摘要
随着世界柴油机保有量的持续增加,柴油机微粒排放物对环境和生物造成的危害
也愈加严重,因此从人类生存环境以及自身健康出发,分析微粒中的有机和无机成分
及其危害性,进而减少有害物排放,具有极大的现实意义。但是,目前国内对现代车
用柴油机微粒中不同组分的成分及危害的研究报道较少,特别是对有机可溶成分中不
同组分的生物毒性和对环境的影响这些方面的研究还处于刚刚起步的阶段。
本文针对东风朝阳柴油机有限责任公司生产的CY6102BZLQ型柴油机,采用十三
工况法采集微粒样本。对萃取出的有机可溶成分(用F0表示)采用硅胶柱色谱法和化
学方法分为有机酸、有机碱、脂肪烃类有机物、芳香烃类有机物、中极性有机物和高
极性有机物六大类(分别用F1~F6表示)。通过称重得出六种组分在SOF中分别占:
11.64%,15.21%,12.32%,9.97%,41.35%和9.51%。采用色谱-质谱联用技术,对
部分组分进行了分析,确定了其中的41种成分。
选择直喷和涡流室两个类型共6个型号的柴油机样品(编号为D1~D6),采用离子
色谱法对阴离子的种类和含量进行了检测。检测结果表明,D1~D3这三种直喷柴油机
N系或S系的阴离子比排放都明显小于D4~D6这三种涡流室式柴油机,并且D1~D3中
没有检测出NO2 排放。对于QD32系列柴油机来讲,增压或增压中冷的改进使发动机
-
阴离子的比排放降低。
利用电感耦合等离子体荧光发射光谱法(ICP-AMS)对金属物质进行检测,结果
显示,对于QD32系列,增压或增压中冷的改进使金属排放降低。Ca的比排放在各机
型中都明显高于其他元素,Zn的比排放最低,而Ti、Fe的比排放量也处于较低水平。
根据前面对柴油机微粒各组分的分析结果绘制出了六种机型中有机可溶成分、硫
系阴离子、氮系阴离子、金属、碳烟等成分在微粒中的分布谱图。
利用Ames试验法研究了F0~F6七种样品的致突变性,使用的菌株为TA98(-S9,
+S9)和TA100(-S9,+S9)。试验结果表明, F1和F4具有最强的致突变性,是造成
SOF致突变性的主要因素,且有明显的剂量反应关系。F5、F6和F0在浓度较高时也呈
阳性,并呈现出一定的剂量反应关系。F2和F3在TA98和TA100的活化和非活化条件
下结果都呈阴性。
With the increase of diesel engines in the world, the pollution of particulate emissions
from diesel engines, which are harmful to the environment and organisms, is getting more
and more serious. So it has a great practical significance to analyze component and
harmfulness of the organic compounds and the inorganic compounds and then proceed to
decrease the diesel emissions. At present, few researchs in the field of component analyse
and harmfulness of various fractions in diesel particulates has been carried out in our
country, especially to the bio-toxicity of different parts in soluble organic fractions (SOF).
In this thesis, samples of particulate matter (PM) were collected with the ECE R49-13
test mode from CY6102BZLQ diesel engine manufactured by Dongfeng Chaoyang Diesel
Engines Company Ltd. The soluble organic fractions(F0) in diesel exhaust were classified
into organic acids(F1), organic bases(F2), aliphatic compounds(F3), aromatic
compounds(F4), moderately polar neutral compounds(F5) and highly polar neutral
compounds(F6) by silica gel column chromatography and chemical methods. After
weighing, percentages of these organic compounds was obtained, which are listed in turn:
11.64%,15.21%,12.32%,9.97%,41.35% and 9.51%. Using the GC-MS technique, 41
kinds of components were confirmed.
Anions in diesel particulates were investigated with ion chromatography test. Among
the samples, there were 6 kinds of diesel engines (D1~D6) which can divided into two
types, the D.I diesel engine and the turbulence chamber diesel engine. The results showed
that all kinds of anions of three directly injection diesel engines (D1~D3) were less than
that of three turbulence chamber diesel engines (D4~D6) significantly. And there was no
NO2 in the samples of D1~D3. To the CYQD32 series, the break specific emission of
-
anions has a decreasing trend with the amelioration adopting turbocharge or charge
inter-cooling technique.
The ICP-AMS was used to determine the kinds and contents of trace metals in
exhaust particulates of D1~D6. According to the experimental results, the break specific
emission of metals of CYQD32 series decreased with the amelioration using turbocharge
or charge inter-cooling technique. Among all the elements, the break specific emission of
Ca was the most and that of Zn was the least. In addition, the break specific emissions of Ti
and Fe were less.
According to the analysis results, the distributing graphs of SOF, S and N species,
trace metals, carbon in the PM samples of 6 kinds of diesel engines were accomplished.
The mutagenicity of F0~F6 were detected with the Salmonella mutagenicity test
(Ames assay) using strain TA98 (-S9, +S9) and TA100 (-S9, +S9). The results indicated
that the mutagenicity of F1 and F4 was the strongest with obvious does-response relations.
F5, F6 and F0 also had positive results and some does-response relations at high
concentrations. F2 and F3 had negative results at all dosage levels.
引文
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