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。     

Theoretical analysis on the exergy destruction mechanisms and reduction under LTC relevant conditions

Low temperature combustion (LTC) is a potential thermodynamic pathway to maximize the thermal efficiency of internal combustion (IC) engines. However, high exergy loss is also observed within this combustion concept. The present study focuses on the homogeneous combustion process and examines the detailed exergy destruction mechanisms under representative LTC engine conditions. By varying both equivalence ratios (φ) and temperatures (T) at initial pressure of 50?bar, it is found that the decreased total exergy destruction fraction (f_ED) with increasing initial temperature mainly results from the decreased exergy destruction in the high temperature heat release stage, while using rich mixture can significantly reduce the f_ED in the ignition delay stage, which is dominated by the reactions involving large molecules (C7 species). Reaction pathway analysis reveals that the detailed exergy destruction sources are significantly affected by the reaction pathways. Furthermore, a qualitative exergy loss φ-T map was created to illustrate the exergy loss reduction potential. It is concluded that the combustion pathway that reforming the rich fuel/air mixtures before ignition followed by the low temperature combustion of lean reforming products offers the potential to simultaneously reduce exergy destruction and avoid soot and NOx formation. However, the potential advantages of this exergy reduction combustion concept still require further work.     

不同燃烧状态飞火颗粒自由燃烧规律研究

飞火是开放空间中大尺度火灾非连续性蔓延的主要形式。本文通过不同热流下的木质飞火颗粒自由燃烧实验,揭示不同燃烧状态飞火颗粒的结构变形、质量损失及温度分布的变化规律。研究表明,颗粒结构变形受材料化学反应机制和热机械力作用共同影响;颗粒燃烧反应易造成热解气体的内部积聚,以致内压激增、诱发喷射或喷溅细小颗粒的现象;阴燃过程颗粒表面温度变化较小但持续时间很长,明火状态的颗粒持续高温并且温度与质量变化剧烈。     

Experimental observations on the thermal degradation of a porous bed of tires

In this paper, an experimental study on the forward combustion of a bed of tires and refractory briquettes is presented. Temperature measurements within the reactor were obtained as a function of time as well as the evolution of the fuel bed. The products of combustion were cooled down, and usable liquid fuel was recovered and measured. The reaction was found to become unstable for fuel concentrations lower than 50%. The results show that the airflow and tire concentration define different modes of combustion while the reaction remains oxygen limited. Oil production is maximized when an increase in airflow leads to a transition from a rate-limited reaction to a heat transfer-limited propagation. Variation of the tire concentration shows the importance of the inert in achieving high conversion rates.     

Influence of water mist on propagation and suppression of laminar premixed flame

The combustion of premixed gas mixtures containing micro droplets of water was studied using one-dimensional approximation. The dependencies of the burning velocity and flammability limits on the initial conditions and on the properties of liquid droplets were analyzed. Effects of droplet size and concentration of added liquid were studied. It was demonstrated that the droplets with smaller diameters are more effective in reducing the flame velocity. For droplets vaporizing in the reaction zone, the burning velocity is independent of droplet size, and it depends only on the concentration of added liquid. With further increase of the droplet diameter the droplets are passing through the reaction zone with completion of vaporization in the combustion products. It was demonstrated that for droplets above a certain size there are two stable stationary modes of flame propagation with transition of hysteresis type. The critical conditions of the transition are due to the appearance of the temperature maximum at the flame front and the temperature gradient with heat losses from the reaction zone to the products, as a result of droplet vaporization passing through the reaction zone. The critical conditions are similar to the critical conditions of the classical flammability limits of flame with the thermal mechanism of flame propagation. The maximum decrease in the burning velocity and decrease in the combustion temperature at the critical turning point corresponds to predictions of the classical theories of flammability limits of Zel'dovich and Spalding. The stability analysis of stationary modes of flame propagation in the presence of water mist showed the lack of oscillatory processes in the frames of the assumed model.     

A mathematical model of hotspot condensed phase ignition in the presence of a competitive endothermic reaction

We consider the propagation of a combustion front resulting from the gasless combustion of a condensed state fuel. The propagation of the front, essentially a premixed laminar flame, is supported by an exothermic reaction subject to possible heat loss through a competitive endothermic reaction. The dynamics of the endothermic process inducing the heat loss strongly depend on the temperature and the local fuel concentration. Through an analysis based on high activation energy, the steady-state values of the final burnt temperature as well as the burning velocity are obtained, and the control parameters are identified. Using a linear perturbation method, we assess the stability of the propagating front and obtain a condition for oscillatory behaviour. The critical parameter values for the transition from steady to oscillatory burning speeds are identified. The results represent a generalization of those obtained by Matkowsky and Sivashinsky to include the effects of heat loss induced by a competitive endothermic reaction.     

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.     

蒸发性对燃油瞬态喷雾撞击壁面的动态传热影响

直喷发动机燃油喷雾撞击壁面形成油膜,导致燃烧效率降低,颗粒物排放增加。伴随撞壁的动态传热过程对油膜蒸发具有重要影响。本文针对正戊烷、甲醇、甲醇汽油混合燃料瞬态喷雾撞击壁面,研究了不同条件下蒸发性对燃油瞬态喷雾撞击壁面动态传热影响。结果表明,提高喷油温度可促进燃油雾化,增大喷油压力或降低喷油距离可提高液滴撞壁强度,缩短液膜存在时间。撞壁瞬态温度与热流密度动态变化特征受燃油蒸发性与喷雾条件联合影响。     

Critical phenomena in the cellular mode of filtration combustion in the presence of heat loss

Critical conditions for combustion failure due to heat loss to the environment are examined. The process of filtration combustion is considered under conditions where a cellular structure of the front is realized, because the planar combustion front loses its stability and splits into separate cells of exothermic chemical conversion, which propagate in self-sustained mode. The size and structure of the cells of chemical interaction depend nonlinearly on the governing parameters, including the rate of heat loss to the environment. Within the framework of a mathematical model of filtration combustion, the steady-state dynamics of the combustion process and the structure of the cell of exothermic chemical reaction of a powder mixture with a gaseous reagent with the formation of solid products are simulated. The specifics of the evolution of the cell before combustion failure as a function of the heat loss rate are studied.     

Effect of radiative transfer of heat released from combustion reaction on temperature distribution: A numerical study for a 2-D system

Both light and heat are produced during a chemical reaction in a combustion process, but traditionally all the energy released is taken as to be transformed into the internal energy of the combustion medium. So the temperature of the medium increases, and then the thermal radiation emitted from it increases too. Chemiluminescence is generated during a chemical reaction and independent of the temperature, and has been used widely for combustion diagnostics. It was assumed in this paper that the total energy released in a combustion reaction is divided into two parts, one part is a self-absorbed heat, and the other is a directly emitted heat. The former is absorbed immediately by the products, becomes the internal energy and then increases the temperature of the products as treated in the traditional way. The latter is emitted directly as radiation into the combustion domain and should be included in the radiation transfer equation (RTE) as a part of radiation source. For a simple, 2-D, gray, emitting-absorbing, rectangular system, the numerical study showed that the temperatures in reaction zones depended on the fraction of the directly emitted energy, and the smaller the gas absorption coefficient was, the more strong the dependence appeared. Because the effect of the fraction of the directly emitted heat on the temperature distribution in the reacting zones for gas combustion is significant, it is required to conduct experimental measurements to determine the fraction of self-absorbed heat for different combustion processes.     

煤油热沉与热裂解反应特性的试验研究

本文设计了一种煤油热裂解反应特性与热沉测量试验系统,利用该试验系统和原始标定法的热损测量方法,测量出了在亚临界和超临界压力下煤油热裂解反应的热沉大小,并进行了热裂解反应主要分解产物成分含量的测定与分析。结果表明：壁温随热流密度增加而增加;在相同燃油温度条件下,压力增大,热沉降低;裂解反应气体的浓度变化主要受到燃油温度和...     

Gasless combustion of a mixture with an extremely low caloricity under heat loss conditions

The gasless combustion of a mixture with an extremely low caloric value in a cylindrical channel is numerically simulated. Because of an intense heat loss, on the surface of the reaction front emerge waves, which lead to cyclic changes in the chemical reaction rate, which acquire axial symmetry in the steady-state regime. In the ignition stage, a ring of reaction sites arises at the lateral surface of the sample. In the stage of depression, combustion persists on circular protrusions of the front, whereas a site of products is formed is the central part of the sample.     

Filtration Combustion of Humid Fuels

A comparative study of the filtration combustion of two types of fuel in mixtures with an inert material at various degrees of humidity was performed. The fuels were activated birch charcoal and pinewood. It was demonstrated that the combustion of activated charcoal was only slightly affected by humidity. In the case of pinewood combustion, an increase in the fuel humidity caused substantial decreases in the gasification mass rate and temperature. The composition of the gaseous products was found to change only for mixtures containing a large amount of pinewood with a humidity of more than 35%. This can be accounted for by a change in the extent of pinewood pyrolysis.     

玉米芯流化床快速热解制取生物油试验研究

本文在流化床上对玉米芯进行了快速热解制取生物油的试验研究.首先在非催化条件下考察了温度、气体流量、床高和物料粒径对热解产物产率的影响,得到了制取生物油的最优工况.在此工况下进行了催化热解试验,研究了FCC催化剂对热解产物产率和生物油品质的影响.结果表明,最优工况下生物油产率为56.8%.同未加催化剂相比,FCC催化剂的存在使得生物油中油组分和焦炭的产率降低,不凝结气体、水分和焦的产率增加.分级冷凝系统的应用较好的实现了重油、轻油和水的分离.对催化条件下第二级冷凝器收集的生物油分析表明,其油组分的氧含量和高位热值分别为13.64%和36.7 MJ/kg,具有很好的应用前景.     

小型流化床内化学链热解煤焦油实验研究

为优化煤焦油化学链热解的工况参数,采用Fe/Al复合载氧体在小型流化床反应器内进行了煤焦油化学链热解实验,考察了燃料反应器温度、载氧体/煤焦油摩尔比及反应时间对热解结果的影响,对炭黑收率、气相产物的体积分数进行分析,并计算了实验系统的碳平衡及能量转化率。结果表明,炭黑收率随温度和载氧体/煤焦油摩尔比升高先增后减,在温度950℃和摩尔比3时达到最大,气相产物中CO和H2体积份额为70%左右,继续升高炉温和摩尔比会降低CO份额。系统碳平衡为95.5%以上,误差较小,则系统能量转化率最高可达到87%.通过表观气速变化改变反应时间从2.1s增大到3.5s时,炭黑收率及能量转化率无明显变化,由此确定了化学链热解煤焦油的优化运行参数.     

A reactive molecular dynamics study of NO removal by nitrogen-containing species in coal pyrolysis gas

Coal splitting and staging is a promising technology to reduce nitrogen oxides (NOx) emissions from coal combustion through transforming nitrogenous pollutants into environmentally friendly gasses such as nitrogen (N₂). During this process, the nitrogenous species in pyrolysis gas play a dominant role in NOx reduction. In this research, a series of reactive force field (ReaxFF) molecular dynamics (MD) simulations are conducted to investigate the fundamental reaction mechanisms of NO removal by nitrogen-containing species (HCN and NH₃) in coal pyrolysis gas under various temperatures. The effects of temperature on the process and mechanisms of NO consumption and N₂ formation are illustrated during NO reduction with HCN and NH₃, respectively. Additionally, we compare the performance of NO reduction by HCN and NH₃ and propose control strategies for the pyrolysis and reburn processes. The study provides new insights into the mechanisms of the NO reduction with nitrogen-containing species in coal pyrolysis gas, which may help optimize the operating parameters of the splitting and staging processes to decrease NOx emissions during coal combustion.     

Determination of pyrolysis temperature for charring materials

An energy and mass balanced method of determining the pyrolysis temperature is proposed. The concept is to find the pyrolysis temperature that consumes the same amount of energy to produce the same amount of mass when using the pyrolysis front model as when using finite rate kinetics models for the entire charring process. The resulting pyrolysis temperature has the form of pyrolysis rate weighted average temperature. Comparisons between finite rate kinetics and pyrolysis front models for various boundary conditions, geometries, heats of decomposition, kinetic parameters and assumptions used in the literature were made to assess the proposed method. Models using energy and mass balanced pyrolysis temperature show good agreement with finite rate models and the experiments. Extensive numerical studies on various factors influencing the charring material pyrolysis show that heat flux, sample size, heat of decomposition and kinetic parameters are the most important factors for determining an appropriate pyrolysis temperature. Thermal conductivity, specific heat and density have a lesser effect on the pyrolysis temperature. For practical application, a non-dimensional correlation is developed to determine the appropriate pyrolysis temperature without solving the problem by using finite rate models. With this correlation the energy and mass balanced pyrolysis temperature can be determined with a standard deviation of 7.6 K. These predictions are validated by comparison with measurements of wood cylinder pyrolysis. A good agreement suggests that simpler pyrolysis front models yield practically useful and accurate results given an appropriate pyrolysis temperature.     

Interactions of NiO particles with polycyclic aromatic hydrocarbons and acetylene generated from the pyrolysis of a model fuel

Experiments have been conducted to study the effects of NiO, a prevalent form of nickel in combustion-generated ash particles, on polycyclic aromatic hydrocarbons (PAH) and other hydrocarbons in a fuel product mixture. The fuel product mixture is generated from the gas-phase pyrolysis, in N₂, of the model fuel catechol in a quartz tube reactor at 1100 K and 5 s, a condition that ensures full conversion of the catechol and produces a mixture—of PAH, hydrocarbon gases, and oxygen-containing species—that is representative of the products of practical liquid and solid fuels in pyrolysis and fuel-rich combustion environments. Once formed, the product mixture is passed, at the same temperature, through a bed of ultrafine NiO particles held in place by quartz wool, in the contact zone of the reactor. The products exiting the reactor are quenched, collected, and analyzed by non-dispersive infrared analyzers, gas chromatography, and high-pressure liquid chromatography with diode-array ultraviolet–visible absorbance detection. The results from the experiments at 1100 K show that—compared to the case of no inorganics in the contact zone—when NiO is present: PAH yields are reduced 86% (from 10.8% to 1.48% fed carbon); all of the highly mutagenic 5- and 6-ring PAH are eliminated; and all of the acetylene, the highest-yield hydrocarbon product when NiO is absent, and other hydrocarbons with carbon–carbon triple bonds are eliminated from the gas phase. Most of the surface-bound carbon is released as CO. Similar experiments at 1275 K show that—except for the release of the surface-bound carbon as CO—the selective surface effects of NiO bring about similar results at higher temperature: 89% reduction in PAH yield, elimination of mutagenic 5- and 6-ring PAH, removal of acetylene and acetylenic species, as well as a decrease in the production of solid carbon (not formed at 1100 K).     

Non-isothermal kinetics of styrene-butadiene-styrene asphalt combustion

The combustion characteristics of styrene-butadiene-styrene （SBS） asphalt are studied by thermogravimetric analysis （TG/DTG） at four different heating rates. According to the saturates/aromatics/resins/asphaltenes （SARA） fractionation method, the combustion process of SBS asphalt can be divided by Gaussian peak fitting into three main stages： oil content release, resin pyrolysis, and asphaltene and char combustion. When the heating rate increases, the mass losses of the oil content and resin pyrolysis increase, and less asphaltenes are formed at a higher temperature. The activation energy values are calculated by the Coats-Redfern method to be in the range 61.6 kJ/mol-142.9 kJ/mol. The Popescu method is used for the kinetic analysis, and the result shows that the three stages of asphalt combustion can be explained by the sphere phase boundary reaction model, the second order chemical reaction model, nucleation, and its subsequent growth model, respectively.     

一种生物柴油代用品在HZSM-5分子筛催化剂上的催化热解

为了深入了解生物柴油在ZSM-5沸石上的催化反应机理,在常压的流动反应器中进行了生物柴油代用品丁酸甲酯在氢型ZSM-5(HZSM-5)催化剂上的热解和催化热解. 热解产物使用气相色谱-质谱法定性和定量测量. 动力学模型和实验表明,气相中氢提取反应是热解过程中丁酸甲酯分解的主要途径,但在HZSM-5上,丁酸甲酯则主要通过解离生成烯酮和甲醇消耗;与无催化反应相比,丁酸甲酯在HZSM-5上的初始分解温度降低了约300 K. 并且通过Arrhenius方程获得了在催化热解和均相热解条件下丁酸甲酯消耗的表观活化能. 明显降低的表观活化能证实了HZSM-5对丁酸甲酯热解的催化性能. 此外催化剂的活化温度对HZSM-5的某些催化性能具有一定的影响. 该研究对进一步的实际生物柴油燃料的催化燃烧具有一定的指导意义.