Conversion and Hydrothermal Decomposition of Major Components of Mint Essential Oil by Small-Scale Subcritical Water Treatment.

Thermal stabilities of four major components (l-menthol, l-menthone, piperitone, and l-menthyl acetate) of Japanese mint essential oil were evaluated via subcritical water treatment. To improve experimental throughput for measuring compound stabilities, a small-scale subcritical water treatment method using ampoule bottles was developed and employed. A mixture of the four major components was treated in subcritical water at 180-240 °C for 5-60 min, and then analyzed by gas chromatography. The results indicated that the order of thermal resistance, from strongest to weakest, was: l-menthyl acetate, l-menthol, piperitone, and l-menthone. In individual treatments of mint flavor components, subsequent conversions of l-menthyl acetate to l-menthol, l-menthol to l-menthone, l-menthone to piperitone, and piperitone to thymol were observed in individual treatments at 240 °C for 60 min. As the mass balance between piperitone and thymol was low, the hydrothermal decomposition of the components was considered to have occurred intensely during, or after the conversion. These results explained the degradation of mint essential oil components under subcritical water conditions and provided the basis for optimizing the extraction conditions of mint essential oils using subcritical water.

Disintegration of the agricultural by-product wheat bran under subcritical conditions.

BACKGROUND: The disintegration of destarched wheat bran in water and sulfuric acid (pH 3) under subcritical conditions (275-300 °C) and at short reaction times (1-4 min) was investigated. A cascade process comprising a stepwise separation of the liquid was applied to reduce the formation of undesired degradation products. RESULTS: The highest degree of biomass disintegration (67% dry mass solubilization) was achieved by application of a cascade process at 275 °C (pH 3). Regarding the dissolution of carbohydrates (monomeric and oligomeric form), the total glucose yields remained below 60%, while the total xylose and arabinose yields were about 76% and 67%. Approximately 74% of the protein and 95% of the mineral fraction could be extracted. The application of the cascade process enabled a substantially reduced formation of degradation products. CONCLUSION: When operating hydrothermally and subcritically in order to avoid some problematic aspects of a biorefinery, an extensive disintegration and monomerization of wheat bran and its constituents remains difficult even under the tested conditions (300 °C, pH 3). However, the applied cascade process proved to be useful to increase the yields and to substantially reduce the formation of undesired degradation products. Despite this fact, increased water consumption has to be conceded. © 2018 Society of Chemical Industry.

Formation process and mechanism of humic acid-kaolin complex determined by carbamazepine sorption experiments and various characterization methods.

To explore the formation process and mechanism of organic matter and organic-mineral complex under humification and mineralization conditions, a series of samples including humic acid, kaolin, and humic acid-kaolin complex were prepared using a subcritical water treatment method (SWT) under specific temperature, pressure and reaction time conditions. HA was used as a surrogate for natural organic matter because it has a similar abundant pore structure, variety of carbon types, and chemical components. These samples were used in carbamazepine (CBZ) sorption experiments and characterized by a variety of techniques. The polymerization of humic acid under the conditions of increased temperature and pressure resulted in an increase in specific surface area and molecular quantity. In addition, the degree of aromaticity rose from 59.52% to 70.90%. These changes were consistent with the transformation from 'soft carbon' to 'hard carbon' that occurs in nature. The results of sorption experiments confirmed the interaction between humic acid and kaolin from the difference between the predicted and actual Qe values. The conceptual model of humic acid-kaolin complex could be deduced and described as follows. Firstly, the aromatic components of humic acid preferentially combine with kaolin through the intercalation effect, which protects them from the treatment effects. Next, the free carboxyl groups and small aliphatic components of humic acid interact on the surface of kaolin, and these soft species transform into dense carbon through cyclization and polymerization. As a result, humic acid-kaolin complex with a mineral core and dense outer carbonaceous patches were formed.

Subcritical water hydrolysis coupled with hydrothermal carbonization for apple pomace integrated cascade valorization.

This study evaluates an integrated biorefinery approach based on the waste hierarchy for the valorization of biodegradable waste, focusing on apple processing residues. Firstly, subcritical water hydrolysis was investigated at different experimental conditions (temperature 80 to 120 °C, dilution factor 10 to 30, residence time 10 to 30 min, initial pressure 10 to 30 bar) with the coincident aim of dissolving fermentable sugars and assess the effects of such treatment on the downstream solids. Secondly, spent solids were further processed by hydrothermal carbonization in the same reactor at fixed conditions (i.e., 180 °C, 3 h). The results showed that not only up to nearly 500 g kgdb-1 of sugars are dissolved but also lignocellulosic structure is amended, improving products valorization potential. Depending on pretreatment conditions, the proposed approach can deliver hydrochar with potential either as soil amendment or for long-term applications, sustainably valorizing food waste.

Hydrothermal degradation of seaweed polysaccharide: Characterization and biological activities.

Fucoidan is a marine sulfated polysaccharide that possesses various biological activities. To enhance the functional properties of fucoidan, it was depolymerized using a green technique viz. subcritical water treatment (SCW) to produce a low molecular weight fucoidan. In this study, response surface methodology (RSM) was used to study the influence of different influences for instance temperature, pressure, liquid to solid ratio, and agitation speed to depolymerize fucoidan. RSM was used to focus on the antioxidant activity and chemical composition of SCW-treated fucoidan. Further, resulting SCW-treated fucoidan was investigated by UV-Vis, FT-IR, Thermal gravimetric analysis (TGA), DSC, Elemental analysis, and ESI-MS. Moreover, the optimized SCW-treated fucoidan was checked for cytotoxicity, antimicrobial, antidiabetic, and anticoagulant activity compared with the untreated fucoidan. The obtained values displayed that SCW treatment breakdowns polymer chain and so it produces low molecular weight fucoidan. Biological activities were improved as the molecular weight was reduced.

Competitive removal of heavy metal ions from squid oil under isothermal condition by CR11 chelate ion exchanger.

Heavy metal ions (HMIs) are serious threats to the environment. Sub-critical water treatment was used to mimic contamination of squid oil in aqueous, metal-soap and oil phases. Isothermal adsorption of HMIs (Cu2+, Pb2+, Cd2+ and Zn2+) was studied from aqueous phase to oil phase (493, 523, 548, and 573K) for solutions with different initial concentration of HMIs was studied. Decomposition of glycerides into fatty acids was favored at high subcritical temperatures, with metal-soap phase showing the highest chelation ability toward Cu2+ (96%, isotherm 573K). The removal-ability of HMIs from contaminated oil was performed by CR11 chelate ion exchanger, showing facilitated removal from metal-soap and oil phases at low temperatures compared to general-purpose PEI-chitosan bead and PEI-chitosan fiber sorbents. The chelation behavior of Pb2+ and Cd2+ was the same in the OIL, with maximum values of 5.7×10-3 (mol/l) and 5.0×10-3 (mol/l) at 573K, respectively. By contrast, concentration of Zn2+ ion showed a slight increase with increasing temperature due to electrostatic forces between Zn2+ and active sites of glycerides in oil phase. For oil solution, the selectivity of adsorption for CR11, especially for Zn2+, was at least five-fold larger compared to PEI-chitosan bead and PEI-chitosan fiber adsorbents.

Hydrolysis of bamboo biomass by subcritical water treatment.

The aim of present study was to obtain total reducing sugars (TRS) from bamboo under subcritical water (SCW) treatment in a batch reactor at the temperature ranging from 170 °C to 220 °C and 40 min hydrolysis time. Experiments were performed to investigate the effects of temperature and time on TRS yield. The maximum TRS yield (42.21%) was obtained at lower temperature (180 °C), however longer reaction time (25 min). X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and scanning electron microscopy (SEM) analysis were used to characterise treated and untreated bamboo samples. The XRD profile revealed that crystallinity of bamboo increased to 71.90% with increase in temperature up to 210 °C and decreased thereafter to 70.92%. The first-order reaction kinetic model was used to fit the experimental data to obtain rate constants. From the Arrhenius plot, activation energy and pre-exponential factor at 25 min time were found to be 17.97 kJ mol(-1) and 0.154 min(-1), respectively.