Control of combustion-generated nitrogen oxides by selective non-catalytic reduction

Controlling nitrogen oxides (NO(x)) emissions is becoming a daunting technical challenge as increasingly strict emission limits are being imposed. The stringent regulations have prompted the innovation and characterization of NO(x) control technologies suitable for various applications. This paper presents a review on NO(x) removal techniques with particular reference to selective non-catalytic reduction (SNCR) technology. This includes initially how SNCR emerged as a technology along with a comparison with other relevant technologies. A review of various features related to selective non-catalytic gas phase injection of ammonia and ammonium salts (as reducing agent) is presented. The use of urea solution as a reducing agent and its performance in laboratory and pilot scale tests as well as large-scale applications is also discussed. Use of cyanuric acid as a potential reducing agent is also presented. The underlying reaction mechanisms have been reviewed for ammonia, urea and cyanuric acid for the explanation of various observations. Computational fluid dynamics (CFD) modeling as applied to SNCR is also presented. Subsequently the use of SNCR coupled with other in-combustion and post-combustion NO(x) control techniques is elaborated. Additionally, a two-stage NO(x) removal strategy to control un-reacted ammonia slip and to improve overall efficiency is discussed. At the end a summary is given which highlights various areas needing further research.     

From waste hot-pot oil as carbon precursor to development of recyclable attapulgite/carbon composites for wastewater treatment

The utilization of waste products as valuable materials was a technical imperative for waste management. In this study, the cost-effective attapulgite/carbon(APT/C) composite was developed for wastewater treatment using waste hot-pot oil as a carbon precursor through a facile one-step calcination process. The APT/C composite prepared at 300°C exhibited the excellent adsorption capacity and rapid equilibrium rate over a broad p H range for the removal of various pollutants. More importantly, the removal ratios of the composites toward Methyl Violet and tetracycline still remained 77.6% and 60.2% of the initial adsorption capacity after ten adsorption–regeneration cycles via a facile thermal regeneration strategy, respectively.Beyond all doubt, this research provided a feasible and economical way for the sustainable utilization of waste hot-pot oil in wastewater treatment, achieving the concept of disposal waste with waste and recycling.     

Modeling thermal analysis for predicting thermal hazards relevant to transportation safety and runaway reaction for 2,2′-azobis(isobutyronitrile)

The pure decomposition behavior of 2,2′-azobis (isobutyronitrile) (AIBN) and its physical phase transformation were examined and discussed. The thermal decomposition of this self-reactive azo compound was explored using differential scanning calorimetry (DSC) to elucidate the stages in the progress of this chemical reaction. DSC was used to predict the kinetic and process safety parameters, such as self-accelerating decomposition temperature (SADT), time to maximum reaction rate under adiabatic conditions (TMR_ad), and apparent activation energy (E_a), under isothermal and adiabatic conditions with thermal analysis models. Moreover, vent sizing package 2 (VSP2) was applied to examine the runaway reaction combined with simulation and experiments for thermal hazard assessment of AIBN. A thorough understanding of this reaction process can identify AIBN as a hazardous and vulnerable chemical during upset situations. The sublimation and melting of AIBN near its apparent onset decomposition temperature contributed to the initial steps of the reaction and explained the exothermic attributes of the peaks observed in the calorimetric investigation.     

Thermal hazard accident investigation of hydrogen peroxide mixing with propanone employing calorimetric approaches

Hydrogen peroxide (H₂O₂), historically, due to its broad applications in the chemical industries, has caused many serious fires and explosions around the world. Its thermal hazards may also be incurred by an incompatible reaction with other chemicals, and a runaway reaction may be induced in the last stage. This study applied thermal analytical methods to explore the H₂O₂ leading to these accidents by incompatibility and to discuss what might be formed by the upset situations. Thermal hazard analysis contained a solvent, propanone (CH₃COCH₃, so-called acetone), which was deliberately selected to mix with H₂O₂ for investigating the degree of thermal hazard. Differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2) were employed to evaluate the thermal hazard of H₂O₂. The results indicated that H₂O₂ is highly hazardous while mixed with propanone, as a potential contaminant. The time to maximum rate (TMR) was used as emergency response time in the chemical industries. Therefore, TMR of H₂O₂ was calculated to be 70 min for runaway reaction (after T₀) and TMR of H₂O₂/propanone was discovered to be 27 min only. Fire and explosion hazards could be successfully lessened if the safety-related data are properly imbedded into manufacturing processes.     

膨胀聚苯乙烯热分解动力学分析和寿命预测

针对既有聚苯乙烯泡沫类外墙外保温系统的防火问题,在空气和氮气气氛下对非阻燃和阻燃型膨胀聚苯乙烯泡沫进行了热重分析。样品由10℃/min、20℃/min、40℃/min和50℃/min四个升温速率从室温加热至800℃。热分解动力学参数由Flynn-Wall-Ozawa(FWO)等转化率方法和多参数非线性回归方法(multivariate non-linear re-gression method)计算,结果表明六溴环十二烷(HBCD)阻燃剂可一定程度上提高EPS的热稳定性。EPS在空气和氮气气氛下热解可认为是单步反应。非阻燃聚苯乙烯泡沫在空气和氮气气氛下的热解过程可由自催化n阶反应机理描述。阻燃EPS在空气气氛下的热解机理为自催化n阶反应,在氮气气氛下则为n阶反应机理。基于动力学参数和反应机理,对聚苯乙烯泡沫在不同温度下的寿命进行了预测。     

Alternative method to prevent thermal runaway in case of error on operating conditions continuous reactor

Thermal runaway was studied in a continuous tubular pilot reactor under steady-state regime. Different accident scenarii were conducted by making some errors on reactant concentrations and/or temperature feed. To prevent thermal runaway, control by direct contact by solvent injection was used at different reactor locations. This injection allowed controlling the maximum reaction temperature. A simplified analytical method to estimate the maximum reaction temperature along the reactor was used.Benefit of this control method was the diminution of computational time. Furthermore, by injecting solvent to control maximum reaction temperature, there is no need to shut down the unit. The control method was validated experimentally.     

基于层次分析法的热塑性聚氨酯及其纳米复合材料火灾危险性综合评价

聚合物的火灾危险性与热、烟、毒的释放密切相关,但采用不同指标对材料的评价结果不一致。以纳米级蒙脱土(MMT)、氢氧化铝(ATH)和聚磷酸铵(APP)为添加剂的热塑性聚氨酯(TPU)纳米复合材料为研究对象,选取其在静态管式炉、稳态管式炉和锥形量热仪中的相关实验数据,以HCN总浓度作为特殊毒性危害指标,CO和CO_2浓度为一般毒性危害指标,以热释放速率峰值、平均热释放速率、总热释放量为热危害指标,以产烟速率峰值、生烟总量为烟危害指标。进一步细分了火灾烟气中不同毒性气体对于火灾风险的影响,并运用层次分析法计算指标权重,综合评价了热塑性聚氨酯及其复合材料的火灾危险性。结果表明,当添加量为6 wt%聚磷酸铵、3 wt%氢氧化铝与3 wt%蒙脱土时,此时复合材料的火灾危险最低,证明了综合热、烟、毒三个层次来降低聚合物材料火灾危险性是可行的。     

Ignition temperatures of dust layers and bulk storages in hot environments

In many industrial installations, particulate solids (cereals, agri-food products, coal, plants, etc.) are stored or processed. Self-heating of these products, which can lead to fires and explosions, can occur in a variety of situations. Examples include large storage at room temperature, formation of a layer on a hot surface, layer deposited on a surface – insulating or conductive – in a hot environment or even storage of product exposed to heating on one side.The main parameters that determine the occurrence of self-heating are the size of the container, the temperature, the residence time and the characteristics of the product. Depending on the type of situation encountered and these implementation conditions, the analysis of self-heating risks must be based on specific models and/or parameters.This paper presents the different variants and combinations of the theoretical model from the theory of thermal runaway to represent self-heating, taking into account in particular the symmetry or asymmetry of heating, reagent consumption and boundary conditions. It also discusses their adaptation to the previous identified industrial situations.Nine products were chosen to be representative of those used in the different considered industrial situations. They were subjected to self-heating basket tests in isothermal ovens in order to determine the parameters for applying the described theoretical models. These results were compared with the results of self-heating tests in layers of different thicknesses in a hot environment, on an insulating or conductive plate, using a specially developed test protocol, as well as with the results of standardized tests of minimum ignition temperature in 5 mm layers.This led to the proposal of the most appropriate theoretical model to represent the self-heating phenomenon for each of the four identified industrial situations.This analysis can promote better design of industrial equipment and production conditions (temperatures, volumes or product flows …) in order to prevent fires and explosions.     

用热分析法研究鼎湖山土壤的粘粒矿物

广东鼎湖山自然保护区的土壤主要为山地黄壤和赤红壤。本文用差热-热重-微商热重(DTA-TG-DTG)联合热分析法,对两种土壤的粘粒矿物进行了初步研究,确认两种土壤的粘粒矿物组成主要为伊利石、高岭石、三水铝石、蛭石、针铁矿等。伊利石、三水铝石、蛭石的含量山地黄壤多于赤红壤,而高岭石则相反。两种土壤的风化程度不高,土壤矿物风化主要处于幼年阶段,山地黄壤尤其明显。另外,对不同林型下的赤红壤也进行了对比研究,其粘粒矿物组成和数量差异不大。     

A very simple yet accurate solution to the thermal explosion problem

A very simple solution to the thermal explosion problem for one-dimensional solids is presented. The solution produces analytical expressions for the criticality condition. Two different solutions are used. One solution gives higher answers than those known from exact solutions and the second solution gives lower answers. This allows bracketing the expected answer with a determined tolerance. The results obtained compare quite favorably with those obtained from known exact numerical solutions. This allows the utilization of the present method for many a practical problem with an acceptable tolerances.