Physicochemical characterization of forest and sugarcane leaf combustion's particulate matters using electron microscopy, EDS, XRD and TGA

Physical characteristics and quantitative elemental composition of PM and residual ash produced from sugarcane leaves (SCL) combustion were investigated using TEM-EDS compared with forest leaves (FRL). SEM-EDS was used to analyze the microstructure and chemical composition of biomass raw leaves and PM. XRD analysis was also performed to investigate the characterization of the crystalline nanostructure, structure of PM, and residual ash compared to the TEM image processing method. The oxidation kinetics of biomass raw materials, PM, and residual ash were investigated by TGA. The morphology of fine and ultrafine agglomerate structure of SCL soot and residual ash are not significantly different from the FRL soot and residual ash. The average diameter sizes of single primary nanoparticles of SCL and FRL soot are approximately 37 nm and 35 nm, while the sizes of residual ash are about 18 nm and 22 nm, respectively. The single primary nanoparticles of soot are mainly composed of curve line crystallites of carbon fringes, while residual ash is composed of straight-line lattice fringes. The average fringe lengths of SCL and FRL soot are about 1.25 nm and 1.04 nm from the outer shell and 0.89 nm and 0.74 nm from the inner core. The interlayer spacing of curve line carbon fringes of SCL and FRL soot is approximately 0.359 nm and 0.362 nm by the TEM image analysis and it was matched with XRD analysis. The biomass PMs are mainly composed of soot, Si, Ca, and K compounds: SiO₂, CaCO₃, and KCl.     

Experimental investigation into the oxidation reactivity, morphology and graphitization of soot particles from diesel/n-octanol mixtures

Aiming to investigate the impacts of n-octanol addition on the oxidation reactivity, morphology and graphitization of diesel exhaust particles, soot samples were collected from a four-cylinder turbocharged diesel engine fueled with D100（neat diesel fuel）, DO15（85% diesel and 15% n-octanol, V/V） and DO30（70% diesel and 30% n-octanol, V/V）. All tests were conducted at two engine speeds of 1370 and 2150 r/min under a fixed torque of 125 N ·m. The soot properties were characterized by thermogravimet...     

柴油/碳酸二甲酯燃烧颗粒的微观结构和分形特征

为降低柴油机颗粒物排放,探讨了柴油机燃用柴油/碳酸二甲酯混合燃料燃烧颗粒微观结构和分形特征的变化规律. 采用扫描电镜、透射电镜和SAXS(同步辐射小角X射线散射)相结合的方法,针对DMC(碳酸二甲酯)添加量(以w计)对柴油机燃烧颗粒微观结构和分形特征参数的影响规律进行了研究. 结果表明:与柴油燃烧颗粒相比,D10〔w(DMC)为10%〕、D20〔w(DMC)为10%〕燃烧颗粒的碳粒子平均层面间距分别增加了5.3%、15.1%,弯曲度平均值分别增加了4.0%和10.3%,表明燃烧颗粒的氧化活性增加;与柴油相比,D10、D20燃烧颗粒的质量分形维数分别增加了0.44和0.52,下限均升高了0.2,SAXS与电镜图像对燃烧颗粒的质量分形维数的分析结果相一致,即质量分形维数随DMC添加量的增加而升高,表明燃烧颗粒的团聚程度提高;与柴油燃烧颗粒相比,D10、D20燃烧颗粒表面分形维数的下限分别升高了0.1和0.2,表明其燃烧颗粒表面的粗糙程度和不规则程度提高;与柴油燃烧颗粒相比,D10、D20燃烧颗粒的活化能分别降低了3.9和7.9 kJ/mol,表明燃烧颗粒的氧化活性随着DMC添加量的增加而增强,验证了燃烧颗粒微观尺寸结构和分形特征的研究结果. 研究显示,柴油中添加DMC能够提高燃烧颗粒的氧化活性,燃烧颗粒的氧化活性越强,其在后处理过程中就越易被氧化,有助于降低柴油机的颗粒物排放.      

发动机燃料组分生烟特性的研究

本文采用火焰高度测定仪系统地评价了构成发动机燃料的单体烃和单体醇的生烟特性,提出并应用碳烟生成的烃正离子概念解释了单体烃和单体醇的生烟规律,为正确调整发动机燃料构成提供了实践基础,也为研究和开发消烟助燃剂奠定了理论基础。     

正丁醇对柴油机颗粒组分与形貌特征的影响

为探讨柴油机燃用正丁醇-柴油混合燃料降低颗粒排放的机理,采用热重分析仪与场发射扫描电子显微镜,重点对正丁醇-柴油混合燃料燃烧的颗粒形貌特征进行研究,分析了颗粒的组分、微观结构以及粒径分布随w(正丁醇)的变化规律. 结果表明:正丁醇-柴油混合燃料燃烧的颗粒呈团簇状结构,随着w(正丁醇)的增加,团聚程度逐渐提高,排列结构更加紧密;颗粒的粒径逐渐减小,柴油、B5、B10〔B5、B10是指w(正丁醇)分别为5%、10%的正丁醇-柴油混合燃料〕燃烧的颗粒平均粒径分别为1.43、0.85、0.52 μm;颗粒中的主要成分为碳烟,其质量分数约为60%,随着w(正丁醇)的增加,碳烟和可溶有机物组分的质量分数有所增加,硫酸盐、金属等不易挥发组分以及金属元素的质量分数逐渐减少. 研究显示,添加正丁醇,可促进颗粒转化、改善颗粒的氧化过程,使颗粒向小粒径方向移动;由于颗粒中可溶有机物组分含量增加,因此提高了颗粒在碰撞过程中凝并的概率,致使颗粒的团聚程度增加.      

基于TEM-EDS对四川盆地大气单颗粒气溶胶的研究

为了解四川盆地大气中单颗粒气溶胶理化特征,分别在该区域典型城市（成都市）和背景地区（峨眉山）进行了大气单颗粒样品采集.基于带能谱的透射电子显微镜（TEM-EDS）对两地累计3923个单颗粒的化学组成、形貌特征及混合状态等进行了全面观测和分析,并对两地颗粒物差异性进行了对比分析.结果发现：两地气溶胶颗粒主要包括有机物、富硫、矿物、烟尘和飞灰/金属颗粒,除了以单独的外混形式存在外,大多数颗粒以两种及两种以上颗粒类型混合（即内混）形式存在.通过对成都市不同污染状况下单颗粒特征对比发现,"污染天"的内混颗粒占比高于"清洁天",分别为74.2%和68.6%;相比"清洁天","污染天"颗粒物粒径分布范围更广且峰值区间更大,表明污染过程中颗粒物的大气混合趋于更强.对比成都市与峨眉山分析结果得知,成都市以内混的有机物-硫颗粒为主导（占比为50.2%）,而峨眉山以外混的有机物颗粒为主导（占比为50.5%）;成都市含硫类颗粒物（如有机物-硫颗粒）贡献高于峨眉山,而峨眉山两种含碳类颗粒（如烟尘和有机物-烟尘颗粒）占比高于成都市;此外,成都市与峨眉山两地大气颗粒物粒径分布范围及峰值区间均存在一定差异,进一步体现了两地颗粒物来源和老化混合的差异.在峨眉山,与非降雨天相比,一些易溶于水的颗粒物（如含硫类颗粒）在降雨天占比明显降低,而源自当地燃烧过程、粒径较小且疏水性强的颗粒物（如烟尘和有机物-烟尘颗粒）占比相应升高.     

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 .     

澳门夏季大气颗粒物单颗粒微观形貌分析

应用高分辨率场发射扫描电镜(FESEM)和图像分析技术,研究了澳门地区夏季(2007年7月)大气可吸入颗粒物的形貌特征以及不同种类颗粒物的数量-粒度和等效体积-粒度分布.结果表明,澳门可吸入颗粒物中,烟尘集合体和矿物颗粒普遍存在;矿物颗粒为不规则状,烟尘集合体有链状、蓬松状等形态;烟尘集合体在数量上平均分别约占30%～40%,矿物颗粒在数量上平均分别约占20%,烟尘集合体颗粒较多说明澳门夏季受机动车尾气影响较重.澳门大气PM₁₀的等效粒径主要分布在0.2～0.4　μm范围内,主要为较细粒子.颗粒物种类有明显的地点差异,交通繁忙的高士德马路路口以烟尘集合体居多(平均47%),且其粒径在较宽范围内都有分布（0.1～0.8 μm）;隧道内亦以烟尘集合体的比例较大,可高达59%;货运码头采样点以矿物颗粒较多.     

Constructing a Raman and surface-enhanced Raman scattering spectral reference library for fine-particle analysis

Fine particles associated with haze pollution threaten the health of over 400 million people in China. Owing to excellent non-destructive fingerprint recognition characteristics, Raman and surface-enhanced Raman scattering (SERS) are often used to analyze the composition of fine particles to determine their physical and chemical properties as well as reaction mechanisms. However, there is no comprehensive Raman spectral library of fine particles. Furthermore, various studies that used SERS for fine-particle composition analysis showed that the uniqueness of the SERS substrates and different excitation wavelengths can produce a different spectrum for the same fine-particle component. To overcome this limitation, we conducted SERS experiments with a portable Raman spectrometer using two common SERS substrates (silver (Ag) foil and gold nanoparticles (Au NPs)) and a 785 nm laser. Herein, we introduced three main particle component types (sulfate-nitrate-ammonium (SNA), organic material, and soot) with a total of 39 chemical substances. We scanned the solid Raman, liquid Raman, and SERS spectra of these substances and constructed a fine-particle reference library containing 105 spectra. Spectral results indicated that for soot and SNA, the differences in characteristic peaks mainly originated from the solid-liquid phase transition; Ag foil had little effect on this difference, while the Au NPs caused a significant red shift in the peak positions of polycyclic aromatic hydrocarbons. Moreover, with various characteristic peak positions in the three types of spectra, we could quickly and correctly distinguish substances. We hope that this spectral library will aid in the future identification of fine particles.     

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.     

3D介孔TiO_2微米球的制备及其光催化降解双酚A的研究

利用水热方法,无需模板一步合成3D介孔TiO2光催化剂.然后采用X射线衍射（XRD）、透射电子显微镜（TEM）、高分辨电子显微镜（HRTEM）和N2吸附-解吸BET技术对其组织结构进行表征,以双酚A为目标物对比介孔TiO2光催化剂和市售P25的光催化性能,并研究了不同温度下TiO2的相变及热重分析（TGA）.结果表明,...     

生物柴油的碳烟形貌及影响因素分析

使用热场发射扫描电子显微镜拍摄了5种生物柴油和0号柴油在常温常压状态下燃烧产生的碳烟照片,分析了碳烟粒子的形貌及影响形貌和生成量的因素。研究表明,碳烟粒子多呈球状,平均直径在35～75nm之间,粒径分布符合高斯分布,总体排列呈现链状或者块状;碳烟形貌及生成量与火焰温度、燃料的氧含量、芳香烃含量、硫含量以及十六烷值等因素有关,与柴油相比,生物柴油燃烧火焰温度高、含氧量高、芳香烃和硫含量少,十六烷值高,使生物柴油的碳烟粒径普遍较小,整体排列更紧密,粘结程度更强。     

Catalytic combustion of soot over ceria-zinc mixed oxides catalysts supported onto cordierite

Modified substrates as outer heterogeneous catalysts was employed to reduce the soot generated from incomplete combustion of diesel or diesel/biodiesel blends, a process that harms the environment and public health. The unique storage properties of ceria(CeO2) makes it one of the most efficient catalysts available to date. Here, we proposed that ceria-based catalysts can lower the temperature at which soot combustion occurs; more specifically, from 610℃ to values included in the diesel exhausts operation range(300–450℃). The sol-gel method was used to synthesize mixed oxide-based catalysts(CeO2:ZnO); the resulting catalysts were deposited onto cordierite substrates. In addition, the morphological and structural properties of the material were evaluated by XRD, BET, TPR-H2, and SEM. Thermogravimetric(TG/DTA) analysis revealed that the presence of the catalyst decreased the soot combustion temperature by 200℃ on average, indicating that the oxygen species arise at low temperatures in this situation, promoting highly reactive oxidation reactions. Comparative analysis of soot emission by diffuse reflectance spectroscopy(DRS) showed that catalyst-impregnated cordierite samples efficiently oxidized soot in a diesel/biodiesel stationary motor: soot emission decreased by more than 70%.     

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.     

Morphology and composition of particles emitted from a port fuel injection gasoline vehicle under real-world driving test cycles

Traffic vehicles, many of which are powered by port fuel injection (PFI) engines, are major sources of particulate matter in the urban atmosphere. We studied particles from the emission of a commercial PFI-engine vehicle when it was running under the states of cold start, hot start, hot stabilized running, idle and acceleration, using a transmission electron microscope and an energy-dispersive X-ray detector. Results showed that the particles were mainly composed of organic, soot, and Ca-rich particles, with a small amount of S-rich and metal-containing particles, and displayed a unimodal size distribution with the peak at 600?nm. The emissions were highest under the cold start running state, followed by the hot start, hot stabilized, acceleration, and idle running states. Organic particles under the hot start and hot stabilized running states were higher than those of other running states. Soot particles were highest under the cold start running state. Under the idle running state, the relative number fraction of Ca-rich particles was high although their absolute number was low. These results indicate that PFI-engine vehicles emit substantial primary particles, which favor the formation of secondary aerosols via providing reaction sites and reaction catalysts, as well as supplying soot, organic, mineral and metal particles in the size range of the accumulation mode. In addition, the contents of Ca, P, and Zn in organic particles may serve as fingerprints for source apportionment of particles from PFI-engine vehicles.     

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.     

脱水污泥/松木锯末水蒸气共气化研究

以城市污水处理厂机械脱水后的污泥(含水率约为80％)和松木锯末的混合物为原料,进行了共气化制取富氢燃气的研究.同时,采用热重分析(TGA)研究了混合样品的热失重特性,并在固定床反应器上考察了不同掺混比对燃气成分、燃气产量和碳转化率的影响.TGA结果表明,随着锯末掺混比的增加,样品的失重量、最大失重率及挥发分析出特性指数增大.在固定床反应器中,脱水污泥中的水分在高温条件下形成蒸气气氛,与产生的半焦发生了蒸气气化反应.实验结果表明,最佳掺混比为40％ ～ 60％,此时氢气含量、燃气产量、碳转化率分别为40％、0.70 m3· kg-1、64.1％.此外,借助BET和SEM对残余半焦的比表面积及表面形貌特征进行了分析.     

La1-xKxMnO3催化剂同时消除柴油机尾气中NO和碳烟性能

采用溶剂热法制备La_1-xK_xMnO₃(x=0, 0.10, 0.15, 0.20, 0.25)钙钛矿型复合金属氧化物催化剂;通过XRD、FT-IR、SEM、H₂-TPR、XPS、NO-TPD等手段对催化剂的物相组成、表面形貌、氧化还原性能等进行了表征;在常压固定床微型反应装置中评价催化剂同时消除NO和碳烟催化性能.结果表明,制备的La_1-xK_xMnO₃催化剂均具有钙钛矿结构;K部分取代La-Mn钙钛矿结构中La后,颗粒结构得以改善,部分Mn³⁺价态升高为Mn⁴⁺,形成较多氧空位和Mn⁴⁺,提高氧化还原性能和吸附NO性能.活性评价结果表明,La_0.80K_0.20MnO₃催化剂表现出较好的同时消除NO和碳烟催化性能,NO最大转化率(Xmax NO)和对应反应温度(Tmax NO)分别为46.5%和436℃,碳烟起燃温度(T_ig)、CO₂浓度峰值温度(Tmax CO₂)和生成CO₂选择性(Smax CO₂)分别为341℃、454℃和98.8%.     

云南宣威地区燃煤排放颗粒物中石英矿物的特征

云南宣威地区是我国人群肺癌死亡率最高的地区之一,过往研究表明,该区的高肺癌死亡率可能与居民室内燃煤排放颗粒物中的多环芳烃(PAHs)有关,而最近研究发现,其中的nm级石英可能是导致肺癌发生的原因, 但鲜见该区燃煤排放颗粒物中细粒石英矿物的研究. 为探究燃煤排放细粒矿物的分布特征,采集了肺癌高发区宣威市来宾镇及周边5个乡镇煤矿中的15个煤样,使用光学显微镜、X射线衍射仪(XRD)、带能谱的扫描电镜(SEM/EDS)分析了煤样的煤岩组分及矿物组成. 结果表明:宣威煤以中挥发分、较高镜质组烟煤为主,煤中主要矿物为石英、鲕绿泥石、高岭石和方解石;不同煤样中,矿物质的结晶程度有所差异;单颗粒统计结果显示,在所统计的775个矿物颗粒中,石英颗粒占37.9%,并且粒径多分布在1~2μm之间; 石英矿物颗粒的形状不规则且以微粒的形式填充在煤缝隙中. 石英与鲕绿泥石共存的现象显示,宣威煤中石英来源于富含Fe和Al的硅质热液流,而非岩石碎屑沉积;此外,在肺癌高发区(来宾镇),其煤中Si+Fe质矿物颗粒含量较Si质矿物高. 今后将重点研究石英颗粒在Fe参与下的生物活性.      

Mesoporous carbon adsorbents from melamine-formaldehyde resin using nanocasting technique for CO2 adsorption

Mesoporous carbon adsorbents, having high nitrogen content, were synthesized via nanocasting technique with melamine–formaldehyde resin as precursor and mesoporous silica as template. A series of adsorbents were prepared by varying the carbonization temperature from 400 to 700°C. Adsorbents were characterized thoroughly by nitrogen sorption, X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), thermogravimetric analysis(TGA), elemental(CHN) analysis, Fourier transform infrared(FTIR) spectroscopy and Boehm titration. Carbonization temperature controlled the properties of the synthesized adsorbents ranging from surface area to their nitrogen content, which play major role in their application as adsorbents for CO_2 capture.The nanostructure of these materials was confirmed by XRD and TEM. Their nitrogen content decreased with an increase in carbonization temperature while other properties like surface area, pore volume, thermal stability and surface basicity increased with the carbonization temperature. These materials were evaluated for CO_2 adsorption by fixed-bed column adsorption experiments. Adsorbent synthesized at 700°C was found to have the highest surface area and surface basicity along with maximum CO_2 adsorption capacity among the synthesized adsorbents. Breakthrough time and CO_2 equilibrium adsorption capacity were investigated from the breakthrough curves and were found to decrease with increase in adsorption temperature. Adsorption process for carbon adsorbent–CO_2 system was found to be reversible with stable adsorption capacity over four consecutive adsorption–desorption cycles. From three isotherm models used to analyze the equilibrium data, Temkin isotherm model presented a nearly perfect fit implying the heterogeneous adsorbent surface.