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.     

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.     

Case study on prevention of fire hazards in coating epoxy-based FRP work with illumination

In this study, we investigated and analyzed the causes of fire hazards on the basis of actual accidents that occurred during epoxy resin fiberglass-coating operations. Results of this study showed that during this process, two major factors could cause a fire. One factor was related to the heat produced during the mixing of the epoxy resin and a polyamide curing agent. From the results of thermal analysis, it was found that the T_onset of the epoxy resin and the polyamide curing agent was 52.8 °C by DSC and T_d10 was 58.9 °C by DT/TGA, causing an exothermic hazard. Further, the results of a pseudo-adiabatic analysis performed in a Dewar vessel showed that the temperature increased from 23.5 °C to 177 °C.The other factor that could increase fire hazard was the illumination source used during the coating operation. Depending on the type of illumination source used, the temperature could increase above 350 °C. The decomposition temperature (T_d10) of PVC was 276.3 °C. The experiments involving epoxy resin fiberglass coating using an illumination source showed serious burn marks, and the polyvinyl chloride (PVC) electrical cable emitted small flames. Therefore, it can be concluded that fire was caused by the combination of two factors—the exothermic reaction between epoxy resin and the polyamide curing agent and the effect of prolonged illumination, both of which caused an increase in temperature leading to auto-ignition of the PVC electric cable.     

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.     

Experimental hazardous risk investigation of energetic styphnic acid analytical reagent in calorimetric analysis

Analytical reagents identify and manage metal pollution, a major environmental issue. Regrettably, these compounds' safety concerns, especially when heated, have been neglected. This research examines the thermal hazard of the extremely reactive analytical reagent styphnic acid. Differential scanning calorimetry, thermogravimetric analysis, and accelerating rate calorimetry examined styphnic acid's thermodynamics. Thermogravimetric analysis showed weight loss reactions starting at 127 °C and peaking at 208 °C. Differential scanning calorimetry showed an endothermic peak at 176 °C. The accelerating rate calorimetry test showed that styphnic acid self-accelerates at 237 °C after 196.5 °C. Kissinger, Ozawa-Flynn-Wall, and Kissinger-Akahira-Sunose thermokinetic models calculated apparent activation energy from 131.677 to 155.718 kJ/mol. A nonlinear regression analysis showed that styphnic acid undergoes a two-step autocatalytic reaction during heat degradation. Thermal safety was assessed by measuring time to conversion limit, maximum rate, total energy release, self-accelerating decomposition temperature, and adiabatic temperature rise. Styphnic acid is less stable at higher temperatures and its thermal hazards depend on heating rate. The computed SADT was 109.04 °C, with alarm and control temperatures of 104.04 and 99.04 °C, respectively. The risk matrix analysis based on T_ad and TMR_ad suggests reducing thermal instability. This study on styphnic acid's thermal risks and safe storage and transit during analytical applications is beneficial.     

Imidazolium based ionic liquids affecting functional groups and oxidation properties of bituminous coal

Low temperature oxidation of coal will result in coal spontaneous combustion in mined-out areas. We proposed to use ionic liquids to inhibit the coal spontaneous combustion in this paper. In order to study the inhibiting effect of ionic liquid (IL) on coal oxidation, we successfully dissolved bituminous coal samples in six kinds of imidazolium based ionic liquids, [AOEmim][BF₄], [HOEmim][BF₄], [Amim][Cl], [Emim][AC], [Bmim][AC] and [Bmim][OTf]. The functional groups in the coal samples pre-treated by different ILs were detected by Fourier Transform Infrared Spectroscopy (FTIR) in detail. It is found that the ILs are capable of breaking the associated hydroxyls into dissociated hydroxyls. And during the interaction between coal and ILs, the carboxyl groups have been created. Thermo Gravimetric experiment results show that the weight loss ratios of the IL-treated coals were less during 20–400 °C stage, compared with the IL-untreated coal, which indicates that most of the easily reductive groups effectively dissolved in the ionic liquids. According to the exothermic rate curves and the computed activation energy values, it is demonstrated that the [Bmim][OTf] and [Bmim][AC] make better effect than the other ILs for depressing the oxidation rate of bituminous coal.     

Thermal characterization of fly ash from one municipal solid waste incinerator (MSWI) in Shanghai

This study aims to develop a methodology for the thermal characterization of MSWI fly ash. We performed TGA–DTA and component variation analysis, microstructure transfer of sintered fly ash, as well as leaching toxicity, volatilization ratio and specification transformation of heavy metals as a function of temperature. It is found that content of crystal phases first increases between room temperature and 800 °C and then decreases between 800 °C and 1200 °C, while that of glass phases registers a reverse trend. Fly ash registers a SiO₂–Al₂O₃–metal oxides system and its content of glass phases is around 57%. Increase of sintering temperature between 600 °C and 1200 °C is conducive to the reduction of soluble As, Cd, Cu, Hg, Pb, Ni and Zn, while content of soluble Cr increases as temperature rises from 800 °C to 1200 °C.     

Flammability estimation of 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

Ionic liquids (ILs) are known as room temperature molten salts, which are considered green replacement to traditional organic solvents. The fire hazards of traditional organic solvents mainly depend on the combustibility of their vapors, thus ILs are generally regarded as nonflammable owing to their low volatility. However, recent studies show that ILs may combust due to the potential hazards of thermal decomposition, indicating the issue of fire and explosion of ILs are eager to be evaluated during the applications. In this study, the fire and explosion hazards of IL 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C₆mim][NTf₂]) are explored in different aspects. The traditional definition of the flammability for the common organic solvent is not thoroughly applicable to [C₆mim][NTf₂] due to the low volatility. Furthermore, the common definition of reactivity for traditional organic solvents also fails to apply, because the decomposition reaction is indeed an endothermic reaction. However, the auto-ignition of some decomposition products will result in fire and explosion hazards for [C₆mim][NTf₂]. Therefore the application of such data in safety purposes should be very careful.     

Simultaneous photocatalytic treatment of Cr(VI), Ni(II) and SDBS in aqueous solutions: Evaluation of removal efficiency and energy consumption

Simultaneous photocatalytic reduction of poisonous Cr(VI) and Ni(II) ions, coupled with photocatalytic oxidation of sodium dodecyl benzene sulfonate (SDBS) were studied with a trace amount of commercial titania nanoparticles and by means of a direct-photo-irradiation reactor. The co-presence of metal ions and SDBS causes metal ions reduction as well as SDBS oxidation to enhance and energy efficiency to improve. XRD, XPS and FTIR analysis were used to characterize TiO₂ particles before and after usage with the aim of evaluating the mechanism of reactions. The effect of major operating parameters, pH and temperature, was investigated. Under conditions of [Cr(VI)]₀ = [Ni(II)]₀ = 5 mg/L, [SDBS]₀ = 10 mg/L, [TiO₂] = 40 mg/L, pH 6 and T = 35 °C; the removal efficiencies of 55.4%, 71.2% and 57.2% were obtained, respectively, for Cr(VI) and Ni(II) reduction, as well as for SDBS oxidation, after 110 min operation. The relevant kinetic model jointed with the Arrhenius equation was introduced. Pseudo-first-order reactions are relevant. Energy consumption (electrical and thermal) evaluations revealed that operations at higher temperatures provide significant cost reduction. Meantime, a criterion was proposed for a consistent assessment of this kind of processes.     

Research on the critical temperature of thermal decomposition for large cartridge emulsion explosives

Emulsion explosives are one type of main industrial explosives. The emergence of the large cartridge emulsion explosives has brought new security incidents. The differential scanning calorimeter (DSC) and the accelerating rate calorimeter (ARC) were selected for the preliminary investigation of the thermal stability of emulsion explosives. The results showed that the initial thermal decomposition temperatures were in the range of 232–239 °C in nitrogen atmosphere (220–232 °C in oxygen atmosphere) in DSC measurements and 216 °C in ARC measurements. The slow cook-off experiments were carried out to investigate the critical temperature of the thermal decomposition (T_c) of the large cartridge emulsion explosives. The results indicated that the larger the diameter of the emulsion explosives, the smaller the T_c is. For the large cartridge emulsion explosives with diameter of 70 mm, the T_c was 170 °C at the heating rate of 3 °C h⁻¹. It is a dangerous temperature for the production of the large cartridge emulsion explosives and it should cause our attention.     

Thermal hazard evaluation for iso-octanol nitration with mixed acid

2-Ethylhexyl nitrate (2-EHN), an important additive to diesel fuel, is produced from the nitration of iso-octanol with HNO₃–H₂SO₄ mixed acid. In this study, the differential scanning calorimeter (DSC), accelerating rate calorimeter (ARC) and reaction calorimeter were used to analyze the thermal stability of 2-EHN and the thermal hazard of iso-octanol nitration. Four samples with different ratios of 2-EHN to mixed acid were tested using DSC. The results indicated that more mixed acid could catalyze the decomposition of 2-EHN. Three samples were tested using ARC and the results showed that sample 4 contained the lowest onset temperatures, T_D8 and T_D24. This shows that there is a higher probability of triggering the decomposition of the product 2-EHN from the iso-octanol nitration process. This conclusion was verified using RC1e tests at different temperatures. The RC1e experiments also indicated that the overall heat generation of these reactions was considerably large despite the high yields of the nitration process at 45 °C and 55 °C. This heat generation makes these semi-batch processes difficult to control, especially on a pilot or plant scale. Based on the maximum temperature of the synthesis reaction (MTSR) corrected by the yield, the only acceptable semi-batch process is the nitration reaction at 10 °C.     

An explosion of a tank car carrying waste hydrogen peroxide

On the Metropolitan Expressway in Tokyo, a tank car exploded because it was carrying hydrogen peroxide (H₂O₂) in a compartment in which copper chloride (CuCl₂) remained. Although the main cause of the accident was trivial, the background on the accident suggested that an induction period in the reaction led to a mistake. This report describes the experimental investigation of the catalytic ability of CuCl₂, and comparing it with two other copper(II) compounds (nitrate: Cu(NO₃)₂; and copper sulfate: CuSO₄) and three iron(III) compounds (chloride: FeCl₃; nitrate: Fe(NO₃)₃; and sulfate: Fe₂(SO₄)₃).The experiments were performed using a reaction calorimeter. During the experiments at 35 °C, 2×10⁻⁵ mol of copper compounds slowly reacted with H₂O₂ and generated a precipitate. The iron compounds allowed the hydrogen peroxide to violently decompose. A 1×10⁻⁴ mol solution of CuCl₂, however, produced a violent decomposition at 35 °C. At 15 °C, a moderate heat release occurred.Based on these results, the concentration and temperature dependence of the catalytic ability of CuCl₂ were postulated to contribute to the induction period observed in the accident.     

Preoptimal analysis of phase characteristic indicators in the entire process of coal spontaneous combustion

To accurately predict the development degree of coal spontaneous combustion (CSC), the CSC process was investigated using a programmed high-temperature-heating experimental system, and the variation law of index gas concentration in the holistic process of CSC and oxidation is formulated. Additionally, the accuracy of the experimental system was evaluated using experimental design for thermal analysis, and the correlation between gas index and apparent activation energy was determined using grey correlation analysis. The results indicated the following. In the critical temperature stage (0–100 °C), φ(CO)/φ(CO₂) should serve as the main index and C₂H₄ should serve as the auxiliary index; in the crack-active-speedup temperature stage (100–260 °C), CO and φ(C₂H₄)/φ(C₂H₆) should serve as the main index and R₁, the Graham index, and φ(C₂H₄)/φ(CH₄) should serve as auxiliary indexes; in the speedup-ignition temperature stage (260–370 °C), R₂ and the Graham index should serve as main indexes and φ(CO)/φ(CO₂), C₂H₄, and R₁ should serve as auxiliary indexes; in the ignition temperature (370–500 °C), R₃ should serve as the main index and R₂, the Graham index and C₂H₄ should serve as auxiliary indexes. Among them, the grey correlation degrees among the Graham index, Grignard fire coefficient, and apparent activation energy were the highest, reaching 0.91.     

Effect of particle size and dust layer size on ignition characteristics of PMMA dust layer on hot surface

Deposition of combustible dust on a hot surface is a hidden danger of fire. In this work, polymethylmethacrylate (PMMA) dust was selected to analyse the influence of dust layer diameter, dust particle size and dust layer thickness on the ignition characteristics of PMMA dust layer. Critical heating temperatures and ignition time had been measured. The STA-GC/MS-FTIR analysis was used to determine that the main products of PMMA pyrolysis were MMA, CO, CO₂, and C₂H₄, of which CO and C₂H₄ were transported to the ambient to cause gas phase combustion on the surface of the dust layer. For 10 mm thick dust layer, the critical heating temperatures of 5 μm PMMA, 100 nm PMMA, and 30 μm PMMA were 300 °C, 330 °C, and 320 °C. As the thickness of the dust layer increased, the gas transport path became longer, the critical heating temperature and ignition time increased. The characteristic particle size (D [3,2]) was utilized to represent the true particle size, and the ignition time increased with the increase of the characteristic particle size. The increase in the diameter of the dust layer had a slight effect on the temperature history and ignition time of the dust layer.     

An improved method of removal for high concentrations of NO by electro-scrubbing process

In the Ag(II)/Ag(I) redox mediator integrated scrubber system, NO reacts with the Ag(II) ions produced by the electrochemical oxidation of Ag(I) in an electrochemical cell present in the scrubbing solution (aqueous HNO₃ acid) to form NO₂. This NO₂ is then absorbed into the scrubbing solution and degraded to nitrate. Numerous experimental runs were carried out to evaluate the feasibility of the integrated system to treat industrial waste gases containing high NO_x levels. The results showed that the levels of NO and NO_x removal increased with increasing Ag(II) loading and contact time. Under optimized conditions, 93.5% and 73.3% of the NO and NO_x, respectively, were removed by a single stage gas scrubber with 1.62 g L^?1 Ag(II) operating at 25 °C and atmospheric pressure.     

Thermal hazard assessment for synthesis of 3-methylpyridine-N-oxide

The exothermic oxidation of 3-methylpyridine with hydrogen peroxide was analyzed by Reaction Calorimeter (RC1e) in semi-batch operation. Heat releasing rate and heat conversion were studied at different operating conditions, such as reaction temperature, feeding rate, the amount of catalyst and so on. The thermal hazard assessment of the oxidation was derived from the calorimetric data, such as adiabatic temperature rise (ΔT_ad) and the maximum temperature of synthesis reaction (MTSR) in out of control conditions. Along with thermal decomposition of the product, the possibility of secondary decomposition under runaway conditions was analyzed by time to maximum rate (TMR_ad). Also, risk matrix was used to assess the risk of the reaction. Results indicated that with the increase of the reaction temperature, the reaction heat release rate increased, while reaction time and exotherm decreased. With the increase of feeding time, heat releasing rate decreased, but reaction time and exotherm increased. With the amount of the catalyst increased, heat releasing rate increased, reaction time decreased and exothermic heat increased. The risk matrix showed that when the reaction temperature was 70 °C, feeding time was 1 h, and the amount of catalyst was 10 g and 15 g, respectively, the reaction risk was high and must be reduced.     

Investigation on removal of p-nitrophenol using a hybridized photo-thermal activated persulfate process: Central composite design modeling

The aim of this work is the study of p-nitrophenol (PNP) removal, as a nitroaromatic compound, using a hybridized photo-thermally activated potassium persulfate (KPS) in a fully recycled batch reactor. Response surface method was used for modeling the process. Reaction temperature, KPS initial dosage and initial pH of the solution were selected as variables, besides PNP degradation efficiency was selected as the response. ANOVA analysis reveals that a second order polynomial model with F-value of 41.7, p-value of 0.0001 and regression coefficient of 0.95 is able to predict the response. Based on the model, the process optimum conditions were introduced as initial pH of 4.5, [KPS]₀ = 1452 mg/L and T = 66 °C. Also experiments showed that using thermolysis and photolysis of the persulfate simultaneously, the role of thermolysis is not considerable. A pseudo first order kinetic model was established to describe the degradation reaction. Operational cost, as a vital industrial criterion, was estimated so that the condition of initial pH of 4.5, [KPS]₀ = 1452 mg/L and T = 25 °C showed the highest cost effective case. Under the preferred mild condition, the process will reach to 84% and 89% of degradation and mineralization efficiencies, after 60 and 120 min, respectively.     

Synthesis of Bio-Diesel and Bio-Lubricant by Transesterification of Vegetable Oil with Lower and Higher Alcohols Over Heteropolyacids Supported by Clay (K-10)

The use of different lower and higher alcohols viz; methanol, ethanol, n-propanol and n-octanol, for the synthesis of methyl, ethyl, propyl and octyl fatty acid esters by transesterification of vegetable oil (triglycerides) with respective alcohols also known as ‘Bio-diesel’ and ‘Bio-lubricants’ was studied in detail. The reactions were carried out in a batch process. The activity with different supports like clay (K-10), activated carbon, ZSM-5, H-beta and TS-1 were compared. The superacids (heteropolyacids, HPA) viz; Dodeca-Tungstophosphoric acid [H₃PO₄·12 WO₃·xH₂O] (TPA) and Dodeca-Molybdo phosphoric acid ammonium salt hydrate [H₁₂Mo₁₂N_3-O₄₀P + aq] (DMAA) was used to increase the acidity and so the activity by loading on the most active support viz; clay (K-10). These HPA loaded on clay as a catalyst was used for the following study: effect of percent HPA loading on clay, effect of different vegetable oils, effect of different alcohols on the triglyceride conversion based on glycerol formation and selectivity based on alkyl esters formation. The data is compared at the best-optimized identical set of operating reaction conditions: 170 °C, 170 rpm, catalyst loading: 5% (w/w of reaction mixture), molar ratio (oil: alcohol): 1:15 and time on stream of 8 h. The generated data is also evaluated based on the reported one.     

Partial nitritation of landfill leachate with varying influent composition under intermittent aeration conditions

The start-up and operation of a partial nitritation sequencing batch reactor for the treatment of landfill leachate were carried out on intermittent aeration mode. Partial nitrite accumulation was established in 15 days after the mode was changed from continuous aeration to intermittent aeration. Despite the varying influent composition, partial nitritation could be maintained by adjusting the hydraulic retention time (HRT) and the air flow rate. An increase in the air flow rate together with a decrease in air off duration can improve the partial nitritation capacity and eventually result in the development of granular sludge with fine diameters. A nitrogen loading rate of 0.71 ± 0.14 kg/m³/d and a COD removal rate of 2.21 ± 0.13 kg/m³/d were achieved under the conditions of an air flow rate of 19.36 ± 1.71 m³ air/m³/h and an air on/off duration of 1.5 min/0.7 min. When the ratio of total air flux (TAF) to the influent loading rate (ILR) was controlled at the range of 163–256 m³ air/kg COD, a stable effluent NO₃^?–N/NO_x^?–N (NO₂^?–N plus NO₃^?–N) ratio below 13% was achieved. Interestingly, the effluent pH was found to be a good indicator of the effluent NO₂^?–N/NH₄⁺–N ratio, which is an essential parameter for a subsequent anaerobic ammonium oxidation (Anammox) reactor.