储油罐硫铁化物自然氧化倾向性的研究

含硫原油储罐中的H2S与内壁铁的主要腐蚀产物Fe2O3 、Fe(OH)3反应生成不同形式的硫铁化物,硫铁化物的氧化放热是引起含硫油品储罐着火的主要原因.研究了硫化温度对Fe2O3硫化产物氧化倾向性的影响,分析了其硫化产物的生成机理.同时考察了不同硫化方式对Fe(OH)3硫化产物的氧化倾向性的影响.结果表明,硫化环境温度越高,硫化产物的氧化倾向性越强,常温下生成的FeS 与S随着温度的升高发生反应生成Fe3S4和FeS2;Fe(OH)3与氢硫酸生成的硫铁化物的自燃性较H2S强.     

用Mn2O3法合成对羟基苯甲醛

研究了以Mn2O3为氧化剂．在硫酸介质中氧化对甲酚合成对羟基苯甲醛的工艺条件。Mn2O3是在923K下灼烧Mn2O3得到的。最适宜的氧化反应温度为318K,c(Mn2O4)=7．0mol儿。用亚硫酸氢钠法分离反应物与产物。氧化反应表现出零级反应特征,反应的活化能为62．5kJ／mol左右。     

纳米燃速催化剂对7-氨基-6-硝基-4,5-二氧化呋咱热分解的影响

用DSC和TG研究了A120a、Fe20a、Ti02、SnOz4种纳米燃速催化剂对7-氨基-6-硝基-4，5-二氧化呋咱(CL-18)热分解特性的影响。结果发现它们均使CL-18的起始反应温度降低、终止反应温度升高；Fe2O3、TiO2、SnO2不仅提高了反应放热量而且使整个反应变得相对平稳，随催化剂含量的增加最大失重速率温度先升高后降低．但CL-18的固态残留物量随催化剂含量的增加却一直减少；SnO2和Al2O3对CL-18的两个活化能影响较大，使CL-18的第一活化能分别降低了13．18kJ／mol和16．25kJ／mol，第二活化能分别降低了40．49kJ／mol和43．96kJ／mol；然而Fe20。仅仅对第二活化能有较大影响，降低了40．41kJ／mol。     

攀枝花钛铁矿高温氧化研究

对攀枝花钛铁矿的高温氧化过程进行了研究。结果表明,钛铁矿的氧化速度随温度的增加、粒度的减小快速增长;温度是影响氧化产物物相的重要因素,当温度低于900℃时,生成物的物相为Fe2Ti3O9、Fe2O3和TiO2,而当温度达到900℃时,氧化产物之间发生相转变反应生成Fe2TiO5。氧化动力学可用二维扩散模型拟合,氧化反应的表观活化能为132.86(±0.51)kJ/mol。     

Mn2O3氧化法合成对氯苯甲醛

研究了以Mn2O3为氧化剂，在硫酸介质中氧化对氯甲苯合成对氯苯甲醛的工艺条件，最适宜的反应温度为343K．硫酸浓度为8．01mol／L。实验中所使用的三氧化二锰是在923K下灼烧二氧化锰得到的，用亚硫酸氢钠法分离反应物与产物。氧化反应表现出零级反应特征，反应活化能为115kJ／mol左右。     

含硫油品储罐腐蚀产物自然氧化实验

为深入研究含硫油品储罐硫腐蚀产物FeS自然氧化倾向性,自建实验台模拟储罐FeS的生成及其自然氧化倾向性,同步热分析仪对FeS进行了热质量实验,通过TG曲线和DSC曲线分析了FeS粒径对其氧化性质的影响.结果表明,Fe3O4、Fe2O3、Fe（OH）3及其混合物经硫化所得FeS具有很强的自然氧化活性,Fe3O4硫化物的氧化速度最快,Fe2O3次之,混合物和Fe（OH）3较慢,温升速率分别达到0.64、0.45、0.34和0.11℃/s;TG曲线经历了质量增加和质量迅速损失的过程,DSC曲线上有明显的放热峰;粒径对FeS氧化性有明显影响,粒径越小,TG曲线向低温方向移动,氧化起始温度和氧化终止温度越低,DSC曲线上放热峰峰值温度越低.     

Ce4+/Ce3+作氧化媒质间接电氧化对氯甲苯的反应动力学研究

在优化的实验条件下分别从产物和反应物2方面进行分析，系统地研究了硫酸浓度为6．425mol/L和7．7mol/L时Ce^4 /Ce^3 作氧化媒质间接电氧化对氯甲苯的有机氧化动力学，确定出总反应为 表观1级反应，并拟合出了相应的表观反应速率常数和表观活化能，当硫酸介质浓度从6．425mol/L增至7．7mol/L时表观活化能显著降低（从122－128kJ/mol降低到84－89kJ/mol）从而大大加速了化学反应速率。     

石灰石与SO2反应动力学的研究

石灰石与ＳＯ２的高温短时的硫酸化反在夹带流反应器中被实验研究，硫酸化反应是一个两阶段反应：初始是一个非常快的零级表面反应且活化能的２１．０ｋＪ／ｍｏｌ，接着是活化能为８０．１ｋＪ／ｍｏｌ的产物层扩散控制反应，初始阶段约０．３ｓ．吸收剂的种类、Ｃａ／Ｓ比、停留时间、反应温度和ＳＯ２分压影响着脱硫反应速率，脱硫反应过程能用缩芯模型来模拟。在Ｃａ／Ｓ＝２、１０００℃Ｔ ２Ｓ的实验条件下，喷射Ｆ－石灰石能     

溶剂热法制备FeS2

研究了用乙二醇（C2H6O2）为溶剂,硫脲（NH2CSNH2）做硫源溶剂热法制备FeS2的反应机理.当反应温度达到300℃后,产物中存在黄铁矿（FeS2）,理论分析表明：这些FeS2是磁黄铁矿（FeS）被硫脲分解出的硫化氢（H2S）氧化后形成的.溶液中的碱性环境令FeS不能完全转化成FeS2.另外,由于乙二醇把部分2价Fe离子氧化成Fe^3＋,实验所获得的最终是FeS,Fe3S4与FeS2的混合物.     

亚硫酸铵非催化氧化动力学研究

脱硫产物亚硫酸铵的氧化是工业化脱硫技术运行的关键问题。在实验室中,采用玻璃填料塔,通过改变气流量、氧气含量、pH值、温度、亚硫酸铵初始浓度以及硫酸铵浓度,对低浓度亚硫酸铵非催化氧化反应动力学进行了研究。结果表明,亚硫酸铵的氧化速率随着气流量、氧气含量、温度的升高而增大;随着亚硫酸铵初始浓度和硫酸铵浓度的增大而减小;在pH值为8.0时,反应活化能为38.17kJ/mol。     

Rutherford Backscattering Spectroscopy Study of the Kinetics of Oxidation of (Mg, Fe)2SiO4

Single crystals of oilivine, (Mg_0.9Fe_0.1)₂SiO₄, have been oxidized in air at temperatures between 700° and 1100°C for times from 0.5 to 100 h. Both an internal and an external oxidation layer developed. Transmission and analytical electron microscopy observations reveal that the internal oxidation layer is composed of precipitates of magnetite plus amorphous silica, which nucleated heterogeneously on dislocations and grew in an Fedepleted matrix of olivine. Rutherford backscattering spec-trometry (RBS) demonstrates that the thin external oxidation layer is free of Si; that is, it is made up of Mg-Fe oxide phases. Thus, the oxidation process is primarily controlled by diffusion of Fe²⁺ and Mg²⁺ ions toward the surface with Si⁴⁺ and O^2- remaining largely immobile. The kinetics of oxidation, as determined from RBS analyses of the external oxidation layer, are parabolic with an activation energy of 140 kJ/mol. Although this activation energy is lower than that reported for self-diffusion of Mg in Mg₂SiO₄, the diffusivity calculated from the reaction rate constant is in good agreement with published values for lattice diffusion of Mg in the limited temperature range in which data overlap. However, the rate of accumulation of Fe in the external layer is more rapid than expected for lattice diffusion, indicating that the transport of Fe is dominated by short-circuit diffusion along the precipitate complexes which decorate dislocations.     

高温悬浮态下硫铁矿的氧化特性研究

硫铁矿的高温氧化是引起水泥生产过程中产生SO2的主要原因。采用一维炉开展了高温悬浮态下硫铁矿氧化的实验研究,并对氧化产物做了X射线衍射（XRD）分析和烧失量检测。XRD分析表明,FeS2在300 ℃时尚未发生氧化反应,从400 ℃开始出现Fe2O3的衍射峰,且随着温度升高,FeS2的衍射峰强度逐步减弱,Fe2O3衍射峰强度逐步增强。在400~800 ℃时,FeS2的氧化产物仅为Fe2O3。基于烧失量的计算表明,在10 s反应时间内,FeS2在300 ℃几乎没有发生氧化,这和XRD检测结果一致。在400 ℃和600 ℃时FeS2氧化率分别达到了50%和85%,800 ℃时达到了92%。将上述结果应用于水泥生产过程,表明在C1~C4预热器中,约64%的FeS2发生了氧化。     

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.     

石英砂高温焙烧-酸洗除铁动力学研究

采用高温焙烧-酸洗方法除石英砂Fe杂质,实验结果表明,900℃焙烧最佳时间为180 min;焙烧后90℃水浴混酸酸洗360 min,石英砂中Fe去除率可达88.3％,Fe杂质含量降为34.61μg/g.通过扫描电子显微镜(SEM)表征该方法处理前后石英砂形貌,结果表明处理后石英砂表面出现明显裂纹和蚀坑,有助于酸液浸入颗粒内部,提高Fe去除率.利用收缩未反应芯模型对实验数据拟合,该酸洗反应控速步骤为产物内扩散控制,焙烧处理后酸洗反应更快,Fe去除率更高,活化能更低.经900℃焙烧,保温180 min处理石英砂,酸洗反应的活化能是30.88 kJ/mol,未焙烧酸洗反应活化能为36.18 kJ/mol,焙烧后酸洗反应活化能下降了17.2％,说明焙烧处理有利于石英砂的酸洗.     

Effect of heating rate and process atmosphere on the thermodynamics and kinetics of the sintering of pre-alloyed water-atomized powder metallurgy steels

During the sintering of powder metallurgy steels the full removal of the iron oxide layer is required in order to develop strong inter-particle necks. Although this iron oxide layer has low thermodynamic stability, its removal from the powder compact is a very complex process that is determined by a number of parameters such as temperature profile, sintering atmosphere, compact properties, powder properties, and additives. This paper summarizes these sintering parameters in correlation with the powder properties through the use of thermogravimetry analysis. In this work, hydrogen additions were identified as the most effective agent for the removal of the surface iron oxide during the early stages of sintering (at temperature range between ~300 and 600°C). The process depends on the heating rate and a rather low activation energy of 48 kJ/mol was determined for this reaction. Carbothermal reduction plays the largest role in the oxide reduction at high temperatures where two main reactions can be distinguished. The first was the reduction of the surface oxide residue and particulates, which occurred at temperatures between 950 and 1150°C. This reaction is characterized by an activation energy of 253 kJ/mol. Second was believed to be associated with the reduction of the internal oxides, occurred at temperatures above 1150°C. This reaction is characterized by rather high activation energy of 422 kJ/mol.     

Steam reforming of ethanol over skeletal Ni‐based catalysts: A temperature programmed desorption and kinetic study

An investigation on reaction scheme and kinetics for ethanol steam reforming on skeletal nickel catalysts is described. Catalytic activity of skeletal nickel catalyst for low‐temperature steam reforming has been studied in detail, and the reasons for its high reactivity for H₂ production are attained by probe reactions. Higher activity of water gas shift reaction and methanation contributes to the low CO selectivity. Cu and Pt addition can promote WGSR and suppress methanation, and, thus, improve H₂ production. A reaction scheme on skeletal nickel catalyst has been proposed through temperature programmed reaction spectroscopy experiments. An Eley‐Rideal model is put forward for kinetic studies, which contains three surface reactions: ethanol decomposition, water gas shift reaction, and methane steam reforming reaction. The kinetics was studied at 300–400°C using a randomized algorithms method and a least‐squares method to solve the differential equations and fit the experimental data; the goodness of fit obtained with this model is above 0.95. The activation energies for the ethanol decomposition, methane steam reforming, and water gas shift reaction are 187.7 kJ/mol, 138.5 kJ/mol and 52.8 kJ/mol, respectively. Thus, ethanol decomposition was determined to be the rate determining reaction of ethanol steam reforming on skeletal nickel catalysts. © 2013 American Institute of Chemical Engineers AIChE J 60: 635–644, 2014     

Kinetics of hydrogen reduction of sodium sulfate mixed with sodium titanate

The hydrogen reduction kinetics of solid sodium sulfate mixed with sodium titanate are studied in a thermogravimetric system. The conversion-time curves of the hydrogen reduction are sigmoidal in shape and are well described by the nucleation and growth model up to about 60% conversion. The reduction rate of this mixture is much faster than that of pure sodium sulfate. In the deceleratory conversion period, the reduction is controlled by gas diffusion through a product layer. Activation energies of 302 and 179 kJ/mol are obtained, respectively, for the nucleation and growth, and diffusion limited period. The influence of hydrogen concentration, steam concentration, sodium sulfate fraction, and sodium sulfide addition is also studied. A reaction mechanism is proposed for the hydrogen reduction in the solid state.     

Gasification rate analysis of coal char with a pressurized drop tube furnace

Two coal chars were gasified with carbon dioxide or steam using a Pressurized Drop Tube Furnace (PDTF) at high temperature and pressurized conditions to simulate the inside of an air-blown two-stage entrained flow coal gasifier. Chars were produced by rapid pyrolysis of pulverized coals using a DTF in a nitrogen gas flow at 1400°C. Gasification temperatures were from 1100 to 1500°C and pressures were from 0.2 to 2 MPa. As a result, the surface area of the gasified char increased rapidly with the progress of gasification up to about six times the size of initial surface area and peaked at about 40% of char gasification. These changes of surface area and reaction rate could be described with a random pore model and a gasification reaction rate equation was derived. Reaction order was 0.73 for gasification of the coal char with carbon dioxide and 0.86 for that with steam. Activation energy was 163 kJ/mol for gasification with carbon dioxide and 214 kJ/mol for that with steam. At high temperature as the reaction rate with carbon dioxide is about 0.03 s⁻¹, the reaction rate of the coal char was controlled by pore diffusion, while that of another coal char was controlled by surface reaction where reaction order was 0.49 and activation energy was 261 kJ/mol.     

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.     

Oxidation of Chemically-Vapor-Deposited Silicon Nitride and Slnglem-Crystal Silicon

Oxidation of {111} single-crystal silicon and dense, chemically-vapor-deposited silicon nitride was done in clean silica tubes at temperatures of 1000° to woo°C. The oxidation rates of silicon nitride under various atmospheres (dry O₂, wet O₂, wet inert gas, and steam) were several orders of magnitude slower than those of silicon under the identical conditions. The activation energy for the oxidation of silicon nitride decreased from 330 to 259 kJ/mol in going from dry O₂ to steam while that for Si decreased from 120 to 94 kJ/mol. The parabolic rate constant for Si increased linearly as the water vapor pressure increased. However, the parabolic rate constant for silicon nitride showed nonlinear dependency on the water vapor pressure in the presence of oxygen. The oxidation kinetics of silicon nitride is explained by the formation of nitrogen compounds (NO and NH₃) at the reaction interface and the counterpermeation of these reaction products.