diesel products and could reduce the cold filter plugging point of 0# diesel by 6-7℃.     

La1-xCexCoO3系钙钛矿型催化剂应用于柴油机尾气净化催化性能的研究

采用低温燃烧法制备了Ce4+部分取代La3+的La1-xCexCoO3系钙钛矿型复合氧化物催化剂，用XRD、TGA、SEM和化学分析等方法对催化剂的组成、结构等进行了表征。利用程序升温反应（TPR）技术，对催化剂应用于柴油机常规排放物中的微粒（PM）、碳氢化合物（THC）、氮氧化合物（NOx）的催化脱除性能进行了研究。结果表明，Ce4+部分取代La3+，催化剂表面氧空位浓度增加，同时形成Co3＋-Co2+共存体系，催化剂对THC、NOx催化活性显著提高,且稳定性良好。但Ce4+的掺杂并没有提高催化剂对PM的催化活性。     

Application of Modulated Temperature DSC to Distillate Fuels and Lubricating Greases

In this work the usefulness of Modulated Temperature DSC (MTDSC) for characterizing petroleum products is illustrated with some typical examples of recent applications. Specifically, the reliability of the method is outlined on the basis of the freezing behaviour of distillate fuels and the thermal analytical characterization of lubricating greases. The results of experiments performed on the evaporation residue of distillate fuels, aimed at providing insights into the structure of degradation products, will also be presented. The experiments were carried out using a DSC 2910 module from TA Instruments Inc., upgraded with the MTDSC option. The samples were exposed to a cyclic heating profile which was generated by an underlying heating (or cooling) rate of 2°C min⁻¹ while superimposing a sinusoidally varying time-temperature wave with an amplitude of ±0.5°C and a period of 40 s. This revised version was published online in August 2006 with corrections to the Cover Date.