水溶性巯基壳聚糖对污染土壤吸附态汞的解吸作用研究

用两种巯基化试剂半胱氨酸(Cys)和硫代乙醇酸(Thi)与壳聚糖(CTS)反应,制备了两种水溶性巯基壳聚糖,即Cys-CTS和Thi-CTS,对比研究了这两种巯基壳聚糖与CTS对被染毒土壤中吸附态汞的提取能力.结果表明,Thi-CTS在pH=3、质量浓度为0.5g/L、用量为20 mL的条件下.对汞的提取率为59.44%,相同条件下CTS和cys-CTS对汞的最高提取率只有31.81%和10.15%.     

不同给水管材对管壁附着生物膜铅、镉的解吸动力学研究

给水管壁生物膜会吸附水中的重金属元素积累在管壁生物膜中,在受到扰动时释放回到水体,危害饮用水水质安全。试验以上海管网末梢水为实验对象,研究了PVC、铸铁和紫铜等三种管材上生物膜对铅、镉的解吸特性。结果表明,PVC、铸铁和紫铜附着生物膜对铅的解吸容量qe分别为:5.92211μmol·m^-2、128.3051μmol·m^-2和21.1808,解吸速率常数k分别为:0.001060 m^2·μmol^-1·min^-1、0.000041 m^2·μmol^-1·min^-1和0.000503 m^2·μmol^-1·min^-1,对于镉元素三种材质的解吸容量qe分别为:14.71519μmol·m^-2、18.50481μmol·m^-2和2.25225μmol·m^-2;解吸速率常数k分别为:0.000102 m^2·μmol^-1·min^-1、0.001070 m^2·μmol^-1·min^-1和0.000103 m^2·μmol^-1·min^-1。     

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.     

水稻和玉米的热氧化分解特性及几种动力学方法结果的比较

利用热重分析仪在空气气氛、不同的升温速率下对带壳稻谷粉和玉米粒粉进行了热重测试,依据热重实验数据,采用多种热解动力学分析方法计算了水稻和玉米的活化能数值并进行比较,结果表明水稻和玉米的热氧化反应活化能随着转化率出现先增加后降低的趋势,并在转化率为70%左右达到了极大值。     

太空环境下锂离子电池热失控与火灾的研究展望

综述了锂离子电池的热失控机理,介绍了由于电池内部电解液、电池隔膜和电极材料分解的链式热反应过程而引发的热失控和火灾现象。同时,讨论了锂离子电池在微重力太空环境中可能产生的烟黑浓度倍增,加速火蔓延,火焰喷射等极端火行为。进而探讨了开展锂离子电池的低压、落塔和抛物飞行等地面实验模拟太空微重力燃烧的方法可行性,建立数值模型预测太空微重力环境下锂离子电池热失控临界条件与火灾行为的必要性,以及如何通过基础研究科学地指导空间站电池热管理和消防系统的设计。     

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.     

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.     

Hazard evaluation for chlorination and amination reactions of fluorocytosine production process

Reaction thermal runaway is one of the most important reasons leading to chemical accidents. With the rapid development of the chemical industry in the world, especially the fine chemical industry, various safety accidents also occur frequently. Therefore, it is necessary to study the exothermic behavior of the reaction process. In this study, reaction calorimeter was used to study the exothermic phenomena during the chlorination reaction and amination reaction. Differential scanning calorimetry was performed on the reactants, and thermogravimetric experiments were performed on the products. In addition, adiabatic experiment was performed to study the thermal runaway behavior of amination products under adiabatic conditions. The results showed that the target reactions generated a large amount of heat in the initial stage. The maximum temperature of amination reaction is higher than the initial decomposition temperature of the amination product under adiabatic condition. The pyrolysis of amination product was divided into three stages. The product had a high apparent activation energy at the beginning of decomposition, and the apparent activation energy decreased as the decomposition progressed.     

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。