PTV用于柴油机燃烧过程中气/颗粒相多环芳香烃分布研究
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摘要
本文以全气缸取样系统为基础,结合先进的仪器分析方法,研究了在柴油燃烧过程中气相/颗粒相多环芳香烃(Polycyclic Aromatic Hydrocarbons, PAHs)的分布特性。实验采用聚氨酯泡沫/树脂(PUF/XAD-2/PUF)吸附柱和玻璃纤维滤膜分别收集柴油燃烧过程中气相和颗粒相PAHs。由于柴油燃烧过程生成的PAHs在单一工作循环中位于超痕量水平,因此在气相色谱-质谱联用仪(Gas Chromatography - Mass Spectrometric, GC-MS)上选择了程序升温大体积进样方法(Programmed Temperature Vaporization, PTV),并使用试验设计对PTV的进样参数进行优化,结果表明该方法能完全满足超痕量PAHs的分析要求。在此分析方法的基础上,使用CO_2模拟废气再循环(EGR),进一步研究了EGR对柴油燃烧过程中气相/颗粒相PAHs分布特性的影响。研究结果表明:
1、使用PUF/XAD-2/PUF吸附柱及玻璃纤维滤膜对气相/颗粒相PAHs采样,回收率范围分别是71.83%～98.64%和86.41%～118.35%。采用2水平全因子设计和中心复合设计法优化PTV进样条件,分别对进样量为50μL和25μL两个条件下PTV参数进行优化,最终采取PTV进样量为25μL的分析方法,因子优化结果的综合合意性为0.83。PTV大体积进样与分流/不分流进样方式相比,既简化样品分析步骤,又不影响分离效果,25μL进样量时检出限提高3.8～59.2倍。
2、柴油机在在整个燃烧过程中,总PAHs(滤膜+吸附柱上PAHs)的质量在有EGR的工况下随着燃烧的进行先增大后减小,无EGR的工况下先降低再升高,最后再降低。各工况燃烧结束时,总PAHs的质量在EGR率为19.5%时最低。
3、在整个燃烧过程中,气相PAHs质量占总PAHs质量的95.15%以上,萘在气相PAHs中含量最多,占97.7%以上,其中燃烧初期和中期最易生成PAHs。燃烧进行时,低环数的萘、苊烯、苊、芴和菲的生成量较多;燃烧结束时,颗粒相PAHs中3环组分占33.5%～49.3%,其中以荧蒽和菲的含量最多,气相PAHs中含量最多的是萘,占99%以上。
4、柴油机燃烧过程中,PAHs在气相的比例随着PAHs分子量的增加而降低。挥发性最强的PAHs主要存在于气相中,4环以上PAHs多吸附在颗粒上,而部分中间的3环和4环PAHs则在两相中均衡分布。燃烧结束时,各种PAHs在气相中的比例随EGR率的增加而降低。
The gas/particle phase distribution of polycyclic aromatic hydrocarbons (PAHs) during diesel combustion process was investigated with advanced instrument analysis methods, and all samples were obtained from the total cylinder dumping system. The particle-phase PAHs were trapped with a glass fiber filter, and the gas-phase PAHs were captured passing through a glass cartridge packed with XAD-2 resin supported by two polyurethane foam (PUF) plugs. Since the PAHs for a single combustion cycle was at a ultra-trace level, the analysis of ultra-trace PAHs were carried out by gas chromatography with mass spectrometric detection (GC–MS) coupled with large-volume programmed temperature vaporization (PTV) injection. The large-volume PTV injection settings were optimized using a statistical design of experiments, and the results indicated that the requirement of analyzing PAHs at the ultra-trace levels can be well met by this method. In light of the method above, the influence of exhaust gas recirculation (EGR), which was efficiently simulated with the CO_2 addition, on the distribution of the gas/particle phase PAHs during the combustion process was studied. The major achievements are listed as follows:
1. The method of selecting a cartridge packed with XAD-2 resin and a glass fiber filter for collecting gas-phase and particle-phase PAHs was reliable, with the PAHs recoveries in the range of 71.83% - 98.64% for the cartridge and 86.41% - 118.35% for the fiber filter. The large-volume PTV injection settings for 50μL injection and 25μL injection were all optimized using two-level full factorial designs and central composite designs (CCD) of experiments. The final injection volume was chosen as 25μL, and the optimized factor settings for 25μL injection provided a composite desirability of 0.83. The large-volume PTV injection method simplified sample analysis steps without affecting the separation effect. For 25μL injection, an increase in sensitivity was 3.8 - 59.2 times as compared with the conventional splitless injection.
2. With the presence of EGR, the total PAHs (PAHs on filter+ cartridge) increased at first, and then decreased as the combustion went on; with the absence of EGR, the total PAHs decreased at the beginning and then increased later, but decreased again at the end of the combustion process. At the end of the combustion process, the minimum of the total PAHs could be obtained at the EGR rate of 19.5%.
3. Throughout the combustion period, gas-phase PAHs acted as a contribution of more than 95.15% in the total PAHs, and naphthalene was the most abundant gas-phase PAHs, exceeding 97.7% of gas-phase PAHs. Of the total analyzed PAHs, the two- and three-ring PAHs such as naphthalene, acenaphthylene, acenaphthene, fluorene and phenanthrene were the dominant species during the combustion process. At the end of the combustion, the PAHs with three-ring arrangement accounted for 33.5% - 49.3% of the total particle-phase PAHs, and fluoranthene and pyrene were the most abundant. In gas-phase PAHs, naphthalene was found to prevail, which accounted for more than 97.7%.
4. During the combustion process, the more the molecular weight of PAH, the lower the proportions of in the gas-phase. The most volatile PAHs were mainly found in the gas-phase, whereas four-ring PAHs and higher-ring PAHs were predominantly absorbed into the particles. Most of three- and four-ring PAHs exhibited an intermediate behavior. A negative correlation was also found between EGR rate and the PAHs distributions in gas-phase at the end of the combustion process.
1、使用PUF/XAD-2/PUF吸附柱及玻璃纤维滤膜对气相/颗粒相PAHs采样,回收率范围分别是71.83%～98.64%和86.41%～118.35%。采用2水平全因子设计和中心复合设计法优化PTV进样条件,分别对进样量为50μL和25μL两个条件下PTV参数进行优化,最终采取PTV进样量为25μL的分析方法,因子优化结果的综合合意性为0.83。PTV大体积进样与分流/不分流进样方式相比,既简化样品分析步骤,又不影响分离效果,25μL进样量时检出限提高3.8～59.2倍。
2、柴油机在在整个燃烧过程中,总PAHs(滤膜+吸附柱上PAHs)的质量在有EGR的工况下随着燃烧的进行先增大后减小,无EGR的工况下先降低再升高,最后再降低。各工况燃烧结束时,总PAHs的质量在EGR率为19.5%时最低。
3、在整个燃烧过程中,气相PAHs质量占总PAHs质量的95.15%以上,萘在气相PAHs中含量最多,占97.7%以上,其中燃烧初期和中期最易生成PAHs。燃烧进行时,低环数的萘、苊烯、苊、芴和菲的生成量较多;燃烧结束时,颗粒相PAHs中3环组分占33.5%～49.3%,其中以荧蒽和菲的含量最多,气相PAHs中含量最多的是萘,占99%以上。
4、柴油机燃烧过程中,PAHs在气相的比例随着PAHs分子量的增加而降低。挥发性最强的PAHs主要存在于气相中,4环以上PAHs多吸附在颗粒上,而部分中间的3环和4环PAHs则在两相中均衡分布。燃烧结束时,各种PAHs在气相中的比例随EGR率的增加而降低。
The gas/particle phase distribution of polycyclic aromatic hydrocarbons (PAHs) during diesel combustion process was investigated with advanced instrument analysis methods, and all samples were obtained from the total cylinder dumping system. The particle-phase PAHs were trapped with a glass fiber filter, and the gas-phase PAHs were captured passing through a glass cartridge packed with XAD-2 resin supported by two polyurethane foam (PUF) plugs. Since the PAHs for a single combustion cycle was at a ultra-trace level, the analysis of ultra-trace PAHs were carried out by gas chromatography with mass spectrometric detection (GC–MS) coupled with large-volume programmed temperature vaporization (PTV) injection. The large-volume PTV injection settings were optimized using a statistical design of experiments, and the results indicated that the requirement of analyzing PAHs at the ultra-trace levels can be well met by this method. In light of the method above, the influence of exhaust gas recirculation (EGR), which was efficiently simulated with the CO_2 addition, on the distribution of the gas/particle phase PAHs during the combustion process was studied. The major achievements are listed as follows:
1. The method of selecting a cartridge packed with XAD-2 resin and a glass fiber filter for collecting gas-phase and particle-phase PAHs was reliable, with the PAHs recoveries in the range of 71.83% - 98.64% for the cartridge and 86.41% - 118.35% for the fiber filter. The large-volume PTV injection settings for 50μL injection and 25μL injection were all optimized using two-level full factorial designs and central composite designs (CCD) of experiments. The final injection volume was chosen as 25μL, and the optimized factor settings for 25μL injection provided a composite desirability of 0.83. The large-volume PTV injection method simplified sample analysis steps without affecting the separation effect. For 25μL injection, an increase in sensitivity was 3.8 - 59.2 times as compared with the conventional splitless injection.
2. With the presence of EGR, the total PAHs (PAHs on filter+ cartridge) increased at first, and then decreased as the combustion went on; with the absence of EGR, the total PAHs decreased at the beginning and then increased later, but decreased again at the end of the combustion process. At the end of the combustion process, the minimum of the total PAHs could be obtained at the EGR rate of 19.5%.
3. Throughout the combustion period, gas-phase PAHs acted as a contribution of more than 95.15% in the total PAHs, and naphthalene was the most abundant gas-phase PAHs, exceeding 97.7% of gas-phase PAHs. Of the total analyzed PAHs, the two- and three-ring PAHs such as naphthalene, acenaphthylene, acenaphthene, fluorene and phenanthrene were the dominant species during the combustion process. At the end of the combustion, the PAHs with three-ring arrangement accounted for 33.5% - 49.3% of the total particle-phase PAHs, and fluoranthene and pyrene were the most abundant. In gas-phase PAHs, naphthalene was found to prevail, which accounted for more than 97.7%.
4. During the combustion process, the more the molecular weight of PAH, the lower the proportions of in the gas-phase. The most volatile PAHs were mainly found in the gas-phase, whereas four-ring PAHs and higher-ring PAHs were predominantly absorbed into the particles. Most of three- and four-ring PAHs exhibited an intermediate behavior. A negative correlation was also found between EGR rate and the PAHs distributions in gas-phase at the end of the combustion process.
引文
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