Theoretical and experimental studies on the thermal decomposition of 1-butyl-3-methylimidazolium dibutyl phosphate

Ionic liquid, an organic molten salt, has efficient flame-retardant performance. Few researchers have attempted to study its flame-retardant mechanism. Moreover, thermal stability and pyrolysis products have a great impact on the flame retardancy. Therefore, this paper focused on the phosphate ionic liquid of 1-butyl-3-methylimidazolium dibutyl phosphate ([Bmim][DBP]) and analyzed its thermal decomposition products and characteristics. The major bond energies of [Bmim][DBP] were calculated using B3LYP/6–311++G(d,p)//M06–2X/6–311++G(d,p) level. The experimental results show that the pyrolysis products were as followed: alkane or alkene with a carbon chain length of 1–4; imidazole and its derivatives; esters. Furthermore, Gas chromatography-mass spectrometer and Fourier transform infrared spectrometer were utilized to measure the gaseous products and solid phase products of [Bmim][DBP], which were obtained during thermogravimetric analysis. The results of theoretical and experimental analysis were highly consistent. Finally, the possible flame-retardant mechanism of [Bmim][DBP] was proposed.     

Peculiar effect of acylamino and cyan groups on thermal behavior of 2-(1-cyano-1-methylethyl)azocarboxamide

2-(1-Cyano-1-methylethyl)azocarboxamide (CABN) is a representative of new-type azo initiator in the radical polymerization industry. The peculiar water and oil soluble characters make it a versatile rising star for the industry to initiate the polymerization of monomers in either polar or nonpolar solvents based continuous phases. This paper decodes the effect of acylamino and cyan groups on thermal stability and hazards of CABN via advanced thermokinetic analysis and numerical simulation. Initially, simultaneous thermogravimetric analyzer was employed to evaluate the thermal stability of CABN and its two structurally similar azo compounds (azos), azobisisobutyronitrile (AIBN) and azodicarbonamide (AC). Followed with calorimetric experiments by differential scanning calorimetry, the effect of two functional groups on thermal behavior parameters, such as decomposition temperature, melting point, and heat of decomposition was estimated. The results indicated that the acylamino group can improve the thermal stability of CABN but with bulkier heat release. Ultimately, through the medium of thermokinetic analysis, the thermal hazard of AIBN, CABN, and AC was simulated based on auto-ignition and thermal explosion theory. The research results would provide references for the synthesis of new-type azo initiators and process safety parameters to the polymerization industry.     

Evaluation of thermal properties and process hazard of three ionic liquids through thermodynamic calculations and equilibrium methods

Industrial and new energy applications of ionic liquids (ILs) may have to be used at high temperatures conditions, such as in batteries and fuel applications, which may cause thermal hazards. However, there are few studies on the thermal hazards of ILs. To ensure the thermal safety of ILs processes, three commonly used ILs were selected for analysis: 1-butyl-3-methylimidazolium nitrate ([Bmim]NO₃), 1-butyl-2,3-dimethylimidazolium nitrate ([Bmmim]NO₃), and 1,3-dimethylimidazolium nitrate ([Mmim]NO₃). The process hazards under adiabatic conditions demonstrated that [Bmmim]NO₃ and [Mmim]NO₃ have extensive explosion hazards. The self-reaction characteristics determined by the isothermal test indicated that the ILs are nth reactions, and the thermal decomposition features were also determined by thermogravimetric analysis. The data were obtained with a nonlinear thermodynamic model and used to establish the basic thermal hazards of the three ILs. In addition, based on the thermal equilibrium theory, the critical safety parameters can be inferred. The effects of heat transfer in 25.0 g and 50.0 g containers were discussed. The results show that [Mmim]NO₃ will produce a thermal runaway reaction at a lower temperature (<100 °C) and has the shortest reaction time (<1 day), which means [Mmim]NO₃ is considered to be the most hazardous material among the three ILs studied.     

Effectiveness and application of modified wind turbine coating: Adding ionic liquids to titanium dioxide and diatomaceous earth

Wind turbines are a green energy source that Taiwan has been endeavouring to develop in the past five years. Excellent onshore wind farms have already been developed; however, offshore development is inevitable because of Taiwan's limited land area. With regard to energy sustainability, operation and trouble-free maintenance of wind farms are essential. If damage to fan components can be mostly prevented, the operating cost and maintenance time would be considerably decreased; thus, remarkable economic benefits could be achieved. An appropriate coating can help a structure resist the stress of the working environment and improve its durability, resulting in lower maintenance cost and less staff being required to perform on-site repairs. Diatomaceous earth (DE) has been widely used to produce composite porous materials. In this study, epoxy resin and titanium dioxide were mixed with DE to increase the hydrophobicity of the surface of coatings and provide them photocatalytic self-cleaning ability. The ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate was also added to the coatings to prevent the corrosion of coated metallic material. This study employed thermal analysis to investigate the thermal stability of the coatings and the corrosion resistance of coated iron blocks. Finally, a self-made quartz container was connected to a volatile organic compound detector, and sun exposure was simulated using ultraviolet light. The results confirmed that the modified coating retained its functionality under the harsh working environment and can be applied to the surfaces of large machinery used in offshore wind turbine towers.     

季铵盐离子液体改性活性炭及其热安全性研究*

为进一步提高活性炭对VOCs的吸附性能和热安全性,采用铵盐类离子液体改性原始活性炭,优化其理化性质。结果表明:改性活性炭表面生成新的无机盐化合物,C=O、-OH、C-O、-COOH和C-S基团增加;孔隙结构增多且分布均匀,比表面积及微孔体积增大;改性后活性炭对甲苯的吸附量提高3.14倍,吸附效率明显提升;在固定碳的燃烧阶段,改性活性炭活化能为54.44 kJ·mol-1,是改性前活性炭的1.38倍,活化能增大,物质稳定性增强;当粒径为120~150目及200目以上时,改性前后活性炭的自燃温度分别从328.4 ℃、319.3 ℃增长至355.1 ℃、345.7 ℃。因此,负载季铵盐离子液体可有效提高活性炭吸附性能和热安全性,研究结果可为优化VOCs处理工艺提供参考。     

基于QSPR方法的活性化合物热稳定性预测研究

为形成安全、可靠、便捷的活性化合物热稳定性预测方法,快速获取活性化合物热稳定性参数,采用定量结构-性质相关性(QSPR)方法,针对38种有机过氧化物和104种硝基化合物的起始放热温度和分解热,结合遗传函数算法(GFA)和“断点原则”筛选出的分子描述符,利用遗传算法(GA)优化的BP神经网络,建立活性化合物的热稳定性GA-BP预测模型,验证分析模型的性能和应用域。研究结果表明:所建立的GA-BP模型具有良好的拟合能力、稳定性和预测能力,优于线性模型,说明活性化合物热稳定性与分子结构之间存在非线性关系;同时,得出影响活性化合物热稳定性参数的主要结构因素。     

氯离子浓度对硝酸基复合肥水溶液热安全性影响研究

为了研究复合肥洗涤液中氯离子浓度对硝酸基复合肥水溶液热稳定性影响,利用自行研制的临界爆炸测试装置对硝酸基复合肥水溶液的热安全性进行测试。结果表明,不同浓度氯离子对硝酸基复合肥水溶液临界爆炸温度影响较大,复合肥水溶液的分解温度随着氯离子浓度的增大呈先降低后升高的趋势。研究结果对硝酸基复合肥的安全生产具有指导意义。     

Validation of liquid nitrogen vaporisation rate by small scale experiments and analysis of the conductive heat flux from the concrete

The vaporisation of a liquid nitrogen pool spilled on concrete ground was investigated in small scale field experiments. The pool vaporisation rate and the heat transfer from the concrete ground were measured using a balance and a set of embedded heat flux sensors and thermocouples. The ability to predict the concrete's thermal properties based on these measurements was investigated. This work showed that a simple, one-dimensional theoretical model, assuming heat conduction through a semi-infinite ground with ideal contact between the cryogenic liquid and the ground, commonly used to describe the heat transfer from a ground to the LNG, can be used to match the observed vaporisation rate. Though estimated parameters, thermal conductivity and thermal diffusivity, do not necessary represent real values. Although the observed vaporization rate follows a linear trend, and thus can be well represented by the model, the overall model prediction seems to be overestimated. The temperature profile inside the concrete is slightly over-predicted at the beginning and under-predicted at later stage of the spill. This might be an effect of the dependence of the concrete's thermal properties on the temperature or may indicate an incorrect modelling and a varying temperature of the ground surface.     

二叔丁基过氧化物的热失控动力学研究

为研究二叔丁基过氧化物(DTBP)热失控危险性,利用C600微量量热仪对DTBP热分解动力学进行试验研究,测定DTBP在不同升温速率下的起始放热温度和分解热,分别用非等转化率法和等转化率法得到DTBP热分解反应的动力学参数。用非等转化率法确定反应的最佳反应级数为1,相应的活化能分别为137.75、132.60、128.61和122.93 kJ/mol,指前因子分别为8.82×1012、6.69×1012、2.06×1012和3.89×10111/s。用等转化率法确定的活化能范围为102～138 kJ/mol,并拟合出活化能与转化率的关系曲线。结合计算出的动力学参数,通过对DTBP分解机理的分析,可以推断其具有热失控危险性。     

Green thermal analysis for predicting thermal hazard of storage and transportation safety for tert-butyl peroxybenzoate

Liquid organic peroxides, such as tert-butyl peroxybenzoate (TBPB), have been widely employed in the petrifaction industry as a polymerization formation agent. This study investigated the thermokinetic parameters of TBPB by isothermal kinetic algorithms and non-isothermal kinetic equations, using thermal activity monitor III (TAM III) and differential scanning calorimetry (DSC), respectively. Simulations of 0.5 L, 25 kg, 55 gallon, and 400 kg reactors in liquid thermal explosion models were performed and compared to the results in the literature. A green thermal analysis was developed for a reactor containing TBPB to prevent pollution and reduce the energy consumption by thermal decomposition. It is based on the thermal hazard properties, such as the heat of decomposition (ΔH_d), activation energy (E_a), self-accelerating decomposition temperature (SADT), control temperature (CT), emergency temperature (ET), and critical temperature (TCR). From the experimental results, the optimal conditions to avoid violent runaway reactions during the storage and transportation of TBPB were determined.     

The thermal hazard evaluation of 1,1-di (tert-butylperoxy) cyclohexane by DSC using non-isothermal and isothermal-kinetic simulations

1,1-Di (tert-butylperoxy) cyclohexane (DTBPH) has been widely employed in the chemical industry. Unfortunately, organic peroxides have been involved in many serious fires and explosions in manufacturing processes, storage, and transportation. This study investigated the thermokinetic parameters by isothermal kinetic and non-isothermal-kinetic simulation, using differential scanning calorimetry (DSC) tests. DSC was applied to assess the kinetic parameters, such as kinetic model, frequency factor (ln k₀), activation energy (E_a), reaction order, and heat of reaction (ΔH_d). Comparisons of non-isothermal and isothermal-kinetic model simulation led to a beneficial kinetic model of thermal decomposition to predict the thermal hazard of DTBPH. Simulations of a 0.5 L Dewar vessel and 25 kg barrel commercial package in liquid thermal explosion models were performed and compared to the results in the literature. From the results, the optimal conditions for use of DTBPH to avoid violent runaway reactions during the storage and transportation were determined. This study established the features of thermal decomposition that could be executed as a reduction of energy potential and storage conditions in view of loss prevention.     

咪唑类离子液体捕集CO_2性能的定量结构-性质相关性(QSPR)研究

CO_2是主要的温室气体,大量CO_2的存在严重影响着人类的生存环境和生态平衡,而咪唑型离子液体具有独特的气体溶解性,在CO_2的捕集分离中有很好的应用前景。基于定量结构-性质相关性(QSPR)原理,研究了咪唑类离子液体捕集CO_2的性能与其结构参数之间的内在定量关系。应用遗传算法获得与捕集量最为密切相关的一组描述符作为输入参数,随后,分别采用多元线性回归算法及支持向量机结合粒子群优化算法建立了咪唑类离子液体捕集CO_2的性能与其描述符之间的线性和非线性模型。多元线性回归算法得出训练集和测试集的复相关系数分别为0.765和0.814,支持向量机算法得出训练集和测试集的复相关系数分别为0.987和0.933。对预测模型进行了评价验证以及稳定性分析,结果表明,2种模型具有良好的稳定性能和预测能力。     

Essential hazard and process safety assessment of para-toluene sulfonic acid through calorimetry and advanced thermokinetics

Para-toluene sulfonic acid is a typical intermediary for the synthesis of pharmaceuticals, pesticides, and dyes and is a catalyst for organic synthesis. The consumption of para-toluene sulfonic acid used in organic synthesis has increased substantially. The toluene sulfonation process is the central path for synthesizing para-toluene sulfonic acid in China. However, the process has risks and has resulted in numerous disasters. This study utilized a reaction calorimeter 1 to reproduce the commercial toluene sulfonation process in a laboratory. The para-toluene sulfonic acid product was examined with an accelerating rate calorimeter and through differential scanning calorimetry. Both differential and integral isoconversional methods were used to determine the thermal stability of and appropriate thermokinetic models for para-toluene sulfonic acid. The safety parameters of para-toluene sulfonic acid were estimated. The research findings can be used for optimization of the toluene sulfonation process and for safe handling of para-toluene sulfonic acid.     

Synthesis of tributyl citrate using acid ionic liquid as catalyst

Synthesis of tributyl citrate (TBC) has been studied by using acid functionalized ionic liquid as catalyst. The results indicated that acidic ionic liquids show good catalytic and reusable performance. Under the optimum conditions, using 1-methyl-3-(3-sulfopropyl)-imidazolium hydrogen sulfate as catalyst, the conversion of citric acid was 97%. After easily separated from the products the ionic liquid could be reused 13 times without any disposal, and the conversion of citric acid was not less than 93%. Therefore, an environmental friendly approach for the synthesis of tributyl citrate is provided.     

Flammability hazard analysis of imidazolium-based ionic liquid binary mixtures under high temperatures

Ionic liquid (IL) mixtures are promising because they can optimize the involved properties according to industrial needs. It has already been demonstrated that IL flammability is due mainly to IL decomposition generating flammable substances. Four different ILs, 1-Butylimidazolium tetrafluoroborate ([BIM][BF₄]), 1-butylimidazolium nitrate ([BIM][NO₃]), 1-butyl-3-methylimidazolium tetrafluoroborate([BMIM][BF₄]), and 1-butyl-3-methylimidazolium nitrate ([BMIM][NO₃]), were selected as the parent salts to form the different imidazolium-based IL binary mixtures. These mixtures were tested via isothermal thermogravimetric analyzer (TGA) at different temperatures (120, 150, 180, 210, and 240 °C), then tested by the flash point analyzer after isothermal heating pretreatment at the above temperatures. Results show that the mixtures' flash point values decrease with the heating temperature increase. Vaporization of the IL mixtures’ decomposition products results in a higher concentration of flammable gases and a flash point decrease, which lead to the flammability hazard increasing. Moreover, results show that the flash points of the studied binary imidazolium IL mixtures are more similar to those of the more unstable IL in their parent ILs. Also, the flammability hazard of IL binary mixtures may obviously increase under the high temperature environment for a long time.     

水成膜泡沫对变压器油池火的窒息特性研究

水成膜泡沫在油类表面的窒息作用是扑灭油类火灾的重要机理之一,针对自行开发的快速型泡沫灭火剂开展了其对油池火的窒息灭火特性研究。首先通过老化试验测试了泡沫液的热稳定性,然后对比了不同成分泡沫液在25＃变压器油表面的铺展特性,之后研究了不同发泡倍率和成分的泡沫液对油池火的窒息灭火效果及影响规律。研究发现,铺展性能不佳的泡沫液会逐渐丧失窒息能力,而铺展性能优异的泡沫液能持续发挥窒息作用。提升泡沫液热稳定性有利于在油面形成稳定的液膜,隔绝氧气并降低可燃分子挥发速率。此外,发泡倍率较低的泡沫液的流动性更强,在相同液体流量条件下低倍数泡沫的窒息灭火效果更优。自研的快速型泡沫灭火剂在热稳定性和铺展性能两方面均具备优良的性能,因此其窒息灭火效率和抗复燃能力优于现有的大部分同类泡沫灭火剂。     

Toxicity of some phenolic derivatives--in vitro studies.

Cytotoxicity of 5 phenol derivatives (phenol, catechol, resorcinol, hydroquinone and phloroglucinol) was tested using a mouse 3T3 fibroblast cell line. Its relationships with structural and physicochemical properties were investigated. Linear regression analysis and Pearson's correlation coefficient were used to characterise the relationship between cytotoxicity (expressed by IC(50) values) and physicochemical parameters of compounds or their toxicity in vivo expressed by LD(50) values. The studies showed that physicochemical properties of compounds seemed to have less influence on their cytotoxic potency than structural properties. Cytotoxicity of the compounds probably depends on the number of -OH groups and their location in the aromatic ring more than on physicochemical properties of compounds. The best correlation was obtained for IC(50) values and LD(50) values determined following rabbit skin administration and experimental skin irritation score.     

活性化合物热稳定性预测技术研究进展

为了研究活性化合物热稳定性预测技术,调研了国内外活性化合物热稳定性预测技术的发展情况,综述了活性化合物起始放热温度、分解热、自加速分解温度的预测方法,着重介绍了定量结构-性质相关性（QSPR）研究方法在热稳定性预测领域的应用情况,分析了活性化合物热稳定性预测早期研究情况。基于量子力学计算的QSPR研究情况、QSPR数据样本的选取、分子描述符的选取、QSPR建模方法的选择,提出了热稳定性QSPR预测领域中存在的问题,并对热稳定性QSPR预测技术未来的发展方向进行了展望。     

Process hazard assessment of energetic ionic liquid with kinetic evaluation and thermal equilibrium

With the continuous development of battery technology, there are new research investments in materials of various parts. In the field of electrolytes, ionic liquids (IL) are considered to be excellent electrolytes and have been widely studied in distinct energy fields. However, it is necessary to pay attention to the safety characteristics of ionic liquids at high temperature due to the application of energy, but there is little research on the reaction and kinetics of ionic liquids. To ensure the safety of ionic liquids, such as high temperature, the common ionic liquid 1-Ethyl-3-methylimidazolium nitrate ([Emim] NO₃) was selected for analysis. The exothermic mode is obtained from the data of differential scanning calorimetry. The basic reaction parameters of [Emim] NO₃ were determined with thermodynamic equation simulation. For ionic liquids in the actual situation, consider adding a heat balance model to estimate its temperature change pattern and find out the hazard temperature and related safety parameters. Temperature changes were estimated by constructing 25.0 g and 50.0 g packages to simulate material reactions and heat transfer in the external environment. The results showed that [Emim] NO₃ had shorter TMR_ad and TCL (<1 day) when the temperature was above 180 °C.     

An experimental and modeling study of continuous liquid fuel spill fires on water

The spread of burning fuel spilled from oil product containers during offshore storage and transportation may cause large damage and trigger further accidents. Some analytical models already exist to predict the spread and burning behavior of liquid fuel spill fires, however, few experimental studies have been conducted to verify the model results. In this paper, continuous n-heptane spill fire experiments were conducted in a rectangular trench covered with water. The burning area, fuel spread rate, and thermal flux with different discharge flow rates and ignition delay times were investigated by both experimental and modeling means. The spill fire burning area, with 5 typical phases during burning, has a quasi-steady value which is directly proportional to the discharge rate but irrelevant to the ignition delay times. The steady burning rate, as the ratio of discharge rate over burning area, was estimated. A spread model was modified to simulate the spread of continuous liquid fuel spill fires in a one-dimensional channel, based on the balance between gravity and viscous forces. A cuboid solid flame model was used to compute the thermal flux from spill fires. The burning fuel spread and the heat flux calculated by the models agree with the experimental results.