柴油脱硫技术研究进展

柴油低硫化及其含硫标准的日趋严格,是世界各国柴油产品质量与标准的发展趋势。综述了目前柴油脱硫技术（非加氢脱硫技术、加氢脱硫技术）的研究进展,并对其前景进行了展望。     

柴油加氢脱硫机理的研究进展

从常规加氢脱硫（HDS）到超深度HDS（S〈10μg/g）的转变面临着非常复杂的技术问题。一些硫化物（4,6-二甲基二苯并噻吩等）在常规脱硫条件下很难脱除。在超低硫柴油的生产过程中,这类硫化物也必须脱除。文章对柴油加氢脱硫机理进行了综述。     

FHUDS-2催化剂在天津石化的工业应用

中国石油化工股份有限公司天津分公司为生产硫含量符合欧Ⅲ排放标准S≯350（μg／g）柴油及满足未来更为严格的欧Ⅳ排放标准S≯50（μg/g）柴油,在320万t/a柴油加氢装置上选用了中国石油化工股份有限公司抚顺石油化工研究院（FRIPP）开发的柴油超深度加氢脱硫催化剂FHUDS-2。工业应用结果表明,FHUDS-2催化剂对各种油品的适应性强,反应温度低,具有优异的加氢脱硫性能,是生产清洁柴油的理想催化剂。     

柴油加氢脱硫催化剂的研究进展

随着环保问题越来越受到世界各国的重视,各国相继推出了高质量的清洁燃料标准。低硫化是柴油清洁利用的发展趋势,研制开发高效稳定的加氢脱硫催化剂是加氢脱硫技术研究的主要方向之一。本文主要阐述了国内外在柴油加氢脱硫方面的研究成果,主要分析了柴油加氢脱硫反应机理、柴油加氢脱硫催化剂的主催化剂、助剂和载体的研究进展。分析表明,柴油加氢脱硫的主要路径是直接脱硫和加氢路径,而柴油中受空间位阻影响大的4.6-二甲基二苯并噻吩的脱除路径主要是加氢路径和烷基转移路径。文章从柴油加氢脱硫催化剂的组成和结构分析了催化剂的加氢脱硫机理,得到加氢脱硫活性与催化剂的表面微观结构紧密相关。分析了近年来催化剂载体的研究进展,发现柴油加氢脱硫催化剂的载体主要是氧化铝及改性的氧化铝。     

清洁柴油的生产技术进展

对国内外清洁柴油主要质量指标的进行了对比.介绍了柴油单段加氢脱硫技术和非加氢脱硫技术.提出在发展柴油加氢脱硫技术的同时,重点发展非加氢脱硫技术,尤其是离子液体脱硫技术、廉价氧化剂催化氧化脱硫技术和生物脱硫技术.     

柴油深度脱硫催化剂完成中试

抚顺石化公司催化剂厂与中国石油大学（华东）联合开发的新一代超高活性柴油加氢深度脱硫改质催化剂，日前完成放大试验。这种新型深度脱硫改质催化剂属于非负载型的金属基催化剂，具有优良的加氢活性，能够生产满足欧Ⅳ标准超清洁柴油的生产要求。目前，该催化剂已完成实验室小试和中试放大试验，活性评价数据较为稳定，达到了预期要求，预计年底将实现工业放大。     

140万吨/年柴油加氢装置开工及运行情况

延安石油化工厂140万吨/年柴油加氢装置,采用抚顺石化研究院（简称FRIPP）开发的MCI-降凝催化剂和中国石化工程建设公司（简称SEI）的加氢处理工艺技术,生产低凝高清洁柴油。应用抚顺石油化工研究院开发的加氢降凝配套催化剂体系,对催化裂化和直馏的混合柴油进行加氢精制,装置运行平稳,产品质量合格,原料脱硫率达98.35...     

生产清洁汽油和柴油催化技术进展(续完)

为面对新世纪清洁燃料生产的新机遇和新挑战，各种生产清洁燃料的催化技术正在竞相开发之中，尤其是生产低硫、超低硫汽油和柴油技术。其中，催化裂化（FCC）降硫催化剂和助剂、选择性加氢处理新催化剂及工艺、汽柴油吸附脱硫、柴油生物催化脱硫和选择性氧化脱硫等新技术尤其引人注目。我国应加快清洁燃料生产催化新技术的开发研究，为生产更清洁的汽油和柴油燃料提供技术储备。     

生产清洁汽油和柴油催化技术进展

为面对新世纪清洁燃料生产的新机遇和新挑战，各种生产清洁燃料的催化技术正在竞相开发之中，尤其是生产低硫、超低硫汽油与柴油技术。其中，催化裂化（FCC）降硫催化剂和助剂、选择性加氢处理新催化剂及工艺、汽柴油吸附脱硫、柴油生物催化脱硫和选择性氧化脱硫等新技术尤其引人注目。我国应加快清洁燃料生产催化新技术的开发研究，为生产更清洁的汽油和柴油燃料提供技术储备。     

柴油脱硫技术新进展

介绍了国内外柴油含硫标准的现行要求和未来发展趋势,以及柴油加氢脱硫技术和非加氢脱硫技术的研究进展。其中非加氢脱硫技术包括氧化脱硫技术、生物脱硫技术、吸附脱硫技术和络合法脱硫技术,指出我国也应加快先进柴油脱硫生产新技术的开发研究,为生产更清洁的柴油燃料提供技术储备。     

柴油低温流动改进剂的研究及工业应用

介绍了T系列柴油低温流动改进剂实验室和工业试验情况。实验室研究结果表明，T系列柴油低温流动改进剂具有较好的柴油感受性，降凝效果较好。工业应用结果表明，T系列柴油低温流动改进剂对大港柴油具有较好的感受性，加剂比在0.1%左右时能大幅度降低柴油的冷滤点，可将+5号及0号柴油分别调合成0号和－10号柴油。     

Physical and chemical properties of ethanol-diesel fuel blends

This paper discusses the physical-chemical properties of ethanol-diesel fuel blends. The attention is focused on the properties which influence the injection and engine characteristics significantly. Main properties have been investigated experimentally. The analysis of experimentally obtained fuel properties of tested fuels and their influence on engine characteristics are presented. Physical and chemical properties of diesel fuel and ethanol-diesel fuel blends were measured according to requirements and test methods for diesel fuel (EN590, 2003). The tested fuels were neat mineral diesel fuel (D100), 5% (v/v) ethanol/diesel fuel blend (E05D95), 10% (v/v) ethanol-diesel fuel blend (E10D90) and 15% (v/v) ethanol-diesel fuel blend (E15D85). It has been proved that, for ethanol-diesel fuel blends, some additives are necessary to keep stability under low temperature conditions. Also, cold weather properties test, such as cloud point and pour point tests are negatively affected by phase separation. The rest of the properties, excepting flash point, were within diesel fuel standard specifications. Based on this study, it can be concluded that using additives to avoid phase separation and to raise flash point, blends of diesel fuel with ethanol up to 15% can be used to fuel diesel engines if engine performance tests corroborate it.     

Combustion and emission characteristics of blends of diesel fuel and methanol-to-diesel

Methanol-to-diesel (MTD) means a synthetic diesel fuel, its raw material is methanol. And it is a liquid alcohol ether mixture with appropriate amount of additives, which can be blended with diesel fuel at various levels. It was synthesized by methanol with 1,2-epoxypropane and epoxyethane using modified calcined Mg/Al hydroxides as catalysts. The test and study on the physical properties of MTD and the fuel consumption and emissions of diesel engine using the mixed MTD and diesel fuel have been performed. The results indicates that there was no significant difference in the power values of diesel and the blend fuels while fuel consumption increasing around 14%, and of much lower emissions of exhaust. When using the diesel fuel mixed with 20-30% of MTD. The conclusion is that MTD is a cheap and clean low power loss additive fuel for diesel engines.     

柴油低温流动改进剂的合成及性能评价

介绍了在甲苯溶液中将甲基丙烯酸酯-马来酸酐二元共聚物用高级脂肪醇、聚乙二醇酯化,得到一系列新聚合物,通过对长庆石化分公司混合柴油的冷滤点的测试,改性后的二元共聚物可降低混合柴油的冷滤点3-4℃;利用多种低温流动改进剂的协同作用,探讨了合成主剂与不同的降凝剂和蜡晶分散剂复配效果;用差示扫描量热法（DSC）对加剂柴油和空白柴油在降温过程中的相变情况进行了研究,实验结果表明加剂后延缓了柴油中石蜡的结晶速度,使石蜡结晶温度降低,改善了柴油的低温流动性。     

Thermal Evaluation of Diesel/Hydrogen Peroxide Fuel Blend

Thermal properties of fossil fuel are the key fundamental characteristics, which can distinguish any compound as a potential fuel. The performance of diesel fuel blend along with stability and solubility parameter designs are evaluated. The results from the experimental study indicate that the increase in hydrogen peroxide (H₂O₂) amount enhances the cetane number of diesel fuel blend significantly. However, the calorific value decreases as compared to pure diesel fuel. All values performed well according to the ASTM D‐975 diesel testing method. The thermodynamics of the prepared fuel blends also revealed that substantial solubility and diesel/H₂O₂ blend stability are provided even at lower temperatures. Such blends can be used as a feasible replacement of pure diesel fuel.     

Formulation of Canola-Diesel Microemulsion Fuels and Their Selective Diesel Engine Performance

Vegetable oils have been considered as an alternative to diesel fuel due to their comparable properties and performance. However, the high viscosity of vegetable oil causes engine durability problems with long-term usage. Vegetable oil viscosity can be reduced by blending with diesel fuel in thermodynamically stable mixtures using microemulsion fuel formulation techniques. This work focuses on the formulation of microemulsion fuels comprising diesel fuel and canola oil as the oil phase with ethanol and sec-butanol as viscosity reducers as well as 1-octanol and oleyl amine as surfactant/cosurfactant. Selective tests on an instrumented diesel engine were performed for formulated microemulsion fuels and No. 2 diesel fuel for comparison. The results show that formulated microemulsion fuels have fuel properties that meet the ASTM requirements for viscosity, cloud point, and pour point for biodiesel. Even more important, they have phase stability over a wide range of temperatures (−10 to 70 °C). Although all of the microemulsion fuels showed higher fuel consumption than diesel fuel, some of the microemulsion fuels had significantly reduced CO and NO_x emissions as well as reduced particulates when compared to baseline diesel fuel. The research demonstrates the potential of these microemulsion fuels as alternative to neat diesel fuel.     

Determination of performance and exhaust emissions properties of B75 in a CI engine application

In this study, performance and exhaust emissions of biodiesel in a compression ignition engine was experimentally investigated. Therefore, biodiesel has been made by transesterification from cotton seed oil and then it was mixed with diesel fuel by 25% volumetrically, called here as B75 fuel. B75 fuel was tested, as alternative fuel, in a single cylinder, four strokes, and air-cooled diesel engine. The effect of B75 and diesel fuels on the engine power, engine torque and break specific fuel consumption were clarified by the performance tests. The influences of B75 fuel on CO, HC, NOx, Smoke opacity, CO₂, and O₂ emissions were investigated by emission tests. The engine torque and power, for B75 fuel, were lower than that of diesel fuel in range of 2-3%. However, for the B75, specific fuel consumption was higher than that of diesel fuel by approximately 3%. CO₂, CO, HC, smoke opacity and NO_x emissions of B75 fuel were lower than that of diesel fuel. The experimental results showed that B75 fuel can be substituted for the diesel fuel without any modifications in diesel engines.     

Utilization of ethyl ester of waste vegetable oils as fuel in diesel engines

Jordan relies heavily on expensive and unreliable imported oil. Therefore, this study was initiated to investigate the potential of ethyl ester used as vegetable oil (VO; biodiesel) to substitute oil-based diesel fuel. The fuels tested were several ester/diesel blends including 100% ester in addition to diesel fuel, which served as the baseline fuel. Variable-speed tests were run on all fuels on a standard test rig of a single-cylinder, direct-injection diesel engine. Tests were conducted to compare these blends with the baseline local diesel fuel in terms of engine performance and exhaust emissions. The results indicated that the blends burned more efficiently with less specific fuel consumption, and therefore, resulted in higher engine thermal efficiency. Furthermore, the blends produced less carbon monoxide and unburned hydrocarbons than diesel fuel. The 100% ester fuel and the blend of 75:25 ester/diesel gave the best performance while the 50:50 blend consistently resulted in the lowest amounts of emissions over the whole speed range tested.     

Properties of rapeseed oil for use as a diesel fuel extender

Chemical and thermal analyses were carried out on degummed and filtered (5 μm) rapeseed oil (referred to as SRO, i.e., semirefined rapeseed oil) to determine its suitability as a diesel fuel extender. The upper rate for inclusion of SRO with diesel fuel is 25%. This fuel blend had a phosphorus level of 2.5 ppm, which was comparable to rape methyl esters (1.0 ppm phosphorus). Thermogravimetric analyses were used to estimate the cetane ratings of the fuels. A 25% SRO/diesel blend had an estimated cetane index of 32.4 compared to 38.1 for diesel fuel only. Differential scanning calorimetry and thermogravimetric analyses were used to compare the volatility ranges of the fuels. SRO needed higher temperatures for volatilization (i.e., 70–260°C for diesel fuel vs. 280–520°C for SRO). This indicated poorer cold-starting performance of SRO compared with diesel fuel. SRO fuel is a low-sulfur, high-oxygen fuel giving SRO a more favorable emissions profile than pure diesel fuel.     

Study of oxygenated biomass fuel blends on a diesel engine

Vegetable methyl ester was added in ethanol–diesel fuel to prevent separation of ethanol from diesel in this study. The ethanol blend proportion can be increased to 30% in volume by adding the vegetable methyl ester. Engine performance and emissions characteristics of the fuel blends were investigated on a diesel engine and compared with those of diesel fuel. Experimental results show that the torque of the engine is decreased by 6%–7% for every 10% (by volume) ethanol added to the diesel fuel without modification on the engine. Brake specific fuel consumption (BSFC) increases with the addition of oxygen from ethanol but equivalent brake specific fuel consumption (EBSFC) of oxygenated fuels is at the same level of that of diesel. Smoke and particulate matter (PM) emissions decrease significantly with the increase of oxygen content in the fuel. However, PM reduction is less significant than smoke reduction. In addition, PM components are affected by the oxygenated fuel. When blended fuels are used, nitrogen oxides (NO_x) emissions are almost the same as or slightly higher than the NO_x emissions when diesel fuel is used. Hydrocarbon (HC) is apparently decreased when the engine was fueled with ethanol–ester–diesel blends. Fuelling the engine with oxygenated diesel fuels showed increased carbon monoxide (CO) emissions at low and medium loads, but reduced CO emissions at high and full loads, when compared to pure diesel fuel.