Measurements of ion concentration in gasoline and diesel engine exhaust

The nanoparticles formed in motor vehicle exhaust have received increasing attention due to their potential adverse health effects. It has been recently proposed that combustion-generated ions may play a critical role in the formation of these volatile nanoparticles. In this paper, we design an experiment to measure the total ion concentration in motor vehicle engine exhaust, and report some preliminary measurements in the exhaust of a gasoline engine (K-car) and a diesel engine (diesel generator). Under the experimental set-up reported in this study and for the specific engines used, the total ion concentration is ca. 3.3×10⁶ cm⁻³ with almost all of the ions smaller than 3 nm in the gasoline engine exhaust, and is above 2.7×10⁸ cm⁻³ with most of the ions larger than 3 nm in the diesel engine exhaust. This difference in the measured ion properties is interpreted as a result of the different residence times of exhaust inside the tailpipe/connecting pipe and the different concentrations of soot particles in the exhaust. The measured ion concentrations appear to be within the ranges predicted by a theoretical model describing the evolution of ions inside a pipe.     

低温等离子体处理柴油机NOx和PM 试验研究

建立了一种具有较强实用性的介质阻挡放电等离子体反应器试验装置.借助静态试验研究其放电特性,通过发动机台架试验探讨了利用低温等离子体处理柴油机2种主要有害排放物NOx和PM的效果和化学反应机理,并通过模拟试验作了处理PM的进一步验证.试验结果表明,放电功率对于低温等离子体活性成分的产生有重要影响,应当优选放电参数以获得高的放电功率从而达到更好的处理效果;采用低温等离子体处理柴油机排气,NOx总量变化不大,主要将NO转化成NO2;低温等离子体可以有效去除柴油机排气中的PM,去除率随能量密度的增大而提高.     

Research on the effects of diesel engine exhaust transport distance on particulate microstructure

This study aims to reveal the evolutionary process of particles during the diesel exhaust transport process and to further understand the effects of diesel exhaust transport distance (D_ET) on a particulate microstructure. Specifically, the micromorphological, particle size distribution, and aggregate characteristics of particles as well as the variation of the structural characteristics of elementary carbon particles (ECPs) as D_ET changed were examined using an engine exhaust particle size spectrometer, a high-resolution transmission electron microscopy system, and a small-angle X-ray scattering system. The results show the following: As D_ET increased, the chains gradually lengthened, the extent of accumulation and stacking increased, and a number of clusters gradually rose. The average particle diameter increased from 23.1 nm at 0 m to 92.7 nm at 3 m. In addition, as D_ET increased, the number of accumulation-mode particles, the number of folded, curved carbon layers in the inner core of carbon particles, and the disorderliness of carbon layers in the outer shell of carbon particles all increased. Moreover, the boundary between the inner core and the outer shell became increasingly obscure. As D_ET increased, there was a gradual decrease in the difference in electron density between particles, and the fractal dimensionality of the distribution, average cross-sectional size, radius of gyration, and axial length of pores were, respectively, 33.3%, 40%, 38.2%, and 50.3% less at 3 m than at 0 m. Besides that, the number of small (< 3 nm) pores gradually increased, and the number of large (> 10 nm) pores gradually decreased. Overall, as D_ET increased, pore size and number decreased. There was a gradual increase in the number of folded and curved carbon layers in the inner core of ECPs and an increase in the disorderliness of carbon layers in their outer shell as D_ET increased. Furthermore, the boundary between the inner core and the outer shell became increasingly obscure as D_ET increased. The crystallite size of ECPs decreased from 1.365 nm at 0 m to 1.098 nm at 3 m. This suggests that the number of continuously arranged carbon atoms decreased, the arrangement of carbon atoms was more disorderly, and the degree of graphitization decreased. As D_ET increased, there was a gradual increase in the interlayer spacing and curvature of ECPs. This suggests that increasing D_ET led to a more disorderly distribution of electron orbitals inside the carbon layers, less electron resonance stability in the carbon layers, greater oxidative activity of ECPs, and greater inherent oxidative capacity of particles.

     

不同Cu交换分子筛脱除柴油机尾气中的NOx

以BEA、ZSM-5和SAPO-34分子筛为载体,采用离子交换法制备了用于柴油机尾气中氨选择性催化还原(NH3-SCR)NOx的Cu改性分子筛催化剂.采用XRF、ICP、H2-TPR、和NH3-TPD等表征对催化剂样品的理化特性进行了分析.结果表明,分子筛类型影响铜交换量和铜物种的存在状态.借助H2-TPR和UV-Vis分析可以清晰地看出,在不同类型的分子筛上Cu的还原能力和配位环境明显不同.铜元素引入后,3类分子筛的SCR活性都有明显的改善.3种Cu-交换分子筛的抗高温水热老化能力却明显不同:老化的Cu-SAPO-34依然保持良好脱硝性能而老化的Cu-ZSM-5严重失活.     

Total diesel exhaust particulate length measurements using a modified household smoke alarm ionization chamber

To evaluate the effectiveness of various means to combat the negative health effects of ultrafine particles emitted by internal combustion engines, a reliable, low-cost instrument for dynamic measurements of the exhaust emissions of ultrafine particulate matter (PM) is needed. In this study, an ordinary ionization-type building smoke detector was modified to serve as a measuring ionization chamber and utilized for dynamic measurements of PM emissions from diesel engines. When used with diluted exhaust, the readings show an excellent correlation with total particulate length. The instrument worked well with raw and diluted exhaust and with varying emission levels and is well suitable for on-board use.     

Polycyclic aromatic hydrocarbon exhaust emissions from different reformulated diesel fuels and engine operating conditions

The study of light-duty diesel engine exhaust emissions is important due to their impact on atmospheric chemistry and air pollution. In this study, both the gas and the particulate phase of fuel exhaust were analyzed to investigate the effects of diesel reformulation and engine operating parameters. The research was focused on polycyclic aromatic hydrocarbon (PAH) compounds on particulate phase due to their high toxicity. These were analyzed using a gas chromatography–mass spectrometry (GC–MS) methodology.Although PAH profiles changed for diesel fuels with low-sulfur content and different percentages of aromatic hydrocarbons (5–25%), no significant differences for total PAH concentrations were detected. However, rape oil methyl ester biodiesel showed a greater number of PAH compounds, but in lower concentrations (close to 50%) than the reformulated diesel fuels. In addition, four engine operating conditions were evaluated, and the results showed that, during cold start, higher concentrations were observed for high molecular weight PAHs than during idling cycle and that the acceleration cycles provided higher concentrations than the steady-state conditions. Correlations between particulate PAHs and gas phase products were also observed.The emission of PAH compounds from the incomplete combustion of diesel fuel depended greatly on the source of the fuel and the driving patterns.     

La-K-Co-Mn-O钙钛矿型复合氧化物同时去除碳颗粒和Nox的性能

采用柠檬酸络合燃烧法合成制备了La1-xKxCo0.5Mn0.5O3(x为K+取代量,x=0、0.1、0.2、0.3、0.4、0.5)系列钙钛矿型复合金属氧化物催化剂,以X射线衍射、红外光谱和比表面积等手段对该催化剂进行表征,以常压固定床微型反应器程序升温氧化还原反应技术评价该催化剂同时去除模拟柴油机尾气中炭黑颗粒(表征柴油机尾气中的碳颗粒)和NOX的催化性能.结果表明,K+部分取代LaCo0.5Mn0.5O3中的La3+后,催化剂催化性能得到明显改善,炭黑颗粒的起燃温度(Tig)、峰值温度(Tm)和燃尽温度(Tf)均降低,NOX的转化率提高,最高为16.6%;La0.6K0.4Co0.5Mn0.5O3具有最佳的催化性能,炭黑颗粒的Tig、Tm和Tf分别为305、350、379 ℃,炭黑颗粒燃烧产物中CO2的体积分数为98.8%,NOX转化率为15.5%.     

Characteristics of trans,trans-2,4-decadienal and polycyclic aromatic hydrocarbons in exhaust of diesel engine fueled with biodiesel

The use of biodiesel fuel as a substitute for fossil fuel in diesel engines has received increasing attention in recent years. This study is the first to investigate and compare the characteristics of mutagenic species, trans,trans-2,4-decadienal (tt-DDE), and polycyclic aromatic hydrocarbons (PAHs) in the diluted exhaust of diesel engines operated with diesel and biodiesel blend fuels. An engine of current design was operated on a dynamometer consistent with the US federal test procedure transient-cycle specifications. Petroleum diesel and a blend of petroleum diesel and biodiesel (B20) were tested. Exhaust sampling was carried out on diluted exhaust in a dilution tunnel with a constant-volume sampling system. Concentrations of tt-DDE and PAHs were analyzed by GC/MS. Although average PAH emission factors decreased from 1403 to 1051 μg bhp-h⁻¹, the results show that tt-DDE is evidently generated (1.28 μg bhp-h⁻¹) in the exhaust of diesel engine using B20 as fuel. This finding suggests that tt-DDE emission from the use of biodiesel should be taken into account in characterization and health-risk assessment. The results also show that tt-DDE is depleted in the diesel engine combustion process and the existence of tt-DDE in biodiesel is the major source of tt-DDE emission. The distribution of tt-DDE in the particulate phase is 55.3% under this study's sampling conditions. For diesel and B20, PAH phase distributions have similar trends. Lower molecular weight PAHs predominate in gaseous phase for both diesel and B20. Cold-start driving has higher tt-DDE and PAH emission factors, as well as a higher percentage of tt-DDE in particulate phase, than for warm-start driving.     

Study of Miller timing on exhaust emissions of a hydrotreated vegetable oil (HVO)-fueled diesel engine

The effect of intake valve closure (IVC) timing by utilizing Miller cycle and start of injection (SOI) on particulate matter (PM), particle number, and nitrogen oxide (NO_x) emissions was studied with a hydrotreated vegetable oil (HVO)-fueled nonroad diesel engine. HVO-fueled engine emissions, including aldehyde and polyaromatic hydrocarbon (PAH) emissions, were also compared with those emitted with fossil EN590 diesel fuel. At the engine standard settings, particle number and NO_x emissions decreased at all the studied load points (50%, 75%, and 100%) when the fuel was changed from EN590 to HVO. Adjusting IVC timing enabled a substantial decrease in NO_x emission and combined with SOI timing adjustment somewhat smaller decrease in both NO_x and particle emissions at IVC??50 and??70 °CA points. The HVO fuel decreased PAH emissions mainly due to the absence of aromatics. Aldehyde emissions were lower with the HVO fuel with medium (50%) load. At higher loads (75% and 100%), aldehyde emissions were slightly higher with the HVO fuel. However, the aldehyde emission levels were quite low, so no clear conclusions on the effect of fuel can be made. Overall, the study indicates that paraffinic HVO fuels are suitable for emission reduction with valve and injection timing adjustment and thus provide possibilities for engine manufacturers to meet the strictening emission limits.

Implications: NO_x and particle emissions are dominant emissions of diesel engines and vehicles. New, biobased paraffinic fuels and modern engine technologies have been reported to lower both of these emissions. In this study, even further reductions were achieved with engine valve adjustment combined with novel hydrotreated vegetable oil (HVO) diesel fuel. This study shows that new paraffinic fuels offer further possibilities to reduce engine exhaust emissions to meet the future emission limits.

Supplementary Materials: Supplementary materials are available for this paper. Go to the publisher's online edition of the Journal of the Air & Waste Management Association for a complete list of analysed PAH compounds.     

Performance and exhaust emission characteristics investigation of compression ignition engine fuelled with microalgae biodiesel and its diesel blends

Biofuels extracted from plant biomass can be used as fuel in CI engines to lower a hazardous atmospheric pollutant and mitigate climate risks. Furthermore, its implementation is hampered by inevitable obstacles such as feedstocks and the crop area required for their cultivation, leading to a lack of agricultural land for the expansion of food yields. Despite this, microalgae have been discovered to be the most competent and unwavering source of biodiesel due to their distinguishing characteristics of being non-eatable and requiring no cropland for cultivation. The objectives of this paper was to look into the potential of a novel, formerly underappreciated biodiesel from microalgae species which could be used as a fuel substitute. Transesterification is being used to extract the biodiesel. Microalgae are blended with petroleum diesel in percentage to create microalgae blends (MAB) as needed for experimentation. The impact of biodiesel on performance as well as exhaust emission attributes of a 1-cylinder diesel engine was experimentally studied. Compared to petroleum diesel, different blend of microalgae biodiesel showed a decline in torque and hence brake power, resulting in an average fall of 7.14 % in brake thermal efficiency and 11.54 % increase in brake-specific fuel consumption. There were wide differences in exhaust emission characteristics, including carbon monoxide and hydrocarbon, as the blend ratio in diesel increased. Moreover, nitrogen oxides and carbon dioxides increase in all algae biodiesel blends, but they are still within the acceptable range of petroleum diesel.

     

低温等离子体技术及其在柴油机排气处理中的应用

概述了等离子体特点及分类 ,介绍了低温等离子体的产生及其净化柴油机排气的应用进展 ,分析了低温等离子体技术有效处理柴油机排气的机理 ,阐述了未来低温等离子体处理柴油机排气的主要方向与应用前景。     

Real-time measurements of jet aircraft engine exhaust

Particulate-phase exhaust properties from two different types of ground-based jet aircraft engines--high-thrust and turboshaft--were studied with real-time instruments on a portable pallet and additional time-integrated sampling devices. The real-time instruments successfully characterized rapidly changing particulate mass, light absorption, and polycyclic aromatic hydrocarbon (PAH) content. The integrated measurements included particulate-size distributions, PAH, and carbon concentrations for an entire test run (i.e., "run-integrated" measurements). In all cases, the particle-size distributions showed single modes peaking at 20-40nm diameter. Measurements of exhaust from high-thrust F404 engines showed relatively low-light absorption compared with exhaust from a turboshaft engine. Particulate-phase PAH measurements generally varied in phase with both net particulate mass and with light-absorbing particulate concentrations. Unexplained response behavior sometimes occurred with the real-time PAH analyzer, although on average the real-time and integrated PAH methods agreed within the same order of magnitude found in earlier investigations.     

Characterization of aging wood chip combustion aerosol in an environmental chamber

Aging of aerosol from wood chip combustion in a stoker burner was monitored in an outdoor environmental chamber for 19–27 h in order to study the size, volatility and organic carbon (OC) content of the combustion aerosol particles during aging. A scanning mobility particle sizer, a volatility tandem differential mobility analyzer (VTDMA), and a thermal–optical carbon analyzer were utilized. The VTDMA and carbon analyses were performed at the beginning, after 17–24 h of aging and at one intermediate point. The size decrease of freshly emitted particles was 6–10% when heated to $360{}^{\circ }\mathrm{C}$, and was found to depend on the experiment start time. For particles aged for 24 h, a 74–86% decrease in particle size at $360{}^{\circ }\mathrm{C}$ was observed. The more volatile OC fraction and the total OC fraction in the particles increased and the less volatile OC fraction decreased with aging. This suggests that during aging more volatile compounds condense on or heavier compounds photodegrade into lighter ones in the particles. Occasionally, new particle formation and growth were observed in the following day. The new particles were found to be composed mainly of volatile material.     

Effects of driving conditions on diesel exhaust particulates

Four driving conditions were examined to characterize how speeds and loads of a medium-duty diesel engine affect resultant diesel exhaust particulates (DEPs) in terms of number concentrations (< or =400 nm), size distribution, persistent free radicals, elemental carbon (EC), and organic carbon (OC). At the medium engine load (60%), DEPs surged in number concentrations at around 40-70 nm, whereas DEPs from the full engine load (100%) showed a distinctive bimodal distribution with a large population of 30-50 nm and 100-400 nm. Under the full engine load, engine speeds insignificantly affected resultant DEP number concentrations. When the engine load decreased from 100% to the medium level (60%), DEPs of ultrafine size and 100-400 nm decreased at least 1.4 times (from 5.6 x 10(8) to 4 x 10(8) #/cm3) and more than 3 times (from 2.7 x 10(8) to 0.8 x 10(8) #/cm3), respectively. The same reduction in the engine load significantly decreased persistent free radicals in DEPs up to approximately 30 times (from 123 x 10(16) to 4 x 10(16) #spin/g). Decreasing the engine load from 100 to 60% also concurrently reduced both EC and OC in total DEPs around 2 times, from 27.3 to 13.9 mg/m3, and from 17.6 to 9.2 mg/m3, respectively. For DEPs smaller than 1 microm, under the full engine load, EC and OC consistently peaked at 170-330 nm under an engine speed of 1800 rpm or 94-170 nm under an engine speed of 3000 rpm, reflecting processes of nucleation, cluster-cluster agglomeration, and condensation. Decreasing the engine load from 100 to 60% reduced EC and OC in DEPs (smaller than 1 microm) at least 3 times (0.6 to 0.2 mg/m3) and 2 times (0.4 to 0.2 mg/m3), respectively. Taken together, decreasing the full engine load to a medium (60%) level effectively reduced the number concentrations (< or =400 nm), persistent free radicals, EC, and OC of total DEPs, as well as the concentration of EC and OC in ultrafine and accumulation-mode DEPs.     

柴油机尾气中微粒粒径分布特征的实验研究

柴油机尾气中的微粒粒径大小分布范围广泛,不同直径的微粒所占的比例以及对环境和人身健康造成的危害各不相同,因此对微粒粒径特征进行研究更具有实际意义.本研究分别采用滤膜称重法和光散射法对厦工XG951Ⅲ装载机配置的国Ⅲ柴油发动机怠速工况下的尾气进行测试,研究了微粒的质量浓度分布、数量浓度分布以及质量浓度与数量浓度分布的关系.研究结果表明,从微粒质量上看,可吸入微粒(PM10)占微粒总量(TSP)的74.0%,可入肺微粒(PM2.5)占可吸入微粒的48.1%;2.5 μm以下粒径范围内的微粒质量浓度是2.5~10 μm粒径范围内微粒质量浓度的将近3倍,是10~100 μm粒径范围内微粒质量浓度的52倍;2.5~10 μm粒径范围的微粒质量浓度是10~100 μm粒径范围内微粒质量浓度的18倍.数量上,在不同的数量级上,微粒数量浓度随粒径变化差距很明显,尤其是1 μm以下的微粒较多.另外,质量浓度的粒径分布滞后于数量浓度.因此PM2.5排放标准中应考虑以个数浓度代替质量浓度为标准.     

Carbon nanotube-like materials in the exhaust from a diesel engine using gas oil/ethanol mixing fuel with catalysts and sulfur

Particulate matter from a diesel engine, including soot and carbon nanomaterials, was collected on a sampling holder and the structure of the materials was studied by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). As a result of employing gas oil/ethanol mixing fuel with sulfur and ferrocene/molybdenum as catalyst sources, formation of carbon nanotubes (CNT)-like materials in addition to soot was observed in the exhaust gas from a diesel engine. It was revealed that CNT-like materials were included among soot in our system only when the following three conditions were satisfied simultaneously: high ethanol fraction in fuel, high sulfur loading, and presence of catalyst sources in fuel. This study confirmed that if at least one of these three conditions was not satisfied, CNT-like materials were not observed in the exhaust from a diesel engine. These experimental results shown in this work provide insights into understanding CNT-like material formation mechanism in a diesel engine.

Implications: Recent papers reported that carbon nanotube-like materials were included in the exhaust gas from engines, but conditions for carbon nanotube-like material formation have not been well studied. This work provides the required conditions for carbon nanotube-like material growth in a diesel engine, and this will be helpful for understanding the carbon nanotube-like material formation mechanism and taking countermeasures to preventing carbon nanotube-like material formation in a diesel engine.     

Improvement of an efficient separation method for chemicals in diesel exhaust particles: analysis for nitrophenols

GOAL, SCOPE, AND BACKGROUND: Diesel exhaust is believed to consist of thousands of organic constituents and is a major cause of urban pollution. We recently reported that a systematic separation procedure involving successive solvent extractions, followed by repeated column chromatography, resulted in the isolation of vasodilatory active nitrophenols. These findings indicated that the estimation of the amount of nitrophenols in the environment is important to evaluate their effect on human health. The isolation procedure, however, involved successive solvent extractions followed by tedious, repeated chromatography, resulting in poor fractionation and in a significant loss of accuracy and reliability. Therefore, it was crucial to develop an alternative, efficient, and reliable analytical method. Here, we describe a facile and efficient acid-base extraction procedure for the analysis of nitrophenols. MATERIALS AND METHODS: Diesel exhaust particles (DEP) were collected from the exhaust of a 4JB1-type engine (ISUZU Automobile Co., Tokyo, Japan). Gas chromatography-mass spectrometry (GC-MS) analysis was performed with a GCMS-QP2010 instrument (Shimadzu, Kyoto, Japan). RESULTS: A solution of DEP in 1-butanol was extracted with aqueous NaOH to afford a nitrophenol-rich oily extract. The resulting oil was methylated with trimethylsilyldiazomethane and subsequently subjected to GC-MS analysis, revealing that 4-nitrophenol, 3-methyl-4-nitrophenol, 2-methyl-4-nitrophenol, and 4-nitro-3-phenylphenol were present in significantly higher concentrations than those reported previously. DISCUSSION: Simple acid-base extraction followed by the direct analysis of the resulting extract by GC-MS gave only broad peaks of nitrophenols with a poor detection limit, while the GC-MS analysis of the sample pretreated with (trimethylsilyl)diazomethane gave satisfactorily clear chromatograms with sharp peaks and with a significantly lowered detection limit (0.5 ng/ml, approximately 100 times). CONCLUSION: The present method involving an acid-base extraction, in situ derivatization, and GC-MS analysis has shown to be a simple, efficient, and reliable method for the isolation and identification of the chemical substances in DEP.     

柴油车排气颗粒物的后处理技术

本文分析探讨了柴油机排气颗粒物的组成、危害及后处理技术。介绍了颗粒捕集器及其消极和积极再生方法、采用氧化催化剂或四效催化剂的催化净化器和低温等离子体 -催化净化技术。     

有害物质环境测试组合舱的研制及性能评价

研制了一种新型有害物质环境测试组合舱,该测试舱由舱体系（内舱和外舱）、恒温恒湿空气处理系统、空气循环装置和信号控制与处理软件组成。该测试舱具有可分别使用内舱和外舱对样品进行测试的特点,并采用美国FLUNT公司开发的air pack软件包对内舱和外舱的气流进行模拟与计算,并划分出内舱的层流区域,同时也对舱体系的性能进行了测试与评价。结果表明,有害物质环境测试组合舱的温湿度的相对标准偏差分别为0.04℃和0.7%,混合性达到90.7%。因此,该有害物质环境测试组合舱对温湿度控制精准,气流稳定,混合性能良好,能为室内空气污染研究提供条件稳定的室内仿真环境。