Effect of surfactant microstructures on photocatalytic degradation of phenol and chlorophenols

The effect of hexadecyltrimethylammonium bromide (HTAB) on the photocatalytic degradation of phenol (Phe), 2,5-dichlorophenol (2,5-DCP) and 2,4,5-trichlorophenol (2,4,5-TCP) in the presence of aqueous TiO₂ suspensions at pH ca. 5 was investigated using a laboratory photoreactor equipped with a medium-pressure mercury lamp. Inhibition of substrate decomposition was observed for phenol, both below and above the surfactant critical micellar concentration, whereas a more complex behaviour was exhibited by chlorophenols. It was found that adsorption of these compounds onto the surfactant-modified semiconductor particles facilitates their faster decomposition, but the competitive partition of substrates between adsorbed surfactant structures and micellar aggregates tends to limit the beneficial kinetic effects at higher amphiphile concentrations. The crucial influence of surfactant adsorption was clearly evidenced in some runs performed at pH 3. Relevant inhibition of chloride release from chlorophenols, observed in the presence of HTAB, indicates a higher persistence of reaction intermediates in the reaction media, suggesting the need for a careful investigation of surfactant effects on all the degradation steps of the process.     

Surface acidity study of Mn+-montmorillonite clay catalysts by FT-IR spectroscopy: Correlation with esterification activity

A simple method for evaluating the surface acidity of different cation-exchanged montmorillonite (mont) clay catalysts, Mⁿ⁺-mont (Mⁿ⁺=Al³⁺, Fe³⁺, Cr³⁺, Zn²⁺, Ni²⁺, Cu²⁺, and H⁺), involving treatment with pyridine is described. After treating with pyridine, the samples were heated at 120 °C and the FT-IR spectra were directly recorded in the region 1650 and 1350 cm⁻¹. The data obtained show the presence of both Lewis and Brønsted acid sites. The activities of the catalysts to bring about Brønsted acid catalysed esterification of succinic acid with iso-butanol to yield di-(iso-butyl) succinate have been studied. The Brønsted acidity data obtained for Mⁿ⁺-mont correlated well with activity in the esterification reaction. The activities of the catalysts were found to decrease in the order of exchange ions Al³⁺ > Fe³⁺ > Cr³⁺ > Zn²⁺ > Ni²⁺ > Cu²⁺ > Na⁺-mont. They also correlated well with the charge to radius ratio of the cations. The catalysts exchanged with trivalent cations showed stronger absorption bands attributed to Brønsted acidity (1540 cm⁻¹) whereas those exchanged with divalent cations showed an increased Lewis acidity (1450 cm⁻¹) and reduced Brønsted acidity along with charge to radius ratio. Zn²⁺-, Cu²⁺- and Ni²⁺-exchanged clays showed an additional peak around 1605 cm⁻¹ which is attributed to the pyridine adsorption on surface sites through its π electrons. The method suggested here to evaluate the acidity is suitable for active sites which are thermally unstable such as water molecules in the hydration shell of a cation in exchanged clay.     

The potential for rapid coke making using microwave energy

This paper describes initial work into the production of coke from high volatile bituminous coal using microwave energy. A series of batch experiments were carried out using an 8 kW multimode microwave to heat 300 g of a UK high volatile bituminous coal, sized at −3 mm, at different treatment times of 10, 25 and 70 min. Devolatilisation started after 1 min of heating and was complete within 5 min. Subsequent heating yielded no further volatiles and the power was maintained to prolong the coking process. Characterization of each product was carried out using thermogravimetric analysis, microscopy and dielectric property measurement in order to investigate the impact of residence time and provide a comparison with coke material produced using conventional methods. The measured characteristics of each sample became increasingly similar to those of two conventional cokes as treatment time was increased.     

轴流压气机旋转失速建模与检测II: 基于北航低速压气机试验台的实验研究

轴流压气机旋转失速和喘振的提前检测对于提高压气机工作效率和稳定性具有重要的意义.本文以北京航空航天大学航空发动机重点实验室的低速轴流压气机实验台为研究对象,基于确定学习理论及动态模式识别方法,开展旋转失速初始扰动近似准确建模和快速检测研究.首先,在压气机机匣壁面周向布置多个动态压力传感器,获取压气机失速前和失速先兆的动态压力信号,基于确定学习理论对旋转失速初始扰动的内部系统动态进行建模;其次,基于以上建模,利用微小振动故障检测方法实现对旋转失速的离线和在线提前检测.实验结果表明,本文所提方法能够在不同转速情况下,提前0.3 s~1 s实现对旋转失速的实时在线检测.     

合成煤中钠对煤燃烧及灰特性影响

准东煤中钠含量高，燃用时锅炉会出现严重结渣问题。通过向准东煤为原料制取的超纯煤中添加灰的模型化合物，得到合成煤。并在此基础上利用热重-差示扫描量热分析法（TG/DTG/DSC）、X射线衍射仪（XRD）和灰熔融温度测定分析手段，研究Na₂O含量对煤燃烧特性和灰熔融性的影响。结果表明：钠主要影响合成煤的着火温度（T_i）与焦炭燃烧阶段，钠含量增加使T_i升高，并且Na₂O在灰中质量分数由5%升高至8%后，钠含量增加使焦炭燃烧速率先减小后加快，并能够改善煤粉燃尽特性。钠能够降低灰熔融温度，并在Na₂O质量分数高于5%后，温度下降更加明显。在三元相图中钠对莫来石的助熔作用是造成灰熔融温度降低的重要原因。XRD分析表明Na₂O含量增加，充当骨架作用的石英在钠的助熔作用下与难熔矿物硅钙石、MgO等生成低熔点长石类矿物，这类矿物在高温下有助熔作用，能够降低灰熔融温度。同时还生成助熔性含钠矿物霞石，加剧了灰熔融。     

Catalytic behavior of potassium containing compounds for diesel soot combustion

Alkali doped oxides were synthesized and tested as catalysts for diesel soot combustion using a combinatorial method. It has been found that potassium shows better promotion of the catalytic activity than other alkali elements, and most of the potassium-rich oxides showed similar catalytic behaviors when catalysts and soot were mixed in a slurry. The influence of different mixing methods, including loose contact, tight contact and slurry (wet) mixing with different soot suspensions, on the catalytic behavior of some transition metal oxides, alkali metal carbonates and potassium-containing oxides were studied through thermogravimetry and XRD. The high activity of potassium-containing catalysts is found to be due to the intimate contact between soot and potassium cations caused by polar solvents. Potassium containing catalysts degraded after repeated thermal cycles due to the loss of potassium. It was also found that the addition of transition elements can inhibit the loss of potassium.     

基于DEM的碎屑流运动特性数值模拟

采用颗粒离散元法建立了碎屑流三维数值模型,分别从整体和局部对碎屑流运动特性进行深入分析。结果表明:碎屑流的运动过程可分为启动加速、高速滑动和减速堆积3个阶段;边坡底面平整时,堆积体中大颗粒堆积在表面,而细小颗粒位于中下部位;碎屑流运动速度和能量损失受颗粒间的接触碰撞影响大;碎屑流不同部位运动速度最大值相同,达到速度峰值的时间与颗粒的初始水平位置有关,与深度无关;堆积体分区明显,堆积体中的颗粒按初始水平位置依次排布;坡脚位置堆积深度最大,往两侧逐渐减小;碎屑流在运动初期和末期横向运动明显,扩大了灾害影响范围。     

吸湿性盐溶液振荡热管的传热特性研究

研究了10%(质量分数)LiCl吸湿性盐溶液作为工质的振荡热管传热特性。测试了在45％～90％充液率、10～100 W加热功率下振荡热管蒸发端温度及热阻的变化，并与去离子水工质的实验数据进行了对比。结果表明：在45％、55％的低充液率下，加热功率达到50 W以上时，LiCl溶液振荡热管的热阻明显比去离子水振荡热管低，能有效延迟烧干现象的发生。在62%的中等充液率，35W加热功率以上，LiCl溶液振荡热管的蒸发端温度较离子水振荡热管振荡频率快，幅度小且热阻低。在80%、90%的高充液率下，两种工质振荡热管的蒸发端温度曲线在平均温度、振荡频率、振荡幅度上都较为相似，热阻也比较接近。     

Performance of solvothermally prepared Ga2O3-Al2O3 catalysts for SCR of NO with methane

The solvothermal reaction of mixtures of aluminum isopropoxide (AIP) and gallium acetylacetonate (Ga(acac)₃) directly yielded the mixed oxides of γ-Ga₂O₃-Al₂O₃. In the solvothermal synthesis, the crystal structure of mixed oxides was controlled by the initial formation of γ-Ga₂O₃ nuclei. The mixed oxides prepared in diethylenetriamine have extremely high activities for selective catalytic reduction (SCR) of NO with methane as a reducing agent. With increasing crystallite size of the spinel structure, the catalytic activity increased. The ratio of the amount of methane consumed by combustion to total methane conversion was proportional to the density of acid sites on the surface of the mixed oxides. The mixed oxide catalysts prepared in diethylenetriamine had lower densities of acid sites and showed a higher methane-efficiency for CH₄-SCR than those prepared in other solvents. These catalysts maintained their high activity even when the reaction was carried out under the severe conditions (i.e., high space velocity and low NO concentration).     

Sulphur functionality study of steam pyrolyzed “Mequinenza” lignite using reductive pyrolysis technique coupled with MS and GC/MS detection systems

Atmospheric pressure–temperature programmed reduction (AP-TPR) and its analogous in oxidative atmosphere coupled “on-line” with a mass spectrometer (MS) were used to study the behaviour of organic sulphur forms of “Mequinenza” lignite during their mild steam pyrolysis. The obtained data were confirmed and completed by the AP-TPR-GC/MS “off-line” analysis. Samples under study were pyrolyzed at different processing parameters (temperature and flow gas). Some peculiarities in the distribution of non-thiophenic sulphur forms depending on experimental conditions were found. Namely, their amounts decreased with temperature increase at the steam treatment. The experiment performed at 500 °C in water vapor flow proved the C–S bond splitting in dibenzothiophene with biphenyl formation. Sulphonic acid compounds were also systematically removed. At higher temperature of the steam pyrolyzed treatment, this effect was more pronounced. At the same time, a relative increase in sulphones was found.The following organic sulphur species in demineralised lignite were detected by the “off-line” AP-TPR-GC/MS technique: methyl- and benzenethiols; mono- and disulphides; alkylthiolanes; alkenyl thiophenes; alkylbenzo[b]thiophenes and alkyldibenzo[bd]thiophenes. Their relative intensities as a function of temperature were followed. A strong preponderance of benzo[b]thiophene and its alkylated homologues above 450 °C were observed. Thiophene presence was temperature independent.