Raman spectroscopy of diesel and gasoline engine-out soot using different laser power

We studied engine-out soot samples collected from a heavy-duty direct-injection diesel engine and port-fuel injection gasoline spark-ignition engine. The two types of soot samples were characterized using Raman spectroscopy with different laser powers. A Matlab program using least-square-method with trust-region-reflective algorithm was developed for curve fitting. A DOE (design of experiments) method was used to avoid local convergence. The method was used for two-band fitting and three-band fitting. The fitting results were used to determine the intensity ratio of D (for “Defect” or “Disorder”) and G (for “Graphite”) Raman bands. It is found that high laser power may cause oxidation of soot sample, which gives higher D/G intensity ratio. Diesel soot has consistently higher amorphous/graphitic carbon ratio, and thus higher oxidation reactivity, compared to gasoline soot, which is reflected by the higher D/G intensity ratio in Raman spectra measured under the same laser power.     

提高柴油/甲醇组合燃烧尾气排放质量的研究

对原机、柴油/甲醇组合燃烧,以及带氧化催化转化器的柴油/甲醇组合燃烧3种情况下的尾气排放进行了比较和研究.针对柴油/甲醇组合燃烧可以使NOx、烟度大幅度下降,但同时PM、CO和HC的排放浓度与原机相比反而增加的现状,通过加装氧化催化转化器,对废气进行处理后,发现HC、CO和PM排放明显减少.与原机相比,不仅可以实现大幅度降低NOx,而且PM排放也有较大幅度下降.采用透射电子显微镜观察发现,与原机相比,柴油/甲醇组合燃烧的PM排放中干炭烟(DS)减少,但是可溶有机物(SOF)增加.经过氧化催化转化器处理后,尾气的PM中大量SOF和HC化合物被消除,致使PM的质量明显减少.     

柴油/甲醇燃烧颗粒的碳结构参数分析

为探讨非道路柴油机燃用柴油/甲醇混合燃料排气颗粒中碳结构的演变规律,降低非道路柴油机的颗粒(PM)排放,采用激光拉曼光谱仪,结合分峰拟合方法,重点针对甲醇掺混比对非道路柴油机燃烧颗粒的碳结构参数和演变规律进行分析,并用颗粒氧化特性试验对拟合分析结果进行验证. 结果表明,随着燃料中甲醇掺混比(以w计)的增加:①NO_x、CO、HC比排放呈上升趋势,与柴油相比,甲醇掺混比为15%时,3种污染物比排放分别升高约12%、49%、62%;颗粒比排放降幅明显,约为59%. ②由于颗粒碳原子和碳键的伸缩振动,在1 350和1 590 cm-1附近出现2个较为强烈并有一定重合的拉曼振动峰;颗粒中C—C的伸缩振动以及弯曲振动加剧,在345 cm-1附近出现较为强烈的拉曼振动峰. ③表征颗粒中无定形成分的D3峰的相对强度(R3值)明显升高,表明颗粒中的碳团簇含量增加,石墨晶体结构的无序程度升高;表征颗粒中石墨化程度的D1~D4、G峰的FWHM(半宽度)和D/G相对强度整体呈上升趋势,说明颗粒的石墨化程度降低,颗粒较容易被氧化. ④颗粒的活化能逐渐降低,也说明掺混甲醇后,颗粒具有较好的氧化性能,有利于加速颗粒在缸内的氧化速度,缩短颗粒捕集器中过滤体的再生时间,降低柴油机的颗粒排放.      

柴油/甲醇组合燃烧(DMCC)减少重载柴油机烟度排放的试验研究

在一台满足国三排放法规要求的重载车用增压中冷电控单体泵柴油机上,将其改造成柴油/甲醇组合燃烧(DMCC)发动机并进行台架试验.利用电控单元控制向进气歧管喷射的甲醇量及其喷射时刻,原柴油机供油系统保持不变.试验主要研究在稳定工况时,不同的负荷以及不同的甲醇对柴油的比例情况下,经催化转化后发动机干炭烟烟度(415烟度)和不透光烟度(439烟度)排放的情况.试验结果表明,在燃用现有市售的燃油条件下,与原机相比,相同工况下采用DMCC的干炭烟烟度和不透光烟度都有大幅度的减少.干炭烟的最大降幅达95%,平均降幅达到50%以上.在柴油喷射量不变的情况下,增加甲醇喷射量,干炭烟烟度会持续减小,而不透光烟度呈先减少后增加的趋势.同负荷时的甲醇对柴油替代率为44.88%到56.73%时,不透光烟度存在最低点,并且发动机的烟度排放存在最优值.在同一工况下,随着柴油对甲醇的比例增加,发动机的干炭烟烟度和不透光烟度排放都逐渐增加.     

复合氧化物催化材料上碳颗粒物的催化燃烧

针对柴油车排放碳颗粒物的控制 ,研制可应用于柴油车排放碳颗粒物催化再生复合氧化物催化材料 .通过运用热分析仪 (TGA)和程序升温氧化反应装置 (TPO)对复合氧化物催化材料的活性进行评价 ,研究了催化材料的组成、原子配比、催化材料与碳颗粒物质量比、H₂O的加入、焙烧温度对催化活性的影响 .实验结果表明 :双组分金属氧化物催化剂中 ,Cu-Mo-O有较好的活性 ;多组分金属氧化物催化剂中 ,Cu-K-Mo-O在原子比Cu∶K∶Mo =1∶1∶2 ,催化剂与碳颗粒物质量比为 5∶1时活性最好 ,其碳颗粒物起燃温度为 32.7℃ ,同时H₂O和焙烧温度对该催化剂的影响较小 ,是能够应用于柴油车排放碳颗粒物控制催化再生的良好催化材料 .     

EGR率对农用单缸柴油机燃用生物柴油的NOx与PM排放特性影响分析

单缸柴油机作为小型农用机械不可或缺的动力源,在使用过程中会产生大量污染物.其中氮氧化合物（NO_x）和颗粒（PM）是气溶胶的主要组成部分,对大气环境造成了严重污染.为有效改善农用单缸柴油机NO_x和PM排放,本研究通过添加生物柴油对柴油进行改质以及采用机内EGR净化技术两种方案,测量了柴油机分别燃用柴油B0,生物柴油调合燃料B20、B50在不同EGR率下的NO_x和PM排放.结果表明,采用EGR技术能够明显改善柴油机的NO_x排放,但同时会引起碳烟排放的增加.通过在柴油中添加生物柴油能够在一定程度上降低碳烟排放,其中高负荷、大EGR率条件下的改善最为明显.在2000 r·min^-1、75%负荷,EGR率为30%时,燃用B50的碳烟排放与燃用B0相比降低了47.3%.总体上柴油中添加生物柴油与EGR技术共同作用能够有效降低柴油机高负荷工况时的颗粒排放总数量.     

POC的结构参数对DMCC发动机排放影响的试验研究

在一台直列4缸增压中冷电控单体泵柴油机的进气道上增加甲醇喷射装置,实现柴油甲醇二元燃料燃烧(DMDF)模式.利用废气分析仪对其主要气体排放进行测量,研究在排气管上加装的柴油颗粒氧化催化转化器结构参数对尾气催化效率的影响,试验结果表明:POC长度越长,对碳烟、THC、和未燃甲醇的转化效果越好,甲醇替代率为30%、POC长度为100 mm时,对碳烟、CO、THC和未燃甲醇的平均净化效率分别为15.00%、91.61%、75.56%、66.96%,长度增加至200 mm后,上述效率明显提高,分别提高到30.37%、99.29%、67.55%、95.44%;POC孔密度增加,POC对碳烟、CO及未燃甲醇的转化效率有小幅增加,甲醇替代率为30%时,孔密度从200目增加到300目,对碳烟、CO和未燃甲醇的催化效率分别从19.61%、94.66%、86.07%提高到23.06%、97.44%和88.56%;POC结构参数的改变对NO_x的转化效率影响不大.     

用柴油/醇组合燃烧法在城市车用柴油机上实现同时降低碳烟与NOx排放的研究

柴油机在部分工况采用柴油扩散燃烧 ,另一部分工况则采用柴油引燃醇燃料形成的均质混合气压燃燃烧 .这种组合燃烧利用醇的高汽化潜热和含氧特性 ,达到同时降低柴油机碳烟及氮氧化物 (NOx)排放的目的 ,并可以避免小负荷燃烧醇燃料带来的高醛类排放问题 .在一台 4 85QDI直喷式柴油机上采用上述组合燃烧法进行了试验 ,醇均质混合气经进气管处喷射形成 ,用电控装置控制醇燃料喷入量及其喷入时刻 .试验结果表明 ,与原机相比 ,碳烟和NOx 排放分别可以减少 5 0 %和 30 %以上 ,同时燃料的消耗率也有大幅度降低 .该方法为降低城市车用柴油机的碳烟排放提出一个新的解决途径     

Soot reduction by addition of dimethyl carbonate in normal and inverse ethylene diffusion flames: Nanostructural evidence

Oxygenated fuel represents an attractive alternative as an additive for reducing soot emissions.Dimethyl carbonate(DMC) is an oxygenated compound which is a good option to reduce soot,but the detailed characteristics of soot produced from combustion of hydrocarbon fuels blended with DMC are still lacking. The present research studied the nanostructure and reactivity of soot particles in ethylene/DMC normal and inverse diffusion flames. High resolution transmission electron microscopy(HRTEM), X-ray diffraction(XRD), and thermogravimetric analysis(TGA)were used to analyze the nanostructure and reactivity of soot. It was found that DMC addition was effective in decreasing the average weights of soot formed in flames. The results of HRTEM images showed that soot particles obtained with DMC addition showed liquid-like material and tight bonding, and exhibited more highly disorganized layers, which give it higher reactivity than soot obtained without DMC addition. Furthermore, HRTEM was used to analyze soot fringe characteristics consisting of fringe tortuosity, fringe length, and fringe separation. XRD was used to crosscheck the results for fringe separation, and was consistent with HRTEM results. In addition, the mass loss curve of TGA experiments showed that DMC addition could enhance the reactivity of soot particles.     

不同后处理器对DMCC发动机PM排放的影响

在一台整车排放达到国Ⅲ标准的YC4D140电控单体泵增压中冷柴油机上加装甲醇喷射系统,改成柴油甲醇组合燃烧(DMCC)发动机.使用AVL 415S烟度计和DMS 500快速颗粒物光谱仪研究不同后处理器对DMCC发动机颗粒物(PM)排放的影响.试验结果表明,各工况下单独CDPF、DOC+CDPF基本可以消除发动机产生的干炭烟.DOC+CDPF后处理方式与单独CDPF相比,颗粒物捕集效率明显提高,且前者对颗粒物中核态部分的捕集效果更加突出.甲醇掺烧后,炭烟和颗粒物几何平均直径降低.经CDPF和DOC+CDPF处理,415S烟度计测得的炭烟进一步降低;DMS颗粒物光谱仪显示的颗粒物粒径,因其中核态部分大部被氧化捕集而仅余较大几何平均直径的部分.小负荷时经CDPF和DOC+CDPF处理,颗粒物的几何平均直径会增大,大负荷时则相反.各工况下相比于CDPF,DOC+CDPF对核态颗粒物捕集更有效.     

高压共轨主喷射时刻对柴油/甲醇双燃料发动机燃烧和排放的影响

在一台四冲程六缸增压中冷的高压共轨柴油机上采用进气总管喷射无水甲醇的方式进行柴油/甲醇组合燃烧实验(DMCC).通过改变共轨柴油喷射的主喷射时刻以及甲醇的喷射量,对柴油机燃烧和尾气排放进行研究.试验发现,纯柴油模式下,压缩冲程缸压随着喷油提前角的减小而增大,推迟喷油,后燃期延长,排气压力增大.甲醇替代率为30%时,随着喷油提前角的增大,峰值缸压和峰值放热率均增大.在柴油/甲醇双燃料燃烧模式下主喷射时刻对减少柴油机氮氧化合物(NO_x)排放具有较好的作用,同一替代率情况下NO_x排放随着主喷射时刻的推后而减少;主喷射时刻对碳烟(Soot)排放的影响则比较复杂,纯柴油模式下碳烟的排放随着主喷射时刻的提前逐步减少,而柴油甲醇二元燃料燃烧(DMDF)模式下碳烟的排放则随着主喷射时刻的提前呈现出先上升后下降的趋势;DMDF模式下主喷射时刻提前CO、HC排放均降低,且替代率越大下降趋势越明显.     

乙醇柴油混合燃料的制备工艺和废气的排放特性

为降低柴油机排放对环境造成的污染,用乙醇部分替代柴油,探索了乙醇柴油混合燃料的制备方法,研究了掺混乙醇及助溶剂对柴油机排放的影响.结果表明:无水乙醇可以和柴油以任意比例混溶,但痕量水(0.2%)的添加即导致混合物分层,合成的有机助溶剂可保证乙醇-柴油-痕量水体系的稳定性基于台架实验,考察了掺混10%、20%、30%乙醇对燃料排放性能的影响乙醇的最佳掺混比为20%在额定工况点(功率为13kW,转速为1540r/min)时,掺混20%乙醇的混合燃料可降低烟度55%,降低HC排放70%,降低CO排放45%.不添加助溶剂时,乙醇的掺混导致排放尾气中产生乙醇、微量乙醛等有机物.而添加非金属离子助溶剂可使HC、乙醇、乙醛排放的浓度明显降低.     

Morphological and semi-quantitative characteristics of diesel soot agglomerates emitted from commercial vehicles and a dynamometer

Diesel soot aggregates emitted from a model dynamometer and 11 on-road vehicles were segregated by a micro-orifice uniform deposit impactor (MOUDI). The elemental contents and morphological parameters of the aggregates were then examined by scanning electron microscopy coupled with an energy dispersive spectrometer (SEM-EDS), and combined with a fractional Brownian motion (fBm) processor. Two mode-size distributions of aggregates collected from diesel vehicles were confirmed. Mean mass concentration of 339 mg/m3 (dC/dlogdp) existed in the dominant mode (180–320 nm). A relatively high proportion of these aggregates appeared in PM1, accentuating the relevance regarding adverse health e ects. Furthermore, the fBm processor directly parameterized the SEM images of fractal like aggregates and successfully quantified surface texture to extract Hurst coe cients (H) of the aggregates. For aggregates from vehicles equipped with a universal cylinder number, the H value was independent of engine operational conditions. A small H value existed in emitted aggregates from vehicles with a large number of cylinders. This study found that aggregate fractal dimension related to H was in the range of 1.641–1.775, which is in agreement with values reported by previous TEM-based experiments. According to EDS analysis, carbon content ranged in a high level of 30%–50% by weight for diesel soot aggregates. The presence of Na and Mg elements in these sampled aggregates indicated the likelihood that some engine enhancers composed of biofuel or surfactants were commonly used in on-road vehicles in Taiwan. In particular, the morphological H combined with carbon content detection can be useful for characterizing chain-like or cluster diesel soot aggregates in the atmosphere.     

DOC+CDPF对生物柴油燃烧颗粒排放特性的影响

以一台满足国五排放法规的车用柴油机为样机,研究加装氧化催化转化器DOC与催化型颗粒捕集器CDPF(DOC+CDPF后处理装置)前后,柴油机燃用B20燃料(燃料含20%体积掺混比的生物柴油)的颗粒排放特性.结果表明,在未加装该后处理装置时,该机排气颗粒数量浓度的粒径分布呈双峰形态,B20燃料的排气颗粒数量浓度的峰值粒径在10nm和50nm附近,纯柴油的排气颗粒数量浓度的峰值粒径在50nm和200nm附近.在颗粒粒径小于120nm的区域,该机燃用B20燃料的排气颗粒数量浓度大于纯柴油.加装该后处理装置后,该机排气颗粒数量浓度的粒径分布呈多峰形态,峰值粒径在10nm、20nm和60nm附近.加装DOC+CDPF后,不论是柴油还是B20燃料,与原机相比,柴油机排气颗粒总数量下降明显,其中60~200nm粒径范围的颗粒数量浓度降幅更为显著.在相同工况下,DOC+CDPF对柴油机燃用B20燃料的颗粒总数量净化效率高于纯柴油.     

柴油烃族组分对柴油机排放的影响

柴油烃族组分可影响柴油的理化特性,从而影响柴油机的燃烧过程,进而对排放产生重要影响.本研究针对烃族组分含量不同的14种柴油,开展了排放特性的试验研究,基于试验结果采用主成分分析法及回归分析法揭示影响柴油机排放性能的关键组分及作用规律,并得到了柴油机排放与关键组分的经验公式,可在一定程度上预测排放特性.分析结果表明,总芳烃是影响柴油机排放的关键组分,当其含量介于5%～17%时,可使NO_x、soot(碳烟)、CO、HC排放均处于较低水平.此外,多环芳烃对柴油机排放有重要影响,其中的苊类、苊烯类对NO_x、碳烟、CO排放的影响作用更为显著,而其他烃族组分与柴油机排放的规律性相对较差.不同工况下,柴油机排放规律有所不同,在低负荷下柴油机排放对总芳烃含量更加敏感.     

重载柴油机采用非SCR和DPF实现国Ⅳ排放研究

在1台电控高压共轨重载柴油机上采用柴油/甲醇二元燃料(DMDF)燃烧方式,后处理采用氧化催化转化器(DOC)紧耦合微粒氧化催化器(POC),对其排放特性开展了试验研究.结果表明:DMDF模式可以同时减少NOx和炭烟排放,且随着甲醇掺烧比例的增加降低效果更加显著;在80%负荷时当甲醇掺烧比例为50%时,NOx和炭烟排放分别减少了25.3%和69.3%;DOC+POC对HC、CO和甲醛排放的催化效率均超过了98%,优于原机水平;经ETC、ESC和ELR检测,柴油机采用DMDF模式结合后处理器DOC+POC可满足国Ⅳ排放要求.     

Size effect of Pt nanoparticles in acid-assisted soot oxidation in the presence of NO

Pt/Al₂O₃ catalysts with mean Pt particle size ranged from 2.7 to 7.1 nm were synthesized by chemical reduction method, and the sulfated counterparts were prepared by impregnation of sulfuric acid. The turnover frequency of platinum for soot oxidation under loose contact conditions in a feed flow containing NO and O₂ are positively correlated with the size of platinum. The sulfated Pt/Al₂O₃ exhibits higher catalytic activity for soot oxidation in the presence of NO despite their reduced ability for NO₂ production. Such a contradiction is more significant for those catalysts with smaller platinum particles. Herein, the catalysts were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), transmission electron microscopy (TEM), inductive coupled plasma (ICP) emission spectrometry, CO chemisorption, thermogravimetric analysis (TGA), NH₃ temperature-programmed desorption (NH₃-TPD), NO temperature-programmed oxidation (TPO) and NO_x temperature-programmed desorption (TPD). Possible effect of Pt particle size for the catalytic oxidation of soot in the presence of NO was presented based primarily on the promoted NO₂ transfer efficiency onto the soot pushed by the acidic catalysts.     

V2O5/TiO2与MoO3/TiO2催化剂表面结构形貌及其对催化氧化碳烟活性的影响

为研究纳米级V₂O₅与MoO₃催化剂表面结构对其催化氧化碳烟活性的影响,以TiO₂为载体,采用等体积浸渍法制备了不同负载率(5%、10%、20%、40%)的V₂O₅/TiO₂与MoO₃/TiO₂催化剂,通过扫描电镜(SEM)、X射线衍射仪(XRD)对比研究了2种催化剂在TiO₂载体上的分散状态及物相结构.以Printex-U碳黑为试验用碳烟,采用热重分析仪对V₂O₅与MoO₃催化剂催化碳烟氧化的活性进行了比较.结果表明:V₂O₅与MoO₃在TiO₂载体上均存在一个单层分散饱和阈值,分别为V20(负载率为20%,下同)、Mo10,在该阈值前后活性组分在载体上分别以单层分散状态和明显的晶态存在.对于V₂O₅催化剂,其最佳催化活性出现在负载率接近单层分散饱和阈值时,与无催化状态相比,T_i(起燃温度)、T_p(最大失重率温度)以及T_f(燃尽温度)分别下降了69.1、46.0、23.0 ℃,有明显的阈值效应.而对于MoO₃催化剂,因其自身低熔点性而表现出良好的表面迁移能力,再加上α-MoO₃晶体特有的层状结构,使其可释放出更多的晶格氧,随着负载率的增加,该催化剂催化氧化碳烟活性持续增加,并且未观察到明显的阈值效应.研究显示,在相同负载率下,MoO₃催化剂催化氧化碳烟活性均高于V₂O₅催化剂.      

Cu-K型低温碳烟氧化催化剂的合成及表征

柴油机排放中碳烟的低温氧化是近年来研究的热点.通过原位合成法制备Cu2K/Al2O3和CuK／Al2O3两种碳烟氧化催化剂,并采用低温氮吸附/脱附实验、X射线衍射、X射线光电子能谱、程序升温氧化对其结构进行系统表征,并用U碳模拟柴油机碳烟,研究其催化活性,评测其对柴油机排气中碳烟颗粒的净化效果.研究表明,Cu2K/Al...     

Experimental study on filtration and continuous regeneration of a particulate filter system for heavy-duty diesel engines

This study investigated the filtration and continuous regeneration of a particulate filter system on an engine test bench, consisting of a diesel oxidation catalyst（DOC） and a catalyzed diesel particulate filter（CDPF）. Both the DOC and the CDPF led to a high conversion of NO to NO2 for continuous regeneration. The filtration efficiency on solid particle number（SPN） was close to100%. The post-CDPF particles were mainly in accumulation mode. The downstream SPN was sensitively influenced by the variation of the soot loading. This phenomenon provides a method for determining the balance point temperature by measuring the trend of SPN concentration.