Kinetics of Manganese Oxides Dissolution in Sulphuric Acid Solutions Containing Oxalic Acid

The kinetics of the interaction of MnO2, Mn2O3, and Mn3O4, with sulphuric acid solutions and the effect of oxalic acid on this process are studied. As the sulphuric acid concentration is increased from 0.1 to 5 N, the dissolution rate of Mn2O3, Mn3O4 to MnO2 and Mn2+ ions decreases, whereas it increases with the concentration of Mn2+ ions. Upon the addition of H2Ox, the complete dissolution of Mn3O4 occurs more quickly. The reaction order with respect to the H+ and O x2- ions is +0.5 ± 0.1. A mechanism of MnO2 dissolution promotion by?O x2- is proposed. The dissolution rate was found to depend on the concentrations of?MnHOx - ions and was highest at pH 1.6 ± 0.2. A rate law and mechanism are suggested for manganese oxides dissolution.

Kinetics of reductive leaching of manganese oxide ore using cellulose as reductant

The kinetics of reductive leaching of manganese from a low-grade manganese oxide ore were studied using cellulose as reductant in dilute sulfuric acid medium.It was found that when the stirring speed was higher than 200 r/min,the effect of gas film diffusion on manganese extraction efficiency could be neglected,and the kinetic behavior was investigated under the condition of elimination of external diffusion influence on the leaching process.Effects of leaching temperature,mass ratio of cellulose and ore,and the sulfuric acid concentration on manganese extraction efficiency were discussed.The kinetic data were analyzed based on the shrinking core model,which indicated that the leaching process was dominated by both ash layer diffusion and chemical reaction at the initial stage,with the progress of leaching reaction,the rate-controlling step switched to the ash layer diffusion.It was also concluded that the sulfuric acid concentration had the most significant influence on the leaching rate,the reaction orders with respect to the sulfuric acid concentration were 2.102 in the first 60 min,and 3.642 in the later 90 min,while the reaction orders for mass ratio of cellulose and ore were 0.660 and 0.724,respectively.An Arrhenius relationship was used to relate the temperature to the rate of leaching,from which apparent activation energies were calculated to be 46.487 kJ/mol and 62.290 kJ/mol at the two stages,respectively.Finally,the overall leaching rate equations for the manganese dissolution reaction with cellulose in sulphuric acid solution were developed.The morphological changes and mineralogical forms of the ore before and after the chemical treatment were discussed with the support of SEM and XRD analyses.

Roles of Ceria on Copper and Manganese Oxides Catalyst——Adsorption of NO and CO

A microreactor system and TPD techniques were used to study the reaction kinetics of the CO+ NO reaction and the adsorption of CO,NO,CO_2 and N_2O over Cu-Mn-O(Ⅰ)and Cu-Mn-Ce-O(Ⅱ) catalysts.The results show that the catalytic activity of(Ⅱ)is higher than that of(Ⅰ)for the CO+NO reac- tion,and the higher the conversion of NO,the larger was the activity difference between(Ⅰ)and(Ⅱ).For (Ⅰ)the rate of NO elimination is dependent on the partial pressures of NO,CO,CO_2 with the kinetics or- ders of 0.48,0.56,0.08,respectively.The TPD study shows that the presence of Ce in(Ⅱ)may promote the adsorption of NO,CO on the surface,i.e.an increase of the coverage θ_(NO),θ_(CO),which result in a decrease of the hindrance of the reaction products.For CO_2 and N_2O the situation is in the opposite,the presence of Ce makes the θ_(CO)_2)and θ_(NO)on(Ⅱ)decrease,which weakens the inhibition of CO_2 for the reaction.

Factors Affecting Cr(Ⅲ) Oxidation by Manganese Oxides

The high oxidation ability of manganese oxides or soils was used to study effects of pH and coatingon Cr(Ⅲ) oxidation. The results indicated that Cr(Ⅲ) oxidation peaked in pH 4.0-6.5. The amount andrate of Cr(Ⅲ) being oxidized by uncoated δ-MnO2 were larger than those by Fe oxide- or CaCO3-coatedone. Inorganic Cr(Ⅲ) was more easi1y oxidized by MnO2 than organic complex Cr(Ⅲ) due to differentsurface affinities. Precipitated Cr(Ⅲ) and adsorbed Cr(Ⅲ) might be transferred onto MnO2 surface andthen oxidized to Cr(VI).

Removing Iron Ions Contaminants from Groundwater Using Modified Nano-Hydroxyapatite by Nano Manganese Oxide

In this article, we study modified nano-hydroxyapatite (HAp) by nano manganese oxide (Mn3O4) as adsorbent material to remove iron ions from groundwater. Different parameters were studied to option optimum conditions of removing such as contact time, pH, initial concentration, a dosage of adsorbent, agitation speed and temperature. Kinetics studies included first order (R2 = 0.915), pseudo-first order (R2 = 0.936), second order (R2 = 0.948), pseudo-second order (R2 = 0.995), Elovich equation model (R2 = 0.977), intraparticle diffusion (R2 = 0.946), Natarajan and Khalaf (R2 = 0.915) were carried out, the obtained results revealed that the pseudo-second order is the best to describe the adsorption process because the correlation coefficient is approaching one (R2 = 0.995). Adsorption isotherm was calculated by using Freundlich, Langmuir and Temkin constants, adsorption capacity from Langmuir model was 0.606 mg/g. Thermodynamic parameters (ΔG, ΔH = ?51 KJ/mol, and ΔS = ?142 (KJ/mol)) for the adsorption process were also calculated and discussed.

KINETIC STUDY OF SPINEL LiMn_2O_4 SYNTHESIZED BY SOLID REACTION WITH SOFT-CHEMICAL METHOD

The differential thermal analysis （DTA） curves were measured at different heating rates in flowing air for studying the synthesis of the spinel LiMn2O3 with Li2CO3 and MnO2, The reaction began at about 503K, and finished at about 873K. The apparent activation energy of Kissinger method was about 122.77kJ.mol^-1, the reaction orderwas 1.67, the frequency factor was 7.81×10^9, and therefore the dinetic epuation was dδ/dt=A·exp（- E/RT）·（1-δ）^n=7.81×10^9, exp（-122770/RT）·（l-δ）^1.67 . Coats-Redfem integral method was used to analyze the DTA curves of the samples at different heating rates, and the calculated apparent activation energy and frequency factor were 112. 13kJ· mol^-1 and 1.18 × 10^9, respectively, rather close to that of Kissinger method. X-ray diffraction （XRD） and scanning electron microscope （SEM） results shown that the synthesized LiMn2O3 possesses pure phase, regular shape and normal particle distribution.

An amorphous manganese iron oxide hollow nanocube cathode for aqueous zinc ion batteries

Aqueous zinc ion batteries(ZIBs) are attracting considerable attentions for practical energy storage because of their low cost and high safety.Nevertheless,the traditional manganese oxide cathode materials suffer from the low intrinsic electronic conductivity,sluggish ions diffusion kinetics,and structural collapse,hindering their large-scale application.Herein,we successfully developed a latent amorphous Mn_(1.8)Fe_(1.2)O_(4) hollow nanocube(a-H-MnFeO) cathode material derived from Prussian blue analogue precursor.The amorphous nature endows the cathode with lower diffusion barrier and narrower band gap compared with crystalline counterpart,resulting in the superior Zn^(2+) ions and electrons transport kinetics.Hollow structure can furnish abundant surface sites and suppress the structural collapse during the repeated charge/discharge processes.By virtue of the multiple advantageous features,the a-H-MnFeO cathode exhibits exceptional electrochemical performance,in terms of high capacity,excellent rate capability,and prolonged cycle life.This strategy will pave the way for the structural design of emerging cathode materials.

高锰酸钾氧化饮用水中醛类嗅味物质的效果及动力学研究

我国北方呼和浩特市以黄河为水源的JH饮用水厂近年来冬季经常有醛类嗅味物质检出,常规处理工艺如混凝、沉淀等对其去除效果有限,需要对其进行其它处理工艺的探究.本文选择高锰酸钾对水厂检出频率和浓度均较高的反,反-2,4-庚二烯醛(tt24hept)、反-2-辛烯醛(t2oa)、反,反-2,4-辛二烯醛(tt24oda)、反,反-2,4-癸二烯醛(tt24dda)和β-环柠檬醛(β-cyclo)5种醛类嗅味物质进行氧化控制研究,探究其去除效果、氧化动力学和氧化机理.结果表明,20℃,pH=7时,2 mg·L^(-1)高锰酸钾氧化5种醛类嗅味物质30 min后,去除率达75%以上.根据动力学分析可知,高锰酸钾氧化5种醛类嗅味物质属于伪二级动力学过程,其伪二级反应速率常数分别为5.25×10^(4)、2.66×10^(4)、4.50×10^(4)、2.71×10^(4)、5.37×10^(3)L·mol^(-1)·min^(-1),醛类嗅味物质结构中含碳碳双键数目越多、含亚甲基数目越少,反应速率常数越大.同时,氧化过程会产生新生态二氧化锰,促进高锰酸钾对嗅味物质的控制效果.最后,通过水厂原水加标实验效果验证,理论反应方程可为饮用水厂应对醛类物质嗅味问题提供相应的理论依据并指导生产.

臭氧在水中溶解度及氧化除锰的动力学研究

采用碘量法研究了不同进口空气流量、pH值、温度等条件对臭氧溶解特性的影响。结果表明,在进口空气流量100 L/h、常温20℃、pH1.5左右时,臭氧在水中的溶解度最高达62.22 mg/L。在此基础上进行了不同空气进口流量下锰脱除的试验和动力学研究。结果表明,随着空气流量的增加,Mn的脱除率呈现出先增加后减小的趋势,当空气流量为100 L/h时,Mn的脱除率最高达99.99%。动力学研究结果表明,臭氧氧化去除水中的锰离子符合拟一级动力学特征,即扩散是其限制性环节,溶液中Mn^(2+)被臭氧氧化后水解形成α-MnO_(2)沉淀形式从溶液中被去除。

活性氧化镁选择性沉淀钴试验研究

针对以刚果(金)铜钴多金属共生矿石为原料的提钴工艺,研究了采用活性氧化镁选择沉淀模拟含钴溶液中的钴并制备粗氢氧化钴,探讨了溶液中氢氧化物沉淀的动力学,考察了氧化镁粒径、氧化镁添加量及添加方式、反应时间、温度对铁、钴、锰沉淀的影响。结果表明:通过添加30%过氧化氢能快速去除模拟含钴溶液中的杂质铁;按照添加量0.68/1、多次加入方式向模拟含钴溶液中添加粒径小于45μm活性氧化镁,在常温下反应6 h所得一级沉淀符合行业标准一级品要求,次级沉淀符合三级品要求。该工艺具有成本低、实用性强等优点,可有效提高氧化镁沉钴效率。

Reduction of Low-grade Manganese Dioxide Ore Pellets by Biomass Wheat Stalk

An investigation on reducing low-grade manganese dioxide ore pellets was carried out by using wheat stalk as reductant. The main impact factors of reduction percent such as particle size, biomass/ore ratio, heating rate, nitrogen flow rate, temperature and time in reduction process were discussed. The morphology and component of manganese dioxide ore particle at different stages were also analyzed by scanning electron microscopy （SEM） and energy dispersive X-ray spectroscopy （EDS）. The results show the increase of the reduction temperature and time, biomass/ore ratio, and the decrease of particle size, heating rate and nitrogen flow rate can significantly enhance reduction efficiency. The reduction kinetic of the manganese ore is controlled by three-dimensional mass diffusion of gaseous reductive volatiles passing from the surface to the core of the ore particles. The activation energy E and frequency factor A were calculated to be 24.15 kJ.mol^-1 and 166 min^-1, respectively. Biomass pyrolysis volatiles adsorbed onto the surface of the ore particle leads to serious variation of the microstructures and chemical composition of the manganese ore particles.

Active manganese oxide on MnOx-CeO2 catalysts for low-temperature NO oxidation：Characterization and kinetics study

MnO_x-CeO_2 catalysts were synthesized to investigate the active sites for NO oxidation by varying the calcination temperature. XRD and TEM results showed that cubic CeO_2 and amorphous MnO_x existed in MnO_x-CeO_2 catalysts. High temperature calcination caused the sintering of amorphous MnO_x and transforming to bulk crystalline Mn_2O_3, H_2-TPR and XPS results suggested the valence of Mn in MnO_x-CeO_2 was higher than pure MnO_x, and decreased with the increasing calcination temperature, The turnover frequency（TOF） was calculated based on the initial reducibility according to H_2-TPR quantitation and kinetic study. The TOF results indicated that the initial reducibility of amorphous MnO_x with high valence manganese ions was equivalent to the active sites for NO oxidation. It can be inferred that the amorphous MnO_x plays a key role in low-temperature NO oxidation.

Redox reactions of iron and manganese oxides in complex systems

Conspectus:Redox reactions of Fe-and Mn-oxides play important roles in the fate and transformation of many contaminants in natural environments.Due to experimental and analytical challenges associated with complex environments,there has been a limited understanding of the reaction kinetics and mechanisms in actual environmental systems,and most of the studies so far have only focused on simple model systems.To bridge the gap between simple model systems and complex environmental systems,it is necessary to increase the complexity of model systems and examine both the involved interaction mechanisms and how the interactions affected contaminant transformation.In this Account,we primarily focused on(1)the oxidative reactivity of Mn-and Fe-oxides and(2)the reductive reactivity of Fe(Ⅱ)/iron oxides in comolex model systems toward contaminant degradation.The effects of common metal ions such as Mn2+,Ca2+,Ni2+,Cr3+and Cu2+,ligands such as small anionic ligands and natural organic matter(NOM),and second metal oxides such as A1,Si and Ti oxides on the redox reactivity of the systems are briefly summarized.

非离子型微乳液介质-天竺牡丹紫催化光度法测定水及土壤中微量锰

研究了以微乳液作为介质 ,在pH 4.5HAc NaAc缓冲溶液中 ,用氨三乙酸作活化剂 ,锰催化高碘酸钾氧化天竺牡丹紫褪色的新指示反应。在 5 80nm处 ,检出限达到 3.8ng L ,线性范围为 0 .4～ 5 .6 μg L。该法用于土壤及水中微量锰的测定 ,相对标准偏差小于 3.6 %,加标回收率在 95 %～ 10 7%范围内 ,取得了令人满意的结果。

高铁三水铝石矿溶出动力学

研究了高铁三水铝石矿常压条件下的溶出动力学。分别考察了矿石粒度、氢氧化钠浓度、溶出温度、搅拌速度对溶出性能的影响。研究发现,常压条件下矿石溶出率大于90%。提高溶出温度或氢氧化钠浓度、减小矿石粒度均可加快矿石的溶出速度。综合考虑矿石粒度、氢氧化钠浓度和搅拌速度的影响,推导出高铁三水铝石矿溶出动力学经验方程为:1-2/3α-(1-α)^(2/3)=1.28×10^(15)×(c_(NaOH))^(1.70)×d^(-0.36)×r^(0.74)×e^(-117402/RT)×t。该方程与内扩散控制的动力学模型吻合较好,反应速率受包覆在晶体表面的针铁矿和赤铁矿固体膜层所控制。

催化动力学光度法测定痕量锰的研究

研究了在 pH 4 .5的乙酸 乙酸钠缓冲介质中 ,在氨三乙酸存在下 ,痕量Mn2 +对高碘酸钾氧化次甲基蓝褪色的强烈催化作用 ,建立了测定金属镁中痕量锰的适宜条件。经过对金属镁样品多次分析 ,相对标准偏差≤ 10 % ,回收率在 93%～ 10 7%

天然锰氧化物矿物氧化废水中苯酚的动力学研究

利用天然锰氧化物矿物在酸性条件下的强氧化性。研究其氧化水中苯酚的动力学．模拟锰氧化物矿物氧化苯酚的反应过程。通过测定初始浓度为100-1000mg／L，pH值为1～2，温度为293-333K时不同氧化时间锰氧化物矿物对苯酚的氧化结果，比较伪一级和伪二级反应方程的线性拟合情况；结果表明，该反应动力学曲线用伪二级反应模型拟合时相关系数高于用伪一级反应方程线性的拟合，所以这个反应可用来模拟伪二级反应。根据动力学数据得出Arrhenius反应活化能Ea为11．62kJ／mol，说明温度对该反应影响不显著，且是一个扩散控制反应。

尖晶石型锰酸锂前驱体的表征与分解活化能

采用不同升温速率的差热分析研究空气气氛中锰酸锂前驱体分解的反应. 利用Doyle- Ozawa法和Kissinger法计算各反应阶段的表观活化能. X射线衍射、粒度分析、扫描电镜和透射电镜分析表明,共沉淀法和煅烧法相结合制备的LiMn2O4物相纯净,粒度分布均匀,形貌规整.

二氧化锰氧化降解五氯酚

以二氧化锰为氧化剂,研究了pH 4.12的水溶液中五氯酚氧化降解的反应动力学,并讨论了反应溶液的pH对反应动力学的影响.结果表明,五氯酚对二氧化锰的氧化作用具有较强的反应感受性.在pH一定和二氧化锰充分过量的条件下,随着反应的进行,五氯酚的降解速度变慢,遵循的不是简单的准一级反应动力学而是复合的反应动力学.此外,随溶液pH由3.5升高6.6,五氯酚的降解速度发生显著地下降.运用溶剂萃取和气质联用仪的分析方法,检测到2个主产物和1个次产物.其中,次产物是由四氯-1,4-氢醌与四氯儿茶酚组成的混合物;2个主产物是由五氯酚氧自由基偶合而成的二聚体,且是同分异构体.在观测到的表面反应动力学和降解产物的基础上,提出了五氯酚被二氧化锰氧化降解的反应流程图.

高铁锰氨氮地下水净化试验及氧化动力学

在水厂,以中试模拟滤柱开展了高铁锰氨氮(8~10℃,TFe 6~14mg/L,Mn 0.8~1.5mg/L,NH_4^+-N 2.0~3.0mg/L)地下水净化试验及氧化动力学分析.结果表明,一级曝气+一级过滤、一级曝气+两级过滤工艺均由于溶解氧(DO)不足,对高铁锰氨氮地下水净化失败;曝气生物滤池由于曝气对水流造成紊动,净化效果最差;曝气生物滤池+两级过滤工艺可实现高铁锰氨氮地下水净化,但是运行滤速仅有6.0m/h;两级曝气+两级过滤工艺净化效果最优,可实现高铁锰、氨氮地下水(8~10℃,TFe 17.66mg/L,Mn 1.71mg/L,NH_4^+-N 3.37mg/L)净化,一级和二级滤速分别可达13.25m/h和12.75m/h,且在低温下亦适用,可实现低温高铁高锰高氨氮(5~6℃,TFe 9.72mg/L,Mn 3.29mg/L,NH_4^+-N 3.44mg/L)地下水的净化,一级和二级极限滤速分别为10.0m/h和8.0m/h.氧化动力学分析表明,铁氧化去除遵循一级化学氧化动力学规律,其氧化动力学常数为(1.02~1.18)×10.氨氮和锰的去除均遵循零级酶促反应动力学规律,其氧化动力学常数分别为(0.15~0.83)×10^(-1)和(0.31~1.20)×10^(-1).除铁除锰生物滤池中,铁的氧化去除速率最快,优先完成去除,锰和氨氮完成氧化去除的先后顺序受基质浓度大小影响较大.