Diffusion Mass Exchange in Dissolving Silica in Na2O – SiO2 Melts

Based on experimental materials on the kinetics of dissolution of silica grains accumulated in the literature, a generalized dependence is obtained, according to which kinetic dissolution curves in diffusion mass exchange are uniquely determined by the chemical composition (silica modulus), the melting temperature, and the initial granulometric composition of silica-bearing batch components.     

STUDY ON THE PYROLYSIS AND RECYCLING OF PVC WASTE AS AN ENERGY SOURCE

The pyrolysis dechlorination of PVC (polyvinyl chloride) has been carried out by batch operation under atmospheric pressure. The kinetics involved in the PVC thermal decomposition was studied by using thermogravimetric technique. Several tests were carried out at the heating rate of 5-10℃/min, the yields of products and the distribution of chlorine were also studied. The kinetic parameters such as activation energies, reaction orders and preexponential factors under nitrogen atmosphere were calculated by applying Friedmans method. The results showed that the PVC thermal degradation is substantially a two-step process. The first step mainly involves dechlorination of the polymers. HCI is the main volatile product and this reaction can be seen as a first-order reaction. A kinetic model for the thermal dechlorination of PVC has been developed.     

焦炭颗粒在不同控制区域中的燃烧特性

针对焦炭颗粒在煤粉炉内的复杂燃烧过程,建立相互耦合的导热、气相传质模型及改进的随机孔模型. 通过FORTRAN编程,研究了焦炭颗粒在不同控制区域中的燃烧特性,应用改进的随机孔模型,研究了焦炭颗粒在扩散-化学反应动力学控制区中的燃烧特性. 结果表明,在扩散-化学反应动力学控制区,碳基上的小孔内部存在O2浓度梯度,焦炭颗粒的转化速率在转化率约为0.39时出现最大值,随燃烧过程进行先增大后减小.     

大中型硫酸装置转化升温设备的选择

介绍硫酸生产中常用的三种转化升温方式：烟道气直接升温、燃烧炉配预热器间接升温及电炉升温,论述电炉升温的功率定额选定及影响因素。烟道气直接升温由于会危害催化剂故不提倡使用;电炉升温一次性投资较低、设备及操作简单、热效率高、可调节性强,如果电网供电不存在问题并且运行费用可以接受,建议在大中型硫酸装置中使用。     

基于Aspen Plus的桦甸式油页岩干馏工艺系统模拟

引言油页岩是一种富含有机质、具有微细层理、可燃烧的细粒沉积岩,油页岩作为能源资源,既可以干馏炼油也可以燃烧发电。油页岩储量丰富,截至2005年底,37个国家油页岩探明总储量折算     

Thermogravimetric analysis of polystyrene: Influence of sample weight and heating rate on thermal and kinetic parameters

This article studies the influence of the heating rate and sample weight on the thermal decomposition of polystyrene (first-order kinetics). For this purpose, the kinetic parameters (i.e., frequency factor and activation energy), variables at the maximum decomposition rate (such as conversion, reaction rate, and temperature), as well as some characteristic temperatures have been determined for a series of experiments where the heating rate varies (0.5–11.5 K/min) and also, the sample weight (6.0–25.1 mg). Some mathematical equations have been developed that allow: (1) evaluation of the activation energy of thermal decomposition by different ways and comparing the results obtained; (2) relating different parameters between themselves, such as the heating rate with the temperature at the maximum decomposition rate or the frequency factor with the heating rate and sample weight. Finally, some theoretical explanations of the variation of thermal and kinetic parameters have been proposed. © 1996 John Wiley & Sons, Inc.     

Kinetic study of the hydrothermal reaction of fly ash with ca(oh)2 in the preparation of desulfurant sorbents

Sorbents prepared by hydration of fly ash and Ca(OH)2 are widely used in flue gas desulfurization process. In this work, kinetic data for this hydration reaction in the conditions established in previous works were obtained by determining the conversion of Ca(OH)2 with the time. The purpose was to find the kinetic model for this pozzolanic reaction and to include the influence of the preparation variables. According to bibliography, the dissolution of silica from the fly ash in the presence of hydroxyl ions from Ca(OH)2 was considered to be the rate-limiting step, so a liquid-solid reaction takes place. Results showed that the reaction rate was not affected by the stirring rate. Results obtained at different reaction conditions fit rather well (standard deviation equal or lower than 8%) to the equation corresponding to the shrinking core model with diffusion ontrol. Liquid to solid ratio showed no influence on the reaction rate. Temperature was fitted to the Arrhenius equation, with activation energy of 24 Kcal./mol.Alinear fit of the fly ash/Ca(OH)2 ratio in the mathematical expression and their parameters were also found.     

KINETIC STUDY OF THE HYDROTHERMAL REACTION OF FLY ASH WITH Ca(OH)2 IN THE PREPARATION OF DESULFURANT SORBENTS

Sorbents prepared by hydration of fly ash and Ca(OH)2 are widely used in flue gas desulfurization process. In this work, kinetic data for this hydration reaction in the conditions established in previous works were obtained by determining the conversion of Ca(OH)2 with the time. The purpose was to find the kinetic model for this pozzolanic reaction and to include the influence of the preparation variables. According to bibliography, the dissolution of silica from the fly ash in the presence of hydroxyl ions from Ca(OH)2 was considered to be the rate-limiting step, so a liquid-solid reaction takes place. Results showed that the reaction rate was not affected by the stirring rate. Results obtained at different reaction conditions fit rather well (standard deviation equal or lower than 8%) to the equation corresponding to the shrinking core model with diffusion ontrol. Liquid to solid ratio showed no influence on the reaction rate. Temperature was fitted to the Arrhenius equation, with activation energy of 24 Kcal./mol.Alinear fit of the fly ash/Ca(OH)2 ratio in the mathematical expression and their parameters were also found.     

基于精细自由基反应机理的丙烷裂解炉炉管CFD模拟(英文)

In the radiant section of cracking furnace, the thermal cracking process is highly coupled with turbulent flow, heat transfer and mass transfer. In this paper, a three-dimensional simulation of propane pyrolysis reactor tube is performed based on a detailed kinetic radical cracking scheme, combined with a comprehensive rigorous computational fluid dynamics（CFD） model. The eddy-dissipation-concept（EDC） model is introduced to deal with turbulence-chemistry interaction of cracking gas, especially for the multi-step radical kinetics. Considering the high aspect ratio and severe gradient phenomenon, numerical strategies such as grid resolution and refinement, stepping method and relaxation technique at different levels are employed to accelerate convergence. Large scale of radial nonuniformity in the vicinity of the tube wall is investigated. Spatial distributions of each radical reaction rate are first studied, and made it possible to identify the dominant elementary reactions. Additionally, a series of operating conditions including the feedstock feed rate, wall temperature profile and heat flux profile towards the reactor tubes are investigated. The obtained results can be used as scientific guide for further technical retrofit and operation optimization aiming at high conversion and selectivity of pyrolysis process.     

Applications of hydrothermal electrolysis for conversion of 1-butanol in wastewater treatment

Hydrothermal electrolysis of organic compound in the presence of electrolyte was conducted for a woody biomass model compound. The reaction behavior of 1-butanol as a woody biomass model compound was studied in subcritical conditions at 200-250 °C and 8-12 MPa with a batch autoclave. The autoclave volume was 500 mL and equipped system with agitation stirrer, electric current control, electric heating and temperature control and a pressure gauge. The chemical species in aqueous products were identified by gas chromatography mass spectrometry (GC-MS) and quantified using gas chromatography flame ionization detector (GC-FID). The gaseous products were analyzed by gas chromatography with a thermal conductivity detector (GC-TCD). The effects of reaction temperature, pressure and applied constant current on the conversion process of 1-butanol were presented. The main products from the conversion of 1-butanol were butanal, butyric acid, hydrogen and carbon dioxide. Additionally, the values of reaction rate constant for butanal and butyric acid formation were calculated at 200 and 250 °C by kinetic study.     

Kinetics modeling of a modified epoxy–amine formulation cured by thermal and microwave energy

The reaction kinetics of a rubber-modified epoxy formulation cured by microwave or thermal energy were investigated. Two phenomenological models were developed to predict the time and temperature dependence of the conversion for the neat and the modified systems. Good agreement was observed between the kinetic models and experimental results generated by chromatographic and calorimetric techniques. The same kinetic behavior was observed whatever the curing process (conventional or microwave heating). © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 543–552, 1998     

工业碱木素热化学转化制备酚类化学品

引言 工业碱木素是碱法制浆过程中产生的重要副产物之一,其排放污染问题越来越受到关注,目前工业处理方法只是将其浓缩燃烧以回收能源和残碱.木质素是一种化学结构复杂的天然高分子聚合物(主要由愈创木基丙烷、紫丁香基丙烷和对羟苯基丙烷通过醚键和碳碳共价键相联),其分子量从几千至几十万,数量上仅次于纤维素,利用潜力较大.     

生物质焦CO2高温气化反应动力学研究

利用同步热分析仪,采用程序升温法研究了生物质焦CO₂气化反应速率特性,主要考察了升温速率对生物质焦气化反应性的影响,并用Friedman-Reich-Levi法对其动力学参数进行了计算。结果表明：DTG曲线峰值温度和最大反应速率随着升温速率的增大而增大;以二氧化碳作保护气,改变升温速率,当升温速率为15 ℃/min时,热解得到的生物质焦的反应活性最好,即气化速率最快;升温速率越大,反应速率随着温度的变化越明显;生物质焦气化阶段的活化能在-4 984.41~1 408.39 kJ/mol之间变化,气化的反应过程复杂。     

Modeling batch melting: Roles of heat transfer and reaction kinetics

Development of mathematical models of heat and mass transfer in glass-melting furnaces began in the 1970s and progressed rapidly with advances in sophisticated experimental/numerical techniques and increasing computational power. Today, practically all newly built or rebuilt furnaces are optimized with these models to meet stringent quality requirements, reduce the unit costs of manufacturing, or control emissions. One remaining hurdle is to model the batch-to-glass conversion accurately enough to reliably assess the glass production rate. This article summarizes two key aspects of the batch-conversion modeling—the heat transfer and the kinetics of conversion—and reviews the current state-of-the-art approaches to simulating them. We critically examine the advantages of the commonly used heat transfer approach, but also explain that its predictive capabilities are significantly restricted by the dependence of batch thermal properties on the time-temperature history. We argue that kinetic approaches to the batch-conversion modeling would offer a significant improvement when coupled with the heat transfer approach. Finally, we summarize key areas requiring further research on the way toward a realistic model of the batch blanket.     

Non-isothermal kinetic study of high-grade magnesite thermal decomposition and morphological evolution of MgO

Thermal decomposition was the prerequisite and basis for the utilization of magnesite resources. However, the calcination of magnesite was usually accompanied by high energy consumption, which not only caused serious waste of magnesite resources, but also restricted its high value-added utilization. Therefore, calcination conditions were the key to controlling thermal decomposition process of magnesite. The kinetics of high-grade magnesite thermal decomposition was elaborated by non-isothermal thermogravimetric analysis, and meanwhile the effect of heating rate on the magnesite thermal decomposition reaction and morphology of MgO particles were characterized. Both Doyle and Gorbatchev approximate functions were used to simulate the magnesite thermal decomposition process, where the experimental data (correlation coefficient) fitted by the latter could obtain more acceptable kinetic parameters of the magnesite thermal decomposition. The good linear relationship between the activation energy and the pre-finger factor allowed for a kinetic compensation of the thermal decomposition of magnesite. Furthermore, higher heating rate induced the formation of terraced grains, grain network group, cubic grains, and spherical grains for the samples sintered at 1200°C. The heating rate largely affected the magnesite particle morphology, grain size distribution and activity, and also provided important technical indicators in the actual production of magnesia refractory raw materials.     

Rapid firing of silica

Summary It was shown to be possible to fire silica in 200-ton periodic kilns in 160–170 h without worsening their properites.Experiments on the rapid heating and cooling of silica need to be continued both in test and in industrial furnaces.In an experimental furnace the firing time was reduced by about 80%, but this schedule was not proven in an industrial kiln.The obtained thermal-physical properties of the green goods permit a more accurate calculation of the permitted rated of heating. It is necessary to explain the influence of grading, batch composition and pressing conditions on the thermal-physical properties of green silica goods.     

Dolomite decomposition in a high temperature fluidised bed reactor

The decomposition of dolomite was investigated in a bench-scale fluidised bed reactor (30 cm diameter) at temperatures between 600°C and 1000°C in batch and continuous operations. The composition of the solids was determined by X-ray analysis, the gas composition by infrared (i.r.) spectroscopic analysis. The reaction kinetics were investigated in a small fluidised bed (2.6 cm diameter) as well as in the bench-scale equipment and compared with kinetic data evaluated from differential thermal gravimetric (DTG) curves. The measurements were carried out by adding small amounts of dolomite into the isothermal fluidised bed. The resulting CO₂ concentration within the gas could then be very low, thus MgCO₃ and CaCO₃ decompose as parallel reactions (singlestage reaction). At somewhat higher CO₂ gas concentrations prevailing in technical operational conditions the decomposition mechanism changes into a two-stage reaction where MgCO₃ decomposes first. The bed temperature, pressure drop, superficial gas velocity, solid conversion, and specific interfacial area of solids were determined as functions of time and/or reactor wall temperature with a constant temperature increase rate for batch runs. The distributions of the residence time of solids indicate that in the continuously operated fluidised bed well-mixed conditions prevail. The concentrations of dolomite, CaCO₃, MgO, CaO, and solid conversion as well as the specific surface area of particles were determined as functions of the mean residence time in the continuous reactor. By means of the CO₂ concentration in the gas phase and the mean residence time the conversions of the consecutive reactions can be controlled.     

Kinetic study of agglomerate growth in coal-oil agglomeration process

The kinetics have been studied of agglomerate growth in coal-oil agglomeration, an emerging process for the treatment of coal fines. The growth of agglomerates in the batch process follows second-order kinetics for the two types of coals examined. The second-order kinetic equation with two constants describes the growth kinetics adequately. The effects of operating variables, such as furnace oil dosage, degree of agitation and feed size, on these two constants are considered. The significance of the work in modelling the process is discussed.     

Thermal behavior and kinetics during the stabilization of polyacrylonitrile precursor in inert gas

The thermal behaviors of polyacrylonitrile precursor during thermal stabilization in inert gas were investigated by differential scanning calorimetry, thermomechanical analysis, and thermogravimetry. Combining these methods with the tracing of chemical changes by Fourier transform infrared spectroscopy indicated that complex reactions, including cyclization and pyrolytic reactions occurred sequentially. An imine‐enamine tautomeric structure was formed at around 240°C and was converted to a conjugated structure when the temperature was increased to 400°C. A thermal stabilization mechanism was proposed and confirmed experimentally by using a two‐step heating process. The apparent activation energies and the pre‐exponential factors for these stabilization reactions were also estimated by the Kissinger, Ozawa, and “Improved Coats‐Redfern” methods. To obtain a fit to the experiment data, a new kinetic model, named the “Three Regions Kinetic Model,” was proposed using the Improved Coats‐Redfern method. The applicability of this model and the prediction of the stabilization profile at a given heating rate were verified by plotting conversion rate against conversion profiles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Glycerolysis of Fatty Acid Methyl Esters: 1. Investigations in a Batch Reactor

The present work focused on the glycerolysis of fatty acid methyl esters. The aim was to develop and test a kinetic model that could be used to reliably simulate different process alternatives for this reaction. A prerequisite was the identification and characterization of the factors that affect the reaction kinetics. Experiments were carried out in a batch reactor with and without forced removal of methanol, which is one of the reaction products. Concentrations of all components in the two-phase system were measured. It was found that the methanol concentration has a strong effect on the reaction rate and equilibrium conversion. Near-complete conversions were obtained by stripping methanol with an inert gas. The glycerol concentration in the ester phase was found to increase as the reaction proceeds, which also accelerates the reaction. Effects of mass transfer on the reaction rate were not found to control the reaction rate under well-agitated conditions. A semi-empirical model was used to simulate the reaction. The results from the semi-empirical model show good agreement with experimental results.