Effect of nitrogen on multifront detonation parameters

A faster increase in the cell size and other very important multifront detonation parameters compared with that predicted by the kinetic calculations has been shown for nitrogen-diluted fuel-oxygen mixtures of hydrogen and typical hydrocarbons. Dilution of mixtures with other inert gases does not lead to a similar effect. This may be associated with the increase in the chemical reactivity of nitrogen under the action of the electric field of a detonation wave. A more correct method of calculating the ignition delays of various nitrogen-containing mixtures for detonation conditions is proposed. Translated fromFizika Goreniya i Vzryva, Vol. 34, No. 1, pp. 79–83, January–February, 1998     

Dimethyl ether autoignition in a rapid compression machine: Experiments and chemical kinetic modeling

Dimethyl ether (DME) autoignition at elevated pressures and relatively low temperatures is experimentally investigated using a rapid compression machine (RCM). DME/O₂/N₂ homogeneous mixtures are studied over an equivalence ratio range of 0.43–1.5 and at compressed pressures ranging from 10 to 20 bar and compressed temperatures from 615 to 735 K. At these conditions RCM results show the well-known two-stage ignition characteristics of DME and the negative temperature coefficient (NTC) region is noted to become more prominent at lower pressures and for oxygen lean mixtures. Furthermore, the first-stage ignition delay is found to be insensitive to changes in pressure and equivalence ratio. To help interpret the experimental results, chemical kinetic simulations of the ignition process are carried out using available detailed kinetic models and, in general, good agreement is obtained when using the model of Zhao et al. [Int. J. Chem. Kinet. 40, 2008, 1–18]. Sensitivity analyses are carried out to help identify important reactions. Lastly, while it is implicitly assumed in many rapid compression studies that chemical changes from the initial charge conditions that might occur during compression are negligible, it is herein shown with the help of Computational Singular Perturbation (CSP) analyses that chemical species formed during compression with little evolved exothermicity can considerably affect autoignition observations. Therefore, it is essential to simulate both compression and post-compression processes occurring in the RCM experiment, in order to properly interpret RCM ignition delay results.     

Chemical Kinetics of Detonation in Some Liquid Mixtures

The main objective of this work is to study the chemical kinetics of detonation reactions in some nitroester mixtures and solutions of nitrocompounds in concentrated nitric acid. The main source of information on chemical kinetics in the detonation wave was the experimental dependence of failure diameter on composition of mixtures. Calculations were carried out in terms of classic theory of Dremin using the SGKR computer code. Effective values for the activation energies and pre‐exponential factors for detonation reactions in the mixtures under investigation have been defined.     

Reliability of kinetic data used for estimating multifront detonation parameters

A faster increase in the cell size and other important parameters of multifront detonation than that predicted by kinetic calculations is obtained for fuel-oxygen mixtures of hydrogen and typical hydrocarbons diluted by nitrogen. In a stoichiometric hydrogen-oxygen mixture diluted by an additional amount of oxygen or hydrogen, experimental and calculated data are also found to diverge with increasing concentration of the added species. This effect, however, is not observed if these mixtures are diluted by helium or argon. An assumption about the reason for this difference in data is put forward. A conclusion is made that kinetic data should be corrected as applied to detonation conditions. __________ Translated from Fizika Goreniya i Vzryva, Vol. 45, No. 3, pp. 89–94, May–June, 2009.     

Kinetics of Chemical Reactions During Detonation of Mixtures of Organic Substances with Nitric Acid

The kinetics and mechanism of chemical reactions in detonation waves propagating in mixtures of nitric acid with nitroglycol, ethylene glycol dinitrate, and acetic anhydride were studied within the framework of the Dremin—Trofimov theory of the detonation failure diameter. The state parameters in shock and detonation waves were calculated using the SGKR software package. It was shown that the decomposition of mixtures of nitric acid with organic substances in a detonation wave is a complex reaction which includes several stages. Various kinetic models are considered; effective values of the kinetic parameters are calculated for each model and for the entire process.     

On mixing of the products of detonation of composite explosives in the chemical reaction region

The problem of mixing of the products of detonation of composite explosives is of principal importance for the synthesis of ultrafine diamond from composite mixtures and also for chemistry of detonation processes as a whole. An analysis of mixing in the chemical reaction region due to molecular diffusion shows that this mechanism may be important only for grain sizes of several micrometers. If the grain sizes reach tens or hundreds of micrometers, only partial mixing on the grain boundaries is possible. Investigations of the hydrodynamic mechanism of mixing shows that it may occur owing to a nonuniform velocity field behind the detonation wave front in the mixture and to the development of turbulence and cumulative processes during pore implosion. In mixtures with grain sizes of the order of 30 μm, these processes can lead to appreciable mixing during the time of ≈0.5 μs and longer. Theoretical estimates are compared with the results of experiments performed at the Lavrentyev Institute of Hydrodynamics of the Siberian Branch of the Russian Academy of Sciences and at the Altai Scientific and Industrial Enterprise (Biisk) for studying the synthesis of ultrafine diamond with the use of the isotope method.     

THE ELUCIDATION OF THE KINETICS AND MECHANISMS OF THE CATALYTIC OXIDATION OF TRACE AMOUNTS OF DIMETHYL ETHER IN OXYGEN BY TRANSIENT PHENOMENA

Thermal desorption experiments with different heating schemes were used to study the kinetics and mechanisms of the catalytic oxidation of dimethyl ether (DME) on supported Pt catalysts. The experimental apparatuses were fully automated by using a microcomputer control system. This made possible direct evaluations of several key kinetic parameters as well as long-term evaluations of the catalysts. The oxidation of DME catalyzed by Pt/SiO₂-Al₂O₃, catalyst has been shown to involve the chemisorption of DME on the support and the chemisorption of oxygen on Pt metal sites. The surface reaction between chemisorbed DME and oxygen was found to be the rate-determining step under the experimental conditions investigated. The proposed reaction mechanism using the kinetic parameters estimated from the thermal desorption experiments predicts the experimental results very well. Acetylene was found to have a promotional effect for the reaction. It is believed that carbon from acetylene plays a key role in this reaction enhancement.     

Comparison between the shock wave and chemical initiation in detonation of acetylene—oxygen mixtures

Detonation of different compositions of acetylene-oxygen mixtures by both chlorine gas injection and a shock wave as initiators is studied in this research. The chlorine gas is injected into the detonation tube through a reticular plate nozzle at the moment when a thin aluminum foil separating the injection system from the detonation tube is torn by a pressurized nitrogen gas. The results of experiments show that chemical initiation may be as effective as direct initiation of detonation and, therefore, replace more complicated methods of initiation. The best results are obtained in acetylene— oxygen mixtures with the molar ratio of 1: 1.     

Experimental investigation on detonation initiation with a transversal flame jet

This paper reports on an investigation of detonation initiation with a transversal flame jet. Series of single-cycle experiments are performed, where stoichiometric propane-oxygen mixtures with nitrogen dilution at atmospheric initial pressure are used, both in the flame sub-chamber with varying configurations and in the test tube 70 mm in diameter and 1550 mm long. The experimental results show that the flame jet orifice diameter slightly affects the detonation initiation sensitivity, and the flame sub-chamber configurations exert a minor effect on the deflagrationto-detonation transition (DDT) distance, but the DDT time decreases as the flame sub-chamber length increases. Conventional spark ignition is investigated as a comparison experiment, and detonation initiation is not observed in mixtures with nitrogen dilution up to 65%.     

Mixed Explosives and Determination of Their Detonation Parameters

A model of the effective characteristics of heterogeneous systems is given. The model is based on the methods of field theory of many bodies. The suitability of the given approach for a quantitative assessment of the characteristics of explosives and detonation is shown. In particular, two‐component mixtures of TNT/RDX and three‐component mixtures of aluminum with energetic materials are considered. The values of a few parameters (density, impact sensitivity, heat of explosion, detonation velocity) calculated by means of the proposed model agree satisfactorily with known experimental data.     

Isotope studies of detonation mechanisms of TNT,RDX, and HMX

An analysis is performed of experimental data from isotopic tracer studies of the detonation mechanism and formation of the diamond phase of carbon in the detonation products of TNT, RDX, HMX, and their mixtures. Dependences of the relative yield and phase composition of carbon in the detonation products of components of composite explosives on the particle sizes of the explosives are given. __________ Translated from Fizika Goreniya i Vzryva, Vol. 43, No. 5, pp. 96–103, September–October, 2007.     

乙醇和二甲醚微射流火焰燃烧特性研究

采用实验及数值计算研究了乙醇和二甲醚微圆管射流火焰燃烧特性。通过实验观察到不同燃料流速下乙醇和二甲醚火焰都具有四种典型的火焰形态；使用平面激光诱导荧光测试系统获得了微射流火焰的OH基元分布，实验结果表明在较高流速下稳定燃烧的乙醇火焰比二甲醚火焰直径小，且略高于二甲醚火焰；采用考虑详细化学反应机理的数值计算对乙醇和二甲醚火焰进行了数值模拟，计算结果与实验现象吻合较好；利用一维非预混对冲火焰计算进一步研究了这两种燃料的化学反应路径，分析结果表明乙醇和二甲醚火焰的中间产物有显著差异，两种燃料化学反应特性的差异导致了不同的微火焰结构。     

Computer simulation of the structure and electronic and detonation properties of energy materials

Computer modeling is used within the framework of the theory of density functional to determine the physical and chemical properties of a set of energy materials, which correlate with detonation parameters and sensitivity factors. There are two models of prediction of detonation parameters and sensitivity factors formulated for molecules and explosive crystals that satisfactorily correlate with the experimental data.     

Experimental study on the hazards of the jet diffusion flame of liquefied dimethyl ether

Dimethyl ether (DME) has been considered as a substitute for diesel fuel because it has a low auto-ignition temperature and produces less NO_x, SO_x, and particulate matter. However, the introduction of DME vehicles needs widely available DME supply stations. Moreover, the preparation of safety regulations for DME supply stations is very important, and so safety data is needed. Therefore, the present paper reports the hazards of the DME jet diffusion flame, which is one of several hazardous properties of DME, by studying the results of leaking gas and liquid DME. DME jets were released horizontally from circular nozzles whose diameters were 0.2, 0.4, 0.8 and 2 mm, and the release pressure was varied from the saturated vapor pressure to 2 MPa. When gaseous DME was released at the saturated vapor pressure, the flame was blown out. However, when liquefied DME was released, the flame formed. We obtained the experimental equations for estimating the scale and thermal hazards of DME diffusion flames.     

Simulation of DME synthesis from coal syngas by kinetics model

DME (Dimethyl Ether) has emerged as a clean alternative fuel for diesel. There are largely two methods for DME synthesis. A direct method of DME synthesis has been recently developed that has a more compact process than the indirect method. However, the direct method of DME synthesis has not yet been optimized at the face of its performance: yield and production rate of DME. In this study it is developed a simulation model through a kinetics model of the ASPEN plus simulator, performed to detect operating characteristics of DME direct synthesis. An overall DME synthesis process is referenced by experimental data of 3 ton/day (TPD) coal gasification pilot plant located at IAE in Korea. Supplying condition of DME synthesis model is equivalently set to 80 N/m³ of syngas which is derived from a coal gasification plant. In the simulation it is assumed that the overall DME synthesis process proceeds with steadystate, vapor-solid reaction with DME catalyst. The physical properties of reactants are governed by Soave-Redlich-Kwong (SRK) EOS in this model. A reaction model of DME synthesis is considered that is applied with the LHHW (Langmuir-Hinshelwood Hougen Watson) equation as an adsorption-desorption model on the surface of the DME catalyst. After adjusting the kinetics of the DME synthesis reaction among reactants with experimental data, the kinetics of the governing reactions inner DME reactor are modified and coupled with the entire DME synthesis reaction. For validating simulation results of the DME synthesis model, the obtained simulation results are compared with experimental results: conversion ratio, DME yield and DME production rate. Then, a sensitivity analysis is performed by effects of operating variables such as pressure, temperature of the reactor, void fraction of catalyst and H₂/CO ratio of supplied syngas with modified model. According to simulation results, optimum operating conditions of DME reactor are obtained in the range of 265–275 °C and 60 kg/cm². And DME production rate has a maximum value in the range of 1–1.5 of H₂/CO ratio in the syngas composition.     

甲醇-空气层流火焰速度的数值研究和预测模型

收集总结分析了现有的甲醇层流火焰速度的实验数据,比较了三种典型的描述甲醇氧化的详细化学反应机理(Li机理、USC Mech-Ⅱ和Burke机理)对层流火焰传播速度的预测精度。结果表明三种机理均能定性反映甲醇层流火焰速度的变化规律,但在富燃料侧,机理计算值明显高于实验结果。反应动力学分析表明甲醇脱氢反应对层流火焰速度的影响至关重要。根据文献中的最新成果,修正了Li机理中甲醇脱氢反应的速率常数,提高了Li机理对甲醇-空气层流火焰速度的预测精度。针对工程需求,给出了两个甲醇层流火焰速度的快速预测模型,经过校核,所提出的预测模型能够较为准确地预测不同初始温度和压力下甲醇层流火焰速度。     

Dehydration of Methanol to Dimethyl Ether by Catalytic Distillation

The kinetics of liquid catalytic dehydration of methanol over an ion exchange resin (Amberlyst 35) has been determined for the temperature range 343 to 403 K using a batch reactor. The experimental data are described well by an Eley‐Rideal type kinetic expression, for which the surface reaction is the rate‐determining step. A catalytic distillation process for methanol dehydration to dimethyl ether (DME) has been modeled using the experimentally determined kinetic data. The results were incorporated into the rate‐controlled reaction mode for RadFrac, a part of the commercial simulation program Aspen Plus. It was shown that synthesis of high purity DME can be achieved using a single catalytic distillation column. Thus there is significant potential for reduction of overall capital cost for a plant for methanol dehydration to DME when compared to conventional production facilities that involve separate reaction and distillation processes.     

一水合双四唑乙烷氨基胍的制备及性能研究

采用一锅法制备了新型高氮化合物——一水合双四唑乙烷氨基胍盐(CH7N4·C4H4N8·H2O)。用红外光谱和元素分析对其单晶进行了表征,用X射线单晶衍射法测定了其晶体结构;用TG-DTG法和DSC法测试了其热性能;用Kissinger法和Ozawa法计算了其非等温动力学参数;用氧弹量热法测试了其燃烧热;用K-J方程计算了其爆速、爆压,并测试了其机械感度。结果表明,该晶体属于单斜晶系,空间群为C2/c(No.15),晶胞参数为:a=1.126 1(2)nm,b=0.710 62(14)nm,c=2.724 1(5)nm,β=95.95(3)°,V=2.168 2(8)nm3,Z=4,理论密度为1.527g/cm3;该化合物在289.3℃开始分解,具有良好的热稳定性,其非等温动力学反应活化能为219.05kJ/mol,指前因子lg(A/s-1)为38.61;燃烧热为9.515MJ/kg,生成焓为2 892.2kJ/mol,爆速为6.95km/s,爆压为19.3GPa;撞击感度高于50cm,摩擦感度为0,表明该化合物具有较低的机械感度和良好的热稳定性。     

Detonation characteristics of diluted liquid explosives: Mixtures of nitromethane with methanol

Detonation in mixtures of nitromethane with methanol as an inert (nonexplosive) diluent is studied. Ignition experiments with mixtures in steel tubes of various diameters provided information on the effect of the degree of dilution on detonability. Mass velocity profiles with a chemical spike characteristic of detonation waves were recorded at the unsteady detonation front in all mixtures studied. This made it possible to distinguish the Chapman-Jouguet state and obtain a fairly complete set of detonation parameters. The dependence of the pressure in the detonation products on the methanol concentration is determined, which is required, in particular, to find the true (absolute) limit of detonation propagation for the concentration of diluted liquid explosives using the method proposed and validated by A. N. Dremin. Some results were found to be inconsistent with one-dimensional detonation theory.