基于火探管式的锂离子电池灭火技术研究

为研究锂离子电池灭火方案,基于火探管灭火技术同时利用新型清洁灭火剂Novec 1230,组装成火探管灭火系统。在灭火测试平台上以功率为200 W的电热管作为外热源引发单电池或电池模组热失控,通过改变火探管的布置位置,记录相应的灭火行为以及灭火效率,并对实验结果进行了分析。研究结果表明,当火探管灭火系统直接布置在电池正上方时,在起火后的5.6s内控制火情;随着灭火剂用量增加可以显著降低体系温度,防止电池复燃以及连锁热失控现象发生;火探管有效覆盖区域外的失控电池作为热源将继续加热临近电池,引发连锁热失控,造成灭火系统失效;根据电池热失控后的燃烧行为以及传热行为,提出相应的火探管灭火系统复合方案。     

Effect of pyrolysis and oxidation characteristics on lauric acid and stearic acid dust explosion hazards

The effect of pyrolysis and oxidation characteristics on the explosion sensitivity and severity parameters, including the minimum ignition energy MIE, minimum ignition temperature MIT, minimum explosion concentration MEC, maximum explosion pressure P_max, maximum rate of pressure rise (dP/dt)_max and deflagration index K_st, of lauric acid and stearic acid dust clouds was experimentally investigated. A synchronous thermal analyser was used to test the particle thermal characteristics. The functional test apparatuses including the 1.2 L Hartmann-tube apparatus, modified Godbert-Greenwald furnace, and 20 L explosion apparatus were used to test the explosion parameters. The results indicated that the rapid and slow weight loss processes of lauric acid dust followed a one-dimensional diffusion model (D1 model) and a 1.5 order chemical reaction model (F1.5 model), respectively. In addition, the rapid and slow weight loss processes of stearic acid followed a 1.5 order chemical reaction model (F1.5 model) and a three-dimensional diffusion model (D3 model), respectively, and the corresponding average apparent activation energy E and pre-exponential factor A were larger than those of lauric acid. The stearic acid dust explosion had higher values of MIE and MIT, which were mainly dependent on the higher pyrolysis and oxidation temperatures and the larger apparent activation energy E determining the slower rate of chemical bond breakage during pyrolysis and oxidation. In contrast, the lauric acid dust explosion had a higher MEC related to a smaller pre-exponential factor A with a lower amount of released reaction heat and a lower heat release rate during pyrolysis and oxidation. Additionally, due to the competition regime of the higher oxidation reaction heat release and greater consumption of oxygen during explosion, the explosion pressure P_m of the stearic acid dust was larger in low concentration ranges and decayed to an even smaller pressure than with lauric acid when the concentration exceeded 500 g/m³. The rate of explosion pressure rise (dP/dt)_m of the stearic acid dust was always larger in the experimental concentration range. The stearic acid dust explosion possessed a higher P_max, (dP/dt)_max and K_st mainly because of a larger pre-exponential factor A related to more active sites participating in the pyrolysis and oxidation reaction. Consequently, the active chemical reaction occurred more violently, and the temperature and overpressure rose faster, indicating a higher explosion hazard class for stearic acid dust.     

Thermal decomposition mechanism of 65% lysine sulfate powder and its thermal stability based on thermal analysis

Lysine is widely used in the fields of food, medicine and feed, which generally appears in the form of lysine sulfate or lysine hydrochloride dust because of the high instability of the free L-lysine. The L-lysine Sulfate is in high risk of decomposition, spontaneous ignition and even the dust explosion, because the control temperature in its production process is high up to 90 °C. Thus, the thermal behaviors and its thermal stability of 65% lysine sulfate are experimentally explored in Air and Nitrogen using the simultaneous TG-DSC measurements. Results show: (1) the decomposition of 65% lysine sulfate can be divided into three stages both in the atmospheres of air and nitrogen, and most of the weight loss occurred in the first two stages, which are related with the decarboxylation and deamination process. (2) The effects of atmosphere on the decomposition of 65% lysine sulfate mainly occur at the third stage. In this stage, the weight loss in nitrogen is only 14.2%, which is much lower than that in air (34.3%), which is related to the oxidative degradation at high temperature. Besides, the active energy is slightly increased in nitrogen compared to that in air. (3) The initial temperatures of the decomposition of the 65% lysine sulfate are 145 °C and 155 °C, for the air and nitrogen atmosphere, respectively, which are much lower than that (260 °C) of the pure lysine.     

Inherent thermal runaway hazard evaluation method of chemical process based on fire and explosion index

Thermal runaway hazard assessment provides the basis for comparing the hazard levels of different chemical processes. To make an overall evaluation, hazard of materials and reactions should be considered. However, most existing methods didn't take the both into account simultaneously, which may lead the assessment to a deviation from the actual hazard. Therefore, an integrated approach called Inherent Thermal-runaway Hazard Index (ITHI) was developed in this paper. Similar to Dow Fire and Explosion Index(F&EI) function, thermal runaway hazard of chemical process in ITHI was the product of material factor (MF) and risk index (RI) of reaction. MF was an indicator of material thermal hazards, which can be determined by initial reaction temperature and maximum power density. RI, which was the product of probability and severity, indicated the risk of thermal runaway during the reaction stage. Time to maximum rate under adiabatic conditions and criticality classes of scenario were used to indicate the runaway probability of the chemical process. Adiabatic temperature rise and heat of the desired reaction and secondary reaction were used to determine the severity of runaway reaction. Finally, predefined hazard classification criteria was used to classify and interpret the results obtained by this method. Moreover, the method was validated by case studies.     

Study of lignocellulosic biomass ignition properties estimation from thermogravimetric analysis

In the last decade, the use of renewable resources has increased significantly in order to reduce the energetic dependence on fossil fuels, as they have an important contribution to the global warning and greenhouse gasses effect. Because of that, research on biofuels has been increased in the last years as its characteristics of use match those of the conventional fuel's: solid biomass can be used instead of coals, and biodiesel could replace diesel. Research on solid biomass ignition properties has been considerably developed because of the amount of industrial accidents related to the treatment and use of solid biomass (self-ignition, dust explosions, etc.). On the other hand, thermogravimetric analysis (TGA) is becoming and important characterization technique as it can be used to determine a wide spectrum of properties, such as kinetics, composition, proximate analysis, etc. This research aims to combine thermal analysis and ignition properties, by using the TGA to obtain the elemental composition of lignocellulosic biomass and compare those results to Minimum Ignition Energy (MIE) values test output, so a relation between composition and MIE can be found.To achieve this aim, biomass samples from different origins have been used: oil palm wastes (empty fruit bunches, mesocarp fiber and palm kernel shell), agricultural wastes (straw chops) and forestry wastes (wood chips and wood powder). Also, raw materials and torrefied biomass were compared. The hemicellulose/cellulose ratio was calculated and compared to different flammability properties, finding out that the greater the ratio and the lower the onset temperature (temperature at which the pyrolysis reaction accelerates), the lower was the minimum ignition energy. From this basis it was possible to define “tendency areas” that grouped the samples whose MIE values were similar. Three tendency areas were found: high minimum ignition energy, medium minimum ignition energy, and low ignition energy.     

两种有机锌络合物处理棉花的霉变及热解行为研究

棉花是纺织业的重要原料,是人民群众生活不可或缺的必需品,同时也是我国进出口重要的商品。研究如何安全有效地进行棉花的储备具有十分重要的现实意义。棉纤维本身含有脂肪、蜡质和果胶等适合微生物生长繁殖的营养物质。在棉花储备中,高的回潮率会加速微生物的繁殖,进而产生热量。热量的累积会引起温度升高以及棉花霉变,不利于棉花的安全有效储存。因此,通过静电吸附法将安全无毒的有机锌络合物附着在棉纤维表面,研究表明,相同条件下,处理棉的霉变状况明显得到抑制。加速发霉条件下,未处理棉的相对于白纸的平均色差值为28.10,而双乙酸锌以及苯甲酸锌防霉处理棉的色差值分别为5.16和5.86,下降了81.6%和79.1%。自然发霉条件下,双乙酸锌以及苯甲酸锌防霉处理棉的色差值分别下降了53.8%和50.7%。同时研究了纯棉以及处理棉氮气下的热分解动力学,相比于未处理棉,双乙酸锌防霉处理后活化能下降了15.8%,而苯甲酸锌防霉处理后活化能下降了10.9%。此外,利用实时红外和热重红外联用技术得到了样品在热解过程中固相以及气相的裂解产物的红外谱图,发现防霉处理能一定程度上抑制棉花热解。     

The inhibitory combustion reaction performance and tail gas analysis of composite ultra-fine dry powder extinguishing agent containing different additives

For lack of an extinguishing agent with high-efficiency, non-toxic and environmentally friendly, a new type of extinguishing agent was fabricated to solve such an urgent problem. In this study, the zinc borate (ZB) and ferrocene (Fe(Cp)₂) were utilized as two additives for extinguishants to suppress combustion reaction and the toxicity of the tail gas was detected. The mass fraction of ZB corresponding to the optimal inhibitory effect was determined to be 0.5–1.5%, by contrast, the optimum interval of Fe(Cp)₂ was detected as 0.5–1.0%. Similarly, with the increasing proportion of the two additives, the homologous inhibitory action was gradually weakened. From the perspective of thermogravimetric analysis (TGA), it was indicated that the ZB accelerated the pyrolysis process of the extinguishant, making its thermal decomposition process more thoroughly. Meanwhile, the differential scanning calorimetry (DSC) demonstrated that the decomposition efficiency was markedly improved when the amount of ZB was maintained at 0.5–1.5%. Besides, the tail gas tests were implemented to assess the extent of toxic and harmful properties. In terms of the carbon monoxide (CO) and carbon dioxide (CO₂) generated, once the mass fraction of ZB and Fe(Cp)₂ was less than 1.5% and 1.0% respectively, the concentration of CO and CO₂ was distinctly lower than that without additives. Moreover, the inhibitory ability on nitrogen oxides (NOx) was enhanced when the mass fraction of the two additives was kept below 1.0%. The results confirmed that a more practical extinguishant was proposed and it can provide guidance for the application and development of extinguishants.     

Evaluation of thermal reaction for two azo compounds by using 20-L apparatus and calorimetry

Azo compounds are widely involved in the industrial processes of dyes, pigments, initiators, and blowing agents. Unfortunately, these compounds have a bivalent unstable –NN– composition, which can be readily broken when the ambient temperature is elevated. Self-accelerating decomposition might cause a runaway reaction and lead to a fire, explosion, or leakage when the cooling system fails or other events occur. This study investigated the explosion properties, thermal stability parameters, and thermal hazard and mechanism of 2,2′–azobisisobutyronitrile (AIBN) and 2,2′–azobis–2–methylbutyronitrile (AMBN). We used a 20-L apparatus, vent sizing package 2, synchronous thermal analysis, and differential scanning calorimetry under explosive, adiabatic, and dynamic conditions to acquire the explosive curves, thermal curves, and thermodynamic parameters of the substances. Moreover, the differential isoconversional method (Friedman method) and ASTM E698 equation were employed to obtain the apparent activation energy E_a. All the experimental results revealed that AIBN is more dangerous than AMBN. The E_a of AIBN was lower than that of AMBN. The results can be used to construct an azo compound thermal hazard database for use for searches and reference examples by industry and related research areas.     

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.     

钻屑法测定煤层H_2S含量

为了测定煤层硫化氢(H2S)含量,防治矿井H2S涌出,提出一种通过钻屑法测定煤层H2S含量的方法。在未受采动影响的新鲜煤壁,采用钻屑法取样,通过测定煤样H2S解吸量、取样过程损失量和H2S残存量确定煤层H2S含量。根据溶于水中H2S的p H值和色谱分析解吸气体中H2S体积分数,确定H2S解吸量;根据煤样解吸规律和气样H2S体积分数,确定H2S损失量;根据色谱分析残存气体中H2S体积分数,确定其残存量。用此方法,对山西某矿H2S涌出煤层进行现场和实验室测定。研究表明,该矿H2S含量为(4.465~6.701)×10-3m3/t。钻屑法测定煤层H2S含量是可行的,可以为矿井H2S治理提供基础数据。