城市生活垃圾在热解处理中的产气特性研究

通过对沈阳市皇姑区内的3个垃圾排放点进行实地采样并分类称量,得出其组分含量,得到了生活垃圾的主要物料组份.在此基础上在外加热固定床式热解试验台上,用热解实验的方法对8种城市生活垃圾中的主要物料中的典型成分进行热解试验.通过数据分析总结出不同工况下产气特性和热解气体的组分含量、热值,并建立热解气体析出模型进行产气量预测.     

Influence of plants on the reduction of hexavalent chromium in wetland sediments

This work addresses the effect that plants (Typha latifolia and Carex lurida) have on the reduction of Cr(VI) in wetland sediments. Experiments were carried out using tubular microcosms, where chemical species were monitored along the longitudinal flow axis. Cr(VI) removal was enhanced by the presence of plants. This is explained by a decrease in the redox potential promoted by organic root exudates released by plants. Under these conditions sulfate reduction is enhanced, increasing the concentration of sulfide species in the sediment pore water, which reduce Cr(VI). Evapotranspiration induced by plants also contributed to enhance the reduction of Cr(VI) by concentrating all chemical species in the sediment pore water. Both exudates release and evapotranspiration have a diurnal component that affects Cr(VI) reduction. Concentration profiles were fitted to a kinetic model linking sulfide and Cr(VI) concentrations corrected for evapotranspiration. This expression captures both the longitudinal as well as the diurnal Cr(VI) concentration profiles.     

Competing pathways of cresol formation in toluene photooxidation: OH-toluene adducts react with NO2 or with O2?

Methyl-hydroxy-cyclohexadienyl radicals (OTAs) are the key products of the photooxidation of toluene, with implications for the fate of toluene. Hence, we investigated the photooxidation mechanisms and kinetics of three main OTAs (o-OTA, m-OTA, and p-OTA) with NO₂ using quantum chemical calculations as well as the fate of OTAs under the different concentration ratios of NO₂ and O₂. The mechanism results show that the pathway of H-abstraction by NO₂ to anti-HONO (anti-H-abstraction) is more favorable than the syn-H-abstraction pathway, because the strong interaction between OTAs and NO₂ is formed in the transition states of the anti-H-abstraction pathways. The branching ratios of the anti-H-abstraction pathways are more than 99% in the temperature range of 216−298 K. The total rate constant of the OTA-NO₂ reaction is 9.9 × 10⁻¹² cm³/(molecule∙sec) at 298 K, which is contributed about 90% by o-OTA + NO₂, and the main products are o-cresol and anti-HONO. The half-lives of the OTA-NO₂ reaction in some polluted areas of China are 35 times longer than those of the OTA-O₂ reaction. In the atmosphere, the NO₂- and O₂- initiated reactions of OTAs have the same ability to form cresols as [NO₂] is up to 142.1 ppmV, which is impossible to achieve. It implies that under the experimental condition, the [NO₂]/[O₂] should be controlled to be less than 7.8 × 10⁻⁵ to simulate real atmospheric oxidation of toluene. Our results reveal that for the photooxidation of toluene, the yield of cresol is not affected by the concentration of NO₂ under the atmospheric environment.     

改性污泥活性炭吸附废水中Cr(Ⅵ)的性能研究

以污水处理厂剩余污泥为原料,1.0 mol/L KOH做活化改性剂,制备污泥活性炭,探讨不同条件下其对废水中Cr(VI)的吸附性能.结果表明,污泥活性炭对Cr(VI)吸附的最佳条件为:pH为2,温度为25℃,污泥活性炭投加量为5 g/L,吸附时间为40 min.此条件下,废水中Cr(VI)的去除率可达99%以上.动力学分析表明,污泥活性炭对Cr(VI)废水的吸附符合准二级动力学方程与Langmuir等温式.     

Using polarized muons as ultrasensitive spin labels in free radical chemistry

In a chemical sense, the positive muon is a light proton. It is obtained at the ports of accelerators in beams with a spin polarization of 100%, which makes it a highly sensitive probe of matter. The muonium atom is a light hydrogen isotope, nine times lighter than H, with a muon as its nucleus. It reacts the same way as H, and by addition to double bonds it is implemented in free radicals in which the muon serves as a fully polarized spin label. It is reviewed here how the muon can be used to obtain information about muonium and radical reaction rates, radical structure, dynamics, and local environments. It can even tell us what a fragrance molecule does in a shampoo.     

Modeling the effects of concentration history on the slow desorption of trichloroethene from a soil at 100% relative humidity

To determine the effects of concentration history on slow sorption processes, desorption kinetic profiles for trichloroethene (TCE) were measured for a soil at 100% relative humidity subject to different exposure concentrations and exposure times. Exposure concentrations ranged from 1% to 80% of the saturation vapor pressure (Ps) for TCE, and exposure times (i.e., time allowed for sorption before desorption begins) ranged from 1 to 96 days. A spherical diffusion model based on a gamma distribution of sorption rates and a gamma distribution of desorption rates was developed and applied to the data. At 80% P/Ps, the entire gamma distributions of sorption and desorption rates were available for TCE. In accordance with a micropore filling mechanism, the fraction of these distributions available for TCE sorption decreased with decreasing P/Ps. Experimental results are consistent with a micropore-filling mechanism, where the amount of slow desorbing mass decreased with decreasing exposure time, and the fraction of slow desorbing sites filled decreased with decreasing exposure concentration. Simulation results suggest that diffusion limits the rates that micropores fill, and that rates of sorption and desorption for soil contaminated at smaller values of P/Ps are, on average, less than those at larger values of P/Ps (i.e., slow desorption rates are a function of exposure concentration). Simulation results also suggest that the model adequately describes the effects of exposure concentration and exposure time on the rates of sorption and desorption, but not on the capacity of the slow sites for TCE. This work is important because contaminant concentrations in the subsurface vary in space and time, and the proposed model represents a new and mechanistically based approach to capture the effects of this heterogeneity on slow desorption.     

水中臭氧分解动力学研究

在磷酸盐缓冲液中研究了臭氧的自分解,根据臭氧分解机理推导出其动力学方程。由不同温度和pH值下的实验结果确定出kT,0,n以及活化能E。      

Prediction of high-density polyethylene pyrolysis using kinetic parameters based on thermogravimetric and artificial neural networks

● Reducting the sampling frequency can enhance the modelling process. ● The pyrolysis of HDPE was investigated at three different heating rates. ● The average E_a and k₀ were calculated by Friedman, KAS, FWO, and CR methods. ● ANN was employed to predict the HDPE weight loss with the optimal MSE and R². Pyrolysis is considered an attractive option and a promising way to dispose waste plastics. The thermogravimetric experiments of high-density polyethylene (HDPE) were conducted from 105 °C to 900 °C at different heating rates (10 °C/min, 20 °C/min, and 30 °C/min) to investigate their thermal pyrolysis behavior. We investigated four methods including three model-free methods and one model-fitting method to estimate dynamic parameters. Additionally, an artificial neural network model was developed by providing the heating rates and temperatures to predict the weight loss (wt.%) of HDPE, and optimized via assessing mean squared error and determination coefficient on the test set. The optimal MSE (2.6297 × 10⁻²) and R² value (R² > 0.999) were obtained. Activation energy and pre-exponential factor obtained from four different models achieves the acceptable value between experimental and predicted results. The relative error of the model increased from 2.4 % to 6.8 % when the sampling frequency changed from 50 s to 60 s, but showed no significant difference when the sampling frequency was below 50 s. This result provides a promising approach to simplify the further modelling work and to reduce the required data storage space. This study revealed the possibility of simulating the HDPE pyrolysis process via machine learning with no significant accuracy loss of the kinetic parameters. It is hoped that this work could potentially benefit to the development of pyrolysis process modelling of HDPE and the other plastics.     

锌在石灰性土壤中的吸附动力学初步研究

采用恒流淋洗法研究了外加锌在石灰性土壤中的吸附动力学特性.通过对石灰性土壤样品,人工模拟样品和纯CaCO_3物质吸附锌的动力学实验,结果衰明,石灰性土壤中的CaCO_3组分是外加锌的主要载体,且被CaCO_3组分所保持的锌不易被0.01mol/LCaCl_2溶液解吸下来。还拟用了几种动力学方程(一级动力学方程,Elovich方程和抛物线扩散方程)对本实验得到的动力学曲线进行描述和数据处理,结果表明石灰性土壤吸附锌的动力学特征主要由土壤中CaCO_3组分决定的。     

铁(Ⅲ)-羧酸配合物对水溶性染料的光化学脱色动力学的比较研究

铁-柠檬酸，铁-酒石酸，铁-丁二酸，铁-草酸配合物在高压汞灯（λmax＝313nm，250W）的照射下，能使活性艳红X－3B染料水溶液脱色。染料初始浓度在10mg／L～50mg／L时，染料脱色为动力学一级反应，脱色速率随初始浓度增大而降低。在pH2．0～3．0时铁-柠檬酸，铁-滴石酸，铁-丁二酸的染料溶液脱色效果较佳，在pH4．0时铁-草酸的染料溶液脱色效果最好。铁／羧酸盐配比对染料脱色速率也有影响。