土壤中积累态磷活化动力学的研究Ⅰ.有机质的影响

研究了潮土和红壤中积累态磷的活化动力学及其有机质的影响。四种动力学方程均能很好地描述积累态磷的活化。用H2 O2 去除有机质加快了潮土中积累态磷的活化 ,对红壤影响不明显。施加 2 %葡萄糖培育促进了红壤中积累态磷的活化 。

低渗透油藏活化动力学探索

通过室内实验,研究了低渗透油层的孔隙结构特征及流体渗流特征,对水驱油过程的分析与推证后认为,流体渗流阻力是增大的,这种变化起因于所发生的多种物理化学变化,其结果将诱导相互关联的介质和流体系统的结构和功能随空间和时间而变化,这是呈现非达西渗流特征的本质所在.水驱后,利用研发的烷醇酰胺非离子表活剂进行了驱油实验,结果表明,表面活性剂可激活滞留油,提高油水的相对渗透率和可流动渗透率.活化动力学的研究要求从系统的微观结构对分子行为特征给出热动力学描述,进而揭示其非线性渗流机理,这必将开拓渗流力学新的研究领域.

土壤中积累态磷活化动力学的研究Ⅱ.沸石的影响

本文研究了NH4-沸石对潮土和红壤中积累态磷的活化动力学的影响。修正的Elovich公式和双常数速率公式对土壤中积累态磷的活化动力学拟合最好。土壤中添加了NH4-沸石后 ,土壤中积累态磷的活化释放明显增快。NH4-沸石有较强的释磷作用 ,可以促进土壤中积累态磷的活化释放。

贵州煤制活性炭工艺及其活化过程动力学

设计煤制活性炭的工艺流程,以探索贵州典型煤种制活性炭的可行性。以贵州无烟煤、烟煤及二者混合物为原料,经除灰、炭化后以水蒸汽为活化剂进行活化制活性炭,考察了活化温度、活化时间、水蒸汽流量及水蒸汽压力对活性炭亚甲蓝吸附值的影响,发现所制备活性炭的亚甲蓝吸附值随各因素的变化均存在极大值点,从而确定了适宜的活化条件,无烟煤、烟煤、混合煤所制活性炭的最大亚甲蓝吸附值分别为209、159、223 mg·g^(-1),比表面积分别为1121.37、908.58、1342.88 m^(2)·g^(-1),优于其他活性炭。实验结果也表明:贵州煤制活性炭存在协同效应,混合煤基活性炭具有最好的亚甲蓝吸附性能,且制备条件比单一煤基活性炭更加缓和。基于吸附理论建立了活化过程动力学,回归得到活化过程的速率参数;扫描电子显微镜(SEM)显示,混合煤基活性炭比单一煤基活性炭更加疏松,孔隙更加发达。

DNMR法测量分子内转动动力学活化参数

讨论了如何用 DNMR法测量分子内转动动力学的活化参数 ,如活化焓变化和活化自由能变化等参数。实验结果表明要想用 DNMR法得到较为可靠的分子内转动动力学活化参数 ,必须在较宽的温度范围内用诸如完全线形拟合法、自旋磁化强度迁移法和自旋锁定技术等具体的 DNMR实验技术在不同的温度范围内测得分子内转动的速率参数。

Effects of Fe content on photocatalytic activity of CaTiO_3-Fe_x

CaTiO 3-Fex was characterized by X-ray diffractometry, scanning electron microscopy equipped with an energy dispersive spectrometry system, Fourier transform infrared spectra, and UV-visible spectra. Effects of Fe content on photocatalytic activity of CaTiO3-Fex were investigated through measuring photocatalytic degradation rate of methylene blue. The results show that chemical compositions of CaTiO3-Fex remained unchanged with increasing Fe content from 0 to 4.745%. However, the light absorption ability of CaTiO3-Fex exhibited a significant increase with increasing Fe content. Photocatalytic degradation of methylene blue over CaTiO3-Fex followed the first-order reaction kinetics. Based on changes of the concentration of methylene blue and its degradation kinetics, CaTiO3-Fe0.474% has shown to have optimal photocatalytic activity. The degradation rate of methylene blue over CaTiO3-Fe0.474% was almost 100% under UV-visible light irradiation for 3.0 h. The kobs of methylene blue over CaTiO 3-Fe0.474% was 1.33 h-1 and was 7 times that over CaTiO3-Fe0.

Photocatalytic activity of Fe-doped diopside

UV-visible light induced photocatalytic degradation of methylene blue (MB) over Fe-doped diopside was investigated. The structure, composition, morphology and absorption property of UV-visible light of as-prepared samples were characterized using XRD, SEM, FTIR and UV-vis DRS. The experimental results show that doping Fe3+ induced the formation of some new species in diopside, and promoted light adsorption property of diopside in UV-visible region. Photochemical reactivity of Fe-doped diopside obviously depended on the content of doping Fe3+. The diopside with 1.848% Fe3+ exhibited the superior photocatalytic activity with 95% degradation of MB under UV-visible light for 3 h. The photocatalytic degradation kinetics of MB over all samples showed the first-order reaction nature.

Effect of mechanical activation on dissolution kinetics of neutral leach residue of zinc calcine in sulphuric acid

Neutral leach residue of zinc calcine （NLRZC） was mechanically activated by a stirring ball mill. Subsequently, the changes in physicochemical properties and dissolution kinetics in sulphuric acid were studied. The crystalline structure, morphology, particle size and specific surface area of the non-activated and mechanically activated NLRZC were characterized by X-ray diffraction, scanning electron microscope, particle size analyzer and volumetric adsorption analyzer, respectively. The characterization results indicate that mechanical activation （MA） induced remarkable changes in the physicochemical properties of NLRZC. The leaching experiments show that MA significantly enhances the leaching reactivity of NLRZC using the zinc extraction as evaluating index. After NLRZC is mechanically activated for 30 min and 60 min, the activation energy decreases from 56.6 kJ/mol of non-activated NLRZC to 36.1 kJ/mol and 29.9 kJ/mol, respectively. The reaction orders of the non-activated, 30 and 60 min activated NLRZC dissolution with respect to H2SO4 concentration were found to be 0.34, 0.30, and 0.29, respectively.

Ti-10Mo双相合金的吸氢性能

研究了低温(90℃以下)和高温(400—500℃)吸氢循环两种活化方法对Ti-10Mo双相合金吸氢动力学特性及吸氢后抗粉碎能力的影响。发现高温活化样品的抗破裂能力优于低温活化样品,但低温活化样品的吸氢动力学性能明显优于高温活化样品,这一现象可用样品具有不同的吸氢受控机制和相变过程来解释。

Kinetics analysis of decomposition of vanadium slag by KOH sub-molten salt method

A novel process was developed for the decomposition of vanadium slag using KOH sub-molten salt under ambient pressure, and the effects of reaction temperature, alkali-to-ore mass ratios, particle size, and stirring speed on vanadium and chromium extraction were studied. The results suggest that the reaction temperature and KOH-to-ore mass ratio are more influential factors for the extraction of vanadium and chromium. Under the optimal reaction conditions （temperature 180 °C, initial KOH-to-ore mass ratio 4：1, stirring speed 700 r/min, gas flow 1 L/min, and reaction time 300 min）, vanadium and chromium extraction rates can reach up to 95% and 90%, respectively. Kinetics analysis results show that the decomposing process of vanadium slag in KOH sub-molten salt can be well interpreted by the shrinking core model under internal diffusion control. The apparent activation energies for vanadium and chromium are 40.54 and 50.27 kJ/mol, respectively.

Non-isothermal thermal decomposition kinetics of high iron gibbsite ore based on Popescu method

The thermal decomposition kinetics of high iron gibbsite ore was investigated under non-isothermal conditions.Popescu method was applied to analyzing the thermal decomposition mechanism.The results show that the most probable thermal decomposition mechanism is the three-dimensional diffusion model of Jander equation,and the mechanism code is D3.The activation energy and pre-exponential factor for thermal decomposition of high iron gibbsite ore calculated by the Popescu method are 75.36 kJ/mol and 1.51×10-5 s-（-1）,respectively.The correctness of the obtained mechanism function is validated by the activation energy acquired by the iso-conversional method.Popescu method is a rational and reliable method for the analysis of the thermal decomposition mechanism of high iron gibbsite ore.

Leaching kinetics of gold bearing pyrite in H_2SO_4-Fe_2(SO_4)_3 system

Gold bearing pyrite leaching was conducted in H2SO4-Fe2（SO4）3 system at different reaction temperatures,with different ferric ion concentrations,sulfuric acid concentrations and stirring speeds.The leaching kinetics and mechanism were studied.When the temperature ranged between 30-75 °C,the pyrite leaching was mainly controlled by chemical reaction with positive correlation to the ferric ion concentration.The activation energy obtained from Arrhenius empirical formula is 51.39 k J/mol.The EDS and XPS analyses suggest that the oxidation of sulfur within pyrite is through a series of intermediate stages,and eventually is oxidized to sulphate accompanied with the formation of element sulfur.This indicates a thiosulfate oxidation pathway of the gold bearing pyrite oxidation in H2SO4-Fe2（SO4）3 system.

TGA-FTIR联用技术研究ABS树脂热降解行为

采用热失重-傅里叶变换红外光谱(TGA-FTIR)联用技术研究了在N_2气氛下ABS(丙烯腈-丁二烯-苯乙烯三元共聚物)的热稳定性及其分解失重情况。结果表明,ABS的TGA曲线只有1个失重区间,随着升温速率的增加,起始和峰值失重温度增加,热分解温度为380～480℃;ABS热分解活化能(E_a)在59.39～74.70kJ/mol,通过E_a变化发现,分解可分为多个阶段:经FTIR测试发现,ABS的热分解过程首先是橡胶相PB(聚丁二烯)主链上接枝的SAN(苯乙烯-丙烯腈共聚物)侧链降解,随着温度升高PB主链开始分解,失重质量分数大于50%时,以连续相的高相对分子质量SAN分解为主。

Kinetics and Mechanism of Decomposition of Nano-sized Calcium Carbonate under Non-isothermal Condition

Experiments on thermal decomposition of nano-sized calcium carbonate were carried out in a thermo-gravimetric analyzer under non-isothermal condition of different heating rates (5 to 20K·min-1). The Coats and Redfern's equation was used to determine the apparent activation energy and the pre-exponential factors. The mechanism of thermal decomposition was evaluated using the master plots, Coats and Redfern's equation and the kinetic compensation law. It was found that the thermal decomposition property of nano-sized calcium carbonate was different from that of bulk calcite. Nano-sized calcium carbonate began to decompose at 640℃, which was 180℃lower than the reported value for calcite. The experimental results of kinetics were compatible with the mechanism of one-dimensional phase boundary movement. The apparent activation energy of nano-sized calcium carbonate was estimated to be 151kJ·mol-1 while the literature value for normal calcite was approximately 200kJ·mol-1. The order of magnitude of pre-exponential factors was estimated to be 10~9 s-1.

Recovery of valuable metals from lepidolite by atmosphere leaching and kinetics on dissolution of lithium

The lepidolite located in Yichun, Jiangxi Province, China, was adopted to investigate the recovery of alkali metals and leaching kinetics of lithium with sulphuric acid solution under atmospheric pressure. The results show that the recoveries of alkali metals were achieved under the leaching conditions: mass ratio of lepidolite with particle size less than 180 μm to sulphuric acid 1.2, leaching temperature 411 K, liquid-solid ratio 2.5∶1, and leaching time 10 h. Under the selected conditions for leaching experiment, the leaching rates of lithium, potassium, rubidium and caesium are 94.18%, 93.70%, 91.81% and 89.22%, respectively. The X-ray diffraction analysis for leaching residue indicates that no insoluble product forms during leaching. The chemical compositions of leaching residue reveal that trace iron, manganese and calcium disappear after acid leaching. The kinetics of leaching process for lithium follows shrinking core model of mixed control and the apparent activation energy is 17.21 kJ/mol. The reaction orders with respect to sulphuric acid concentration and liquid-solid ratio are determined to be 2.85 and 1.66, respectively. A semi-empirical rate equation was obtained to describe the leaching process. The kinetic analysis shows that the leaching process is controlled by diffusion through the insoluble layer of the associated minerals.

Diffusion of Chloride Ions in Soils: Ⅱ. Kinetic and Thermodynamic Characteristics

The amounts of chloride ions diffused in four soils of different textures at the same water content under different temperature and at varied time were measured by the diffusion cell method using 36Cl-labelled CaCl2 solution. Five kinetic models were used to fit the dynamic process of the diffusion of chloride ions in the soils. It was found that Elovich equation or power function equation was the best model to describe the process. The pseudothermodynamic parameters, i. e. the net reaction energyl the activation entropy,activation enthalpy and activation free energy of the diffusion, were derived from the absolute reaction-rate theory. The results showed that these parameters decreased in the order of loessal soil > black in soil >lou soil > yellow cinnamon soil, which indicated that the force and the heat-energy barrier to be overcome for diffusion decreased, the diffusion rate increased and the disorder of the soil-solution-ion system due to diffusion decreased successively with the texture becoming heavier in the four soils.

Kinetic Study of Hydrothermal Stripping from Iron-Loaded Organic Phase

The iron-loaded organic phase of naphthenic acid-isooctyl alcohol-kerosene was prepared, and the process kinetics of hydrothermal stripping of iron from the phase was studied. Several factors affecting hydrothermal stripping, such as the polymer of naphthenic acid, initial concentrations of iron and naphthenic acid, temperature and agitation time, were investigated, and based on experimental results and theoretical analysis, two kinetic models were established.The stripping rate equation suggests that the hydrothermal stripping process activation energy is 96.4 kJ·mol-1 and the stripping is controlled by hydrolysis of naphthenic complex of iron. The values calculated by the stripping fraction equation comparatively accord with the experimental data.

Research on Dynamics Design for Active Sludge System

In order to describe the relationship between dynamic process and sludge removing load in active sludge system, a new method for designing the volume of aeration tanks was put forward based on the Michaelis and Menten equation. the influence of sludge returning was considered in the design. The result shows that the parameter of sludge reflux ratio plays a very important role in the design of active sludge system. In some given conditions,there exists an optimum reflux ratio which can make the volume of aeration tank be the minimum.

Temperature Effect on Boron Adsorption-Desorption Kinetics in Soils

The effect of temperature on the properties of boron adsorption-desorption in brown-red soil, yellowbrown soil and calcareous alluvial soil of Hubei Province was investigated with the mobile displacement technique. The experimental data of B adsorption-desorption amounts and reaction t line at 25 and 40℃ were fitted by the zero-order, first-order and parabolic diffusion kinetic equations. The adsorption process was in conformity with the parabolic diffusion law at both the temperatures, and the values of rate constant of the parabolic diffusion equation in B adsorption were 0.138, 0.124 and 0.105 mg kg-1 min-1/2 at 25℃, and 0.147, 0.146 and 0.135 mg kg-1 min-1/2 at 40℃ for the brown-red soil, yellow-brown soil, and calcareous alluvial soil, respectively. The relationship between amount of B desorption and reaction time could be well described by the first-order kinetic equation, and the corresponding values of rate constant were 0.0422, 0.0563 and 0.0384 min-1 at 25℃, and 0.0408, 0.042 3 and 0.0401 min-1 at 40℃ for the brown-red soil, the yellow-brown soil and the calcareous alluvial soil, respectively. Therefore, the desorption process of B might be related to the amount of B adsorbed in soil. The higher the temperature, the lower the amount of B adsorption for the same soil in the same reaction time. The values of the apparent activation energy of B adsorption in the three soils calculated with the rate constants of parabolic diffusion equation were 3.27, 8.44 and 12.99 kJ mol-1, respectively, based on the experimental data of B adsorption amounts and reaction time at 25 and 40℃.

Arrhenius parameters determination in non-isothermal conditions for mechanically activated Ag_2O-graphite mixture

The non-isothermal kinetics of mechanochemical reduction of Ag2O with graphite was studied by DSC and TGA with a model of fitting Malek approach and a model-free advanced isoconversional method of Vyazovkin. To evaluate the kinetics parameters, Ag2O–graphite mixture of as-received and milled for 2 and 4 h samples were selected. Based on the results obtained by Vyazovkin method calculation, however, the difference between the maximum and minimum values of activation energy is less than 20%-30%of the average activation energy （（99.38±2.36） kJ/mol） and thermal decomposition of mechanically activated Ag2O for 2 h is a multi-step process. Moreover, the thermal decomposition of mechanically activated Ag2O–graphite powder activated for 4 h is a single-step process （the average activation energy=（93.68±2.26） kJ/mol）. The kinetics modeling shows that the complexity of thermal decomposition of as-received Ag2O–graphite mixture is higher than that of the others. While, the autocatalytic tendency of as-received Ag2O–graphite mixture is lower than that of the others.