燃油碳烟颗粒的表面特性与润滑油黏度行为

发动机燃油碳烟颗粒不可避免地会进入润滑油中,引起润滑油黏度的增长,从而影响发动机的润滑特性和使用性能。借助傅里叶红外光谱仪、X射线光电子能谱仪、全自动微孔物理吸附和化学吸附分析仪、光学法接触角/界面张力仪、Zeta电位仪等仪器,对比分析了生物质燃油碳烟颗粒(BS)和0^#柴油碳烟颗粒(DS)的表面特性,探讨了BS和DS对液体石蜡(LP,润滑油基础油的模拟物)和碳烟分散体系的黏度的影响及碳烟表面特性对黏度的影响机理。结果表明,40℃时油品的相对黏度随碳烟浓度的增加呈指数函数增加,并且相同碳烟浓度下DS污染的油品相对黏度更大,高浓度碳烟污染的油品呈明显剪切稀化行为,DS污染的LP的黏度受剪切转速的影响更大。BS和DS表面主要元素是碳和氧,且BS氧含量高于DS,表面均带有一些含氧官能团。 表面特性分析显示,DS的比表面积大于BS,表面能高于BS,亲油性弱于BS,致使DS在LP中比BS更易团聚成大颗粒,这是DS对润滑油黏度的影响大于BS的主要原因。     

纳米氟化镧对生物质燃油碳烟颗粒流润滑特性影响

为探索极端乏油工况下碳烟颗粒在发动机摩擦副界面的功效及润滑油添加剂的作用,本文采用往复摩擦磨损试验机研究了纳米氟化镧（nano-LaF₃）颗粒对往复滑动条件下生物质燃油碳烟（BS）颗粒流润滑性能的影响。借助拉曼光谱仪、3D激光扫描显微镜、X射线光电子能谱仪等仪器探讨了滑动条件下nano-LaF₃对BS颗粒流润滑特性的影响作用机理。结果表明：当nano-LaF₃的添加质量分数大于20%时能显著改善往复滑动条件下BS颗粒的抗磨减摩性能,并且随着nano-LaF₃添加浓度的增大,摩擦表面碳烟石墨化程度和石墨微晶尺寸均增大。nano-LaF₃在含BS颗粒流润滑的摩擦界面形成了LaF₃摩擦膜以及含镧化合物、碳氧化合物及铁氧化合物的化学复合反应膜,同时nano-LaF₃会加大诱导碳烟的石墨化作用,从而增强了BS颗粒流润滑的减摩性。     

表面织构对含氟化物碳烟颗粒干摩擦性能影响

在多功能往复摩擦磨损试验机上考察表面织构对含氟化物的生物质燃油碳烟(BS)颗粒润滑性能的影响。发现添加LaF_3的碳烟颗粒润滑时,表面织构能促进干摩擦时的抗磨减摩性能。而添加TiF_3时表面织构对抗磨性能有明显促进,但不利于减摩性。拉曼光谱分析发现添加氟化物的碳烟干摩擦颗粒润滑时,BS的无序结构会发生石墨化转变,在织构凹坑边缘碳烟颗粒石墨化转变最明显,凹坑中心最不明显。原因在于摩擦热、局部高接触应力及氟化物的共同作用。     

生物质燃油碳烟颗粒的分散特性

碳烟分散性能是柴油机油的一项重要性能指标,采用黏度法、斑点实验法及粒径分布法考察了生物质燃油碳烟(BS)和0^#柴油碳烟(DS)在液体石蜡(LP)中的分散性能及商用分散剂聚异丁烯丁二酰亚胺(T154)对其分散性的影响,并借助X射线光电子能谱仪和傅里叶红外光谱仪分析其分散机理。结果表明,BS和DS表面均带有一些含氧官能团且BS氧含量高于DS;DS对体系增稠作用大于BS,T154对BS和DS在LP中的分散性均有良好的作用,但对BS的分散效果更好。T154亦可作为BS在润滑油中的分散剂使用,因为BS表面含有羧基、酚羟基等含氧酸性基团,可与T154中丁二酰亚胺依靠酸碱作用吸附分散剂。同时,BS表面的极性基团与N-H单元产生氢键而吸附T154。     

生物质固定床热解碳烟结构特征及反应活性

在固定床上进行了麦秆与木屑2种生物质的热解实验,对热解碳烟产物的产率、微观形貌等理化性质进行了表征,并在热天平上测定其氧化/气化特性。研究了在不同热解温度下两种生物质产生碳烟的产率、粒径分布及内部纳观结构的变化趋势,在此基础上分析了碳烟反应活性的影响因素,并将结果与采用一维沉降炉热解方式获得的碳烟对比。结果表明：采用固定床热解获得的碳烟具有较高的纯度。随着生成温度的升高,碳烟结构排列更加有序,石墨化程度提高,基本粒子的几何平均粒径变小,同时碳烟的反应活性变差,说明碳烟内部结构的变化对反应活性的影响起主要的控制作用。单位空间内生物质的燃料浓度会影响碳烟的产率、粒径等特性。高的原料空间浓度倾向于生成更多的碳烟,并且碳烟具有更大的粒径。木屑碳烟相比麦秆碳烟石墨化程度更高,反应活性较差。     

考虑多组分颗粒运动各向异性的鼓泡流化床生物质气化数值模拟

考虑鼓泡流化床生物质气化过程多组分颗粒运动特点,建立多组分颗粒速度脉动二阶矩模型,结合化学反应动力学方法描述鼓泡流化床内生物质气化过程。模拟的气体组分结果与采用原始颗粒动理学模型的模拟结果进行了比较,并给出了两种粒径碳颗粒的浓度与温度瞬时分布。分析了两种碳颗粒的速度时均径向分布及速度脉动二阶矩时均径向分布,两种碳颗粒的速度分布一致,说明不同粒径碳颗粒混合充分。粒径较大的碳颗粒速度脉动二阶矩在轴向与径向上均较大,粒径的增加使得颗粒速度脉动增强。模拟统计了计算域内两种颗粒的速度脉动各向异性随颗粒浓度变化关系,各向异性随颗粒浓度的增加逐渐减弱,粒径较大的碳颗粒在计算域内的各向异性平均效果不如粒径较小的碳颗粒明显。     

生物质油改性方法研究进展

生物质快速裂解液体产物生物油(简称生物质油),具有水含量高、氧含量高、热值低、粘度大、热不稳定和化学不稳定等特性,在一定程度上影响了其广泛应用,因此必须通过精制改善其品质.按生物质快速裂解的反应过程,将提高生物质油品质的方法归纳为三类:第一类(反应前),快速裂解反应前,原料脱水和脱碱金属处理;第二类(反应中),快速裂解反应过程中,生物质油蒸汽不经冷凝直接改质;第三类(反应后),快速裂解反应完成后,采用对收集到的生物质油催化加氢、催化裂解、催化酯化、乳化、添加溶剂或添加抗氧化剂等方法进行改质.     

生物质油加氢脱氧精制研究进展

随着石油能源渐趋匮乏,生物质高温裂解制备生物质油备受关注。而生物质油中氧含量高达40%,这将影响生物质油的稳定性、极性、热值、粘度和酸性等,应必须对其进行加氢脱氧精制处理。文中介绍了裂解生物质油的组成分布和特点,阐述了裂解生物质油加氢脱氧精制的反应过程和影响因素。     

生物质油加氢脱氧精制研究进展

随着石油能源渐趋匮乏,生物质高温裂解制备生物质油备受关注。而生物质油中氧含量高达40%,这将影响生物质油的稳定性、极性、热值、粘度和酸性等,应必须对其进行加氢脱氧精制处理。文中介绍了裂解生物质油的组成分布和特点,阐述了裂解生物质油加氢脱氧精制的反应过程和影响因素。     

生物质催化热解制油及油品改性提质研究进展

基于国家碳中和背景，生物质作为一种重要的可再生资源，其有效利用至关重要。生物质热解制油具有规模化潜力，成为目前生物质利用的主要方式。生物质热解技术按照液化方式不同分为直接液化和间接液化，但生物质直接液化所得生物油组分不稳定，间接液化所得生物油品质取决于反应器型式、反应温度及催化剂类型等，不同制备方法的生物油品质差别较大，生物油改性提质成为其实际应用的必要条件。归纳比较了生物质热解过程中提高生物油品质的催化剂类型，着重综述了原生物油分离为轻质组分和重质组分后分别改性提质的技术路线，可转化为燃气、燃油甚至化学品，实现生物油的高值化。针对轻质油组分的改性方法有水蒸气重整制氢、催化裂解、加氢脱氧、催化酯化等，催化剂类型以分子筛及贵金属为主；而重质油组分水含量低、黏性大，相关提质研究较少，目前报道以加氢、裂化、酯化、添加溶剂、气化为主。生物油提质改性方法中，催化剂、氢源、耗能是限制其规模化、工业化应用的主要原因，降低催化剂成本及提高催化剂寿命、减少氢源使用或利用低成本氢源、简化工艺及降低反应温度是生物油提质技术发展方向。     

An Inter-Comparison of Instruments Measuring Black Carbon Content of Soot Particles

Inter-comparison studies of well-characterized fractal soot particles were conducted using the following four instruments: Aerosol Mass Spectrometer-Scanning Mobility Particle Sizer (AMS-SMPS), Single Particle Soot Photometer (SP2), Multi-Angle Absorption Photometer (MAAP), and Photoacoustic Spectrometer (PAS). These instruments provided measurements of the refractory mass (AMS-SMPS), incandescent mass (SP2) and optically absorbing mass (MAAP and PAS). The particles studied were in the mobility diameter range from 150 nm to 460 nm and were generated by controlled flames with fuel equivalence ratios ranging between 2.3 and 3.5. The effect of organic coatings (oleic acid and anthracene) on the instrument measurements was determined. For uncoated soot particles, the mass measurements by the AMS-SMPS, SP2, and PAS instruments were in agreement to within 15%, while the MAAP measurement of optically-absorbing mass was higher by ～ 50%. Thin organic coatings (～ 10 nm) did not affect the instrument readings. A thicker (～ 50 nm) oleic acid coating likewise did not affect the instrument readings. The thicker (～60 nm) anthracene coating did not affect the readings provided by the AMS-SMPS or SP2 instruments but increased the reading of the MAAP instrument by ～ 20% and the reading of the PAS by ～ 65%. The response of each instrument to the different particle types is discussed in terms of particle morphology and coating material.     

Characterization of Soot Aerosol Produced from Combustion of Propane in a Shock Tube

The knowledge of yields and properties of soot from combustion of hydrocarbon fuels is crucial for accurate evaluation of the impacts of primary aerosols on air quality and climate. This study presents measurements of soot generated from combustion of propane in a shock tube, using independently adjustable fuel equivalence ratio (φ), temperature, and pressure. The characterization of soot yields inside the shock tube by in situ laser extinction is complemented with a set of comprehensive measurements of soot transferred into a fluoropolymer chamber, including particle size distributions, elemental carbon (EC) mass fraction, effective density, mass fractal dimension (Dfm), dynamic shape factor (χ), and optical properties. The properties of soot particles and the soot yield are sensitive to combustion conditions and the duration of the combustion experiment. High-temperature combustion with φ = 2.5 produces small fractal (Dfm = 2) soot particles composed mainly of EC (up to 90%), at a low mass yield. Particles from lower temperature combustion contain a significant fraction of organic material (～50%). Using rich fuel mixtures (φ = 4.0 and 8.0) significantly increases particle size and soot mass yield. At lower temperatures, compact (Dfm = 3) and nearly spherical (χ = 1.1) aggregates with high organic content are formed, whereas at higher temperatures, the particles are fractal and closely resemble those obtained using φ = 2.5. Single scattering albedo (SSA) varies from 0.15 for fractal particles to 0.75 for compact particles. For soot generated at high equivalence ratios, SSA can be used as a proxy for particle morphology and EC content.

Copyright 2012 American Association for Aerosol Research     

Effect of ethanol addition in gasoline and gasoline–surrogate on soot formation in turbulent spray flames

The effect of ethanol on soot formation has been studied in turbulent spray flames of gasoline/ethanol and gasoline–surrogate/ethanol mixtures containing 10%, 20% and 30% of alcohol in volume. A hybrid burner specially designed to stabilize different liquid fuels flames with identical hydrodynamic conditions has been used. Spatially resolved measurements of soot volume fraction and of soot precursors concentration have been carried out by coupling Laser-Induced Incandescence (LII) at 1064 nm and Laser-Induced Fluorescence (LIF) at 532 nm. Significant reductions of the concentrations of soot and soot precursors have been observed when adding ethanol to gasoline. A similar behaviour has been obtained with a gasoline–surrogate which has been found to reproduce well the sooting propensity of the unleaded gasoline used in this work. The analysis of the correlation existing between the peak soot volume fraction measured in flames and the Threshold Soot Index (TSI) of the different mixtures tested in this work revealed that the effect of ethanol was not only a dilution one but that the oxygen contained in the alcohol also influence the soot formation. Finally, the comparison of the LII fluence curves and time decays obtained in gasoline/ethanol mixtures showed that soot particles oxidized faster when ethanol is added to the base fuel.     

Coating Mass Dependence of Soot Aggregate Restructuring due to Coatings of Oleic Acid and Dioctyl Sebacate

Soot particles in the atmosphere can be coated with organic or nonorganic material, which may affect particle morphology and optical properties. The effect of the mass of coating on the morphology of soot particles was studied using oleic acid and dioctyl sebacate (DOS) coatings. A wide range of coatings were used, with up to 10 times as much coating as the mass of the soot. It is shown that as the coating mass increases the degree of collapsing increases until the coating is so large that the soot particle becomes completely contained within a spherical droplet of the coating material. Higher amounts of coating will not cause further collapse of the particle. The degree of collapse is also a function of the initial size of the soot particle but was independent of the coating materials tested, which have similar surface tensions. A model is presented to predict the change in mobility diameter as a function of coating mass ratio. The effect of coating mass on effective density, shape factor, and fractal dimension is also reported.

Copyright 2013 American Association for Aerosol Research     

A Potential Soot Mass Determination Method from Resistivity Measurement of Thermophoretically Deposited Soot

Miniaturized detection systems for nanometer-sized airborne particles are in demand, for example in applications for onboard diagnostics downstream particulate filters in modern diesel engines. A soot sensor based on resistivity measurements was developed and characterized. This involved generation of soot particles using a quenched co-flow diffusion flame; depositing the particles onto a sensor substrate using thermophoresis and particle detection using a finger electrode structure, patterned on thermally oxidized silicon substrate. The generated soot particles were characterized using techniques including Scanning Mobility Particle Sizer for mobility size distributions, Differential Mobility Analyzer—Aerosol Particle Mass analyzer for the mass–mobility relationship, and Transmission Electron Microscopy for morphology. The generated particles were similar to particles from diesel engines in concentration, mobility size distribution, and mass fractal dimension. The primary particle size, effective density and organic mass fraction were slightly lower than values reported for diesel engines. The response measured with the sensors was largely dependent on particle mass concentration, but increased with increasing soot aggregate mobility size. Detection down to cumulative mass as small as 20–30 μg has been demonstrated. The detection limit can be improved by using a more sensitive resistance meter, modified deposition cell, larger flow rates of soot aerosol and modifying the sensor surface.     

TEM study on volatility and potential presence of solid cores in nucleation mode particles from diesel powered passenger cars

Nucleation mode particles were investigated for their morphology using TEM and the presence or absence of solid cores was addressed. At cold start idle nucleation particles were observed in the exhaust of a diesel passenger car. These particles occurred with both low and high S fuel and were only partly volatile in a thermodenuder, which indicates that the composition was not sulfate and as derived from TEM/EDX (transmission electron microscopy/energy dispersive X-ray analysis) probably not ash. It could be high boiling hydrocarbons, or primary soot particles. With all fuels at warm idle no nucleation particles and only soot particles were observed in the SMPS and the TEM. With 3.0×10¹¹ s^?1 the total soot particle number during idle was much less than during driving, e.g. at 120 km h^?1 the emission rate was 6.7×10¹² s^?1.At high load and high S fuel 10–20 nm nucleation particles were observed by SMPS and TEM. A thermodenuder at 280 °C and TEM showed that all nucleation particles were volatile. EDX gave a weak S-signal only. Some nucleation particles contained smaller spots (1–3 nm) with a very high contrast, which might be due to heavy elements. However, under the electron beam of the TEM these spots disappeared and EDX analysis was not possible. With low S fuel at 120 km h^?1 only soot particles and no nucleation particles were observed.     

Effects of volatile coatings and coating removal mechanisms on the morphology of graphitic soot

We have measured morphological changes of combustion-generated mature soot with various quantities of hydrocarbon coating and different coating-removal mechanisms. We made these measurements on soot extracted from a burner and then (1) coated with oleic acid, (2) coated with oleic acid and then denuded using a thermodenuder, (3) coated with oleic acid and then heated with a laser, and (4) coated with oleic acid, denuded with a thermodenuder, and then laser heated. We compared these results to results for untreated soot from the burner. The soot samples were size selected using a differential mobility analyzer prior to coating. Uncoated, coated, and denuded particles were characterized by electric-mobility size, particle and coating mass, and particle morphology. Our results show that the particles are restructured (become compact) when coated. Particles sent through the thermodenuder are irreversibly restructured. Laser desorption of coatings with thicknesses ⩾20% by mass, however, returns the soot particles to a less compact morphology with some fragmentation as the coating rapidly vaporizes. A majority of laser-heated heavily coated particles stay associated with unvaporized oleic acid droplets despite some fragment ejection from the droplet. Thermally denuded particles neither return to a less compact morphology nor fragment when laser heated.