Analysis of fractal particles from diesel exhaust using a scanning-mobility particle sizer and laser-induced incandescence

The emission regulations for diesel particulate matter (PM) are becoming increasingly strict. The focus of regulations is turning to reducing the number of nanosized particles as well as the total mass. A more precise measurement technique for particle numbers and mass must be developed to meet these new regulations. In this study, a new method for estimating the mass weighted size distribution of diesel PM was investigated by measuring the size of primary particles and the number concentration distribution of particle aggregates. Time-resolved laser-induced incandescence was used for primary particle size measurement and a scanning-mobility particle sizer was used to quantify the number concentration of aggregates. The results from these two conventional measurement techniques were combined using fractal analysis formulas to relate the electrical mobility diameter, the number of primary particles per aggregate, primary particle size, and fractal dimension. This method, applied to single-cylinder diesel engine exhaust with various engine loads and injection pressures, successfully estimated the mass weighted size distribution of particle aggregates. The procedure is very simple and the estimations are comparable with those based on effective density, making this method a useful and reliable tool for estimating mass weighted size distribution of fractal particles such as diesel PM.     

Physical Characterization of the University of Toronto Coarse,Fine, and Ultrafine High-Volume Particle Concentrator Systems

Particle concentrators allow exposure to controlled levels of concentrated ambient particulate matter (PM) over a broad range of concentrations. The performance of these systems can be influenced by the physicochemical characteristics of PM and so it is vital to characterize the concentrators at a given site. The quasi-ultrafine PM (<0.2 μm), fine PM (0.15–2.5 μm), and coarse PM (2.5–10 μm) concentrators at the Southern Ontario Center for Atmospheric Aerosol Research (SOCAAR), University of Toronto, were characterized as a part of the “Health Effects of Aerosols in Toronto (HEAT)” campaign held during February–March, 2010. The full size distributions of ambient and concentrated particles were simultaneously measured in terms of number, surface area, and volume using high time-resolution instruments. Examination of the complete size distribution, including the unconcentrated particles beyond the cutpoints of the concentrator systems, revealed that particles in the unconcentrated size ranges made significant contributions to the particle number and surface area present in the concentrated airstreams of fine and coarse concentrators. Further transients in the ambient ultrafine particle concentrations were evident as dampened signals in these concentrated airstreams. The ultrafine concentrator exhibited a significant size shift when the ambient particle size distribution had a mode ≤30 nm. Overall the fine and coarse concentrators provided a reasonable concentrated reproduction of the ambient PM mass while questions remain regarding the representativeness of the ultrafine concentrator.

Copyright 2012 American Association for Aerosol Research     

Further observations on the rheological behaviour of dense suspensions

The literature and recent WSL results on suspensions of spherical particles are surveyed and summarised. It is concluded that the steady shear properties of a dense suspension is not characterised by an unique viscosity or flow curve, but rather it is described by a wide viscosity distribution or a shear stress - shear rate flow band whose mean and standard deviation are functions of solids concentration, particle size distribution and viscometric geometry and dimensions. The standard deviation (or data spread) increases with solids concentration and with decreasing viscometer gap to particle diameter ratio. This property is due to poor sample reproducibility in respect of solids concentration and particle size distribution and the inherent two-phase nature of suspension which gives rise to particle migration and consequently non-uniform packing density or structure in a sample. Because a dense suspension is increasingly sensitive to these factors as concentration is increased, the standard deviation can be very large. Because the details of packing structure vary with flow, the viscosity distribution or flow band depends on viscometric flow geometry and measuring element dimensions. The implications of this conclusion on the study and characterisation of dense suspension property and the prediction of its behaviour in industrial handling and process equipment are discussed.     

燃煤微细颗粒迁移过程的动力学

基于矩方法将燃煤生成的典型多分散性颗粒系统分为粗颗粒和细颗粒两个模态,构造了较完整的颗粒物迁移过程的计算模型.在考虑细颗粒自身的布朗碰撞凝并过程、粗颗粒自身的非均相凝结过程以外,还重点考虑了细颗粒向粗颗粒表面的扩散,即粗颗粒对细颗粒的捕集过程.以此为基础,对典型煤燃烧环境中细颗粒的数密度分布变化规律进行了预报与分析.     

Uncertainty Budget of the SMPS–APS System in the Measurement of PM1, PM2.5, and PM10

The effects of particulate matter on environment and public health have been widely studied in recent years. In spite of the presence of numerous studies about this topic there is no agreement on the relative importance of the particles' size and origin with respect to health effects among researchers. Nevertheless, air quality standards are moving, as the epidemiological attention, towards greater focus on the smaller particles. The most reliable method used in measuring particulate matter (PM) is the gravimetric method since it directly measures PM concentration, guaranteeing an effective traceability to international standards. This technique, however, neglects the possibility to correlate short term intraday atmospheric parameter variations that can influence ambient particle concentration and size distribution as well as human activity patterns. Besides, a continuous method to determine PM concentrations through the measurement of the number size distribution is the system constituted by a Scanning Mobility Particle Sizer (SMPS) and an Aerodynamic Particle Sizer (APS). In this article, the evaluation of the uncertainty budget in measuring PM through the SMPS–APS system, as well as a metrological comparison with the gravimetric reference method in order to analyze the compatibility, was carried out and applied with reference to an experimental campaign developed in a rural site. This choice allowed to assume the hypothesis of spherical particle morphology. The average PM₁₀, PM_2.5, and PM₁ uncertainties obtained for the SMPS–APS system are equal to 27%, 29%, and 31%, respectively. Here the principle influence parameter is the particle density that has to be directly measured with low uncertainty in order to reduce the PM uncertainty.     

H2O(g)对富氧燃烧超细颗粒物生成特性影响

为实现富氧燃烧技术的广泛推广,对煤粉燃烧在富氧气氛下的颗粒物排放特性进行了研究。在1800 K管式炉内进行煤焦燃烧试验,研究了富氧气氛下H₂O(g)体积分数(0、5%、10%、20%、30%)对煤焦燃烧超细颗粒物的影响;采用荷电低压撞击器(ELPI+)获得超细颗粒物质量和数量浓度粒径分布并进行分析。结果表明,H₂O(g)对超细颗粒物质量浓度和数量浓度粒径分布无影响,但会导致超细颗粒物的峰值波动。超细颗粒物总数量由最小粒径超细颗粒物决定,5种水蒸气浓度下EL?PI+第1级撞击器收集到的超细颗粒物数量占比均超过65%。超细颗粒物总质量由最大粒径超细颗粒物决定,5个水蒸气浓度下ELPI+第7级撞击器收集到的超细颗粒物质量占比均超过94%。低H₂O(g)浓度会抑制超细颗粒物生成,H₂O(g)体积分数为5%时的抑制作用最显著;高H₂O(g)浓度会促进超细颗粒物生成。这是因为一方面H₂O(g)与煤焦发生气化反应,使煤焦颗粒周围产生还原性气氛,促进矿物质还原为单质,进一步促进矿物质蒸发;另一方面气化反应是吸热反应,会降低煤焦颗粒燃烧温度,同时H₂O(g)加入也导致烟气热容增加进一步降低,煤焦燃烧温度抑制煤中矿物质的蒸发,导致超细颗粒物生成减少,是2种作用相互竞争的结果。此外,H₂O(g)的加入使超细颗粒物平均粒径增大,0~5%H₂O(g)时超细颗粒物平均粒径增大最迅速。     

哈尔滨市大气中TSP、PM_(10)和PM_(2.5)相关性分析

对哈尔滨市大气环境中的TSP、PM10、PM2.5进行了采集和质量浓度的分析。实验结果表明:细颗粒(PM2.5)所占比例全年变化比较明显,1月、10月、11月和12月含量较高,均占到总量的55%以上,同时PM2.5/PM10也处于全年最高值,说明此期间细颗粒污染较为严重,环境危害较大;PM10含量全年变化相对稳定,PM10/TSP变化幅度仅为0.71~0.79,说明全年颗粒物质量分布的变化主要由PM2.5和PM2.5-10引起。根据TSP和PM10、PM10和PM2.5之间的相对关系曲线可以看出,两种大气颗粒物均来自相似的污染源,且污染源排放大气颗粒物的粒度分布长期比较稳定,而PM10和PM2.5的相关系数R值为0.973,也具备一定的相关性,可认为两者的变化趋势是一致的。     

Characterization of Submicron Exhaust Particles from Engines Operating Without Load on Diesel and JP-8 Fuels

Diluted exhaust from a selection of Air Force ground support vehicles was subjected to gravimetric, carbon, and size distribution analyses in September 1999. The vehicles operated on diesel and JP-8 fuels. In most cases, the engines involved were similar to civilian counterparts. The tests involved "low" and "high" idle settings but no external loads were imposed. Particle size distribution data, obtained over the 10 to 352 nanometer diameter range using an SMPS instrument, showed that the relative number count of accumulation mode particles increased with respect to nucleation mode particles as the engine rpm increased. The SMPS distributions often explained the main variations in the integrated PM 2.5 gravimetric mass data. Particulate mass derived from the SMPS data and from cascade impactor measurements were well correlated (regression slope 1.02). Empirically determined "elemental" carbon (EC) and "organic" carbon (OC) were the main constituents of the PM 2.5 gravimetric mass (regression slope 0.89). EC contributed less, and OC contributed more to the PM 2.5 mass than was found in some recent studies of exhaust from vehicles operated under external loads. The observed particle nucleation modes were attenuated by coagulation with accumulation mode particles, but it does not appear that artifact particle formation was operative in these experiments. The estimated - 1 σ measurement precisions range from about - 4% for the largest impactor mass concentration determinations to - 24% for some of the SMPS mass concentration estimates.     

660MW燃煤锅炉细微颗粒物中次量与痕量元素的分布特性

应用承重撞击器(DGI)采样系统在南昌某电厂2^#锅炉电除尘器前进行颗粒物采集,并同时采集了原煤样和底灰样。对飞灰的质量粒径分布、底灰和飞灰中次量与痕量元素的分布特性进行了分析。结果表明PM_1.0和PM_2.5质量分别占PM₁₀质量的16.0%~17.4%和46.9%~50.6%;Na、Mg、P、S主要富集在亚微米颗粒物中,Al、Si、Ca、Ti、Fe、K主要富集在超微米颗粒物中;随着颗粒物粒径的减小,As、Cd、Cr、Pb的浓度逐渐增大,且在亚微米颗粒物中的增幅大于超微米颗粒物,Mn在各级颗粒物中浓度相近;As、Cd、Cr、Pb大量富集于亚微米颗粒物之上,Mn在各级颗粒物中富集特性无明显差异,且各痕量元素挥发特性存在以下规律:As>Cd>Cr>Pb>Mn;文中给出了无控制条件下痕量元素的排放因子,PM_1.0中各元素排放比例存在以下规律:As>Cd>Cr>Pb>Mn。     

The influence of conditioning and regeneration on the separation behaviour of rigid surface filters for the separation of particles from gases

Rigid ceramic filter media can be used for the separation of particles from gas streams at elevated temperatures. In order to characterize comparatively the separation behaviour of differently structured filter media over a multitude of filtration cycles, experiments were performed in a filter test rig. The filter test rig used is built in accordance with VDI guideline 3926 and equipped with a special type of optical particle counter, which has the advantage of measuring both the particle size and the particle concentration simultaneously and in situ on the clean gas side.

It is demonstrated that by far largest share of the particles reaches the clean gas as a result of the filter regeneration process. During the subsequent formation of the dust cake, the particle penetration is almost zero. The regeneration parameters, actually in essence only the tank pressure, possess the decisive influence on the separation behaviour. In the course of a filtration experiment, the number of particles reaching the clean gas reduces with the increasing number of filtration cycles due to the filter conditioning. The particles arriving in the clean gas during regeneration are extremely fine. The mean particle size is almost entirely independent of the regeneration conditions and the filter cycle number. The fine particulate emissions measured here are an anthropogenic source of particulate matter in ambient air. They have to be considered as relevant with respect to the new standards of ambient air quality (PM 10 and PM 2.5).

It is shown that membrane-coated ceramic filter media at identical operating conditions exhibit, as expected, a better separation and regeneration behaviour than fibrous ceramic, open-pored filter media. However, the advantages are at the expense of a 10 times higher pressure loss, which is essentially attributed to the membrane layer.     

A model for turbulent binary breakup of dispersed fluid particles

Accurate predictions of particle size distributions, and therefore of the underlying processes of fluid particle breakup and coalescence are of vital importance in process design, but reliable procedures are still lacking. The present paper aims at developing a modular formulation for the turbulent particle breakup process. The model is to be included in a population balance model which is formulated such as to facilitate the direct future implementation into a full multifluid CFD model.The breakup process is described without introducing adjustable parameters. The current model is a further development of an existing model by Luo and Svendsen (AIChE J. 42 (5) (1996) 1225), which has been expanded and refined, and where an inherent weakness regarding the breakup rate for small particles and small daughter particle fragments are removed. A new criterion regarding the kinetic energy density of the colliding turbulent eddy causing breakup has been introduced. This new criterion is a novel concept describing the breakup process. The details are thoroughly discussed together with possible further modifications. The results from the new model are encouraging because the breakup rate is greatly reduced when the dispersed fluid particles are reduced in size. Further, the response to changes in system variables is reasonable and the distribution of daughter sizes vary in a reasonable way for the different collision possibilities.     

Smoke Characterization and Feasibility of the Moment Method for Spacecraft Fire Detection

The Smoke Aerosol Measurement Experiment (SAME) has been conducted twice by the National Aeronautics and Space Administration and provided real-time aerosol data in a spacecraft micro-gravity environment. Flight experiment results have been recently analyzed with respect to comparable ground-based experiments. The ground tests included an electrical mobility analyzer as a reference instrument for measuring particle size distributions of the smoke produced from overheating five common spacecraft materials. Repeatable sample surface temperatures were obtained with the SAME ground-based hardware, and measurements were taken with the aerosol instruments returned from the International Space Station comprising two commercial smoke detectors, three aerosol instruments, which measure moments of the particle size distribution, and a thermal precipitator for collecting smoke particles for transmission electron microscopy (TEM). Moment averages from the particle number concentration (zeroth moment), the diameter concentration (first moment), and the mass concentration (third moment) allowed calculation of the count mean diameter and the diameter of average mass of smoke particles. Additional size distribution information, including geometric mean diameter and geometric standard deviations, can be calculated if the particle size distribution is assumed to be lognormal. Both unaged and aged smoke particle size distributions from ground experiments were analyzed to determine the validity of the lognormal assumption. Comparisons are made between flight experiment particle size distribution statistics generated by moment calculations and microscopy particle size distributions (using projected area equivalent diameter) from TEM grids, which have been returned to the Earth.

Copyright 2015 American Association for Aerosol Research     

电除尘器飞灰粒径表征及细颗粒降温团聚

基于50000m³/h实烧烟气中试系统,采用Mastersizer 2000E激光粒度分析仪和电子低压冲击仪（ELPI）,首次对电除尘器飞灰几何粒径和空气动力学粒径进行全面表征。结果表明,电除尘器入口及各电场的飞灰几何粒度分布均呈双峰分布特征,各电场峰值依次右移,但末级旋转电极电场≤ 1μm的颗粒占比略有升高,电除尘器入口及第1～5电场飞灰几何中位径分别为6.607μm、17.378μm、2.884μm、2.577μm、2.460μm、2.480μm;温度降低,电除尘器入口飞灰几何粒度分布的双峰均右移,颗粒团聚现象明显,80℃、90℃、110℃、130℃、150℃时电除尘器入口飞灰几何中位径分别为13.183μm、10.500μm、10.171μm、6.607μm、7.586μm,从130℃降至90℃,电除尘器入口几何粒径≤ 1μm、≤ 2.5μm、≤ 10μm的飞灰占比分别减少了19.8%、19.2%、12.6%;不同温度时,电除尘器对空气动力学粒径0.03～10μm段颗粒的个数浓度、质量浓度均有较高脱除效率,均在75%以上,最高可达99.9%;温度降低,电除尘器进出口空气动力学粒径不同粒径段颗粒个数浓度和质量浓度均有不同程度降低,从130℃降至90℃、80℃,对应电除尘器入口PM_2.5团聚效率分别为46.76%、60.08%,对应电除尘器出口PM₁₀减排分别为59.80%、91.08%,PM_2.5减排分别为45.94%、76.22%,PM1减排分别为40.40%、62.12%。     

Electroless Copper Coating of Zirconia Utilizing Palladium Catalyst

Electroless Cu coating of zirconia particles using a Pd⁰ catalyst is investigated in this paper. Uncoated and Cu-coated ZrO₂ particles are characterized by various analytical techniques to understand the mechanism of electroless Cu coating of ZrO₂ particles, which involves reduction of Pd²⁺ on ZrO₂ particle surfaces by Sn²⁺ to produce pure metallic Pd⁰ clusters, which provide catalytic sites for Cu deposition. The concept of XPS core-level binding energy shift due to small cluster size is utilized to predict the size of pure Pd⁰ clusters. The electroless Cu-coating process can be utilized in the future to produce Cu-doped ZrO₂ particles required for various potential applications.     

Characterization of combustion‐derived individual fine particulates by computer‐controlled scanning electron microscopy

Particulate matter (PM) emission from the combustion of solid fuels potentially poses a severe threat to the environment. In this article, a novel approach was developed to examine the properties of individual particles in PM. With this method, PM emitted from combustion was first size‐segregated. Subsequently, each size was characterized by computer‐controlled scanning electron microscopy (CCSEM) for both bulk property and single particle analysis. Combustion of bituminous coal, dried sewage sludge (DSS) and their mixture were conducted at 1200°C in a laboratory‐scale drop tube furnace. Three individual sizes smaller than 2.5 μm were investigated. The results indicate that a prior size‐segregation can greatly minimize the particle size contrast and phase contrast on the backscattered images during CCSEM analysis. Consequently, high accuracy can be achieved for quantifying the sub‐micron particles and their inherent volatile metals. Regarding the PM properties as attained, concentrations of volatile metals including Na, K, and Zn have a negative relationship with particle size; they are enriched in the smallest particles around 0.11 μm as studied here. Strong interactions can occur during the cofiring of coal and DSS, leading to the distinct properties of PM emitted from cofiring. The method developed here and results attained from it are helpful for management of the risks relating to PM emission during coal‐fired boilers. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Molecular weight (M n) and functionality effects on CUP formation and stability

The formation of colloidal unimolecular polymer (CUP) particles from single polymer strands was investigated as a function of molecular weight. The CUP particle size was correlated with the absolute molecular weight and its distribution. The characteristics of the particles were evaluated with respect to viscosity, acid number, size distribution, and stability. The particle size varied from less than 3 nm to above 8 nm representing polymers with molecular weight in the range of 3000–153,000. Lower molecular weight polymers were found to be unstable. Particle size measurements using dynamic light scattering technique indicated a normal distribution which corresponded to the molecular weight distribution of the copolymer. The statistical distribution of the acid groups in the polymer chains played a significant role in the stability of low molecular weight polymers.     

Network model for straining dominated particle entrapment in porous media

A network model has been developed to study and describe formation damage resulting from particle entrapment in porous media by straining or size exclusion. Unlike the previous network models, this model considers the simultaneous entry of a number of particles into the network, as well as the effects of fluid flow on the particle transport path. A systematic study has been carried out on the flow and entrapment of monodispersed particles as well as particles with a size distribution through different networks. The effects of various parameters such as network size, particle size distribution and pore size distribution on the extent of formation damage, manifested by permeability reduction have been discussed in this paper. The model has also been used to determine the degree of prefiltration required to prevent damage to injection wells during water flooding. The model predictions show good agreement with experimental data for several different runs. A single parameter is used to match the exact number of pore volumes required to produce damage to the porous media. This parameter was found to be constant for the two different sandstones studied and for different concentrations of particles in the suspension. The simulation was also performed using the “random walk model” (which does not account for the fluid flow effects on particle flow) for purposes of comparison. The permeability responses predicted by this random walk model show trends that are significantly different from those observed experimentally. The network model developed in this paper has wide application in water flooding and matrix acidizing operations where diverting agents are used.     

Effect of titanium–magnesium catalyst morphology on the properties of polypropylene upon propylene polymerization in a liquid monomer

The effect of the particle size of an IK-8-21 domestic titanium-magnesium catalyst on the properties of polypropylene (PP) produced during the polymerization of propylene in a liquid monomer is studied. Catalysts with particle sizes of 20 to 64 μm are shown to have high activity and identical sensitivity to hydrogen and allow PP to be obtained with a narrow distribution of particles over size, high isotacticity, and close values of crystallinity, melting temperature, and physicomechanical properties. A slight decrease in the activity and bulk density of PP powder is observed when the average size of catalyst particles is increased from 20 to 43 μm. A more notable reduction in the activity and bulk density of PP powder is observed for catalyst with particle sizes of 62 to 64 μm. IK-8-21 catalyst is not inferior to its foreign analogues with respect to the properties of the resulting PP.     

Numerical simulation of nanoparticle synthesis in diffusion flame reactor

A computational model combining the fluid dynamics with the particle kinetics was employed to study TiO₂ nanoparticle synthesis in a diffusion flame reactor. A one-step chemical kinetics approach was used to model titanium tetraisopropoxide (TTIP) decomposition that leads to homogeneous nucleation and particle formation. The momentum, heat, and mass transfer, Brownian coagulation and diffusion, surface growth, coalescence and thermophoresis have been taken into account. Based on the particle size distributions, an efficient quadrature method of moments was allowed to approximate the general dynamics equation of particle, and the eddy dissipation concept (EDC) combustion model was used to estimate the flame temperature field. Excellent agreements between the model predictions and experimental data, with respect to the flame temperature distribution and particle kinetics, are reached. By taking the particle size and surface area as independent variables, the full distributions of volume equivalent diameters, evolution of the agglomerate number, the geometric standard deviation based on volume and agglomerate fractal nature, mean primary particle size and the number of primary particles per agglomerate are revealed. The variation of oxygen flow rate has an important influence on the temperature distribution and hence on the particle kinetics accordingly.     

燃煤锅炉SCR对颗粒物排放特性影响

我国电厂多数采用选择性催化还原（SCR）脱硝技术降低电厂NO_x排放,目前关于电厂中SCR对颗粒物排放特性的影响研究十分匮乏。本研究对一热电联产锅炉SCR前后颗粒物和飞灰进行取样,分析颗粒物质量粒径分布以及化学成分。采用计算机控制扫描电镜（CCSEM）对飞灰进行分析,获得颗粒物单颗粒成分。结果表明SCR前后PM₁₀均呈双峰分布。经过SCR后,PM_0.21浓度降低约62%（质量）,而PM_0.21-1浓度升高19%（质量）;PM₁中SO₂相对含量增加约6%（质量）,SiO₂和Al₂O₃相对含量降低,而CaO相对含量没有明显变化;经过SCR后,PM_1-10浓度降低约17%（质量）,成分基本没有变化,但是颗粒成分变得更均一,说明经过SCR后,PM_1-10发生交互作用。因此经过SCR后PM_1-10浓度降低不仅由于颗粒物在SCR中发生沉积,更有可能是颗粒物之间交互作用导致。