Thermodynamic analysis of supercritical water gasification of methanol,ethanol, glycerol,glucose and cellulose

In the present work the Gibbs free energy minimization, using a non-linear programming formulation and an approximation in the gas fugacities, was used to calculate the equilibrium composition for supercritical water gasification of methanol, ethanol, glycerol, glucose and cellulose. The proposed formulation mathematically ensures finding the global optimal solution with no need of an initial estimate and the numerical results are close to the ones calculated using non-ideal gas formulation. Therefore, the proposed approach is reliable and easy to use, without numerical difficulties, such as an undesirable local minimum. The model predictions show a good agreement with the experimental studies in all cases studied in this work.     

Supercritical fluid extraction of antioxidant and antimicrobial compounds from Laurus nobilis L. Chemical and functional characterization

Extraction of laurel leaves by using supercritical carbon dioxide was carried out on a supercritical fluid (SF) pilot-scale plant. The extraction pressure and temperature were set to 250 bar and 60°C, respectively, using a 4% of ethanol as modifier. The employed apparatus, owing to a two-stage separation, allowed us to obtain two different fractions (F1 and F2), whose antioxidant and antimicrobial activities were investigated. Two different methods, β-carotene bleaching test and DPPH^• free radical–scavenging assay, were carried out to determine the antioxidant activity. Moreover, antimicrobial activity of laurel fractions was tested against Staphylococcus aureus ATCC 25923, Bacillus subtilis ATCC 6633, Pseudomonas aeruginosa ATCC 10145, Escherichia coli ATCC 11775, Candida albicans ATCC 60193 and Aspergillus niger ATCC 16404. Minimum inhibitory concentration (MIC) and minimal bactericidal and fungicidal concentration (MBC) were obtained. Both fractions showed a similar antioxidant activity, although it was slightly higher for the fraction recovered in separator 2. However, antimicrobial activity against the microorganisms tested was only found when fraction 2 was used. Staphylococcus aureus was the most sensitive microorganism to this fraction, with maximal inhibition zones (25 mm) and the lowest MBC values (1.25 mg/ml), whereas the least susceptible was the fungi Aspergillus niger. In order to determine the compounds responsible for the antimicrobial activity, fraction 2 was analysed by GC–MS; results obtained showed that most of the compounds identified in the supercritical extract have been previously described to show antimicrobial activity; among them, the major compound found in the supercritical extract corresponded to a sesquiterpene lactone of the germacrolide type (6-epi-desacetyllaurenobiolide) previously described in laurel.     

Thermodynamic models for H2O–CO2–H2 mixtures in near-critical and supercritical regions of water

The PVTx properties of the H₂O–CO₂–H₂ mixtures have significant applications in the technology of supercritical water gasification of coal. Here, we first carry out the molecular dynamics simulations of the PVTx properties of the H₂O–CO₂–H₂ mixtures in the near-critical and supercritical regions of water to generate 600 datasets at 750–1150 K and 4.0–443.5 MPa. The molar fraction of each composition in the ternary mixtures ranges from 10% to 80%. Later we investigate the applicability of a well-known thermodynamic model for the ternary mixtures, namely the Duan-Møller-Weare equation of state (DMW EOS). It is observed that the DMW EOS shows great potential in the prediction of the PVTx properties of the ternary mixtures. However, it is noted that the mixing parameters describing the binary interactions of H₂O–H₂ and CO₂–H₂ are still unknown in the DMW EOS. By determining the missing mixing parameters using the Levenberg-Marquardt algorithm, the accuracy of the original DMW EOS is improved for the ternary mixtures. Moreover, optimizing the coefficients in the DMW EOS further promotes the accuracy of the model for the H₂O–CO₂–H₂ mixtures. The results from this work may facilitate the development of supercritical water gasification of coal.     

二次再热超临界机组热力系统经济性定量分析方法

该文针对二次再热超临界机组采用了二次再热和高低压加热器回热抽汽均设有外置蒸汽冷却器进行过热度跨级利用的特点，基于等效热降理论，经过严格的理论分析和数学推导，得出了各加热器名义和真实抽汽等效热降及抽汽效率的计算方法，给出了二次再热超临界机组热力系统经济性的局部定量分析法则，形成了一套完整的经济性定量计算方法。利用该模型仅用3个公式即可以方便、快捷、准确地计算出热力系统发生局部调整和变化时机组经济性指标的变化，为此类机组的经济性分析和节能诊断提供了一种简捷、准确的定量方法。并通过实例计算验证了该模型的可行性和准确性。     

Continuous salt precipitation and separation from supercritical water. Part 2. Type 2 salts and mixtures of two salts

Using a continuously operated laboratory plant for the catalytic hydrothermal gasification of biomass featuring a supercritical water salt separator we investigated the separation performance of three different binary type 2 salt-water mixtures and three ternary salt-water mixtures that consisted either of two type 1 salts or two type 2 salts dissolved in water. It turned out that a concentrated salt brine could not be recovered at the salt separator for the binary type 2 salt-water mixtures of Na₂CO₃, Na₂SO₄, and K₂SO₄. These salts precipitate as solids from supercritical water and thus lead to salt deposits inside the salt separator vessel.The ternary mixtures of two type 1 salts dissolved in water (KH₂PO₄-K₂HPO₄-H₂O and three different mixtures of NaNO₃-K₂CO₃-water) exhibited a separation performance similar to the binary solutions of type 1 salts that were discussed in Part 1 of this article. However, the mixtures showed separation performances that were different from the corresponding single salt solutions.It was also possible to recover a concentrated brine when feeding solutions containing the two type 2 salts Na₂CO₃ and K₂SO₄. For these mixtures a certain amount of the type 1 salt K₂CO₃ might form in supercritical water leading to salt separation efficiencies up to 95% for these mixtures.     

Solubility analysis of clozapine and lamotrigine in supercritical carbon dioxide using static system

The experimental techniques used to obtain the solubilities of clozapine and lamotrigine in supercritical carbon dioxide include a simple static technique. The solubility measurements were performed at temperatures between 318 and 348 K and pressures between 121.6 and 354.0 bar. These chemicals have solubilities with values ranging from 3.6 × 10⁻⁶ to 4.2 × 10⁻⁵ (clozapine) and 1 × 10⁻⁶ to 6 × 10⁻⁵ (lamotrigine) mole fraction. The solubility data were correlated using four semi-empirical density-based models (Chrastil, Bartle, K-J and M-T models). Correlation of the results shows good self-consistency of the data obtained with the Bartle model for clozapine with an overall average absolute relative deviation (AARD%) of 11.21. The calculated results with each four models show satisfactory agreement with the experimental data for lamotrigine with an overall AARD% 11.72, 8.99, 2.75, 3.86 for Chrastil, K-J, Bartle, M-T models, respectively. Using the correlation results, the heat of drug-CO₂ solvation and that of drug vaporization were approximated.