催化剂对CaO固硫反应动力学的影响

提高CaO的固硫率是对煤炭燃烧污染防治的研究热点。本研究探索用催化剂提高CaO固硫率的可行性及其对固硫反应动力学的影响。用热天平测试了在CaO中添加不同催化剂的固硫反应的进程,并采用等效粒子模型处理实验数据,计算了表面化学反应控制阶段及产物层扩散控制阶段的动力学参数。实验表明,CaO固硫反应初期为表面化学反应控制阶段,后期转为产物层扩散控制阶段。以碱金属的盐类为催化剂,它们均能使固硫反应前期的化学反应控制阶段的反应活化能下降,并按Li,Na,K,Cs的顺序依次递减,而碱金属盐的负离子主要影响产物层扩散阶段的固硫反应。     

焦炭溶损反应动力学及其模型研究

利用未反应核收缩模型对高炉焦炭与CO2的反应动力学进行了研究，建立了以可测参数（R）表达的焦炭与CO2的反应动力学关系式。并对反应速率常数和有效扩散系数、表观反应活化能和有效扩散活化能及反应过程中各步骤阻力进行了分析。结果表明，（1）焦炭与CO2的反应符合未反应核收缩模型。（2）反应的表观活化能Ea=124.5kJ/mol，有效扩散活化能ED=642.4 kJ/mol；界面化学反应的阻力随反应温度升高而增加；残余灰层内的内扩散传质阻力相对比例随温度升高而下降。（3）焦炭溶损反应在低温区主要受内扩散控制，随着温度升高，反应由外扩散、化学反应和内扩散三步控制；当进入高温区，反应进行一段时间后主要受内扩散控制。     

催化剂对CaO固硫反应活性的影响研究

用热天平研究了在CaO中添加不同催化剂对固硫反应进程及固硫反应转化率的影响,并采用等效粒子模型处理实验数据,计算了固硫反应两个阶段(表面化学反应控制阶段及产物层扩散控制阶段)的动力学参数。实验表明不同的催化剂对CaO固硫的影响效果和机制不同：催化剂KNO3,NaNO3使表面化学反应活化能和产物层扩散控制阶段反应活化能降低,但同时也使表面化学反应指前因子和扩散系数指前因子降低;而催化剂Fe2O,V2O5增大了表面化学活化能和产物层扩散控制阶段反应活化能,但同时也增大了表面化学反应指前因子和扩散系数指前因子。并发现几种催化剂对活化能和指前因子的影响都具有耦合性,因此单以表面化学反应活化能或产物层扩散控制阶段反应活化能来判断固硫反应活性是不够全面的,应计算出具体温度下的反应速率常数和产物层扩散系数值,才能准确地反映固硫反应的活性。     

烧结程度对CaO固硫反应转化率及动力学参数的影响

The conversion and kinetic parameters of desulfurizors of CaO of different particle agglomeration degree are investigated with themogravimetric method (TG). The results showed that the CaO particle agglomeration degree increases when CaO calcined temperature or time increases. The dusulfurizors that have higher particle agglomeration degree have low conversion in the desulfurization reaction. The kinetic behavior of desulfurization can be explained by a grain model. The activity energies of suface reaction (Ea) and of product layer diffusion (Ep) were determined by using the grain model. The overall rates of desulfurization are controlled initially by surface chemical reaction, and then shift to product layer diffusion control. The activity energy of surface reaction (Ea) enhances when the CaO particle agglomeration degree increases.     

赤泥的固硫特性及其机理研究

燃烧固硫技术作为洁净煤技术的一个重要发展方向,一直受到研究者的关注.其中,对固硫剂的研究也是热点之一.     

热重分析法研究贝壳固硫反应动力学

采用热分析法研究了贝壳和石灰石固硫反应过程, 用等效粒子模型对固硫反应过程进行了表征, 计算分析了其固硫反应动力学参数. 结果表明, 贝壳比石灰石含有较多的碱金属盐, 其作用是提高了贝壳固硫反应速率常数和有效扩散系数. 贝壳固硫反应中存在补偿效应. 根据等动力学温度判别固硫剂活性适用于不同反应控制区的活性判断. 碱金属成分对钙基固硫剂活性有正负两个方面的影响, 含量过大或过小都会削弱固硫剂活性, 因而存在最适含量. 在1 073～1 273 K温区固硫时, 钙基固硫剂中碱金属离子与钙离子摩尔比为1∶50左右时固硫活性较高.     

Interface diffusion and chemical reaction of PZT layer/Si (111) sample during the annealing treatment in air

The interface diffusion and chemical reaction between a PZT (PbZrxTi1-xO3) layer and a Si(111) substrate during the annealing treatment in air have been studied by using XPS (X-Ray Photoelectron Spectroscopy) and AES (Auger Electron Spectroscopy). The results indicate that the Ti element in the PZT precursor reacted with residual carbon and silicon, diffused from the Si substrate, to form TiCx, TiSix species in the PZT layer during the thermal treatment. A great interface diffusion and chemical reaction took place on the interface of PZT Si also. The silicon atoms diffused from silicon substrate onto the surface of PZT layer. The oxygen atoms, which came from air, diffused into silicon substrate also and reacted with Si atoms to form a SiO2 interlayer between the PZT layer and the Si (111) substrate. The thickness of SiO2 interlayer was proportional to the square root of treatment time. The formation of the SiO2 interlayer was governed by the diffusion of oxygen in the PZT layer at low annealing tempera     

Phenomenological kinetics of the thermal decomposition of sodium hydrogencarbonate

Aiming to find rigorous understanding and novel features for their potential applications, the physico-geometrical kinetics of the thermal decomposition of sodium hydrogencarbonate (SHC) was investigated by focusing on the phenomenological events taking place on a single crystalline particle during the course of the reaction. The overall kinetics evaluated by systematic measurements of the kinetic rate data by thermogravimetry under carefully controlled conditions were interpreted in association with the morphological studies on the precursory reaction, mechanism of surface reaction, structure of the surface product layer, diffusion path of evolved gases, crystal growth of the solid product, and so on. The precursory reaction was identified as the decomposition of impurity, taking place at the boundary between the surface of the SHC crystal and the adhesive small SHC particles deposited on the surface. In flowing dry N(2), the thermal decomposition of SHC proceeds by two-dimensional shrinkage of the reaction interface controlled by chemical reaction with the apparent activation energy of about 100 kJ mol(-1), after rapid completion of the surface reaction and formation of porous surface product layer. Atmospheric CO(2) and water vapor influence differently on the overall kinetics of the thermal decomposition of SHC. Added gas phase of CO(2) slightly inhibits the overall rate because of the increasing contribution of the surface reaction. Under higher water vapor pressure, the physico-geometrical mechanism of the surface reaction changes drastically, indicating the preliminary reformation of reactant surface and the formation of needle crystals of solid product on the surface. The mechanistic change and extended contribution of the surface reaction result in the deceleration of the surface reaction and acceleration of the established reaction.     

Direct sulfation reaction of SO2 with calcium carbonate

The direct sulfation reaction of SO₂ with CaCO₃ has been investigated by thermogravimetry (TG) under the condition that the CaCO₃ does not decompose to CaO prior to sulfation by controlling CO₂ partial pressure. The direct sulfation process can be described by using a shrinking-core model for constant particle size. The model shows that the reaction rate and the diffusion rate of SO₂ through the product layer are equally important. Temperature effects can be correlated by the activation energy of 35.9 kJ mol⁻¹ for the sulfation reaction and 66.5 kJ mol⁻¹ for the product layer diffusion. The sulfation reaction is found to be first order with respect to SO₂. With larger pore volume and surface area of limestone samples, the sorbents have a stronger reactivity of SO₂ removal. A 70% CaCO₃ conversion can be achieved in 10 min at 800°C and 2000 ppm SO₂.     

甲苯甲醇侧链烷基化反应中甲酸盐的形成及其作用

将碱金属碳酸盐修饰的KX和NaY沸石用于催化甲苯甲醇侧链烷基化反应,并结合甲醇吸附的红外光谱以及异丙醇和甲醇催化分解反应结果,剖析了甲酸盐的形成及其作用.结果表明,碱金属碳酸盐的负载能提高碱金属离子交换八面沸石的催化活性.在反应过程中催化剂表面形成了不同数量的甲酸盐,尤其是K2CO3修饰的KX上;甲酸盐主要来源于碳酸盐与甲醇分解产物甲醛的反应,它的形成对催化剂甲苯甲醇侧链烷基化活性的影响较大,类似于碱金属硼酸盐的修饰,改善了催化剂的表面酸碱性,形成了更为有效的活性中心.     

氧化锌颗粒脱硫中固体扩散的动力学分析

用电子探针显微分析 (EPMA)对ZnO基脱硫剂的脱硫颗粒径向硫分布行为进行了考查 ,对颗粒最外层粒子的实验结果分别用未反应收缩核模型及改良收缩核模型进行了动力学处理 ,给出了固体扩散活化能的参数估值。通过与热重研究的比较 ,进一步证实了固体粒子扩散的作用。     

金刚石颗粒表面Cr金属化及薄膜间界面扩散反应的研究

运用直流磁控溅射法可在金刚石颗粒表面沉积150nm的金属Cr层.在超高真空条件下,经300-600℃的热退火处理,可促进Cr膜与金刚石基底间的界面扩散和反应.利用俄歇电子能谱研究了Cr/金刚石颗粒界面的结合状态,发现Cr与金刚石薄膜发生了强烈的界面扩散,Cr元素渗入金刚石层达90nm,并在界面上发生化学反应形成Cr的碳化物层.对界面扩散反应动力学的研究表明,Cr/金刚石界面扩散反应的表观活化能为38.4kJ/mol,界面扩散反应主要由碳的扩散过程控制.热处理温度越高,界面扩散及反应越显著,但不利于碳化物层生成的氧化反应速度也会有所增加,界面反应产物从Cr₂C₃转变为Cr₂C物种.延长热处理时间有利于金属碳化物的生成,同样导致界面反应产物从Cr₂C₃转变为Cr₂C物种.     

钛酸锌高温煤气脱硫剂再生行为的研究

在热天平装置上研究了再生反应温度、反应气体中氧气体积分数、脱硫剂颗粒粒径对钛酸锌高温煤气脱硫剂再生行为的影响。实验结果表明，较高的反应温度和氧气体积分数，较小的颗粒粒径有利于提高脱硫剂的再生反应速率。由于二次反应的影响，脱硫剂再生过程中有硫酸盐生成，提高反应温度或降低反应气体的氧气体积分数可以减少硫酸盐的生成。利用收缩核模型对其动力学行为进行了分析，结果表明，脱硫剂的再生过程存在动力学控制步骤的转移。脱硫剂再生转化率较低（<65%）时，再生过程主要受化学反应控制；再生转化率较高（>75%）时，再生过程主要受颗粒内扩散控制。表观化学反应速率常数的指前因子为8.01×10－2 m/s，活化能为19.11 kJ/mol；有效扩散系数的指前因子为3.12×10－4 m2/s，扩散活化能为48.84 kJ/mol。     

Kinetic modeling of liquid-phase adsorption of phosphate on dolomite

The adsorption of phosphate from aqueous solution on dolomite was investigated at 20 and 40 degrees C in terms of pseudo-second-order mechanism for chemical adsorption as well as an intraparticle diffusion mechanism process. Adsorption was changed with increased contact time, initial phosphate concentration, temperature, solution pH. A pseudo-second-order model and intraparticle diffusion model have been developed to predict the rate constants of adsorption and equilibrium capacities.The activation energy of adsorption can be evaluated using the pseudo-second-order rate constants. The adsorption of phosphate onto dolomite are an exothermically activated process. A relatively low activation energy and a model highly fitting to intraparticle diffusion suggest that the adsorption of phosphate by dolomite may involve not only physical but also chemisorption. This was likely due to its combined control of chemisorption and intraparticle diffusion. However, for phosphate/dolomite system chemical reaction is important and significant in the rate-controlling step, and for the adsorption of phosphate onto dolomite the pseudo-second-order chemical reaction kinetics provides the best correlation of the experimental data.     

CaO固硫过程中Ca~(2+)在CaSO_4产物层内扩散的研究

应用标记实验技术，研究CaO固硫反应过程中产物层扩散控制阶段的反应机理 。利用扫描电镜和反射式光学显微镜，对压制烧结并带有Pt标记的CaO样品在固硫 反应前后的形貌变化观察，结果表明：经过较长时间的固硫反应后，在Pt标记层外 表面形成一层覆盖物，XRD分析结果证明该覆盖物是CaSO_4。利用电化学综合测试 仪测量了CaO及CaSO_4在高温下的电导率，结果表明在1000 ℃时CaSO_4的电导率达 到了10~(-3)数量级，说明在高温下CaSO_4内Ca~(2+)有较高的离子迁移特性。根据 标记实验、电导率测试的结果和CaO掺杂体系的固硫动力学数据的分析认为：CaO固 硫反应在后期的扩散层控制阶段的主要反应是Ca~(2+)通过CaSO_4产物层扩散至 CaSO_4外表面与SO_2和O_2进行反应，生成CaSO_4，而不是SO_2和O_2气体通过 CaSO_4产物层向内扩散，在颗粒内部与CaO发生固硫反应。     

A kinetic study of the oxidation of uranium dioxide

Summary A kinetic model for the oxidation of a UO₂ pellet is suggested by considering the mass transfer and the diffusion of oxygen molecules. The kinetic parameters were estimated by a fitting of the experimental data. The activation energies for the chemical reaction and the product layer diffusion were calculated from the kinetic model. The suggested model explains well the oxidation behavior of UO₂.     

Interfacial polymerization of an isocyanate and a diol

The interfacial reaction between a liquid polyfunctional aromatic isocyanate and a diol was studied using infrared spectroscopy to follow the reduction in concentration of the isocyanate group. It was shown that the product polyurethane formed a gel layer around dispersed isocyanate droplets which were swollen by the diol but not by the isocyanate. A model for the process is suggested based on the reaction occuring at the interface of a diminishing droplet surface. It is suggested that the reaction is controlled by the reaction kinetic parameters and the mass transfer by diffusion of the diol through the product layer. Quantitative evaluation is based on steady and nonsteady state diffusion theories.     

Kinetics of H<Superscript>+</Superscript>/Na<Superscript>+</Superscript> solid-phase ion exchange on iron(III) hydrogen sulfate

The kinetics of solid-phase reaction between iron(III) hydrogen sulfate and sodium chloride was studied by thermal analysis followed by analysis of leaving gases. The exchange kinetics are described by the soft cylinder model. The hydrogen and sodium ion interdiffusion coefficients were determined for various temperatures, as well as the activation energy of interdiffusion. Sodium ion diffusion through the product layer is the rate-controlling stage of the reaction.     

On stability of model electrocatalytic process with frumkin adsorption isotherm occurring on spherical electrode

The method of impedance spectroscopy was used for theoretical studies of the conditions of appearance of Hopf instability in a model electrochemical system with a preceding homogeneous chemical reaction in the Nernst diffusion layer and electrocatalytic reaction on the spherical electrode surface under potentiostatic conditions. It is shown within the suggested electrochemical instability model based on the potential-dependent adsorption/desorption that the effective rate of the preceding homogeneous chemical reaction may affect the system stability. The effect diminishes at a decrease in the electrode radius. The instability region grows at an increase in the thickness of the Nernst diffusion layer.     

钛酸锌脱硫剂硫化过程的动力学分析

利用固定床反应器对钛酸锌高温煤气脱硫剂硫化过程的动力学进行了研究,考察了硫化反应温度、H2S体积分数对脱硫反应过程的影响。结果表明,脱硫剂具有良好的脱硫反应活性,在400 ℃～600 ℃,脱硫剂的硫化反应速率随着硫化反应温度的升高、反应器入口H2S 体积分数的增大而增大。在实验数据的基础上,利用等效粒子模型对其反应动力学进行了分析,发现该脱硫剂的硫化反应主要受固体内扩散控制,固体内扩散活化能为 61.4 kJ/mol,相应的频率因子为 4.4×105 m2/min。硫化反应后脱硫剂比表面积、孔体积显著减小,脱硫剂表面有颗粒聚集物存在,进一步验证了该脱硫剂的硫化反应主要是通过产物层的体相扩散控制的。