Kinetics and mechanism of oxidation for nickel-containing pyrrhotite tailings

X-ray powder diffraction, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetry, differential scanning calorimetry, and mass spectrometry have been used to study the products of nickel-containing pyrrhotite tailings oxidation by oxygen in the air.The kinetic triplets of oxidation, namely, activation energy(E_a), pre-exponential factor(A), and reaction model(f(α)) being a function of the conversion degree(α), were adjusted by regression analysis. In case of a two-stage process representation, the first step proceeds under autocatalysis control and ends at α = 0.42. The kinetic triplet in the first step is E_a = 262.2 kJ/mol, lg A = 14.53 s~(-1), and f(α) =(1 –α)~(4.11)(1 + 1.51 ×10~(–4)α). For the second step, the process is controlled by the two-dimensional diffusion of the reactants in the layer of oxidation products. The kinetic triplet in the second step is Еa = 215.0 kJ/mol, lg A = 10.28 s~(-1), and f(α) =(–ln(1 –α))~(–1). The obtained empirical formulae for the rate of pyrrhotite tailings oxidation reliably describe the macro-mechanism of the process and can be used to design automatization systems for roasting these materials.     

Oxidation pathway and kinetics of titania slag powders during cooling process in air

The oxidation pathway and kinetics of titania slag powders in air were analyzed using differential scanning calorimetry(DSC) and thermogravimetry(TG). The oxidation pathway of titania slag powder in air was divided into three stages according to their three exothermic peaks and three corresponding mass gain stages indicated by the respective non-isothermal DSC and TG curves. The isothermal oxidation kinetics of high titania slag powders of different sizes were analyzed using the ln-ln analysis method. The results revealed that the entire isothermal oxidation process comprises two stages. The kinetic mechanism of the first stage can be described as f(α) = 1.77(1-α) [-ln(1-α)]~((1.77-1)/1.77),f(α) = 1.97(1-α) [-ln(1-α)]~((1.97-1)/1.97), and f(α) = 1.18(1-α) [-ln(1-α)]~((1.18-1)/1.18). The kinetic mechanism of the second stage for all samples can be described as f(α) = 1.5(1-α)~(2/3)[1-(1-α)~(1/3)]~(-1). The activation energies of titania slag powders with different sizes(d_1 0.075 mm, 0.125 mm d_2 0.150 mm, and 0.425 mm d_3 0.600 mm) for different reaction degrees were calculated. For the given experimental conditions, the rate-controlling step in the first oxidation stage of all the samples is a chemical reaction. The rate-controlling steps of the second oxidation stage are a chemical reaction and internal diffusion(for powders d_1 0.075 mm) and internal diffusion(for powders 0.125 mm d_2 0.150 mm and 0.425 mm d_3 0.600 mm).     

Oxidation of O'-SiAlON-ZrO2 Composite Ceramics

The oxidation kinetics of O'-SiAlON-ZrO₂ composite ceramics in the temperature range of 1373-1773K has been studied. The oxidation experiments with powder and plates of O'-SiAlON-ZrO₂ composite ceramics in air have been carried out. The overall activation energy of oxidation reaction is 263.69 kJ/mol. The products and structures of O'-SiAlON-ZrO₂ oxidation layer have been analysed by XRD (X-ray diffraction), SEM (scanning electron microscope) and AFM (atomic force microscope).     

低氧LiF–NdF3熔盐体系阳极过程的电化学行为研究

The oxidation of oxygen ions and the generation of an anode effect at a low oxygen content of 150 mg/kg were discussed in this paper. Cyclic voltammetry and square-wave voltammetry tests were conducted to explore the anodic processes of LiF–NdF₃ melt after a lengthy period of pre-electrolysis purification at 1000°C (during which the oxygen content reduced from 413 to 150 mg/kg). The oxidation process of oxygen ions was found to have two stages: oxidation product adsorption and CO/CO₂ gas evolution. The adsorption stage was controlled by diffusion, whereas the gas evolution was controlled by the electrochemical reaction. In comparison with oxygen content of 413 mg/kg, the decrease in the amplitude of the current at low oxygen content of 150 mg/kg was much gentler during the forward scanning process when the anode effect occurred. Fluorine-ion oxidation peaks that occurred at about 4.2 V vs. Li/Li+ could be clearly observed in the reverse scanning processes, in which fluorine ions were oxidized and perfluorocarbons were produced, which resulted in an anode effect.     

Phase transformation and reduction kinetics during the hydrogen reduction of ilmenite concentrate

The reduction of ilmenite concentrate by hydrogen gas was investigated in the temperature range of 500 to 1200℃. The microstructure and phase transition of the reduction products were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), and optical microscopy (OM). It was found that the weight loss and iron metallization rate increased with the increase of reduction temperature and reaction time. The iron metallization rate could reach 87.5% when the sample was reduced at 1150℃ for 80 min. The final phase constituents mainly consist of Fe, M₃O₅ solid solution phase (M=Mg, Ti, and Fe), and few titanium oxide. Microstructure analysis shows that the surfaces of the reduction products have many holes and cracks and the reactions take place from the exterior of the grain to its interior. The kinetics of reduction indicates that the rate-controlling step is diffusion process control with the activation energy of 89 kJ·mol-1.     

Thermodynamics and kinetics of extracting zinc from zinc oxide ore by the ammonium sulfate roasting method

Thermodynamic analyses and kinetic studies were performed on zinc oxide ore treatment by (NH₄)₂SO₄ roasting technology. The results show that it is theoretically feasible to realize a roasting reaction between the zinc oxide ore and (NH₄)₂SO₄ in a temperature range of 573-723 K. The effects of reaction temperature and particle size on the extraction rate of zinc were also examined. It is found that a surface chemical reaction is the rate-controlling step in roasting kinetics. The calculated activation energy of this process is about 45.57 kJ/mol, and the kinetic model can be expressed as follows:1-(1-α)1/3=30.85 exp(-45.57/RT)·t. An extraction ratio of zinc as high as 92% could be achieved under the optimum conditions.     

Kinetics study on biomass pyrolysis for fuel gas production

Kinetic knowledge is of great importance in achieving good control of the pyrolysis and gasification process and optimising system design. An overall kinetic pyrolysis scheme is therefore addressed here. The ki-netic modelling incorporates the following basic steps: the degradation of the virgin biomass materials into pri-mary products ( tar, gas and semi-char), the decomposition of primary tar into secondary products and the continuous interaction between primary gas and char. The last step is disregarded completely by models in the literature. Analysis and comparison of predicted results from different kinetic schemes and experimental data on our fixed bed pyrolyser yielded very positive evidence to support our kinetic scheme.     

Roasting and leaching behaviors of vanadium and chromium in calcification roasting–acid leaching of high-chromium vanadium slag

Calcification roasting–acid leaching of high-chromium vanadium slag (HCVS) was conducted to elucidate the roasting and leaching behaviors of vanadium and chromium. The effects of the purity of CaO, molar ratio between CaO and V₂O₅ (n(CaO)/n(V₂O₅)), roasting temperature, holding time, and the heating rate used in the oxidation–calcification processes were investigated. The roasting process and mechanism were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermogravimetry–differential scanning calorimetry (TG–DSC). The results show that most of vanadium reacted with CaO to generate calcium vanadates and transferred into the leaching liquid, whereas almost all of the chromium remained in the leaching residue in the form of (Fe_0.6Cr_0.4)₂O₃. Variation trends of the vanadium and chromium leaching ratios were always opposite because of the competitive reactions of oxidation and calcification between vanadium and chromium with CaO. Moreover, CaO was more likely to combine with vanadium, as further confirmed by thermodynamic analysis. When the HCVS with CaO added in an n(CaO)/n(V₂O₅) ratio of 0.5 was roasted in an air atmosphere at a heating rate of 10℃/min from room temperature to 950℃ and maintained at this temperature for 60 min, the leaching ratios of vanadium and chromium reached 91.14% and 0.49%, respectively; thus, efficient extraction of vanadium from HCVS was achieved and the leaching residue could be used as a new raw material for the extraction of chromium. Furthermore, the oxidation and calcification reactions of the spinel phases occurred at 592 and 630℃ for n(CaO)/n(V₂O₅) ratios of 0.5 and 5, respectively.     

Improved hemimorphite flotation using xanthate as a collector with S(Ⅱ) and Pb(Ⅱ) activation

The flotation of hemimorphite using the S(Ⅱ)–Pb(Ⅱ)–xanthate process, which includes sulfidization with sodium sulfide, activation by lead cations, and subsequent flotation with xanthate, was investigated. The flotation results indicated that hemimorphite floats when the S(Ⅱ)–Pb(Ⅱ)–xanthate process is used; a maximum recovery of approximately 90% was obtained. Zeta-potential, contact-angle, scanning electron microscopy–energy-dispersive spectrometry (SEM–EDS), and diffuse-reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements were used to characterize the activation products on the hemimorphite surface and their subsequent interaction with sodium butyl xanthate (SBX). The results showed that a ZnS coating formed on the hemimorphite surface after the sample was conditioned in an Na₂S solution. However, the formation of a ZnS coating on the hemimorphite surface did not improve hemimorphite flotation. With the subsequent addition of lead cations, PbS species formed on the mineral surface. The formation of the PbS species on the surface of hemimorphite significantly increased the adsorption capacity of SBX, forming lead xanthate (referred to as chemical adsorption) and leading to a substantial improvement in hemimorphite flotation. Our results indicate that the addition of lead cations is a critical step in the successful flotation of hemimorphite using the sulfidization–lead ion activation–xanthate process.     

Kinetics of Hydrogen Absorption in Hydrogen Storage Alloy

Hydrogenation kinetics of MLNi_3.8(Co,Mn,Al)_1.2 and MLNi_3.7(Co,Mn,Al)_1.2Cu_0.1 alloy in α + β phase at the temperature range of 30~70 ℃ has been studied. The kinetic mechanism of hydrogen absorption is not affected by initial hydrogen pressure. Temperature does not influence the rate of hydrogen absorption obviously. In the prior and later period of hydrogen absorption the rate-controlling step is chemical reaction and hydrogen diffusion in the hydride phase respectively for MLNi_3.8(Co,Mn,Al)_1.2 alloy. Adding Cu, the rate-controlling step changes from chemical reaction to the nucleation and growth of β phase in the prior period and the process of hydrogen absorption still controlled by diffusion in the later period.     

聚丙烯酸钠的热分解动力学

采用TG/DTA联用技术,在10、15、202、5 K.min-1不同线性升温条件下,研究了聚丙烯酸钠的热分解过程.结果表明,在空气气氛下,聚丙烯酸钠的热分解主要分为两个阶段.应用非等温多重扫描速率法对热分解过程的第一阶段进行了动力学分析,并计算得到了聚丙烯酸钠热分解的动力学3因子,分别是热分解活化能E=132.88 KJ.mol-1,指前因子lg(A)=9.103,以及相边界反应型的机理函数,其积分形式G(α)=1-(1-α)12和微分形式f(α)=2(1-α)12.     

多升温速率等温法的动力学分析在一水草酸钙脱水反应中的应用

用一种新的方法求算热分析动力学的三因子 :(1)用迭代的等转化率法求出较为可靠的 Ea;(2 )用多升温速率等温法判定出可能的机理函数 ,并在 Ea和的基础上计算出 A.用该法对一水草酸钙 (Ca C2 O4· H2 O)脱水反应的热分析动力学三因子进行研究 ,得出其对应的机理函数的方程为 ;f (a) =n(1-a) 1- 1/n;Ea为 82 .83 k J· mol- 1;A为 1.14 2× 10 5～ 1.2 3 5× 10 5s- 1     

无水醋酸锌与无水草酸固相反应动力学的研究

用等温热重法研究了无水醋酸锌与无水草酸的固相化学反应,反应分2步进行,通过对转化率数据α进行动力学拟合得到了反应的动力学方程.转化率α较低时发生第一步反应,动力学方程(1－α)－1/2=Ae－E/RTt式中E=70.72kJ/mol、A=4.43×108min－1;转化率α较高时发生第二步反应,动力学方程(1－2α/3)－(1－α)2/3=Ae－E/RTt式中E=122.7kJ/mol、A=9.81×1014min－1.     

多组分钼铋系催化剂补氧再生本征动力学

利用热重法研究了一种用于生产丙烯腈的多组分钼铋催化剂的补氧再生本征动力学。通过应用Achar-Brindley-Sharp微分和Coats-Redfern积分对照的方法得到了动力学三因子,分别为：活化能125.4kJ/mol,指前因子(A)为1.82×10⁸min^-1,动力学机理函数的积分形式为g(α)= ln1-α),表明再氧化反应机理为单分子成核生长。     

四苯基锌卟啉催化氧气氧化对硝基乙苯的表观动力学研究

本文在研究氧气氧化对硝基乙苯反应时,发现双-(α-甲基-4-硝基苄基)过氧化物为关键中间产物,对硝基苯乙酮为主产物,在此基础上建立了四苯基锌卟啉（TPPZn）催化氧气氧化对硝基乙苯的反应模型和速率方程,对其表观动力学行为进行了深入的研究。同时,根据110-150℃范围内所测得的实验数据,计算出了相应的反应速率常数,确立了对硝基乙苯氧化生成双-(α-甲基-4-硝基苄基)过氧化物的第一步为零级反应,表观活化能为39.5kJ/mol;双-(α-甲基-4-硝基苄基)过氧化物分解生成对硝基苯乙酮的第二步反应为1/2级反应,表观活化能为44.6kJ/mol。对比同一温度下的反应速率常数k1和k2,发现低温时k2和k1基本相等,而高温时k2大于k1。通过比较两步反应的表观活化能和反应速率常数,发现升高反应温度有利于对硝基苯乙酮的生成,且可以提高其生成速率。     

空冷条件下钛渣颗粒的氧化路径及氧化动力学

The oxidation pathway and kinetics of titania slag powders in air were analyzed using differential scanning calorimetry (DSC) andthermogravimetry (TG). The oxidation pathway of titania slag powder in air was divided into three stages according to their three exothermic peaks and three corresponding mass gain stages indicated by the respective non-isothermal DSC and TG curves. The isothermal oxidation kin-etics of high titania slag powders of different sizes were analyzed using the ln-ln analysis method. The results revealed that the entire isotherm-al oxidation process comprises two stages. The kinetic mechanism of the first stage can be described as f (α)=1.77 (1?α) [?ln (1?α)](1.77?1)/1.77 , f (α)=1.97 (1?α) [?ln (1?α)](1.97?1)/1.97 , and f (α)=1.18 (1?α) [?ln (1?α)](1.18?1)/1.18 . The kinetic mechanism of the second stage for all samples can be described as f (α)=1.5(1?α)2/3[1?(1?α)1/3]?1 . The activation energies of titania slag powders with different sizes (d1 < 0.075 mm, 0.125 mm < d2 < 0.150 mm, and 0.425 mm < d3 < 0.600 mm) for different reaction degrees were calculated. For the given experimental conditions, the rate-controlling step in the first oxidation stage of all the samples is a chemical reaction. The rate-controlling steps of the second oxidation stage are a chemical reaction and internal diffusion (for powders d1 < 0.075 mm) and internal diffusion (for powders 0.125 mm < d2 <0.150 mm and 0.425 mm < d3 < 0.600 mm).     

三溴偶氮氯膦-Mn（Ⅱ）-KIO4催化体系测定痕量锰的研究

实验研究发现：在pH=4.74的NaAc-HAc缓冲溶液介质中以氨三乙酸（NTA）作活化剂,Mn（Ⅱ）可以强烈地催化高碘酸钾氧化三溴偶氮氯膦褪色的反应。通过实验确定该反应体系的最佳条件,测定催化动力学参数及催化反应的表观活化能Ea′=37.73kJ/mol,表观速率常数为k′=8.85×10-4s-1,探讨了反应机理,确立反应的速率方程（）lgA0A=K？Δt？CMn（∏）,由此建立一个测定痕量锰的新方法。本方法的检测限是2.3×10-9g/mL,测定范围为2.3～10.0ng/mL。该法具有较好的选择性,用于枸杞、茶叶、环境水体试样中痕量锰的测定,结果令人满意     

NaHCO3热分解动力学研究

用稍加改装的Vicotor Meyer法测分子量装置,跟踪NaHCO_3热分解产物CO_2体积变化,对常压NaHCO_3等温热分解反应动力学探索。实验表明,动力学方程为lg(1-x)=-Kt,表观活化能为103.34kJ/mol,在1atm CO_2中,NaHCO_3热分解产物只影响反应速度,不影响反应模式。     

催化裂化汽油萃取-光化学脱硫的动力学模型

以在正辛烷中添加不同量和不同种类的硫化物为模拟体系,介绍了萃取一光化学脱除催化裂化（FCC）汽油中硫化物工艺,探究了该工艺的脱硫机理,并建立了脱硫动力学方程,其动力学方程为（-rA）=dcA/dt=0.4352cA-462.28, Ea=16.9kJ/mol, k0=1.19。并通过3种FCC汽油的萃取-光化学脱硫的实验数据对该动力学模型进行验证,结果表明：该动力学方程适用于1#FCC汽油和3#FCC汽油;对于2#FCC汽油,由于其烯烃含量比较高,对实验结果有一定的影响,因此,计算结果与实验数据存在一定的偏差。     

蛋白质酶促水解反应机理与动力学模型

研究蛋白质酶促水解制备生物活性多肽的反应机理与动力学行为，并建模表征不同反应机制的酶解曲线。基于对不同实验条件下反应时程特性的分析，以经典的米氏方程为理论基础，提出了同时考虑蛋白质单底物水解、蛋白酶失活以及底物或产物抑制因素的机理模型，并构建了指数形式动力学方程dh／dt=aexp（-bh），其中参数（a和b对于不同反应机理具有不同的表达形式和确定的数值结果，对于牛血清白蛋白（BSA）-胰蛋白酶（trypsin）模型体系，经实验拟合平均相对误差为4．73％，并求得该体系相应热力学和动力学常数：Km=0．0748g/L，Ks=7．961g/L，Kd=9．358min^-1，K2=38．439min^-1，Ea=64．826kJ／mol，Ed=80．031kJ／mol。所建整套模型可用于蛋白质酶解反应过程的模拟、热动力学常数的计算和生物反应器的优化设计。