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.     

Effect of superfine KHCO3 and ABC powder on ignition sensitivity of PMMA dust layer

In order to evaluate the flame-retardant capacity of KHCO₃ and ABC on the ignition of PMMA dust layer accumulation on hot surfaces, the ignition time and critical heating temperature of PMMA/KHCO₃ and PMMA/ABC dust layer were experimentally investigated. The thermal stability of the mixed dust, the condensed phase products and gas phase products of the mixed dust combustion were analyzed to reveal the flame-retardant mechanism. The ignition time of 30 μm PMMA was obviously longer than that of 5 μm PMMA, and the critical heating temperature was close to that of 5 μm PMMA. KHCO₃ and ABC could greatly extend the ignition time of the PMMA dust layer and increase the critical heating temperature of the dust layer. ABC was more effective than KHCO₃. The decomposition of KHCO₃ and ABC absorbed the heat and inhibits the pyrolysis of PMMA. The HPO₃ and P₂O₅ generated by the decomposition of ABC would cover the surface of PMMA aggregates or particles and act as a physical barrier. The main light combustible gas produced by PMMA pyrolysis were CO and C₂H₄. The CO₂ generated during the decomposition of KHCO₃ could dilute the combustible gas in the ambient to inhibit the combustion of PMMA.     

Pyrolysis and gasification of meat-and-bone-meal: Energy balance and GHG accounting

Meat-and-bone-meal (MBM) produced from animal waste has become an increasingly important residual fraction needing management. As biodegradable waste is routed away from landfills, thermo-chemical treatments of MBM are considered promising solution for the future. Pyrolysis and gasification of MBM were assessed based on data from three experimental lab and pilot-scale plants. Energy balances were established for the three technologies, providing different outcomes for energy recovery: bio-oil was the main product for the pyrolysis system, while syngas and a solid fraction of biochar were the main products in the gasification system. These products can be used – eventually after upgrading – for energy production, thereby offsetting energy production elsewhere in the system. Greenhouse gases (GHG) accounting of the technologies showed that all three options provided overall GHG savings in the order of 600–1000 kg CO₂-eq. per Mg of MBM treated, mainly as a consequence of avoided fossil fuel consumption in the energy sector. Local conditions influencing the environmental performance of the three systems were identified, together with critical factors to be considered during decision-making regarding MBM management.     

Thermal degradation of hexachlorobenzene in the presence of calcium oxide at 340–400 °C

Hexachlorobenzene (HCB) in the milligram range was co-heated with calcium oxide (CaO) powder in sealed glass ampoules at 340–400 °C. The heated samples were characterized and analyzed by Raman spectroscopy, elemental analysis, gas chromatography/mass spectrometry, ion chromatography, and thermal/optical carbon analysis. The degradation products of HCB were studied at different temperatures and heated times. The amorphous carbon was firstly quantitatively evaluated and was thought to be important fate of the C element of HCB. The yield of amorphous carbon in products increased with heating time, for samples treated for 8 h at 340, 380 °C and 400 °C, the value were 17.5%, 34.8% and 50.2%, respectively. After identification of the dechlorination products, the HCB degradation on CaO at 340–400 °C was supposed to through dechlorination/polymerization pathway, which is induced by electron transfer, generate chloride ions and form high-molecular weight intermediates with significant levels of both hydrogen and chlorine, and finally form amorphous carbon. Higher temperature was beneficial for the dechlorination/polymerization efficiency. The results are helpful for clarifying the reaction mechanism for thermal degradation of chlorinated aromatics in alkaline matrices.     

Fatty Acids as Phase Change Materials (PCMs) for Thermal Energy Storage: A Review

Abstract

Thermal energy storage (TES) technologies in general and phase change materials (PCMs) in particular, have been topic in research for the last 20 years. Traditionally, available heat has been stored in the form of sensible heat (typically by raising temperature of water, rocks, etc). Latent heat storage on the other hand, is a novel and developing technology, which has found considerable interest due to its operational advantages of smaller temperature swing, smaller size, and lower weight per unit of storage capacity. The interest on thermal energy storage by using fatty acids as PCM has risen in recent times since they have desired thermodynamic and kinetic criteria for low temperature latent heat storage. An added advantage is that fatty acids are derived from the vegetable and animals oil that provides an assurance of continuous supply. This article will review the development of fatty acids as PCMs for solar thermal energy storage application.     

Exploitation of Trichoderma harzianum mycelial waste for the removal of rhodamine 6G from aqueous solution

The harvested mycelial waste of Trichoderma harzianum was used as an adsorbent for the removal of rhodamine 6G and was studied in batch mode. The effects of agitation time and initial dye concentration, adsorbent dosage and pH were examined. The study revealed that the amount of dye adsorbed (mgg(-1)) increased with increase in agitation time and reached equilibrium after 120 min, for dye concentrations of 10-50 mg L(-1). The adsorbent dosage of 1.0 g/50 mL and pH of 8.0 were found to be optimum for maximum dye removal. The batch mode adsorption data followed both the Langmuir and Freundlich isotherms. The pseudo first- and second-order rate kinetics were applied to the adsorbent system. The adsorption kinetics of rhodamine 6G showed that the pseudo-second-order kinetic model provided the best correlation of the equilibrium data. The study implies that it is possible to develop a dye removal system by using T. harzianum biomass, which occurs as sludge in waste stream of fermentation industries.     

Biosorption of heavy metals by activated sludge and their desorption characteristics

The biosorption of different metals (Cu2+, Cd2+, Zn2+, Ni2+ and Pb2+) was investigated using activated sludge. The optimum pH was 4 for Cd, Cu and Pb sorption and 5 for Ni and Zn. Biomass metal uptake clearly competed with protons present in the aqueous medium, making pH an important variable in the process. Protons consumed by biomass in control tests versus protons exchange in biosorption tests confirmed a maximum exchange between metal cations and protons at pH 2. The study of the influence of biomass concentration revealed that the amount of protons released from biomass increased with biomass concentration. This would confirm the hypothesis of ion exchange between both types of ions. The application of the Langmuir and Freundlich models showed a better fitting of experimental data to the first model. The maximum sorption uptake of the studied metals by the activated sludge showed the following decreasing order: Pb>Cu>CdZn>Ni. Desorption experiments showed that HCl was a good eluent for the five metals tested, particularly at low pH values (1 and 2). At pH 3 or 4 the desorption yield was significantly lower. However, its use did not allow the reuse of biomass in subsequent loading and unloading cycles. EDTA was also a good desorption agent, achieving the total recovery for the five metals tested at a concentration of 1mM, with the advantage that biomass could be reused for three sorption-desorption cycles.     

A mathematical model for predicting thermal hazard data

A systematic procedure and mathematical model for predicting thermal behavior is proposed. This model has been verified by experimental data. The results show that the model will predict thermal hazard behavior precisely. A procedure for predicting thermal hazard data is also developed. Some examples of predicting real behavior are simulated.     

Studies of Thermal Transformations of Humic and Fulvic Acids in Soils I. Infrared Spectroscopy and Temperature-Programmed Pyrolysis Mass Spectrometry

Temperature-programmed pyrolysis mass spectrometry and Fourier-transform infrared spectroscopy have been used to monitor structural changes of humic and fulvic acids isolated from soils in China, in the temperature range of 25-550°C. in this work, we found that decarboxylation is obvious as the main reaction with dehydration reaction from 150°C to 400°C, the anhydride can be identified from FT-IR spectra at temperature range from 200°C to 400°C; there are evident changes of the aromatic nucleus of humic and fulvic acids above 400°C, even remaining up to 550°C. Besides, some changes of adsorption water can be distinguished before 200°C, and the mass signal of sulphur dioxide was detected.     

Comparative sorption and desorption behaviors of PFHxS and PFOS on sequentially extracted humic substances

The sorption and desorption behaviors of two perfluoroalkane sulfonates（PFSAs）, including perfluorohexane sulfonate（PFHx S） and perfluorooctane sulfonate（PFOS） on two humic acids（HAs） and humin（HM）, which were extracted from a peat soil, were investigated. The sorption kinetics and isotherms showed that the sorption of PFOS on the humic substances（HSs） was much higher than PFHx S. For the same PFSA compound, the sorption on HSs followed the order of HM 〉 HA2 〉 HA1. These suggest that hydrophobic interaction plays a key role in the sorption of PFSAs on HSs. The sorption capacities of PFSAs on HSs were significantly related to their aliphaticity, but negatively correlated to aromatic carbons,indicating the importance of aliphatic groups in the sorption of PFSAs. Compared to PFOS,PFHx S displayed distinct desorption hysteresis, probably due to irreversible pore deformation after sorption of PFHx S. The sorption of the two PFSAs on HSs decreased with an increase in p H in the solution. This is ascribed to the electrostatic interaction and hydrogen bonding at lower p H. Hydrophobic interaction might also be stronger at lower p H due to the aggregation of HSs.