生物质气化燃气中固体颗粒物的恒温临氧热解机理研究

在固定床反应器中考察了不同气氛下PBG恒温热解特性的差异,结合XPS与^(13)C NM R等技术手段分析了400℃恒温热解条件下PBG固相产物的化学结构变化。结果表明,PBG在400℃恒温热解时,生物质气化燃气(BAG)与N_2气氛下更易生成焦油,其析出量分别为50.71与37.45 mg/g,而临氧燃气气氛(BAG+2%O_2)下焦油析出量仅为11.96 mg/g,说明适量O_2的存在可有效抑制焦油的生成。进一步进行化学结构分析表明,在燃气(BAG)恒温热解条件下,PBG主要发生以脱氢脱氧为主的芳香化缩聚反应,易形成焦油类的大分子多环芳烃;而在临氧燃气(BAG+2%O_2)恒温热解条件下,PBG表面的有机基团易与O_2发生表面氧化反应,生成表面含氧官能团,在一定程度上抑制了芳香环缩聚反应,进而有利于降低焦油类物质的产率。因此,在生物质气化燃气实际高温过滤过程中适当添加氧(如:2%O_2),可有效降低PBG焦油收率,且不会形成大分子多环芳烃,有助于解决粗燃气过滤的过滤介质堵塞问题。

Study on the Phase Behavior of Coating Matrix in Supercritical or Sub-critical Carbon Dioxide

The high-pressure phase behavior of coating-solvent-supercritical or sub-critical carbon dioxide system was investigated experimentally. The coating matrix used was 108-acrylic resin at concentration ranging from 10% to 50% (by mass) in mixtures with n-butyl acetate. The experiments were conducted in a high-pressure view cell for temperatures from 35℃ to 65℃ and for pressures from 3.0MPa to 8.0MPa. The effect of temperature, pressure and content of every component on the phase behavior of the systems was observed. Finally, the ternary phase diagram for resin-solvent-CO2 was plotted.

Clinical application of full automatic animal experimental cabin of normobaric/hypobaric hypoxia and high carbon dioxide

To explore the feasibility of the full automatic animal experimental cabin to establish the animal models in normobaric/hypobaric hypoxic and high carbon dioxide environment. Methods： Sixty SPF-class male DS rats were divided into 2 groups, 20 for normobaric, hypoxic conditions and the other 40 for hypobaric, hypoxic conditions. For each group, the pulmonary arterial pressure and carotid arterial pressure indicators of rats were examined by using the physiological multi-detector, and the pulmonary vascular changes in the structure were observed. Results： The normobaric/hypobaric hypoxic with high carbon dioxide environment can promote the formation of pulmonary hypertension and accelerate changes in pulmonary vascular remodeling, and promote the right ventricular hypertrophy. Conclusion： Clinical applications showed that the animal experimental cabin has observed and controlled accurately. The result was safe, reliable and reproducible. The cabin can successfully establish the pulmonary hypertension model in normobaric/hypobaric hypoxic with high carbon dioxide environment, and in order to study the physiological mechanism of a variety of circulation and respiratory diseases caused by lack of oxygen, which provided an experimental technology platform for clinical research.

COD Removal Efficiencies of Some Aromatic Compounds in Supercritical Water Oxidation

Some aromatic compounds, phenol, aniline and nitrobenzene, were oxidized in supercritical water. It was experimentally found that the chemical oxygen demand (COD) removal efficiency of these organic compounds can achieve a high level more than 90% in a short residence time at temperatures high enough. As temperature, pressure and residence time increase, the COD removal efficiencies of the organic compounds would all increase. It is also found that temperature and residence time offer greater influences on the oxidation process than pressure. The difficulty in oxidizing these three compounds is in the order of nitrobenzene ＞ aniline ＞ Phenol. In addition, it is extremely difficult to oxidize aniline and nitrobenzene to CO2 and H2O at the temperature lower than 873.15 K and 923.15 K, respectively. Only at the temperature higher than 873.15 K and 923.15 K, respectively, the COD removal efficiencies of 90% of aniline and nitrobenzene can be achieved.

Aniline destruction by supercritical water oxidation and its reaction kinetics

Supercritical water oxidation （SCWO） is an effective method for wastewater treatment. In this study, a lot of experiments are carried out to study the influence of various factors on the aniline destruction rate in the SCWO process with a novel experiment setup. The experimental results show that the aniline destruction rate rises with the increase of the residence time, the reaction temperature and the reaction pressure. A dynamics analysis of the aniline SCWO reaction is conducted and the dynamic equation is obtained.

Energy analyses for the energetically self-sufficient supercritical water oxidation process

One of the bottle-neck problems to the commercial development of supercritlcal water oxidation （SCWO） is high operation cost. In this study the condition to realize an energetically self-sufficient SCWO process is analyzed. The reaction heat is recovered by means of Organic Rankine Circle. The process of SCWO for phenol is simulated with the Aspen Plus~ process simulator, and the results show that the influence of temperature on reaction heat is small at a constant pressure. It is reasonable to neglect the effect of temperature and to estimate the heat of reaction with average temperature when the temperature changes in a small range. The necessary condition to realize an energetically self-sufficient SCWO process is that the released energy is not less than consumed one. Whether a waste system with given chemical composition is energeticallyself-sufficient can be estimated by ^QR^QH 〉 W The thermodynamics analysis shows that energetically self-sufficient SCWO process with an Organic Rankine Cycle is a feasible technology for the recovery of SCWO reaction heat,and the energy balance point for phenol is 2wt%.

Synthesis of poly (vinyl acetate) oligomersand their phase behavior in supercritical carbon dioxide

Three poly(vinyl acetate)(PVAc)oligomers with controlled molecular weight and narrow molecular distribution are synthesized by reversible addition-fragmentation chain transfer(RAFT)polymerization.The effects of the reaction temperature and the added amount of initiator of the PVAc polymerization are discussed.In addition,the phase behavior of the prepared PVAc in pressured CO2 is determined via the cloud point method.The results indicate that the cloud point of PVAc increases with the increase in the molecular weight,the PVAc concentration,and the temperature.The cloud point pressures for the PVAc mass concentration of 0.12%with the molecular weight of 1 550,2 120,and 2 960 g/mol are 13.48,13.83 and 15.43 MPa,respectively,at the temperature of 35℃.It reveals that the solubility of PVAc in ScCO2 at relatively low pressure is remarkably limited.

Recent trends in the use of polyoxometalate-based material for efficient water oxidation

Polyoxometalates （POMs）, with their attractive topological and electronic properties, have been demonstrated over the last few decades to be efficient catalysts for many reactions. In a new direction, POMs having a purely inorganic framework are now being explored as efficient catalysts for water oxidation. This review focuses on very recent developments of POM-based catalysts for water oxidation to O2. In the very extensive family of POMs, tetra-core sandwich-type Ru- and Co-containing POM complexes, namely [Ru404（OH）2（H20）4（y-SiW10O36）2]10- and [CO4（H2O）2（a-PWgO34）2]10- exhibit the ability to facilitate water oxidation under electrocatalytic and/or photocatalytic conditions. However, it is concluded that much work still needs to be done to explain the catalytic mechanisms and optimize these catalytic systems. In addition, recent trends in using ionic liquids as media to modify the electrolytic environment and enhance water oxidation are highlighted.

Photoactivity of titanium dioxide/carbon felt composites prepared with the assistance of supercritical carbon dioxide: Effects of calcination temperature and supercritical conditions

TiO2-coated carbon felt(TCF)composite catalysts have been prepared via a supercritical treatment of titanium tetraisopropoxide(TTIP)as the precursor.The physical properties of the catalysts were characterized by means of thermogravimetric and differential thermal analysis(TG–DTA),X-ray diffraction(XRD),fluorescence spectroscopy,scanning electron microscopy (SEM),and BET surface areas techniques.The photocatalytic activities of the materials were evaluated using the degradation of Congo red(CR)as a probe reaction.All the composites showed much higher photocatalytic activity than commercial P25 due to significant synergistic effects.Reused TCF retained high photocatalytic activity for degradation of CR.The photocatalytic efficiency in CR degradation was found to be strongly dependent on the TiO2-coating ratio and calcination temperature.A possible mechanism for the enhanced reactivity involves shuttling of electrons from TiO2 particles to the carbon felt(CF)as a result of an optimal arrangement in TCF that stabilizes charge separation and reduces charge recombination.In addition to the significant synergistic effects,the abundant spaces between adjacent carbon fibers allow UV light to penetrate into the felt-like photocatalyst to a considerable depth,so that a three-dimensional environment is available for the photocatalytic reaction.