Oxidation of garbage in supercritical water

Abstract

In the present study, 17 kinds of organic materials selected from groups of vegetable, meat, fat and fish as main components of garbage were oxidized with H₂O₂, using a batch reactor system under the condition of supercritical water, in order to treat organic wastes of high water content and low calorific value. It was found that they were easily oxidized, and remarkable influence of the kind of material in each group on the TOC decomposition was not recognized, but meats, fats and fishes, especially beef suet, were more difficult to be oxidized than vegetables.

The residual intermediate product was acetic acid in reactions of one minute at 400°C for all materials. Based on this result, the rate expression for supercritical water oxidation of acetic acid was determined.     

Continuous flame oxidation in supercritical water

Abstract

Continuous flames have been observed in Supercritical water oxidation (scWO) of isopropyl alcohol (IPA), using a vertical continuous reactor with sapphire windows and a mixing nozzle. Two types of continuous flame were confirmed: the one was long pale blue colored and the other was red short cone shaped, changing blue to red at around air ratio 2.0. The flame was strongly influenced by IPA concentration, air ratio and design of the mixing nozzle. Results for decomposition of PA are presented for IPA concentrations ranging from 600 up to 28260 ppm as TOC and initial reactor temperatures, were mostly around 490°C, at 25 MPa. Decomposition rate at steady state was over 99.9%. Experimentally measured CO₂ and O₂ concentrations at the flue gas were in good agreement with theoretically calculated values. Even for low air ratio as 1.1, high decomposition rate without CO, NO, NO₂ was achieved.     

Corrosion on continuous supercritical water oxidation for polychlorinated biphenyls

Abstract

The corrosion resistance of Hastelloy C-276 and titanium alloy G5 against C1 anion which was generated by supercritical water oxidation (scWO) of 3-chlorobiphenyl (3-PCB) in a flow reactor was investigated over a period of 336 hours at a constant pressure of 30 MPa. The condition of the scWO reaction zone was fixed at 750 K. The concentration of chlorine in the effluent collected after cooling to ambient temperature was about 850 wppm. The Hastelloy C-276 has a nominal ratio of approximately 3.7 Ni/l Cr. The Ni/Cr ratio in the effluent was the same with the nominal ratio, and the Hastelloy C-276 was proved to be corroded on the surface located between the bottom of the reactor and the cooling parts, which are under sub- and near- critical conditions of water. The corrosion rate was found to be 5 to 34mm/y in the zone where the temperature ranged from 543 K to 650 K and the corrosion spread over the whole surface of the alloy; however, one can hardly observe such a serious corrosion except the zone located in the between the reactor and the cooling part.     

Ultrasound-assisted oxidative process for sulfur removal from petroleum product feedstock

A procedure using ultrasonic irradiation is proposed for sulfur removal of a petroleum product feedstock. The procedure involves the combination of a peroxyacid and ultrasound-assisted treatment in order to comply with the required sulfur content recommended by the current regulations for fuels. The ultrasound-assisted oxidative desulfurization (UAOD) process was applied to a petroleum product feedstock using dibenzothiophene as a model sulfur compound. The influence of ultrasonic irradiation time, oxidizing reagents amount, kind of solvent for the extraction step and kind of organic acid were investigated. The use of ultrasonic irradiation allowed higher efficiency for sulfur removal in comparison to experiments performed without its application, under the same reactional conditions. Using the optimized conditions for UAOD, the sulfur removal was about 95% after 9 min of ultrasonic irradiation (20 kHz, 750 W, run at 40%), using hydrogen peroxide and acetic acid, followed by extraction with methanol.     

Noncatalytic organic rearrangement using supercritical water

Abstract

Significant acceleration of Beckmam and pinacol rearrangements can be achieved by using supercritical water (scH₂O), especially just near the critical point even in the absence of any acid catalysts. A high-pressure, high-temperature flow reactor system with FTlR operable at 500°C and 50 MPa was suaxssfdy developed, wherein the non-catalytic Beckmam and pinacol rearrangements using scH₂O were carried out and monitored. It has been demonstrated that scH₂0 itself acts very effectively in the place of conventional acid catalysts for both the rearrangements. The rate of the pinacol rearrangement using scH₂O is 28,200-fold rate of that in 0.871 M HCl solution at 46.7 MPa under distillation conditions. The high rate of reaction may be attributed to a great increase in the local proton concentration around the organic reactants.     

Low-temperature oxidation of SiC surfaces by supercritical water oxidation

The oxidation process on silicon carbide (SiC) surfaces is important for wide bandgap power semiconductor devices. We investigated SiC oxidation using supercritical water (SCW) at high pressure and temperature and found that a SiC surface can be easily oxidized at low temperature. The oxidation rate is 10 nm/min at 400 °C and 25 MPa, equal to that of conventional thermal dry oxidation at 1200 °C. Low-temperature oxidation should contribute to improved performance in future SiC devices. Moreover, we found that SCW oxidation at 400 °C forms a much smoother SiO₂/SiC interface than that obtained by conventional thermal dry oxidation. A higher oxidation rate and smaller microroughness are achieved at a lower oxidation temperature owing to the high density of oxidizers under SCW conditions.     

Diffusion of ions in supercritical water: Dependence on ion size and solvent density and roles of voids and necks

We have performed molecular dynamics simulations of alkali metal (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺) and halide (F⁻, Cl⁻, Br⁻, I⁻) ions in supercritical water at 673 K. The calculations were done for water at three different densities of 1.0, 0.7 and 0.35 g cm⁻³ to investigate the effects of solute size on the diffusion of ions in supercritical water. On increase of ion size, we observe a maximum for diffusion of ions in supercritical water of higher densities (1.0 and 0.7 g cm⁻³). However, no such maximum is found for ion diffusion in the supercritical water of low density (0.35 g cm⁻³) or for diffusion of neutral solutes at all densities. These results are analyzed in terms of passage through voids and necks present in supercritical water. Correlations of the observed diffusion behavior with the sizes of ions and voids present in the systems are discussed.     

Ab initio molecular dynamics investigations of structural, electronic and dynamical properties of water in supercritical carbon dioxide

Ab initio molecular dynamics simulations of a solitary perdeuterated water molecule solvated in supercritical carbon dioxide have been performed along an isotherm at three different densities. Electron donor-acceptor interactions between the oxygen atom of water and the carbon atom of CO₂ as well as hydrogen bonded interactions between the two molecules have been shown to play a dominant role in the solvation. The mean dipole moment of the water molecule increases with the density of the solution, from a value of 1.85 D at low density to around 2.15 D at the highest density. The increase in the solvent density causes the water molecule to exhibit a range of behavior, from a free molecule to one that interacts strongly with CO₂. A blue shift in the bending mode of water has been observed with increasing solvent density. The carbon dioxide molecules which are present in the first neighbor shell of water are found to exhibit larger propensity to deviate from a linear geometry in their instantaneous configurations.      

Dynamics of hydrogen bonds in water and consequences for the unusual behaviour of supercooled water

The dynamics of liquid water is evaluated by the coherent quasi-elastic scattering at two different momentum transfers, in order to discriminate hydrogen bond lifetime from molecular dynamics. The results indicate a possible issue for the puzzle of the behaviour of supercooled water.      

Ultrasonic degradation, mineralization and detoxification of diclofenac in water: Optimization of operating parameters

The 20 kHz ultrasound-induced degradation of non-steroidal, anti-inflammatory drug diclofenac (DCF) was investigated. Several operating conditions, such as power density (25–100 W/L), substrate concentration (2.5–80 mg/L), initial solution pH (3.5–11), liquid bulk temperature and the type of sparging gas (air, oxygen, argon), were tested concerning their effect on DCF degradation (as assessed measuring absorbance at 276 nm) and hydroxyl radicals generation (as assessed measuring H₂O₂ concentration). Sample mineralization (in terms of TOC and COD removal), aerobic biodegradability (as assessed by the BOD₅/COD ratio) and ecotoxicity to Daphnia magna and Artemia salina were followed too.DCF conversion is enhanced at increased applied power densities and liquid bulk temperatures, acidic conditions and in the presence of dissolved air or oxygen. The reaction rate increases with increasing DCF concentration in the range 2.5–5 mg/L but it remains constant in the range 40–80 mg/L, indicating different kinetic regimes (i.e. first and zero order, respectively). H₂O₂ production rates in pure water are higher than those in DCF solutions, implying that decomposition basically proceeds through hydroxyl radical reactions. Mineralization is a slow process as reaction by-products are more stable than DCF to total oxidation; nonetheless, they are also more readily biodegradable. Toxicity to D. magna increases during the early stages of the reaction and then decreases progressively upon degradation of reaction by-products; nevertheless, complete toxicity elimination cannot be achieved at the conditions in question. Neither the original nor the treated DCF samples are toxic to A. salina.     

A classical molecular dynamics study of a Diels Alder cycloaddition in supercritical water

Molecular dynamics simulations were performed to investigate the Diels Alder cycloaddition of cyclopentadiene and methyl vinyl ketone in high pressure, high temperature water. It was found that the reaction was favoured by high temperatures at 1000?atm due to increasing entropy. Similarly, at 400?atm, the entropy caused both the equilibrium and rate constant to increase to a peak at 698?K before rapidly falling once more with increasing temperature. At a constant temperature of either 598?K or 898?K, increasing pressure resulted in a lowering of the equilibrium constant. This effect was significantly more pronounced for 898?K, caused by less favourable solvation of the products and an increasing amount of work required for reaction.     

水中脉冲放电产生过氧化氢及其影响因素

采用介质涂覆的球-筒电极结构,用以脉冲电压条件下在水中产生放电,通过比色法检测放电产生的过氧化氢,研究了不同电压脉冲幅值、脉冲宽度（储能电容的大小）、水的电导率以及脉冲频率对过氧化氢产生速率的影响,实验结果表明过氧化氢的产率随电压脉冲幅值的增大而增大。当电压脉冲幅值足够高时,水中放电由流注放电形式转换为电弧放电形式,此时过氧化氢产率也大幅提高,而在相同电压条件下,随水的电导率的增大,过氧化氢的产率减小。在相同电压下,脉冲频率的增大,导致放电平均功率增大,水中放电产生过氧化氢的浓度提高。在3.3 W功率时,120 min后水中过氧化氢浓度达到0.2 mmol/L,从而证明了所用电极结构的优越性。     

水中脉冲放电产生过氧化氢及其影响因素

采用介质涂覆的球-筒电极结构,用以脉冲电压条件下在水中产生放电,通过比色法检测放电产生的过氧化氢,研究了不同电压脉冲幅值、脉冲宽度(储能电容的大小)、水的电导率以及脉冲频率对过氧化氢产生速率的影响,实验结果表明过氧化氢的产率随电压脉冲幅值的增大而增大。当电压脉冲幅值足够高时,水中放电由流注放电形式转换为电弧放电形式,此时过氧化氢产率也大幅提高,而在相同电压条件下,随水的电导率的增大,过氧化氢的产率减小。在相同电压下,脉冲频率的增大,导致放电平均功率增大,水中放电产生过氧化氢的浓度提高。在3.3 W功率时,120 min后水中过氧化氢浓度达到0.2 mmol/L,从而证明了所用电极结构的优越性。     

Ultrasound (US), Ultraviolet light (UV) and combination (US + UV) assisted semiconductor catalysed degradation of organic pollutants in water: Oscillation in the concentration of hydrogen peroxide formed in situ

Application of Advanced Oxidation Processes (AOP) such as sono, photo and sonophoto catalysis in the purification of polluted water under ambient conditions involve the formation and participation of Reactive Oxygen Species (ROS) like OH, HO₂, O₂⁻, H₂O₂ etc. Among these, H₂O₂ is the most stable and is also a precursor for the reactive free radicals. Current investigations on the ZnO mediated sono, photo and sonophoto catalytic degradation of phenol pollutant in water reveal that H₂O₂ formed in situ cannot be quantitatively correlated with the degradation of the pollutant. The concentration of H₂O₂ formed does not increase corresponding to phenol degradation and reaches a plateau or varies in a wave-like fashion (oscillation) with well defined crests and troughs, indicating concurrent formation and decomposition. The concentration at which decomposition overtakes formation or formation overtakes decomposition is sensitive to the reaction conditions. Direct photolysis of H₂O₂ in the absence of catalyst or the presence of pre-equilibrated (with the adsorption of H₂O₂) catalyst in the absence of light does not lead to the oscillation. The phenomenon is more pronounced in sonocatalysis, the intensity of oscillation being in the order sonocatalysis > photocatalysis ⩾ sonophotocatalysis while the degradation of phenol follows the order sonophotocatalysis > photocatalysis > sonocatalysis > sonolysis > photolysis. In the case of sonocatalysis, the oscillation continues for some more time after discontinuing the US irradiation indicating that the reactive free radicals as well as the trapped electrons and holes which interact with H₂O₂ have longer life time (memory effect).     

Synthesis of nanocrystalline SnO<Subscript>2</Subscript> in supercritical water

Nanocrystalline SnO₂ was synthesized in supercritical water at 385–415°C and 30 MPa (38–106 s residence time) in a tubular flow reactor from an aqueous solution of 0.1–0.4 M SnCl₄. The conversion rate was between 53 and 81%, but increased to 97.8% when 0.1 M NaOH was added. Nanoparticles were analyzed by a series of independent analytical techniques, including TEM, Raman, XRD, SEM, EDX and FT-IR. The initial size of the particles was about 3.7 nm. After calcination at 450°C for 2 h, the particle size increased to 4 nm. The particles were of low crystallinity, as indicated by the weak Raman and XRD signals. All particles were composed of Sn and O, as verified by the EDX spectra. The crystals were tetragonal, as confirmed by the weak XRD spectrum. After calcination at 600°C for 10 h, the particle size increased to 9 nm, while high crystallinity was confirmed by Raman and XRD analyses. All the crystals had the same structure, as indicated by TEM electron diffraction patterns. Using this one-step supercritical water process, nanoparticles of SnO₂ can be conveniently produced continuously in a flow reactor in less than 2 min.     

Near-infrared spectroscopy as a rapid tool for water content analysis in the partial oxidation of ethanol

Abstract

The oxidation of ethanol to acetaldehyde was previously investigated in a continuous flow bench scale reactor using a zirconium-oxide-supported vanadium catalyst. Products were analyzed by near-infrared spectroscopy, a fast and accurate tool for the determination of water, ethanol, and acetaldehyde content. Water content was calibrated by Karl Fischer titration while gas chromatography was used to calibrate ethanol and acetaldehyde contents. Near-infrared spectroscopy is a fast, cost-effective method for the determination of water, ethanol, and acetaldehyde products from partial ethanol oxidation.     

The surface properties and the activities in catalytic wet air oxidation over CeO2-TiO2 catalysts

No-noble metal CeO₂-TiO₂ catalysts prepared by sol-gel method were developed and examined for catalytic wet air oxidation (CWAO) of acetic acid. The structure of the catalysts was measured by BET, SEM, XRD, XPS and DTA-TG. We investigated the effect of the interactions of Ce and Ti on the structure of CeO₂-TiO₂ catalysts. The mechanisms of the relationships between the different content of Ti and the activity of CeO₂-TiO₂ catalysts were discussed. The results showed that the average crystal size of CeO₂ decreased and the surface areas increased; the low valence of Ce³⁺ increase, and the chemisorbed oxygen slightly decreased with the increase of Ti content on the surface of CeO₂-TiO₂ catalysts. The order of the activity in CWAO of acetic acid followed: Ce/Ti 1/1 > Ce/Ti 3/1 > Ce/Ti 1/3 > Ce/Ti 5/1 > CeO₂ > TiO₂ > no catalyst. In CWAO of acetic acid, the optimal atomic ratio of Ce and Ti was 1, and the highest COD removal was over 64% at 230 °C, 5 MPa and 180 min reaction time over Ce/Ti 1/1 catalyst. The excellent activity and stability of CeO₂-TiO₂ catalysts was observed in our study.     

Interaction of the excited state intramolecular proton transfer probe 3-hydroxy-2-naphthoic acid with poly N-vinyl-2-pyrrolidone polymer in water: An insight into the water structure in the binding region

The enhancement of the excited state intramolecular proton transfer (ESIPT) emission of 3-hydroxy-2-naphthoic acid (3HNA) in presence of poly N-vinyl-2-pyrrolidone (PVP) has been investigated by time resolved fluorescence and anisotropy measurement. In other water soluble polymers and monomers there is no enhancement of the ESIPT emission of 3HNA. The microenvironment of the probe in PVP-water mixture is investigated by comparing the ESIPT emission of 3HNA in mixed solvents of acetonitrile-toluene. The anisotropy, rotational correlation time and the blue shift observed in the ESIPT emission in PVP-water mixture have been ascribed to both the polarity and the motional restriction of the probe imposed by the bound water region of PVP.     

Interfacial tension in water/n-decane/naphthenic acid systems predicted by a combined COSMO-RS theory and pendant drop experimental study

The interfacial tension of systems containing water, n-decane, and model naphthenic acids were investigated using a predictive model based on COSMO-RS theory and experimental pendant drop measurements. Five naphthenic acid homologues that are considered to be representative of surfactants inherent to crude oil were dissolved in n-decane at equal concentrations. The interfacial tensions of the five systems at an acid concentration of 1.66?mol% relative to n-decane were experimentally determined to be 27–30?mN/m. The interfacial tensions of the five different acid-decane phases against water were also predicted using density functional theory (DFT) calculations and COSMO-RS theory. The accuracy of the predictions was very good as confirmed through pendant drop measurements of the interfacial tension. The mean-absolute-deviation between experimental and predicted values was 2.6?mN/m thus demonstrating the high predictive power of COSMO-RS theory for calculating the interfacial tension at oil–water interfaces in the presence of surface-active compounds.