Burning Behaviour of ADN Formulations

The application of ADN for an effective oxidizer of propellants and explosives requires a detailed knowledge of the burning behaviour. The physical and chemical mechanisms of the combustion depend on pressure. Especially profiles of temperature and species in the flame are important to design propellant formulation of high performance and low signature of the rocket plume. In the presented study, pure ADN and ADN/paraffin mixtures were investigated as strands in an optical bomb at pressures of 0.5 MPa to 10 MPa. The application of non-intrusive combustion diagnostics for the investigation of fast burning energetic materials allowed the measurement of burning rates and profiles of temperature and gas components at various distances above the burning propellant surface. The burning rate was determined by using a video system and a special frame analysis. The acquisition and analysis of emission spectra in the UV/VIS allowed the investigation of rotational temperatures, the determination of particle temperatures and the identification of transient flame radicals. The vibrational temperatures of final combustion products resulted from band spectra emitted in the near and mid infrared spectral range. Burning rates of 5 mm/s to 70 mm/s were recorded showing a mesa/plateau-effect in the pressure range of 4 MPa to 7 MPa. The UV/VIS spectra indicated an emission from OH, NH and CN radicals. The strong emission of OH bands of the ADN/paraffin mixture allowed the investigation of rotational temperatures with a mean value of 2700 K which is closely below the adiabatic flame temperature of 2950 K. Additionally, one-dimensional intensity profiles of the flame radicals were measured. As combustion end products H₂O, CO, CO₂ and NO were found. NO could only be detected at a distance up to 2 mm above the propellant surface. The measured CO/CO₂ fraction was higher as 10/1. Water could only be detected far above the propellant surface.     

A Novel Kind of Green Solid Propellant Containing H2O2 Cured at Room Temperature (SPHP)

A novel kind of green solid propellant containing H₂O₂ cured at room temperature (SPHP) was prepared by a “two‐steps” method, and its stability, mechanical properties, sensitivity, and combustion behavior were characterized. Stable storage of SPHP can be achieved at room temperature by selecting propellant ingredients with perfect compatibility with H₂O₂ and the addition of a complex stabilizer into propellant formulation. In addition, the obtained SPHP showed a lower tensile strength and higher elongation compared with conventional solid propellant. The experimental results showed that the sensitivity of SPHP was considerably low, but its combustion efficiency and C* efficiency were really high. The hot firing tests demonstrated the stable and smokeless combustion of SPHP, as well as its combustion behavior within the pressure range of 2–10 MPa was in agreement with Vieille’s law and thus can be represented by r=9.95P^0.57.     

Combustion Mechanism of Azide Polymer

The combustion wave structure and thermal decomposition process of azide polymer were studied to determine the parameters which control the burning rate. The azide polymer studied was glycidyl azide polymer (GAP) which contains energetic – N₃ groups. GAP was cured with hexamethylene diisocyanate (HMDI) and crosslinked with trimethylolpropane (TMP) to formulate GAP propellant. From the experiments, it was found that the burning rate of GAP propellant is significantly high even though the adiabatic flame temperature of GAP propellant is lower than that of conventional solid propellants. The energy released at the burning surface of GAP propellant is caused by the scission of N N₂ bond which produces gaseous N₂. The heat flux transferred back from the gas phase to the burning surface is very small compared with the heat generated at the burning surface. The activation energy of the decomposition of the burning surface of GAP propellant, E_s, is determined to be 87 kJ/mol. The burning rate is represented by r = 9.16 × 10³ exp(–E_s/RT_s) where r (m/s) is burning rate, T_s (K) is the burning surface temperature, and R is the universal gas constant. The observed high temperature sensitivity of burning rate is correlated to the relationship of (∂T_s/∂T₀)_p = 0.481 at 5 MPa, where T₀ is the initial propellant temperature.     

Influence of HCl on CO and NO emissions in combustion

The influence of HCl on CO and NO emissions was experimentally investigated in an entrained flow reactor (EFR) and an internally circulating fluidized bed (ICFB). The results in EFR show the addition of HCl inhibits CO oxidation and NO formation at 1073 K and 1123 K. At the lower temperature (1073 K) the inhibition of HCl becomes more obvious. In ICFB, chlorine-containing plastic (PVC) was added to increase the concentration of HCl during the combustion of coal or coke. Results show that HCl is likely to enhance the reduction of NO and N₂O. HCl greatly increases CO and CH₄ emission in the flue gas. A detailed mechanism of CO/NO/HCl/SO₂ system was used to model the effect of HCl in combustion. The results indicate that HCl not only promotes the recombination of radicals O, H, and OH, but also accelerates the chemical equilibration of radicals. The influence of HCl on the radicals mainly occurs at 800-1200 K.     

Effects of operation parameters on NO emission in an oxy-fired CFB combustor

Oxy-fuel Circulating Fluidized Bed (CFB) combustion technology, a very promising technology for CO₂ capture, combines many advantages of oxy-fuel and CFB technologies. Experiments were carried out in a 50 kW_th CFB facility to investigate how operation parameters influence the NO emission in O₂/CO₂ atmospheres. The simulated O₂/CO₂ atmospheres were used without recycling the flue gas. Results show that NO emission in 21% O₂/79% CO₂ atmosphere is lower than that in air atmosphere because of lower temperature and higher char and CO concentrations in the dense bed. Elevating O₂ concentration from 21% to 40% in O₂/CO₂ atmosphere enhances fuel-N conversion to NO. Increasing bed temperature or oxygen/fuel stoichiometric ratio brings higher NO emission in O₂/CO₂ atmosphere, which is consistent with the results in air-fired CFB combustion. As primary stream fraction increases, NO emission increases more rapidly in O₂/CO₂ atmosphere than that in air atmosphere. Stream staging is more efficient for controlling NO emission in oxy-CFB combustion than that in air combustion. Oxygen staging provides an efficient way to reduce NO emission in oxy-CFB combustion without influencing the hydrodynamic characteristic in the riser.     

Spectral studies of the gas component of an aluminum dust flame

The combustion zone of a steady-state laminar diffusion flame of aluminum particles of diameter 4.8 μm at a metal weight percentage of 0.4 kg/m³ was studied by atomic and molecular emission spectra. Absolute measurements of the luminosity of the sequence of bands due to AlO made it possible to determine the gas-phase temperature (3200± 100 K) and the AlO vapor concentration [(1.5 ± 0.5) · 10²¹ m⁻³] at the flame front. From an analysis of measurement data on the intensity and contour of the resonance line of aluminum, it is concluded that the metal particles burn individually to form microflames. Estimates were made of the size of the combustion zone of an individual particle and the gas-phase temperature near a particle (3150 ± 200 K). Some features of the combustion mechanism of fine aluminum particles in the dust flame are analyzed. The capabilities of spectral methods for studying the thermal and concentration structures of dust flames are demonstrated. __________ Translated from Fizika Goreniya i Vzryva, Vol. 44, No. 4, pp. 72–79, July–August, 2008.     

Analysis of the behaviour of pollutant gas emissions during wheat straw/coal cofiring by TG-FTIR

The behaviour of pollutant gas emissions during the firing of wheat straw and coal blends was examined experimentally by using thermogravimetric analysis (TGA). Typical anthracite coal and wheat straw in central China were selected in this study. The ratio of coal to wheat straw by mass was set as 10:90, 15:85, 40:60 and 60:40 and the firing was carried using simulated air with oxygen and nitrogen gases. The emission characteristics of gas pollutants such as HCl, SO₂, CO₂ and NO_x were determined by coupled Fourier transform infrared (FTIR) measurements. The results showed that HCl, SO₂, CO₂ and NO_x emissions were closely related to the volatile combustion and char reacting stages. HCl emission was mainly released during the volatile combustion at the temperature between 220 and 450 °C. The profiles of HCl against temperature exhibit a single-peak, and the HCl peak occurred at 310 °C for all blends no matter what the ratio. The emission profiles of SO₂, and NO_x against temperature had the characteristic of two peaks. The first peak occurred around 320 °C for all blends, and however the second peak shifted towards higher temperatures as the coal content was increased in the blends. The study showed that combining the straw and coal can produce better emission control by reducing the magnitude of the peak releases. The analysis showed that the blended sample with 40% coal and 60% straw by mass produced the lowest levels of HCl, NO_x and SO₂ gas emissions. The CO₂ emission was mainly produced in the char combustion stage and purely increased with the carbon content in the blends.     

Combustion of Aluminum Particles near the Burning Surface in AP/AN Composite Propellants

Aluminum (Al) particles are commonly used in ammonium perchlorate (AP) composite propellants of solid rockets for increasing performance. When propellants including Al particles burn, Al particles easily agglomerate on the burning surface of the propellant. The diameters of agglomerated Al particles are greater than those of mixed particles. The combustion efficiency of the propellant decreases with increasing burning time of the agglomerated Al particles. Therefore, it is important to observe how the agglomerated Al particles burn on the burning surface of AP composite propellant. A lot of researchers have studied Al agglomerate characteristics. Previous studies clarified the relation between the agglomerated Al particle diameter and luminous flame diameter around Al particles near the burning surface. The shapes of luminous flames around agglomerated Al particles are spherical or elliptical. This study evaluates the shapes of the luminous flame around agglomerated Al particles at a constant diameter or a different diameter. When the proportion of the luminous flame diameter (D_f) to the diameter of agglomerated Al particles (D₀) is 1.54–1.71 at a constant D₀, the luminous flames are almost perfectly spherical. Otherwise, the luminous flames are elliptical at a constant D₀. Furthermore, when D_f/D₀ is close to the mean value, the luminous flame is more spherical than elliptical at different D₀. The evaporation rate and the burning rate of Al vapor are inversely proportional to D₀. The oxidation gas temperatures were changed and the activation energy of Al vapor was obtained as 39.2 kJ mol⁻¹.     

含AP包覆硼的富燃推进剂燃烧机理研究

通过微热电偶测温和火焰单幅照相技术测试了含硼富燃料推进剂燃烧波温度分布及燃烧火焰结构;用扫描电镜对熄火表面形貌进行了观察,并通过能谱仪进行局部元素分析;对DSC曲线进行积分,得到推进剂的凝相放热量;测量推进剂燃烧的爆热和低压燃速,获得了其低压燃烧特性和一次燃烧放热情况。结果表明,含AP包覆硼的推进剂燃烧更剧烈,推进剂的绝热火焰温度更高,AP包覆硼提高了含硼富燃料推进剂的凝相放热、爆热和低压燃速。初步确定了该类推进剂的燃烧过程,为建立含硼富燃料推进剂燃烧物理模型提供了依据。     

Real-fluid flamelet modeling for gaseous hydrogen/cryogenic liquid oxygen jet flames at supercritical pressure

The primary goal of this study is to numerically model the transcritical mixing and reacting flow processes encountered in liquid propellant rocket engines. In order to realistically represent turbulence-chemistry interactions, detailed chemical kinetics, and non-ideal thermodynamic behaviors related to the liquid rocket combustion at supercritical pressures, the flamelet approach is coupled with real-fluid modeling based on the Soave-Redlich-Kwong (SRK) equation of state. To validate the real-fluid flamelet model, a gaseous hydrogen/cryogenic liquid oxygen coaxial jet flame at supercritical pressure has been chosen as a benchmark case. Numerical results are compared with experimental data obtained for the OH radical and the temperature distribution. It was found that weak flow recirculation is induced by the sudden expansion of cold core cryogenic oxygen associated with the pseudo-boiling process. This weak recirculation zone substantially influences the fundamental characteristics of liquid propellant reacting flows at supercritical pressures in terms of the spreading and the flame length. For the flame conditions employed in this study, the predicted contours of the OH radical are in good agreement with the experimental Abel transformed emission image in terms of the flame spreading angle and the flame location. Numerical results suggest that the real-fluid based flamelet model is capable of realistically predicting the overall characteristics of a turbulent non-premixed GH₂/LOx flame at supercritical pressures.     

位移钝体稳燃的旋流预混燃烧污染物生成特性

石化炉、加热炉等设备中燃烧过程的污染物控制具有重要意义。旋流预混燃烧过程具有低NO _x 排放的潜力,引发了学术界和工业界的广泛关注。结合钝体燃烧和旋流燃烧各自的优势,本文设计了带有位移钝体的旋流预混燃烧器。首先研究了不同钝体结构下的污染物的生成情况,确定了最优的钝体结构,在此基础上进一步研究了在不同旋流数下污染物生成、火焰形态和温度场分布情况。研究发现,钝体角度为30°、体积较小的倒锥形钝体具有较低的NO _x 和CO生成量。NO _x 生成量随着旋流数从0增加到0.83呈先减小后增加的趋势,并且当旋流数为0.25时,NO _x 生成量最低。在同一热功率下,火焰高度随着旋流数的增加而减小。在同一旋流数下,火焰宽度随热功率增大呈增大趋势。NO _x 生成量变化规律与其火焰温度分布规律一致,即NO _x 生成量最低的工况下火焰温度也比较低。由此推测旋流引发的温度变化是NO _x 生成量变化的主要影响因素之一。本文的研究结论对旋流预混燃烧器的设计提供了理论基础。     

Computational study of the combustion process and NO formation in a small-scale wood pellet furnace

This paper presents a computational study of the combustion process of wood pellets in a small-scale grate fired furnace. The objectives were to obtain detailed information on the combustion characteristics and NO formation in the furnace, and to examine the effect of secondary air on the combustion process. The simulation results were compared with experimental data in terms of flame temperature and distributions of species concentrations, including CO and NO. It was shown that the combustion process is strongly controlled by the inflow turbulence from the secondary and tertiary air jets. The combustion process is not sensitive to the bed combustion process in the present test case. The high speed air flow from the secondary and tertiary air inlets ‘destroys’ the history of the effluent volatile gases from the fuel bed. Different paths for the NO emission were investigated, including the thermal NO, the fuel-NO and NO from the N₂O intermediate mechanisms. The fuel-NO path is responsible for the rapid NO increase and the high NO peak near the fuel bed. Fuel-NO is rather low far downstream owing to the rather low nitrogen content in the fuel (less than 0.1% on mass basis), and the de-NO_x reactions with NH₃. NO is likely formed from the N₂O intermediate mechanism far downstream.     

NEPE推进剂燃烧机理研究

应用微热电偶测温和燃烧火焰单幅照相技术测得 NEPE推进剂在稳态燃烧条件下的燃烧波温度分布及火焰结构 ,研究了该推进剂中主要组分对燃烧性能的影响 ,同时利用扫描电镜 -能谱仪观测了熄火表面形貌和元素分布规律。经过综合分析 ,提出了 NEPE推进剂的燃烧过程 ,为该类推进剂燃烧物理模型的建立奠定了基础     

Stability of Calcium Chloride in the Air–Steam Gasification of Solid Fuel in Filtration Mode

The emission of HCl from calcium chloride during the air–steam gasification of solid fuel in the filtration combustion mode was studied. The limiting amounts of HCl released into the gas phase under real conditions of a shaft kiln gasifier were estimated. It was shown that the most important factors responsible for the stability of CaCl₂ are the humidity of an oxidant gas and the process temperature.     

Combustion characteristics of lignite-fired oxy-fuel flames

This experimental work describes the combustion characteristics of lignite-fired oxy-fuel flames, in terms of temperature distribution, gas composition (O₂, CO₂, CO, total hydrocarbon concentration and NO) and ignition behaviour. The aim is to evaluate the flame structure of three oxy-fuel cases (obtained by changing the flue gas recycle rate) including a comparison with an air-fired reference case. Measurements were performed in Chalmers 100 kW test unit, which facilitates oxy-fuel combustion under flue gas recycling conditions. Temperature, O₂ and CO concentration profiles and images of the flames indicate that earlier ignition and more intense combustion with higher peak temperatures follow from reduction of the recycle rate during oxy-fuel operation. This is mostly due to higher O₂ concentration in the feed gas, reduced cooling from the recycled flue gas, and change in flow patterns between the cases. The air case and the oxy-fuel case with the highest recycle rate were most sensitive to changes in overall stoichiometry. Despite significant differences in local CO concentration between the cases, the stack concentrations of CO are comparable. Hence, limiting CO emissions from oxy-fuel combustion is not more challenging than during air-firing. The NO emission, as shown previously, was significantly reduced by flue gas recycling.     

Experimental Investigation on Laser Ignition and Combustion Characteristics of NEPE Propellant

The ignition and combustion property of solid propellant is the main content in internal ballistic research, which has a great significance for propulsion application and combustion mechanism. In this study, the detailed gas‐phase reaction mechanism of Nitrate Ester Plasticized Polyether Propellant (NEPE) was developed. It is helpful to understand the intricate processes of solid‐propellant combustion. The factors which may have influences on ignition delay time and temperature distribution of propellant surface was analyzed by laser ignition experiment. Using high‐speed camera and an infrared thermometer, the ignition and combustion process and the surface temperature distribution of NEPE propellant under laser irradiation were measured. Laser heat flux, ambient pressure and initial temperature of NEPE propellant have an influence on the ignition delay time and the surface temperature. Results show that the ignition delay time decreases with the increase of laser heat flux, ambient pressure and initial temperature of NEPE propellant. At the same time, with the increase of laser heat flux, the influences of ambient pressure and initial temperature on the ignition delay time decrease. Besides, laser irradiation, ambient pressure and initial temperature have significant influences on the surface temperature distribution of the propellant.     

Mathematical modelling of NO emissions from high-temperature air combustion with nitrous oxide mechanism

A study of the mathematical modelling of NO formation and emissions in a gas-fired regenerative furnace with high-preheated air was performed. The model of NO formation via N₂O-intermediate mechanism was proposed because of the lower flame temperature in this case. The reaction rates of this new model were calculated basing on the eddy-dissipation-concept. This model accompanied with thermal-NO, prompt-NO and NO reburning models were used to predict NO emissions and formations. The sensitivity of the furnace temperature and the oxygen availability on NO generation rate has been investigated. The predicted results were compared with experimental values.The results show that NO emission formed by N₂O-intermediate mechanism is of outstanding importance during the high-temperature air combustion (HiTAC) condition. Furthermore, it shows that NO models with N₂O-route model can give more reasonable profile of NO formation. Additionally, increasing excess air ratio leads to increasing of NO emission in the regenerative furnace.     

Study on flame structures and emissions of CO and NO in Various CH<Subscript>4</Subscript>/O<Subscript>2</Subscript>/N<Subscript>2</Subscript>–O<Subscript>2</Subscript>/N<Subscript>2</Subscript> counterflow premixed flames

An oxygen-diluted partially premixed/oxygen-enriched supplemental combustion (ODPP/OESC) counterflow flame is studied in this paper. Flame images are obtained through experiments and numerical simulations with the GRI-Mech 3.0 chemistry. The oxygen dilution effects are revealed by comparing the flame structures and emissions with those of a premixed flame and partially premixed flame (PPF) at the same equivalence ratio (?_Σ = 0.95 and ? _f = 1.4). The results show that both PPF and ODPP/OESC flames have distinct double flame structures; however, the location of the premixed combustion zone and the distance between premixed/nonpremixed combustion zone are significantly different for these two cases. For the ODPP/OESC flame, the temperature in the premixed combustion zone is lower and the premixed zone itself is located farther downstream from the fuel nozzle, which leads to reduction of NO and CO emissions, as compared to those of the PPF. Therefore, by adjusting the distribution of the oxygen concentration in the premixed and nonpremixed combustion zones, the ODPP/OESC can effectively balance the chemical reaction rate in the entire combustion zone and, consequently, reduce emissions.     

扩散过滤燃烧火焰特性

扩散过滤燃烧是新的燃烧技术,具有扩散燃烧和预混过滤燃烧的某些特性。通过二维双温模型,使用单步总包反应,数值研究氮气稀释的甲烷和氧气同轴同平板扩散过滤燃烧特性。模型中考虑热弥散和组分弥散效应。研究小球直径、气体混合物速度和甲烷质量分数对火焰高度和火焰形态的影响。结果表明,与预混过滤燃烧不同,气体和固体高温区存在于燃烧器的不同位置;而在高温区域之外,气体和多孔介质固体的温差很小。当填充床小球直径从6.66 mm减小到2.02 mm,火焰高度从0.048 m增大到0.12 m。增大混合物速度,甲烷的质量分数导致火焰变宽,火焰高度增大。数值模型的有效性得到了实验验证。     

Determination of the Temperature in a Solid Propellant Flame by analysis of emission spectra

Two methods are described to determine the temperature in a solid propellant flame by analysis of emission spectra. First, experimental spectra of NH and CN radicals were compared with calculated spectra using a least squares fit routine with the parameters temperature T and halfwidth of the line profile Δλ. Second, in flames where no or only small band intensities were observed, the occurring continuous spectra were fitted to a Planck radiation. The emission coefficient ϵ was there by suggested as a function of wavelength λ and temperature T. The first technique was applied to the nitrmine propellant HMX, the second to a composite propellant consisting of 15% AI, 15% GAP and 70% ammonium perchlorate. TO detect the emission, propellant strands were burnt in an optical bomb under nitrogen atmosphere at various pressures (octogen at 0.1 MPa, composite at 2 MPa). To calibrate the intensities of the continous spectra tungsten strip lamp was used. The maximum time resolution of the used spectrometer system is about 10 ms. The determined temperature range was from 2300 K to 3000 K, which is about 20% below the corresponding adiabatic temperature (nitramine propellant: 2900 K, composite propellant: 3500 K).