基于红外光谱研究沥青燃烧机理和有害气体成分分析

利用Rosemount气体分析仪和定碳炉搭建起固定床燃烧反应试验平台,通过红外光谱分析技术定量分析沥青及其胶浆在高升温速率条件下燃烧反应的有毒气态产物成分、及其释放规律。研究表明,在高升温速率、近等温条件下,沥青及胶浆的燃烧过程可近似分为活泼挥发组分析出燃烧、二次挥发析出结合残炭燃烧两个阶段,其主要气态产物为CO₂,CO,NO,NO₂及SO₂。沥青材料中活泼挥发组分含量是影响燃烧气态产物释放规律的关键因素之一,减少沥青材料中活泼挥发组分的含量可有效降低燃烧气态产物的生成、尤其是CO的产生。     

Experimental and modeling study on centimeter pine char combustion in fast-heating Macro TGA

Biomass energy is an important renewable resource, and thermochemical conversion, including pyrolysis and combustion, is one of the main methods of biomass energy utilization. In industrial reactors, the biomass particles will experience a fast heating (∼1000 °C/min) process during pyrolysis. The particle size of biomass applied in industry has a wide range (from millimeter to centimeter scale). The study of the reaction characteristics of biomass pyrolysis and combustion is helpful for optimizing furnace design and working condition selection. In this research, the combustion of centimeter-scale pine char was studied with a newly built fast-heating Macro Thermal Gravimetric Analyzer (Macro TGA). This Macro TGA is able to conduct the pyrolysis and combustion of large biomass samples (up to 40 mm) with a fast heating rate (∼1000 °C/min), which is able to reflect the working conditions in industrial-scale reactors such as grate furnaces and dual fluidized beds. This Macro TGA can measure the online sample weight, temperature and sample size simultaneously during pyrolysis and combustion experiments. The combustion characteristics of different sizes of pine chars were investigated at various temperatures and oxygen concentrations. A zero-dimensional model was established to predict the sample weight loss, temperature change and sample shrinkage during the pine char combustion process. Three kinetic parameters α, A and E were applied in the model, and the values of the kinetic parameters were optimized by a genetic algorithm. The model prediction and experimental results are consistent with each other. Compared with previous studies, this study developed a new experimental method to measure the reaction characteristics (including sample weight, temperature and size) of centimeter-scale biomass under similar pyrolysis and combustion reaction conditions compared to industrial reactors, and a zero-dimensional model was established to describe the pine char combustion process.     

垃圾混煤热解特性的实验研究

以固定床热解反应器为背景,研究掺煤量和加热速率对垃圾混煤物料热解特性的影响,实验结果表明:提高加热速率可以有效缩短热解时间,增加掺煤量可以改变反应床结构,提高料层传热速率,缩短热解时间;在19.6 kW供热条件下,掺煤100 g和掺煤200 g热解时间分别为110 min和99 min;气体产率分别为25.6％和28.1％,气体热值分别为18255 kJ/m3和19830 kJ/m3。     

胜利油田稠油组分的光谱法研究

用红外光谱, 紫外光谱及同步荧光光谱对胜利油田稠油中的沥青质和胶质进行了分析。红外光谱分析结果表明,胶质、沥青质分子含有可形成氢键的羟基、胺基、羧基、羰基等极性基团,说明原油中 胶质分子之间、沥青分子之间及二者相互之间有强烈的氢键作用,具有很强的极性。通过紫外吸收光谱及同步荧光光谱的测定,并与模型化合物的紫外吸收特征峰及荧光光谱的特征峰相比较,结果表明, 芳香单片是研究稠油中胶质、沥青质组分结构的最基本单位。单元芳香片中芳香环的个数以3～4个环为主,共轭芳香环的排列形式主要为“线性排列”,即渺位缩合。但胶质和沥青质的结构也存在着差异, 即胶质中主要含有3～4个环的共轭芳香片,而沥青质中含有少量多于5个环的共轭芳香片,并且这些共轭芳香片有部分“面性排列”,即迫位缩合。     

1H NMR法对改性沥青中SBS含量精确测试的研究

建立了核磁共振氢谱（¹H NMR）法测定改性沥青中聚苯乙烯-聚丁二烯-聚苯乙烯嵌段式聚合物（SBS）精确含量的方法.首先,建立了改性沥青¹H NMR谱中SBS特征峰和基质沥青峰的积分面积之比与SBS实际掺量的线性关系,结果表明两者间线性关系良好;其次,验证了该方法的准确度和精确度,并证实该方法的准确度高于傅里叶变换红外光谱（FTIR）法;最后利用此方法评价了改性沥青混匀装置的好坏.SBS含量的测定,目前还没有建立国家测量标准,也没有利用NMR进行定量测试的相关报道.本研究结果表明NMR技术可用于快速和精确测试SBS改性沥青中SBS含量,对实际应用有一定指导意义.     

生物油及其重质组分的热解动力学研究

采用热重分析法对生物油及其三种重质组分模型化合物的热解特性进行了对比研究,并对动力学参数进行了求解.结果表明:生物油的热解包括挥发组分的蒸发及重质组分的裂解两个阶段,反应级数都是4级,活化能分别为29～36kJ/mol及13～19 kJ/mol;三种重质组分模型化合物中左旋葡聚糖也存在两个失重区间,反应级数分别为1和2,且表观活化能最高;3,4二甲氧基苯甲醛和丁香酚则只有一个失重区间,且相应的反应级数分别为0.8和0.5,表观活化能也依次降低.     

Continuous catalytic pyrolysis of oily sludge using U-shape reactor for producing saturates-enriched light oil

Continuous catalytic pyrolysis of oily sludge was carried out in a special U-shape reactor for producing saturates-enriched light oil. The sludge underwent thermal pyrolysis first and then catalytic pyrolysis. During the thermal pyrolysis, chain hydrocarbons were first cracked and further polymerized into aromatics. The effect of temperatures (400–800 °C) on the products was investigated and the maximum liquid yield (67.7%) was obtained at 500 °C. High temperature promoted polymerization, thus the distribution of aromatics in the liquid product was increased and was more concentrated in polyaromatics at 800 °C. In the catalytic upgrading stage, dolomite was used as catalyst and aromatics were adsorbed on it, either aggregated or decomposed. As a result, a light oil product with 57.0% saturates was obtained at the residence time of 8.9?s due to the conversion of aromatics and heavy hydrocarbons into light aliphatic hydrocarbons such as straight chain hydrocarbons. Compared with the oil phase in the raw sludge sample, the content of saturates was increased by 45.0% and that of the asphaltenes was reduced by 88.5%. Meanwhile, the inherent moisture in the oily sludge could participate in the steam reforming reaction, promoting the decomposition of aromatics and leading to an increase in the H₂ generation. Moreover, the release of H₂S was reduced from 0.132 to 0.005?mol per kg sludge and the sulfur content of the oil product was also decreased in the presence of dolomite. The deactivation of dolomite can be attributed to the carbonization of CaO and deposition of polyaromatic coke on the catalyst surface.     

A functional-group-based approach to modeling real-fuel combustion chemistry – III: Application to biodiesels

Real biodiesel fuels are mixtures comprising many high molecular weight components, making it a challenge to predict their combustion chemistry with detailed kinetic models. Our group previously proposed a functional-group approach (FGMech) to model the combustion chemistry of real gasoline and jet fuels; this approach has now been extended to model real biodiesel combustion and mixtures with petroleum fuels. As in our previous work, a decoupling philosophy is adopted for construction of the model. A lumped reaction mechanism describes the (oxidative) pyrolysis of fuels, while a detailed base chemistry model represents the oxidation of key pyrolysis intermediates. However, due to the presence of the ester group, several oxygenated species are identified as additional primary products and incorporated into the lumped reaction steps. In addition to the lumped reactions initiated by unimolecular decomposition and H-atom abstraction reactions, a lumped H-atom addition-elimination reaction is also incorporated as a new reaction class to account for the presence of double bonds. Stoichiometric parameters are obtained based on a multiple linear regression (MLR) model, which establishes relationships between the fuel's functional group distributions and the stoichiometric parameters of the lumped reactions. Global rate constants are developed from consistent rate rules obtained from pure fuels. New pyrolysis experimental data for methyl pentanoate/methyl nonanoate and methyl heptanoate/n-heptane mixtures (50%/50% in mol) are obtained in a jet-stirred reactor at atmospheric pressure. In general, kinetic models developed using the FGMech approach can reasonably reproduce all the validation targets obtained in this work, as well as those in the literature, confirming that functional-group-modeling is a promising approach to simulate combustion behavior of diesel/biodiesel surrogate fuels and real biodiesels.     

衰减全反射红外光谱法快速测定糠醛抽出油烃族组成含量方法研究

提出了一种衰减全反射红外光谱法快速测定糠醛抽出油烃族组成含量的方法,设计了一套重油烃族组成快速分析系统。实验收集了62个减压蜡油经糠醛精制后的抽出油样品,采用NB/SH/T0509-2010方法测定其饱和烃、芳烃含量,由差减法求得胶质和沥青质总含量。采用偏最小二乘法(PLS)分别建立了糠醛抽出油饱和烃、芳烃和胶质+沥青质含量的定量校正模型,其SEC分别为1.43%,0.91%和1.61%,SEP分别为1.56%,1.24%和1.81%,均小于NB/SH/T0509-2010方法规定的再现性误差,模型预测精密度小于标准方法的重复性误差要求。与现行标准方法相比,该方法速度快,操作简单,可显著提高糠醛抽出油烃族组成分析效率。该分析系统也可用于其他重油分析,具有很好的推广应用前景。     

Prediction of NOx emissions from a simplified biodiesel surrogate by applying stochastic simulation algorithms (SSA)

A stochastic simulation algorithm (SSA) approach is implemented with the components of a simplified biodiesel surrogate to predict NOx (NO and NO₂) emission concentrations from the combustion of biodiesel. The main reaction pathways were obtained by simplifying the previously derived skeletal mechanisms, including saturated methyl decenoate (MD), unsaturated methyl 5-decanoate (MD5D), and n-decane (ND). ND was added to match the energy content and the C/H/O ratio of actual biodiesel fuel. The MD/MD5D/ND surrogate model was also equipped with H₂/CO/C₁ formation mechanisms and a simplified NOx formation mechanism. The predicted model results are in good agreement with a limited number of experimental data at low-temperature combustion (LTC) conditions for three different biodiesel fuels consisting of various ratios of unsaturated and saturated methyl esters. The root mean square errors (RMSEs) of predicted values are 0.0020, 0.0018, and 0.0025 for soybean methyl ester (SME), waste cooking oil (WCO), and tallow oil (TO), respectively. The SSA model showed the potential to predict NOx emission concentrations, when the peak combustion temperature increased through the addition of ultra-low sulphur diesel (ULSD) to biodiesel. The SSA method used in this study demonstrates the possibility of reducing the computational complexity in biodiesel emissions modelling.     

液化残渣的微波热解与常规热解对比分析

采用微波加热和常规电加热两种条件进行液化残渣(DCLR)的热解实验,考察了热解产物固体焦、焦油及煤气的组成及结构的变化规律,采用红外分析(FTIR)与气相色谱-质谱(GC-MS)联用技术对热解产品进行了分析表征。研究表明,在微波场中,DCLR的升温速率很快,20 min左右物料温度就可达到900 ℃,最大升温速率可达到329 ℃·min-1,而常规加热的升温速率基本保持恒定。与常规热解相比,微波热解后固体焦的产率降低2.85%,而焦油和煤气产率分别增加了0.66%和2.19%。DCLR热解后固体焦的索氏萃取组分重油(HS)、沥青烯(A)及前沥青烯(PA)含量均大幅降低,而四氢呋喃不溶物(THFIS)则有所增加,但是两种热解条件下得到的固体焦的四种索氏组成差异不是很大,说明DCLR的热解过程是以HS,A与PA的转化为主的。微波热解后固体焦红外谱上3 437.6,1 632.0 cm-1以及1 079.99 cm-1处吸收峰的强度与常规热解相比明显降低,说明微波场中DCLR的热解更为彻底。热解后焦油和煤气产率均有所增加,煤气中H₂含量均达到60%以上。GC-MS分析表明,经由石油醚萃取后的热解焦油中脂肪类、芳香类与醇类物质组成以及C_1~5,C_11~20与C₂₀以上组分的含量均没有发生明显变化,而微波热解焦油中沥青质的含量则下降了7.7%,说明微波作用可有效促进DCLR中沥青质的热分解,有利于热解焦油的轻质化。     

聚对苯二甲酸丁二醇酯二聚体键离能的理论研究

采用密度泛函理论方法对聚对苯二甲酸丁二醇酯(PBT)二聚体的键离能进行了计算.为了选取较为精确的方法来计算PBT各个键的键离能,以与PBT具有相同的酯基官能团的乙酸乙酯为模型参照物.采用M062X, B3P86, M06, PBE0, wB97xD方法分别在基组6-31G(d), 6-311G(d), 6-311+G(d, p), 6-311++G(d, p), cc-pVDZ, cc-pVTZ水平下对乙酸乙酯的键离能进行计算.通过对比计算结果与iBonD数据库的乙酸乙酯实验测定值可知,M062X在基组6-311G(d)水平下计算结果与实验值最为接近.因此,本研究采用M062X方法在基组6-311G(d)水平下对聚对苯二甲酸丁二醇酯(PBT)二聚体的键离能进行计算.计算结果表明：在PBT的各键中C-C_arcmatic键的键离能最大,主链上的C-C键离能最小,为370.9 kJ/mol.其次就是C-O键,为404.6 kJ/mol.基于PBT键离能的计算结果,设计了3条PBT二聚体热降解过程可能形成的反应路径,分析了热解产物的形成机理.结果表明PBT二聚体热解过程可...     

Effect of ultrasonic irradiation on the properties and performance of biodiesel produced from date seed oil used in the diesel engine

In the present study, the effect of ultrasound irradiation on the transesterification parameters, biodiesel properties, and its combustion profiles in the diesel engine was investigated. Moreover, date seed oil (DSO) was firstly utilized in the ultrasound-assisted transesterification reaction. DSO was extracted from Zahidi type date (Phoenix dactylifera) and was esterified to reduce its Free Fatty Acid (FFA) content. Biodiesel yield was optimized in both heating methods, so that the yield of 96.4% (containing 93.5% ester) at 60 °C, with 6 M ratio of methanol/oil, 1 wt% of catalyst (NaOH) and at 90 min of reaction time was reported. The ultrasound irradiation did not influence the reaction conditions except reaction time, reduced to 5 min (96.9% yield and 91.9% ester). The ultrasonic irradiation also influenced on the physicochemical properties of DSO biodiesel and improved its combustion in the diesel engine. The analysis results related to the engine and gas emission confirmed that the ultrasound-assisted produced biodiesel has lower density and viscosity, and higher oxygen content facilitating injection of fuel in the engine chamber and its combustion, respectively. Although, B40 (biodiesel blend consisting of 40% biodiesel and 60% net diesel fuel) as a blend of both fuels presented higher CO₂ and lower CO and HC in the emissions, the DSO biodiesel produced by ultrasound irradiation presented better specifications (caused about 2-fold improvement in emissions than that of conventional method). The findings of the study confirmed the positive effect of the ultrasound irradiation on the properties of the produced biodiesel along with its combustion properties in the diesel engine, consequently reducing air pollution problems.     

傅里叶红外光谱法研究GAP/AP混合体系的快速热裂解

用T-Jump/FTIR在线联用分析技术,研究了GAP/AP混合体系在模拟燃烧条件下快速加热高温高压的热裂解。结果表明,GAP/AP混合体系的主要热裂解气相产物的组成发生了变化,说明组分之间存在相互作用。压力对GAP/AP混合体系气相产物有明显的影响,表明混合体系组分GAP和AP之间的相互作用是通过AP分解气相产物进行的,混合体系不但存在气相之间的反应,也存在气相/凝聚相反应。而温度并没有影响AP对GAP的作用。用T-Jump/FTIR在线分析技术能够实现模拟燃烧条件下含能材料实时气体产物分析,为从微观反应的角度探索含能材料的快速高压热裂解及其组分之间的相互作用提供一条技术途径。     

Insight into the calcium carboxylate release behavior during Zhundong coal pyrolysis and combustion

In this paper, the dynamic behavior of calcium carboxylate release during Zhundong coal pyrolysis and combustion is studied via reactive molecular dynamics (ReaxFF MD) simulation. The molecular structure model of Zhundong coal is constructed based on the combination of the classic Hatcher coal model and experimental characterizations. Pyrolysis simulations on the coal model are performed at different temperatures ranging from 2000 K to 2800 K. The pyrolysis experiments are also carried out to validate the ReaxFF simulation. The results show that most of the calcium are released into the volatiles by the thermal decomposition of CM-Ca (coal/char matrix with calcium bonded) after releasing CO₂. The distributions of the calcium bonded to gas, tar and inorganics as well as the atomic calcium in the volatiles are quantitatively classified. The thermal cracking of tar fragments are significant at high temperatures leading to the conversion of calcium from tar into the organic gas. Furthermore, the nascent char model is constructed to study the release behavior of calcium in char combustion stage. The calcium is initially released in the form of oxidized calcium and atomic calcium. With increasing temperature, the oxidized calcium trends to convert to the organically bonded calcium. By using the Arrhenius expression, the kinetic parameters for the release of calcium into various species during pyrolysis and char combustion stages are quantitatively determined.     

Influence of limestone fillers on combustion characteristics of asphalt mortar for pavements

Asphalt materials will be ignited and release significant toxic fumes within tunnel fires. Thus, combustion character- istics of asphalt materials used in road tunnel should be studied in order to limit such an adverse effect. In the present work we study the influence of limestone fillers on combustion characteristics of asphalt mortar by thermogravimetric and kinetic analysis. It is shown that the combustion of asphalt mortar is not just a linear superposition of asphalt and limestone. The limestone will increase the ignition point and the activation energy of the primary volatile release, and will catalyze the char formation from the primary volatile release. Kinetic analysis shows that the primary volatile release stage of asphalt mortar combustion can be explained by a three-dimensional diffusion model, the secondary volatile release and char combustion stage can be explained by a model under the assumption of random nucleation and nuclei growth, whereas the limestone decomposition stage appears to follow the one-dimensional phase boundary model.     

Important roles of multiphase process in enhancement mechanism of micro plastic particle combustion

Thermal recycling of recovered plastic resin has been investigated by supplying plastic resin powder as an additional fuel to the proposed twin-fuel industrial burner. The results emphasize the necessity of fundamental investigations, such as high-speed microscopic observations of micro plastic particles under abrupt heating. To observe the multiphase process of macro plastic particles under abrupt heating and to elucidate their combustion enhancement mechanism, some original devises are introduced; one for optical imaging and three for abrupt heating and ceasing. The former is a mini optical composite which enables simultaneous photographing of the direct silhouetted and schlieren images. The latter three are reforming of a rugged resin particle into a spherical one, a vertical type circular mini-burner for abrupt heating, and a mini-puff generator for abrupt extinguishment. Three types of fine supports made of tungsten, silicon-carbide, and quartz glass are used. Detailed optical observations clarify many characteristics concerning the multiphase process of plastic resin particles under abrupt heating, such as the occurrence of multiple internal micro bubbling, multiple micro explosions and jets. The burning rate constant is also estimated based on the temporal reduction rate of the particle surface area. It is found that the values obtained for three supporting wires are greater than those of typical liquid fuels, and that the key factor to the prominent enhancement rate of micro PET particle combustion can be attributed to the occurrence of the multiphase process particular to micro plastic particles.     

Dynamically Vulcanized Styrene-Butadiene Rubber/Ethylene-Vinyl Acetate Copolymer/High Impact Polystyrene Blends Compatibilized by Styrene-Butadiene-Styrene Block Copolymer

Thermoplastic vulcanizates (TPVs) based on styrene-butadiene rubber (SBR)/ethylene-vinyl acetate copolymer (EVA)/high-impact polystyrene (HIPS) blends were prepared by dynamic vulcanization, and the TPVs was compatibilized by styrene-butadiene-styrene block copolymer (SBS). The effects of SBS compatibilizer on mechanical, dynamic mechanical, and morphological properties of the TPVs were investigated systemically. Experimental results indicate that SBS had a good compatibilization effect on the SBR/EVA/HIPS TPVs. The tensile strength went through a maximum value at a compatibilizer resin content of 6 phr, and the elongation at break and tear strength increased with increasing SBS content. Morphology study shows that the vulcanized SBR particles were dispersed in the HIPS matrices. A rubber process analyzer reveals that the elastic modulus increased with increasing frequency and the incorporation of EVA in the TPVs led to the obvious decrease of elastic modulus; however, the further addition of compatibilizer SBS affected the elastic modulus less. The tan δ decreased continuously with increasing frequency. The addition of SBS in the TPVs led to enhanced hysteresis behavior and relatively high tan δ.     

激光辐照下复合材料树脂基热分解3维温度场模型

 采用控制体积法,从质量和能量守恒角度,推导了激光辐照下复合材料树脂基热分解时温度变化的基本方程。用多步模型描述树脂的热分解反应。提出了热分解气体的1维运动假设,这使得可以在3维情况下考虑热分解气体对流传输的影响,且在不引入力学量的前提下实现3维温度场模型的封闭。考虑到树脂基复合材料的各向异性,对部分分解材料的导热率计算公式进行了推导,并重新推导了部分分解材料对激光的吸收系数计算公式。在一定的简化下,推导的能量守恒方程与文献结果一致。     

石油焦渣油浆燃烧特性的试验研究

石油焦渣油浆是为电站燃油锅炉开发的一种新型代用燃料,本文对南京金陵石化所提供的渣油和石油焦所制成石油焦渣油浆的燃烧特性进行了试验研究。结果表明,浓度为４０％的石油焦渣油浆可以成功地进行制备、加热、输送和燃烧,并具有较高的燃烧效率;石油焦渣油浆的浓度、油焦浆的加热温度、负荷和氧量对其燃烧效率有很大影响。