Isobaric vapor–liquid–liquid–solid equilibrium of the water + NaCl + 1-butanol system at 101.3 kPa

A mixture of water + NaCl + 1-butanol at 101.3 kPa is studied in order to determine the influence of salt on its experimental vapor–liquid–liquid–solid equilibrium. A detailed analysis of the evolution with temperature of the different equilibrium regions is carried out. The study is conducted at a constant pressure of 101.3 kPa in a recirculating still that has been modified by our research group. The changes in the 1-butanol/water composition ratio in the vapor phase that are provoked by the salt are studied as a function of equilibrium region. In addition, the mutual solubility of 1-butanol and water is assessed in the liquid–liquid and solid–liquid regions.

Large scale optimization of a sour water stripping plant using surrogate models

In this work, we propose a new methodology for the large scale optimization and process integration of complex chemical processes that have been simulated using modular chemical process simulators. Units with significant numerical noise or large CPU times are substituted by surrogate models based on Kriging interpolation. Using a degree of freedom analysis, some of those units can be aggregated into a single unit to reduce the complexity of the resulting model. As a result, we solve a hybrid simulation-optimization model formed by units in the original flowsheet, Kriging models, and explicit equations. We present a case study of the optimization of a sour water stripping plant in which we simultaneously consider economics, heat integration and environmental impact using the ReCiPe indicator, which incorporates the recent advances made in Life Cycle Assessment (LCA). The optimization strategy guarantees the convergence to a local optimum inside the tolerance of the numerical noise.

Pollutant emissions during the pyrolysis and combustion of flexible polyurethane foam

Thermal decomposition of flexible polyurethane foam (FPUF) was studied under nitrogen and air atmospheres at 550 °C and 850 °C using a laboratory scale reactor to analyse the evolved products. Ammonia, hydrogen cyanide and nitrile compounds were obtained in high yields in pyrolysis at the lower temperature, whereas at 850 °C polycyclic aromatic hydrocarbons (PAHs) and other semivolatile compounds, especially compounds containing nitrogen (benzonitrile, aniline, quinolone and indene) were the most abundant products. Different behaviour was observed in the evolution of polychlorodibenzo-p-dioxins and furans (PCDD/Fs) at 550 °C and 850 °C. At 550 °C, the less chlorinated congeners, mainly PCDF, were more abundant. Contrarily, at 850 °C the most chlorinated PCDD were dominant. In addition, the total yields of PCDD/Fs in the pyrolysis and combustion runs at 850 °C were low and quite similar.

Kinetic study and thermal decomposition behavior of viscoelastic memory foam

A systematic investigation of the thermal decomposition of viscoelastic memory foam (VMF) was performed using thermogravimetric analysis (TGA) to obtain the kinetic parameters, and thermogravimetric analysis coupled to Fourier Transformed Infrared Spectrometry (TGA-FTIR) and thermogravimetric analysis coupled to Mass Spectrometry (TGA-MS) to obtain detailed information of evolved products on pyrolysis and oxidative degradations. Two consecutive nth-order reactions were employed to correlate the experimental data from dynamic and isothermal runs performed at three different heating rates (5, 10 and 20 K/min) under an inert atmosphere. On the other hand, for the kinetic study of the oxidative decomposition, the data from combustion (synthetic air) and poor oxygen combustion (N2:O2 = 9:1) runs, at three heating rates and under dynamic and isothermal conditions, were correlated simultaneously. A kinetic model consisting of three consecutive reactions presented a really good correlation in all runs. TGA-FTIR analysis showed that the main gases released during the pyrolysis of VMF were determined as ether and aliphatic hydrocarbons, whereas in combustion apart from the previous gases, aldehydes, amines and CO2 have also been detected as the main gases. These results were confirmed by the TGA-MS.

Marine debris occurrence and treatment: A review

Marine debris produces a wide variety of negative environmental, economic, safety, health and cultural impacts. Most marine litter has a very low decomposition rate (as plastics, which are the most abundant type of marine debris), leading to a gradual, but significant accumulation in the coastal and marine environment. Along that time, marine debris is a significant source of chemical contaminants to the marine environment. Once extracted from the water, incineration is the method most widely used to treat marine debris. Other treatment methods have been tested, but they still need some improvement and so far have only been used in some countries. Several extraction and collection programs have been carried out. However, as marine debris keep entering the sea, these programs result insufficient and the problem of marine debris will continue its increase. The present work addresses the environmental impact and social aspects of the marine debris, with a review of the state of the art in the treatments of this kind of waste, together with an estimation of the worldwide occurrence and characteristics.

Effect of the Concentration of Siliceous Materials Added to Tobacco Cigarettes on the Composition of the Smoke Generated during Smoking

Two as-synthesized meso- and macro-porous siliceous materials (MPSMs), i.e., Al-MCM-41 and SBA-15, were mixed with tobacco to study their effect on tobacco smoke chemistry. A reference cigarette, 3R4F, and a commercial cigarette, Fortuna, containing different percentages of MPSM were smoked in a smoking machine, and the mainstream smoke was analyzed. SBA-15 showed the highest reductions of nicotine; close to 90% when it was added at 8 mass %. The superb behavior of these materials may be related to their high particulate matter filtering efficiency in combination with their catalytic activity. The selectivity of these materials with respect to nicotine was also analyzed. Al-MCM-41 presents higher selectivity for condensed compounds than for gases, whereas SBA-15 presents similar ratios for both fractions. The highest selectivity was obtained for the liquid fraction when smoking 3R4F cigarettes mixed with Al-MCM-41.

TGA/FTIR study of the pyrolysis of diammonium hydrogen phosphate–tobacco mixtures

Diammonium hydrogen phosphate (DAP) is commonly used as a flavor ingredient of commercial cigarettes. In addition, among its other uses, it is employed to expand the tobacco volume, to manufacture reconstituted tobacco sheet, and to denicotinize tobacco. However, the use of DAP as a cigarette ingredient is a controversial issue. Some authors have stated that ammonium compounds added to tobacco increase smoke ammonia and “smoke pH”, resulting in more free nicotine available in the smoke. On the other hand, other researchers have reported that the larger ammonium content of a cigarette blend due to the presence of DAP was not reflected in increased smoke ammonia. In this work, the thermal behavior of DAP, tobacco and DAP-tobacco mixtures has been studied by TGA/FTIR. The chemical processes involved in the different pyrolysis steps of DAP have been suggested. Marked changes in the pyrolytic behavior of both, tobacco and DAP have been detected when analyzing the behavior of the mixtures. A displacement of the decomposition steps mainly related to the glycerol and lignin from tobacco toward lower temperatures has been observed, whereas that associated with cellulose is displaced toward higher temperature. Additionally, no peak corresponding to the phosphorous oxides decomposition has been detected in the curves relating to the DAP-tobacco mixtures. All these features are indicative of the strong interactions between DAP and tobacco. The FTIR spectra show no significant qualitative differences between the qualitative overall composition of the gases evolved from the pyrolysis of tobacco in the absence and in the presence of DAP. Nevertheless, depending on the temperature considered, the addition of DAP contributes to a decrease in the generation of hydrocarbons and an increase in the formation of CO, CO2 and oxygenated compounds in terms of amount generated per mass of pyrolysed tobacco.

Hydrothermal carbonization of lignocellulosic biomass: Effect of process conditions on hydrochar properties

Although hydrothermal carbonization of biomass components is known to be mainly governed by reaction temperature, consistent reports on the effect and statistical significance of process conditions on hydrochar properties are still lacking. The objective of this research was to determine the importance and significance of reaction temperature, retention time and solid load on the properties of hydrochar produced from an industrial lignocellulosic sludge residue. According to the results, reaction temperature and retention time had a statistically significant effect on hydrochar ash content, solid yield, carbon content, O/C-ratio, energy densification and energy yield as reactor solid load was statistically insignificant for all acquired models within the design range. Although statistically significant, the effect of retention time was 3–7 times lower than that of reaction temperature. Predicted dry ash-free solid yields of attained hydrochar decreased to approximately 40% due to the dissolution of biomass components at higher reaction temperatures, as respective oxygen contents were comparable to subbituminous coal. Significant increases in the carbon contents of hydrochar led to predicted energy densification ratios of 1–1.5 with respective energy yields of 60–100%. Estimated theoretical energy requirements of carbonization were dependent on the literature method used and mainly controlled by reaction temperature and reactor solid load. The attained results enable future prediction of hydrochar properties from this feedstock and help to understand the effect of process conditions on hydrothermal treatment of lignocellulosic biomass.

Heavy metal release due to aging effect during zero valent iron nanoparticles remediation

Zero valent iron nanoparticles (nZVI) represent a promising agent for environmental remediation. Nevertheless, their application presents some limitations regarding their rapid oxidation and aggregation in the media. The aim of this study was to determine the effect that nZVI aging has in heavy metal remediation in water. Contaminants studied were Zn, Cd, Ni, Cu and Cr, which are typical elements found in ground and wastewater. Results show a high contaminant removal capacity by the nZVI in the first 2 h of reaction. Nevertheless, for longer reaction times, some of the metal ions that had already been adsorbed in the nZVI were delivered to the water. Cd and Ni show the maximum delivery percentages (65 and 27% respectively after 21 days of contact time). The starting delivery time was shortened when applying lower nZVI amounts. No re-dissolution of Cr was observed in any circumstance because it was the only element incorporated into the nanoparticles core, as TEM images showed. Contaminant release from nZVI is probably due to nanoparticles oxidation caused by aging, which produced a pH decrease and nZVI surface crystallization.

Thermogravimetric and kinetic analysis of the decomposition of solid recovered fuel from municipal solid waste

The thermal decomposition of a solid recovered fuel has been studied using thermogravimetry, in order to get information about the main steps in the decomposition of such material. The study comprises two different atmospheres: inert and oxidative. The kinetics of decomposition is determined at three different heating rates using the same kinetic constants and model for both atmospheres at all the heating rates simultaneously. A good correlation of the TG data is obtained using three nth-order parallel reactions.