APUSM technology for the production of BTX and LPG from pyrolysis gasoline using metal promoted zeolite catalyst

SK Corporation developed an advanced pyrolysis gasoline (pygas) upgrading (APU^SM) technology based on a catalytic process for producing valuable benzene, toluene and xylenes (BTX) and liquefied petroleum gas (LPG) from pygas containing aromatics and non-aromatic hydrocarbons. Hydrodealkylation of heavy aromatics and hydrocracking of non-aromatic hydrocarbons occurred with facility in the conversion of pygas over a proprietary catalyst, metal promoted zeolite. This catalytic process produced benzene and toluene with high purity corresponding to chemical grade while giving mixed xylenes with reduced ethylbenzene. In the present study, we described novel features of the APU^SM technology in terms of the process and catalyst. The influence of the process conditions was also examined. This technology has been commercially proven, and hence is available for licensing through Axens, which is a major engineering and licensing company.     

Benzene elimination from reformate gasoline by high pressure hydrogenation in a fixed-bed reactor

The reduction of benzene from benzene-rich real gasoline fractions has been studied in a high-pressure fixed-bed reactor using a Pt/TiO₂ catalyst. It was found that the yield of this process decreases with the toluene content in the feedstock, but it is independent of the kind of the saturated hydrocarbons. This revised version was published online in August 2006 with corrections to the Cover Date.     

Experimental and modelling study of gasoline surrogate mixtures oxidation in jet stirred reactor and shock tube

The oxidation of several mixtures of surrogate for gasoline was studied using a jet stirred reactor and a shock tube. One representative of each classes constituting gasoline was selected: iso-octane, toluene, 1-hexene and ethyl tert-butyl ether (ETBE). The experiments were carried out in the 800-1880 K temperature range, for two different initial pressures (0.2 and 1 MPa), with an initial fuel molar fraction of 0.001. The equivalence ratio varied from 0.5 to 1.5. Each hydrocarbon sub-mechanism was validated using shock tube data. The full mechanism describing the surrogate fuel oxidation is constituted of the sub-mechanisms for each fuel components and by adding interaction reactions between different hydrocarbon fragments. Good agreement between the experimental results and the computations was observed under JSR and shock tube conditions.     

Measurement of mercaptans in gasoline

In an r-FIA single-line manifold, 10-l portions of 5,5-dithiobis (2-nitrobenzoic acid) and 2% (v/v) ethylenediamine in 80 20 inethanol: acetone are injected from pressurized containers via high-speed on/off valves into a flowing gasoline stream. The reaction product, 2-nitro-5-mercaptobenzoate, is detected optically at 412 nm after a reaction time of 15s. The system is intended for the measurement of mercaptans in the 0–2 mM (0–64 ppm S) concentration range. The response for C1–C10n-mercaptans ranges from 0.766–0.159 mAU/mM, the response to C1–C5n-mercaptans is 630 mAU/mM (±18.5% RSD). The response ratio of C1 and C5 mercaptans is 1 0.653. The system permits extreme conservation of reagents; only 10 l of each reagent is consumed per determination.     

FCC汽油模型化合物光催化氧化脱硫的研究

以噻吩的二甲苯溶液作为FCC汽油的模型化合物, 双氧水为氧化剂, 研究了在光催化作用下, 双氧水体积分数、 高速均质时间和二氧化钛的加入量等工艺条件对脱硫率的影响, 在适宜条件下, 模型化合物的脱硫率可达到80%以上. 以FCC汽油为实际体系, 在适宜的光催化条件下, 脱硫率可达到59%. 分析结果表明, 含硫化合物的氧化产物为更高极性的物质.     

汽油样品类型的模式识别研究与应用

研究了应用化学计量学方法解决汽油单体烃的气相色谱分析中单体烃定性库的自动选择问题。通过提取汽油单体烃谱图中的29个组分及其含量信息作为特征值,利用主成分分析法对不同工艺得到的催化裂化汽油、焦化汽油、直馏汽油、重整汽油和烷基化汽油进行分类,结合相似分析方法(即SIMCA方法)建立了各类汽油样本的类模型,借助这些类模型可以实现对未知样本的类型判别。所提出的识别方法可方便快速地判别待分析样品所属的汽油类别,并据此推荐适合该样品的定性模型库,从而实现汽油单体烃的快速、自动分析。     

Numerical and experimental study on effect of wall geometry on wall impingement process of hollow-cone fuel spray under various ambient conditions

The spray–wall impingement process in gasoline direct injection (GDI) engines, which is caused by the interaction among spray, wall and air to move the air–fuel mixture near the spark plug, directly influences the engine performance and emissions. Therefore, a detailed understanding of this process is very important in designing an injection system and controlling a strategy of GDI engines. The purpose of this study is to understand the spray–wall impingement characteristics for more efficient designing of the injection system in GDI engines and to supply the fundamental data under engine operation conditions. The wall impingement processes of hollow-cone fuel spray according to ambient gas conditions and wall geometry are calculated by validated spray models. The calculated results were compared with the experimental results obtained by the laser-induced exciplex fluorescence (LIEF) technique. It was found that the spray and vortex cloud at the high ambient pressure were distributed at inner area of cavity and the more fuel film mass observed at this condition. The fuel film mass decreased with the increase of ambient temperature, while the fuel film mass increased at high cavity angles.     

Multi-location laser ignition using a spatial light modulator towards improving automotive gasoline engine performance

We report on a study into multi-location laser ignition (LI) with a Spatial Light Modulator (SLM), to improve the performance of a single cylinder automotive gasoline engine. Three questions are addressed: i/ How to deliver a multi-beam diffracted pattern into an engine cylinder, through a small opening, while avoiding clipping? ii/ How much incident energy can a SLM handle (optical damage threshold) and how many simultaneous beam foci could thus be created? ; iii/ Would the multi-location sparks created be sufficiently intense and stable to ignite an engine and, if so, what would be their effect on engine performance compared to single-location LI? Answers to these questions were determined as follows. Multi-beam diffracted patterns were created by applying computer generated holograms (CGHs) to the SLM. An optical system for the SLM was developed via modelling in ZEMAX, to cleanly deliver the multi-beam patterns into the combustion chamber without clipping. Optical damage experiments were carried out on Liquid Crystal on Silicon (LCoS) samples provided by the SLM manufacturer and the maximum safe pulse energy to avoid SLM damage found to be 60 mJ. Working within this limit, analysis of the multi-location laser induced sparks showed that diffracting into three identical beams gave slightly insufficient energy to guarantee 100% sparking, so subsequent engine experiments used 2 equal energy beams laterally spaced by 4 mm. The results showed that dual-location LI gave more stable combustion and higher engine power output than single-location LI, for increasingly lean air-fuel mixtures. The paper concludes by a discussion of how these results may be exploited.     

电感耦合等离子体发射光谱法测定E10乙醇汽油中的钠和锌

车用乙醇汽油是一种新型、清洁的汽车燃料,在燃烧过程中,微量的重金属杂质对汽车的行驶和养护有着至关重要的影响,一些燃烧产物可能会污染环境,威胁人们的身体健康,因此有必要对其中的微量元素进行控制。以异辛烷稀释汽油样品,电感耦合等离子体发射光谱（ICP-OES）法测定车用E10乙醇汽油中钠、锌含量的方法,选择钠和锌的分析谱线分别为：589.592和213.857 nm,实验优化了雾化气流量和蠕动泵速率对信背比的影响,应用了半导体制冷雾化系统（雾化室温度设置为-10 ℃）降低了进样过程中溶液的挥发性,保证了等离子体的稳定性,同时,实验研究了稀释比、内标元素以及稀释剂的类型对测定结果的影响,结果表明：（1）在-10 ℃低温下选择航空煤油为稀释剂,钠和锌的回收率均在120%以上,Y内标比值均在1.20以上,异辛烷为稀释剂时回收率和内标比值均满足要求,可能是航空煤油在低温下的密度和黏度较大导致,得出低温条件下异辛烷比航空煤油更适合作为乙醇汽油的稀释剂;（2）当选择Co做为内标元素时,有些样品的内标元素比值在120%以上,Y为内标元素时,样品的内标元素比值均满足要求,可能是由于Co的稳定性较差或样品里含有Co,得出Y比Co元素更适合做为乙醇汽油的内标元素;（3）本方法的钠和锌元素的检出限分别为0.013和0.005 mg·kg-1,加标回收率为85.1%～106.0%,相对标准偏差(RSD,n=7)为1.0%～4.8%;（4）通过与微波消解-ICP-OES法进行比较,本方法的测定结果与加标理论值较接近,弥补了微波消解法元素易损失的缺点。此法具有快速、灵敏、准确的优点,可应用于乙醇汽油中钠和锌元素的监测。     

分析测试新成果(230~237)2种常见燃油添加剂对汽油燃烧烟尘的影响

采用气相色谱-质谱(GC-MS)联用技术,根据汽油原样中的特征成分,对未加入和分别加入汽油燃油精、海龙燃油宝的汽油燃烧烟尘进行对比分析.结果表明,汽油燃油精的加入会使汽油燃烧烟尘中各类特征成分的百分含量有所变化,但对谱图和特征成分的影响较小;而海龙燃油宝的加入对汽油燃烧烟尘的谱图、特征成分及其个数、各类特征成分的百分含量均产生较大影响.结果为火灾物证鉴定提供一定的参考依据.