氧气浓度对K2CO3催化无烟煤和石墨燃烧的影响

采用综合热分析仪研究不同氧气浓度下K2CO3催化无烟煤和石墨燃烧的特性,考察了氧气浓度对催化燃烧机制的影响. 结果表明,K2CO3提高了燃烧反应和氧气扩散速率,但对燃烧速率的提高幅度大于对氧气扩散速率提高幅度,延长了无烟煤燃烧过程的平台时间. 氧气浓度由21%增加到100%时, K2CO3催化无烟煤着火温度降低幅度由37.7℃增至78.1℃,催化石墨着火温度降低幅度由204.8℃增至233.6℃. 煤燃烧初期K2CO3使燃烧活化能下降,氧气浓度高于40%时,燃烧由扩散向反应控制转变;燃烧后期活化能低于40 kJ/mol,燃烧受扩散控制. 石墨在燃烧初期K2CO3使燃烧活化能下降,但氧气浓度增加并未改变燃烧控制步骤,燃烧受反应控制;燃烧后期氧气浓度由21%增加到100%时, K2CO3催化石墨燃烧活化能由39 kJ/mol增至110 kJ/mol,燃烧由扩散控制向反应控制转变.     

Kinetics of microwave synthesis of AlN by carbothermal‐reduction‐nitridation at low temperature

Aluminum nitride (AlN) was synthesized at 1000‐1400°C from a mixture of alumina and carbon powders using 2.45 GHz microwaves in a N₂ atmosphere. High nitridation ratios (>0.90) were obtained in the temperature range 1200‐1400°C. The apparent activation energy of the carbothermal reduction and nitridation (CRN) reaction using 2.45 GHz microwave irradiation was calculated from the nitridation ratio. The value obtained, 79.9 kJ/mol, is 11% of the energy reported for conventional synthesis using α‐Al₂O₃ as the raw material. This result indicates that 2.45 GHz microwave irradiation could promote the kinetics of the CRN reaction, and AlN could be effectively synthesized at low temperature.     

ANIONIC POLYMERIZATION OF LACTAMS IN MICRODISPERSION. I. KINETIC ASPECTS OF THE PROCESS OF CAPROLACTAM POLYMERIZATION

Kinetics of the anionic polymerization of caprolactam (CL) in microdispersion was investigated at temperatures between 90 and 130°C and at stirring rates between 500 and 2000 rpm, respectively. For the investigated range of temperature data analysis showed pseudo-first order kinetics with respect to the monomer concentration. The rate constants are strongly influenced by temperature, increasing with the increase in temperature. For the associated activation energy, a value of 22.51 kJ/mol was obtained. The reaction order is also influenced by the hydrodynamic regime. It seems that below a threshold value of Reynolds Number, the rate of the reaction is independent of the concentration of CL, following pseudo-zero-order kinetics, which is replaced by first-order kinetics above this threshold value of N _Re. However, in the second region of N _Re, the values of rate constant are almost independent of N _Re.     

Diffusion of Water into Silica Glass at Low Temperature

Diffusion of water into silica glass was measured in the temperature range of 200° to 750° by treating the glass in air containing a constant water vapor pressure and analyzing the concentration profile using a Fourier transform infrared spectrometer. In the short-time diffusion heat treatments, the surface concentration was lower and the apparent diffusion coefficient was higher than the corresponding steady-state values. The temperature dependence of the steady-state diffusion coefficient showed two different activation energies. Above ∼550° the diffusion coefficients were similar to the published results with an activation energy of ∼80 kJ/mol, while below ∼550°, the diffusion coefficient was higher than the value obtained by extrapolation from higher temperatures, and the activation energy was ∼40 kJ/mol. Correspondingly, the water solubility–temperature relation showed a sudden change at around the same temperature: at temperatures above this temperature the solubility increased with decreasing temperature, while at lower temperatures the trend was reversed. It was suggested that this observed peculiarity was caused by the initial nonequilibrium reaction between water and SiO₂ glass and a change in enthalpy of the glass–water reaction.     

Hydrodesulfurization of athabasca fluid coke — conversion and mechanism

Hydrodesulfurization of Athabasca (Syncrude) fluid coke was studied for particle sizes of ?74 + 53, ?53 + 44 and ?44 μm using a quartz reactor. Five flow rates of hydrogen from 1.2 × 10^?6 to 2.5 × 10^?6 m³/s were investigated with from 0.45 to 1.0 g of coke. Gas production — time profiles for H₂S and CH₄ were obtained at temperatures from 973 to 1073 K for each particle size range. Desulfurization rates were functions of particle size and temperature. Results agree with predictions of the shrinking core model, the rate being controlled initially by the gas film and chemical reaction resistances followed by control due to diffusion of hydrogen through the increasing ash layer. Below 998 K, the apparent activation energy was determined to be 293 kJ/mol · K, while at temperatures between 998 and 1073 K it was 29 kJ/mol · K.     

城市污泥与木屑混合薄层干燥实验及动力学分析

角度研究了比,添加木通过对纯污泥和添加木屑的污泥进行薄层干燥对比实验,分别从混合比例、薄层厚度、干燥温度、风速木屑添加对污泥干燥特性的影响,并引入薄层模型对其干燥过程进行模拟。结果表明：与纯污泥干燥相屑后污泥干燥速率明显加快,且木屑添加比例越大、薄层越薄、干燥温度越高干燥速率越快,风速对干燥速率的影响不大;Wang—singh模型能很好的描述两种污泥薄层干燥,利用费克第二扩散定律导出的无限平板公式求出纯污泥和添加木屑的污泥在温度120℃～170℃时的有效扩散系数分别为6．13×10-6m／s～1．11×10-5m／s、1．07×10-5m／s～1．67×10-5m／s;由阿伦尼乌斯方程分别求得活化能为Es=16．67kJ／mol、Es=12．97kJ／mol。     

活化煤气化粗渣盐酸浸取机理研究

考察了颗粒粒径、盐酸浓度和浸取温度3个条件对活化煤气化粗渣（简称活化渣）中铝、铁、钙离子浸取率的影响,并对浸取机理进行了研究。实验结果表明,活化渣为钙铝黄长石（2CaO·Al2O3·SiO2）与三氧化二铁（Fe2O3）的固溶体,与盐酸反应后颗粒粒径不断减小,钙离子较铝、铁离子优先浸出,其浸取过程符合化学反应控制的缩芯模型,相应的表观活化能为71.3 kJ/mol;钙离子浸出后活化渣颗粒成为疏松多孔材料,铝、铁离子的浸取过程则符合 Avrami模型,二者的浸取反应均受内扩散控制,表观活化能分别为24.7 kJ/mol和22.5 kJ/mol。     

钙基吸收剂碳酸化实验研究

对CaO吸收CO2反应的特性进行了实验研究,采用未反应收缩核模型分析碳酸化反应动力学特性.结果表明,化学反应速率常数在650℃～750℃范围内基本为一常数,产物层扩散系数随着温度的增加而增大.化学反应控制段的活化能Ea=29.70 kJ/moL,产物控制段的活化能Ea=92.80 kJ/moL.温度一定时,随着CO2体积分数增加,碳酸化反应速率加快,转化率增大.     

FeS的水蒸汽高温氧化动力学

通过测定脱硫速率。研究了FeS的水蒸汽高温氧化动力学FeS的水蒸汽氧化产物为Fe3O4，未反应物转变成类磁黄铁矿相（Fel-aS）反应初期铁先于硫被氧化，较致密的Fe3O4产物层形成后，流与铁同时被氧化实验数据与界面化学反应和固体产物层扩散共同控制数学模型结果相吻合。反应活化能和扩散活化能分别为122DkJ／mol和90．2kJ／mol．增加水蒸汽流量可使产物层粒度变细，孔隙度降低流量为240ml／s时，脱硫速率出现极大值     

Kinetics and mechanism of solid reactions in a micro fluidized bed reactor

A novel gas–solid Micro Fluidized Bed Reaction Analyzer (MFBRA) was developed to deduce reaction rates and kinetic parameters through measuring time‐dependent composition changes of evolved gases from the reactions. Application of the MFBRA to the decomposition of CaCO₃ powder resulted in an apparent activation energy of 142.73 kJ/mol and a pre‐exponential factor of 399,777 s^?1. This apparent activation energy was much lower than the thermogravimetry‐measured value of 184.31 kJ/mol, demonstrating a quicker reaction in the MFBRA. This was further verified by CuO reduction in CO, as accelerated by the fast diffusion and high heating rate in the MFBRA. Measurement of pyrolysis of coal and biomass in MFBRA found that the reaction process was completed in about 10 s, a time much shorter than the literature‐reported values in larger fluidized bed reactors. By monitoring the release of gas species from reactions at different temperatures, the MFBRA also allowed deeper insight into the mechanism of pyrolysis reactions. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

攀西高锰稀土矿泥盐酸浸取稀土动力学

采用盐酸浸取攀西高锰稀土矿泥,考察了浸取反应温度、矿石粒度及盐酸浓度对浸取速率的影响. 结果表明,当盐酸浓度为2 mol/L时,浸取过程符合缩核模型,表观活化能为9.59 kJ/mol,属内扩散控制,宏观动力学方程为：K=(4.15?10–4)/r02 · exp(9590/RT); 当盐酸浓度大于2 mol/L时,矿石中的锰被大量浸出,其结构被破坏,浸取过程为混合控制.     

Cure kinetics of an epoxidized hemp oil based bioresin system

A novel epoxidized hemp oil (EHO) based bioresin was synthesized by epoxidation in situ with peroxyacetic acid. In this research the cure kinetics of an EHO based bioresin system cured with triethylenetetramine (TETA) was studied by differential scanning calorimetry using both isothermal and nonisothermal data. The results show that the curing behavior can be modeled with a modified Kamal autocatalytic model that accounts for a shift to a diffusion‐controlled reaction postvitrification. The total order of the reaction was found to decrease with an increase in temperature from ～ 5.2 at 110°C to ～ 2.4 at 120°C. Dynamic activation energies were determined from the Kissinger (51.8 kJ/mol) and Ozawa‐Flynn‐Wall (56.3 kJ/mol) methods. Activation energies determined from the autocatalytic method were 139.5 kJ/mol and ?80.5 kJ/mol. The observed negative activation energy is thought to be due to an unidentified competitive reaction that gives rise to the appearance of k₂ decreasing with increasing temperature. The agreement of fit of the model predictions with experimental values was satisfactory for all temperatures. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

微波场中生物炭还原褐铁矿反应动力学实验及模型计算

采用微波失重在线检测装置和XRD分别分析了褐铁矿与生物炭升温至923 K的失重变化及微波焙烧前后的矿相变化;同时基于褐铁矿微波还原焙烧升温失重曲线,采用Achar-Brindley-Sharp-Wendworth微分法和Coats-Redfern积分法,计算了褐铁矿在不同温度段的反应动力学参数. 结果表明,褐铁矿与生物炭在923 K的还原温度下转变为磁铁矿,同时生成少量的硅酸亚铁(Fe2SiO4);其微波还原焙烧过程分为3个阶段进行,在366~470 K,反应的表观活化能(E1)分别为30.7和26.3 kJ/mol,反应机理符合反应级数函数,属于化学反应控制;在470~650 K,表观活化能(E2)分别为40.3和33.1 kJ/mol,反应机理符合Avrami-Erofeer函数,是随机成核和随后生长的化学反应控制;在650~825 K,表观活化能(E3)分别为52.4 和52.9 kJ/mol,反应机理符合Zhuralev-Lesokin-Tempelman函数,属于三维扩散控制.     

The kinetics of combustion of chars derived from sewage sludge

Experiments have been conducted to determine the combustion characteristics of sewage sludge chars in electrically heated beds of silica sand fluidised by air. The effects of the initial size of the char particles, the temperature of the bed and [O₂] in the fluidising gas were investigated. Also, the temperatures of burning particles were measured with embedded thermocouples. The kinetics of combustion were measured at temperatures low enough for the CO formed by initial reaction between the carbon and oxygen to burn at some distance away from the particle. Accordingly, the particle is only heated by the enthalpy of the reaction C+0.5O₂→CO. The activation energy for the intrinsic kinetics of combustion of the char was estimated to be 130–144 kJ/mol. The former value makes allowance for the fact that the particles are at a temperature in excess of that of the bed (determined by a heat balance on a reacting particle), whilst the latter value assumes that the particles are at the same temperature of the bed. It is probable that the lower value is closer to the actual value, thought to be 135±15 kJ/mol, reflecting the catalytic nature of the ash skeleton on which the carbon is supported. It was possible to obtain good agreement between measured burnout times and those predicted using the grain model of Szekely J, Evans JW, Sohn HY. Gas–solid reactions. New York: Academic Press; 1976, for the case where the kinetics are controlled by a combination of: (i) external mass transfer of oxygen from the particulate phase to the external surface of the burning char particle, (ii) diffusion of oxygen from the external surface into the porous matrix to the surfaces of grains, of which the solid is composed, and (iii) diffusion of oxygen into the microporous grains, where reaction occurs with the carbon. It was found that, for particles with diameters of 2 mm or larger, the initial rates of reaction, for bed temperatures in excess of 750 °C, are dominated by external mass transfer. This explains the dependence of the rate of oxidation of unit mass of char on 1/d_p, and the relatively small influence of temperature on these rates. Particles of char from sewage sludge are so reactive that it is essential to make allowance for a difference in temperature between the particle and the bed. Thus, experimental determinations on particles with d_p∼6.5 mm, suggested a difference in temperature of ∼150 K, in line with calculations using a steady-state heat balance.     

石煤灰渣酸浸提钒工艺中钒的浸出动力学

采用液-固多相反应的缩芯模型研究了石煤灰渣中V2O5的浸出动力学,考察了酸浸温度、硫酸浓度对V2O5浸出反应速率的影响. 结果表明,在实验温度范围内,V2O5的浸出过程为固膜扩散控制,浸出反应的表观活化能为29.96 kJ/mol. 当硫酸浓度小于6 mol/L时,浸出属化学反应控制过程;当硫酸浓度大于6 mol/L时,浸出过程为固膜扩散控制,其表观反应级数为1.199. 提高酸浸温度可提高V2O5的浸出率;在硫酸浓度小于6 mol/L时提高硫酸浓度,可提高V2O5的浸出率;而高于该值提高硫酸浓度对V2O5浸出率的提高无明显作用.     

ON THE ANALYSIS OF NONCATALYTIC GAS-SOLID KINETICS DATA HAVING WEAK TEMPERATURE DEPENDENCE

Noncatalytic gas-solid reactions should exhibit strong temperature dependence when the rate is controlled by surface kinetics. However, there are a number of examples in the literature where apparent activation energies less than 10 kcal/mol have been reported as being representative of intrinsic kinetics. This conclusion is often based on electrobalance data in which large gas Row rates were used to eliminate mass transfer resistance and the fact that fractional conversion-time results are consistent with the surface kinetics control version of a gas-solid reaction model.

The oxidation of FeS was studied in an electrobalance reactor as a function of O₂ mol fraction, temperature, and gas flow rate. The global rate was first-order in O₂ and weakly dependent on temperature and flow rate. Data analysis used the approximate solution to the grain model. The single-resistance surface kinetics variation of the model provided good match with the conversion-time data, but the apparent activation energy was only about 7 kcal/mol. A two-resistance mass transfer-product layer diffusion variation provided equally good match with the data, and the dependence of reaction coefficients on reaction variables was in general agreement with theory.     

氢氧化钠亚熔盐体系分解铬铁矿的工艺研究

研究了氢氧化钠亚熔盐体系氧压浸出铬铁矿工艺的主要作用因素对铬浸出率的影响,确定了最佳的工艺参数。结果表明,氢氧化钠亚熔盐氧压浸出过程,对铬浸出影响最显著的因素是温度和氧压力;在铬铁矿粒径为0.038~0.048 mm、矿碱质量比为1∶7、 搅拌速度为650 r/min条件下,氢氧化钠亚熔盐氧压浸出铬的最佳反应条件为：浸出温度为245 ℃、碱浓度为65%（质量分数）、氧气压力为0.8 MPa、反应时间为480 min。在该条件下铬的浸出率为99%以上,活化能为51.49 kJ/mol,动力学方程为1-2/3x-（1-x）2/3=2 124.73 P■ 0.85×e-51 490/RT×t。     

Explaining the abnormally high flow activation energy of thermoplastic polyurethanes

The rheological properties of a thermoplastic polyurethane (TPU) were studied at small and large deformation via three different types of rheometry: dynamic shear, capillary, and torque (an instrumented batch mixer). The effect of degradation during TPU processing on the melt viscosity was investigated and several factors, such as temperature, time, shear stress, and flow type that may affect the degradation were studied. Apparent activation energy of flow (E_a) was determined to be 328 kJ/mol, much larger than expected. A simple model was derived to describe the relationship of molecular weight and thermal dissociation of urethane linkages. Contributions of flow and the degradation reaction of TPU to overall activation energy were found to be additive: E_a=E_η+1.7ΔH_deg. True activation energy of flow (E_η) was estimated to be 144 kJ/mol. While the high apparent flow activation energies in dynamic shear and capillary rheometry can be explained by simple thermal degradation, melt viscosities interpreted from the instrumented batch mixer showed a much lower apparent activation energy (186 kJ/mol). This low value may be due to a combination of effects: errors in the relation between viscosity and mixer torque for TPU, side reactions resulting from air exposure, high stress level during the melting, and extensional stresses.     

Effect of Initial Oxide Layer on Ignition and Combustion of Boron Powder

Only few data exist for experimental studies on ignition and combustion of boron particles with initial oxide thickness. The oxidation, ignition and combustion characteristics including the onset temperatures, weight gain, apparent activation energy, emission spectra during combustion, and ignition delay time of crystalline boron powders with different initial oxide thickness (x₀) were studied by a laser ignition and thermogravimetric (TG) analyses. Simulations of the kinetics of oxide layer during boron ignition were conducted using a common model. The results indicated that the onset temperature was approximately 775 °C, independent of x₀. The total weight gain decreased with increasing x_0, whereas the weight gain at 775 °C did not change. The apparent activation energy was found to be insensitive to x₀ and had a constant value of about 210 kJ mol⁻¹. The intensity of the emission spectra gradually decreased while the ignition delay time increased with increasing x₀. Numerical simulation showed that the removal rate of oxide layer enhanced with increasing x₀. The experimental results revealed that the oxidation of boron powder was no diffusion‐controlled process at low temperatures. But the diffusion of oxygen could become important to the oxidation reaction at high temperatures     

A Study of the Apparent Desorption Energy for OH in the Water Formation Reaction on a Palladium Catalyst

In the H₂/O₂ reaction, the desorption of OH from a polycrystalline palladium foil has been studied with Laser-Induced Fluorescence (LIF) as a function of the hydrogen mixing ratio, α_H2, and the temperature. The water production as a function of α_H2 was also monitored with microcalorimetry. The apparent desorption energy, E_OH ^a, for OH has been measured from α_H2 = 0% to α_H2 = 74%. At α_H2 = 0%, E_OH ^a was measured to be 143 ± 7 kJ/mol; the apparent desorption energy then increases linearly with α_H2 to a maximum value of 223 ± 6 kJ/mol at α_H2 = 40%. At higher α_H2, the apparent desorption energy was measured to be constant at about 200 kJ/mol. The maximum in apparent desorption energy at α_H2=40% occurs at the same α_H2 as the maximum in water production. This phenomenon has also been reported for the platinum metal, although at an α_H2 value of 20%. The relative coverage of intermediates and products on the palladium catalysts was obtained using Chemkin.