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.     

Oxidation of diesel soot on binary oxide CuCr(Co)-based monoliths

Binary oxide systems (CuCr₂O₄, CuCo₂O₄), deposited onto cordierite monoliths of honeycomb structure with a second support (finely dispersed Al₂O₃), were prepared as filters for catalytic combustion of diesel soot using internal combustion engine's gas exhausts (O₂, NO_x, H₂O, CO₂) and O³ as oxidizing agents. It is shown that the second support increases soot capacity of aforementioned filters, and causes dispersion of the particles of spinel phases as active components enhancing thereby catalyst activity and selectivity of soot combustion to CO₂. Oxidants used can be arranged with reference to decreasing their activity in a following series: O₃ >> NO₂ > H₂O > NO > O₂ > CO₂. Ozone proved to be the most efficient oxidizing agent: the diesel soot combustion by O₃ occurs intensively (in the presence of copper chromite based catalyst) even at closing to ambient temperatures. Results obtained give a basis for the conclusion that using a catalytic coating on soot filters in the form of aforementioned binary oxide systems and ozone as the initiator of the oxidation processes is a promising approach in solving the problem of comprehensive purification of automotive exhaust gases at relatively low temperatures, known as the "cold start" problem.     

Oxidation of diesel soot on binary oxide CuCr(Co)-based monoliths

Binary oxide systems (CuCr₂O₄, CuCo₂O₄), deposited onto cordierite monoliths of honeycomb structure with a second support (finely dispersed Al₂O₃), were prepared as filters for catalytic combustion of diesel soot using internal combustion engine's gas exhausts (O₂, NO_x, H₂O, CO₂) and O₃ as oxidizing agents. It is shown that the second support increases soot capacity of aforementioned filters, and causes dispersion of the particles of spinel phases as active components enhancing thereby catalyst activity and selectivity of soot combustion to CO₂. Oxidants used can be arranged with reference to decreasing their activity in a following series: O₃ ? NO₂ > H₂O > NO > O₂ > CO₂. Ozone proved to be the most efficient oxidizing agent: the diesel soot combustion by O₃ occurs intensively (in the presence of copper chromite based catalyst) even at closing to ambient temperatures. Results obtained give a basis for the conclusion that using a catalytic coating on soot filters in the form of aforementioned binary oxide systems and ozone as the initiator of the oxidation processes is a promising approach in solving the problem of comprehensive purification of automotive exhaust gases at relatively low temperatures, known as the “cold start” problem.     

CeO_2-TiO_2复合纳米纤维光催化降解醛酮类污染物的研究

采用同轴静电纺丝法制备了CeO2-TiO2复合纳米纤维,并用X射线衍射仪、扫描电子显微镜、程序升温脱附仪和紫外-可见光谱能谱(UVVis)仪表征了CeO2-TiO2纳米纤维的相组成和微观形貌,分析了CeO2-TiO2纳米纤维对醛酮的吸附强度与光电化学特性.同时,研究了CeO2配比量、光源条件和重复使用性对降解甲醛污染物的影响规律.结果表明,CeO2质量配比为50%的CeO2-TiO2催化剂对甲醛降解效率最高;在无光和可见光条件下,CeO2-TiO2催化剂对甲醛的降解效率分别为13.5%和25.3%,在紫外光下CeO2-TiO2催化剂对甲醛的降解效率为92.5%;随着光催化循环次数的增加,可见光下CeO2-TiO2催化剂对甲醛的降解效率逐渐增高,紫外光下CeO2-TiO2催化剂对甲醛的降解效率维持在92.5%左右.利用催化剂样品CT50对柴油机尾气中醛酮类排放污染物进行光催化降解的应用发现,CeO2-TiO2催化剂对醛类污染物的降解效率为85.4%,酮类污染物的降解效率为81.3%,苯甲醛和甲基苯甲醛的降解效率分别为80.4%和80.3%.表明CeO2-TiO2催化剂具有较强的光催化降解醛酮类污染物的能力.     

纳米TiO2添加剂对DMDF发动机大负荷燃烧及PM排放影响的试验研究

在一台电控增压中冷四缸柴油机的进气道上加装一套电控喷射装置,使其运行柴油/甲醇双燃料(DMDF)模式.研究了甲醇中Ti O_2添加剂的添加量及同一添加剂添加量在不同甲醇分散系喷射量时对发动机大负荷工况的燃烧和颗粒物(PM)排放的影响.结果表明,在甲醇中添加适量(30和100 mg·kg~(-1))的纳米Ti O_2能够使爆发压力升高,对燃烧有一定的促进作用,但添加过量(100 mg·kg~(-1))会对燃烧产生不利影响.加入纳米Ti O_2后,干炭烟烟度排放和积聚态颗粒数明显降低,在添加剂添加量为1000 mg·kg~(-1)时,最大降幅分别达到26.8%和29.4%,而核态颗粒物排放变化不大.在相同添加剂添加量下,增加甲醇分散系替代率R_m会使放热始点后移,放热更加集中,爆发压力增大,干炭烟烟度和颗粒物排放均大幅度降低.在添加剂添加量为100 mg·kg~(-1)时,与R_m=10%相比,R_m=40%时爆发压力增加0.94 MPa,放热率峰值增加53.5%,烟度、核态颗粒数、积聚态颗粒数和颗粒物总数的降幅分别达66.9%、42.3%、67.0%和58.0%.     

SO2气氛下Cu-Ce-O催化剂氧化柴油车排气碳烟的性能

运用程序升温氧化(TPO)对共沉淀法合成的Cu-Ce-O催化剂进行了活性评价,考察了在不同浓度的S0,气氛下cu-Ce-O催化剂氧化模拟碳黑的性能,并用BET、XRD、TPR和FT-IR对催化剂进行了表征.BET和XRD测试显示,cu和ce的结合使催化剂比表面积增大,晶体结构发生变化,形成了复合氧化物;TPO活性测试结果表明,Cu-Ce-O复合催化剂比单一组分的CuO或CeO2具有更好的低温催化活性.复合氧化物cu-Ce-O中Cu原子含量越高,对应硫化后的催化剂氧化碳烟的能力越低,同时催化剂表面生成的硫酸盐越多,即催化剂抗硫中毒能力也降低.浓度低于0.03%的SO2对Cu-Ce-O的催化性能有一定的促进作用,但SO2的体积分数超过0.03%后碳黑燃烧速率变慢;FT-IR初步证实了高体积分数的SO2所产生的大量SO24-可能是抑制催化剂活性的原因.     

Effects of WOx modification on the activity, adsorption and redox properties of CeO2 catalyst for NOx reduction with ammonia

A series of WO₃/CeO₂ (WOx/CeO₂) catalysts were synthesized by wet impregnation of ammonium metatungstate on a CeO₂ support. The resulting solid acid catalysts were characterized by X-ray diffraction (XRD), UV-Vis spectroscopy (UV-Vis), Raman spectroscopy (Raman), in-situ Fourier transform infrared spectroscopy (in-situ FT-IR) of ammonia adsorption, NH₃-TPD, H₂ temperature-programmed reduction (H₂-TPR), NH₃/NO oxidation and activity measurements for NOx reduction by NH₃ (NH₃-SCR). The results show that polytungstate (WOx) species are the main species of tungsten oxide on the surface of ceria. The addition of tungsten oxide enhances the Brönsted acidity of ceria catalysts remarkably and decreases the amount of surface oxygen on ceria, with strong interaction between CeO₂ and WOx. As a result, the N₂ selectivity of NH₃ oxidation and NH₃-SCR at high temperatures (> 300℃) is enhanced. Therefore, a wide working temperature window in which NOx conversion exceeds 80% (NOx conversion > 80%) from 200 to 450℃, is achieved over 10 wt.% WOx/CeO₂ catalyst. A tentative model of the NH₃-SCR reaction route on WOx/CeO₂ catalysts is presented.     

铂、钯蜂窝催化剂高温老化对甲醇深度氧化的影响

本研究对铂、钯蜂窝催化剂及分别添加助化剂CeO_2或WO_3,并于500℃、700℃、900℃或1100℃下经受热老化4h后,考察催化剂比表面、晶相结构及其对甲醇深度氧化活性、产物分布及反应动力学网络变化的情况。实验证明,添加CeO_2后,降低了铂催化剂的耐高温性能,但对钯催化剂无明显影响。添加WO_3,降低了钯催化剂对甲醇的氧化活性。经X-线衍射分析证明,在1100℃高温下,WO_3与堇青石载体中的氧化镁和氧化钙发生强相互作用,生成了相应的钨酸盐。甲醇氧化反应动力学研究表明,甲醇在新鲜和高温热老化的铂催化剂上,反应动力学网络表示式是有区别的。     

Effect of CeO2 and Al2O3 on the activity of Pd/Co_3O_4/cordierite catalyst in the three-way catalysis reactions (CO/NO/CnHm)

The present article studies the effect of CeO₂ and Al₂O₃ on the activity of Pd/Co₃O₄/cordierite catalyst in conversion of NO, CO, C_nH_m. The catalysts were characterized by temperature programmed reduction with hydrogen, X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. It is shown that the effect of CeO₂ on the properties of Pd/Co₃O₄/cordierite catalyst depends on preparation method. The catalyst obtained by co-deposition of cerium and cobalt oxides has higher activity in CO oxidation (CO + O₂ and CO + NO) and total hexane oxidation (C₆H₁₄ + O₂). Such phenomenon is probably caused by more than stoichiometric amount of formed oxygen vacancies, an increase in both mobility of surface oxygen and dispersity of components in the catalytic composition. It is demonstrated that CeO₂ addition promotes the SO₂ resistance of Pd/Co₃O₄/cordierite. The second support decreases the activity of Pd/Co₃O₄/cordierite catalyst in the reactions of CO and C₆H₁₄ with oxygen because of CoAl₂O₄ formation.     

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.     

柴油/甲醇组合燃烧发动机的氮氧化物排放研究

在增压共轨发动机上采用柴油/甲醇组合燃烧(DMCC)方式进行了氮氧化物排放特性研究.对DMCC模式下NO x、NO、NO2等排放与纯柴油模式的对比分析表明:DMCC模式下的NO x排放比原机模式平均下降10%以上,NO平均下降幅度超过40%;采用DMCC模式后,NO2排放量都有明显大幅度的升高,并且NO2/NO比值呈现显著增大,平均高达100%以上.     

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 .     

Catalytic evaluation of promoted CeO2-ZrO2 by transition, alkali, and alkaline-earth metal oxides for diesel soot oxidation

Series of mixed metal oxides were synthesized by gel-combustion method and their catalytic activities for soot oxidation were investigated. The catalysts were M-Ce-Zr （M = Mn, Cu, Fe, K, Ba, Sr）, and χK-20Mn-Ce-Zr （χ= 0, 5, 10, 20）, they were characterized by XRD, SEM, TPR and BET surface area techniques. The results of soot temperature programmed oxidation （TPO） in an O2 oxidizing atmosphere indicate that K-Ce-Zr has the highest catalytic activity for soot oxidation under loose contact condition, due to enhancement of the soot and catalyst contacts. On the other hand, under a tight contact condition, Mn-Ce-Zr and Cu-Ce-Zr nano-composites have high activities for soot oxidation and lower the soot TPO peak temperatures by about 280 and 270℃, respectively, as compared to non-catalytic soot oxidation. Furthermore, the addition of up to 10 wt.% potassium oxides into Mn-Ce-Zr increases its catalytic activity and further reduces the soot TPO peak temperature by about 40℃ under loose contact condition.     

柴油轿车颗粒多环芳烃的排放特性

以一辆柴油轿车为研究样车,分别使用纯柴油、生物柴油掺混比例为10%的B10燃油,进行了NEDC整车循环工况试验,测取了该车HC、CO、NOx、颗粒等法规限制的排放,利用气相色谱-质谱法对采集的排气颗粒样品进行了分析,重点研究了颗粒中多环芳烃的排放特性.结果表明,与柴油相比,燃用B10燃油的HC、CO、NOx和颗粒等常规排放均有所降低;两种燃料产生的颗粒多环芳烃排放中均以荧蒽和芘最多,与纯柴油相比,燃用B10燃油产生的低环数PAHs排放略有增加,中高环数的PAHs排放降幅明显.苯并[a]芘等效毒性分析结果显示燃用B10燃油的BEQs值比纯柴油降低了21.6%,表明柴油轿车燃用生物柴油后,排气颗粒的多环芳烃毒性有所下降.     

含氧柴油对柴油机排放及细颗粒物碳质组分的影响

乙缩醛(1,1-diethoxyethane)与柴油互溶性好, 可替代乙醇作为生物质来源的柴油含氧添加成分. 生物柴油掺混可以提高乙缩醛和柴油混合燃料的闪点及含氧量. 在柴油发动机台架上, 考察柴油和2种含氧柴油(10%乙缩醛+90%柴油和10%乙缩醛＋10%生物柴油＋80%柴油)在2个固定转速不同负荷的5个工况点的排放特性, 分析了NO_x、HC、CO和PM_2.5排放情况, 并用DRI的碳分析仪分析了PM_2.5中的碳质组分.结果表明, 与普通柴油排放相比, 含氧柴油对NO_x排放速率的影响不大, 在某些工况点HC排放速率有较显著的增加. 含氧柴油降低了柴油机PM_2.5排放速率, 最大降低幅度29%. 从碳质组成上看, 含氧燃料降低了PM_2.5中总碳 (total carbon,TC) 的排放速率, 最大降低幅度24%. 含氧柴油的元素碳(elemental carbon,EC)排放速率普遍低于普通柴油; 有机碳(organic carbon,OC)的排放速率在发动机高转速工况时明显低于普通柴油; PM_2.5的OC/EC值在大多数工况下高于普通柴油. 3种燃料排放PM_2.5的碳质组成百分比相似, OC和EC主要为OC1和EC1. 含氧柴油降低了柴油机PM_2.5的排放速率, 颗粒物中OC的比例有所增加, 但对颗粒物的碳质组分组成没有明显的影响.     

正丁醇/柴油复合燃烧对轻型柴油机排放的影响

通过在一台轻型柴油机上加装低压共轨实现在进气歧管上的正丁醇喷射,喷射压力恒定为0.35 MPa;柴油采用缸内直喷,喷射压力恒定为120 MPa;采用自主开发的电控单元(ECU)分别控制柴油与正丁醇的喷射,实现正丁醇/柴油复合燃烧.试验研究了在2800 r·min~(-1)不同负荷下正丁醇喷射量对排放量及颗粒物粒径分布的影响.结果表明:随正丁醇喷射量增加,NO_x和碳烟排放减少,高负荷时降低幅度较大;HC和CO排放增加,低负荷时增加幅度较大;颗粒物生成总量降低且粒径分布重心左移;低负荷时相比于大粒径颗粒物,正丁醇对小粒径颗粒物数浓度的减少更明显;大粒径颗粒物减少比例与小粒径颗粒物减少比例的差距随正丁醇喷射量的增加而减小.     

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.     

Oxidation of diesel soot on binary oxide CuCr(Co)-based monoliths

Binary oxide systems(Cu Cr2O4, Cu Co2O4), deposited onto cordierite monoliths of honeycomb structure with a second support(finely dispersed Al2O3), were prepared as filters for catalytic combustion of diesel soot using internal combustion engine’s gas exhausts(O2, NOx, H2 O, CO2) and O3 as oxidizing agents. It is shown that the second support increases soot capacity of aforementioned filters, and causes dispersion of the particles of spinel phases as active components enhancing thereby catalyst activity and selectivity of soot combustion to CO2. Oxidants used can be arranged with reference to decreasing their activity in a following series: O3 NO2> H2 O > NO > O2> CO2. Ozone proved to be the most efficient oxidizing agent: the diesel soot combustion by O3 occurs intensively(in the presence of copper chromite based catalyst) even at closing to ambient temperatures.Results obtained give a basis for the conclusion that using a catalytic coating on soot filters in the form of aforementioned binary oxide systems and ozone as the initiator of the oxidation processes is a promising approach in solving the problem of comprehensive purification of automotive exhaust gases at relatively low temperatures, known as the "cold start" problem.     

Mo-modified Pd/Al2O3 catalysts for benzene catalytic combustion

Mo-modified Pd/Al2O3catalysts were prepared by an impregnation method and tested for the catalytic combustion of benzene. The catalysts were characterized by N2 isothermal adsorption, X-ray diffraction（XRD）, X-ray photoelectron spectroscopy（XPS）, temperatureprogrammed desorption of NH3（NH3-TPD）, H2temperature-programmed reduction（H2-TPR）, and high-angle annular dark-field scanning transmission electron microscopy（HAADF-STEM）. The results showed that the addition of Mo effectively improved the activity and stability of the Pd/Al2O3catalyst by increasing the dispersion of Pd active components, changing the partial oxidation state of palladium and increasing the oxygen species concentration on the surface of catalyst. In the case of the Pd-Mo/Al2O3catalyst,benzene conversion of 90% was obtained at temperatures as low as 190°C, which was 45°C lower than that for similar performance with the Pd/Al2O3catalyst. Moreover, the 1.0% Pd-5% Mo/Al2O3catalyst was more active than the 2.0% Pd/Al2O3catalyst. It was concluded that Pd and Mo have a synergistic effect in benzene catalytic combustion.     

Efficient degradation of chlorobenzene in a non-thermal plasma catalytic reactor supported on CeO2/HZSM-5 catalysts

Chlorobenzene removal was investigated in a non-thermal plasma reactor using CeO₂/HZSM-5 catalysts. The performance of catalysts was evaluated in terms of removal and energy efficiency. The decomposition products of chlorobenzene were analyzed. The results show that CeO₂/HZSM-5 exhibited a good catalytic activity, which resulted in enhancements of chlorobenzene removal, energy efficiency, and the formation of lower amounts of by-products. With regards to CO₂ selectivity, the presence of catalysts favors the oxidation of by-products, leading to a higher CO₂ selectivity. With respect to ozone, which is considered as an unavoidable by-product in air plasma reactors, a noticeable decrease in its concentration was observed in the presence of catalysts. Furthermore, the stability of the catalyst was investigated by analyzing the evolution of conversion in time. The experiment results indicated that CeO₂/HZSM-5 catalysts have excellent stability: chlorobenzene conversion only decreased from 78% to 60% after 75 hr, which means that the CeO₂/HZSM-5 suffered a slight deactivation. Some organic compounds and chlorinated intermediates were adsorbed or deposited on the catalysts surface as shown by the results of Fourier Transform Infrared (FT-IR) spectroscopy, scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDS) analyses of the catalyst before and after the reaction, revealing the cause of catalyst deactivation.