CaO–SiO2–Al2O3–4.6wt%MgO–Fe2O3废汽车催化剂熔炼渣系的冶金特性研究

本文系统地研究了废汽车催化剂（SAC）与含铜电镀污泥（CBES）协同熔炼过程中形成的CaO?SiO₂?Al₂O₃?4.6wt%MgO?Fe₂O₃五元渣系的冶金特性。通过傅立叶变换红外吸收光谱、拉曼光谱、FactSage热力学计算和粘度测试研究了该渣系的熔渣结构、熔化温度和粘度特性。实验结果表明,Fe₂O₃含量（3.8wt%?16.6wt%）、CaO/SiO₂质量比（0.5?1.3）和SiO₂/Al₂O₃质量比（1.0?5.0）的提高可以促进硅酸盐网络的解聚,同时以四面体和八面体单元形式存在的大量Fe₂O₃确保了Al3+离子的电荷补偿,使得Al₂O₃仅表现为酸性氧化物。热力学计算和粘度测试结果表明,随着Fe₂O₃含量、CaO/SiO₂比和SiO₂/Al₂O₃比的增加,熔渣中发生硅酸盐网络结构解聚和低熔点相变,促进了熔点和粘度的降低;而进一步增加会导致新的高熔点物相形成,反而导致粘度和熔点回升。根据实验分析,优选的低聚合度、粘度和熔点炉渣组成为:Fe₂O₃含量为10.2wt%?13.4wt%,CaO/SiO₂比为0.7?0.9和SiO₂/Al₂O₃比为3.0?4.0。本研究为SAC和CBES协同熔炼过程中的炉渣设计提供了理论支持。     

CaO-SiO2-MgO-Al2O3四元渣系Al2O3活度预测模型

高炉渣系各组元活度对高炉冶炼和产品质量具有重要的影响作用. 基于分子-离子共存理论,建立CaO-SiO₂-MgO-Al₂O₃四元渣系Al₂O₃活度预测模型;结合试验测定值对其进行验证与修正,最终建立了修正的CaO-SiO₂-MgO-Al₂O₃四元渣系Al₂O₃活度预测模型;同时,依据模型计算结果探究R(w(CaO)/w(SiO₂)),w(MgO)/w(Al₂O₃)和w(Al₂O₃)对Al₂O₃活度的影响. 研究结果表明:修正后的CaO-SiO₂-MgO-Al₂O₃四元渣系Al₂O₃活度预测模型具有较高的预测精度,能够很好地预测熔渣Al₂O₃活度;当w(MgO)/w(Al₂O₃)=0.40,w(Al₂O₃)=20%时,随着R增加,Al₂O₃活度逐渐减小;当R=1.25,w(Al₂O₃)=20%时,随着w(MgO)/w(Al₂O₃)增加,Al₂O₃活度逐渐减小;当w(MgO)/w(Al₂O₃)=0.40,R=1.25时,随着w(Al₂O₃)增加,Al₂O₃活度逐渐增大.     

1623 K时SiO2饱和的MnO–SiO2渣和Al2O3饱和的MnO–SiO2–Al2O3渣中NiO的活度系数

MnO–SiO₂二元系作为废旧锂离子电池、海洋锰结核还原熔炼过程中的基础渣型,测定有价金属（如镍）在渣中的溶解度、活度及活度系数热力学数据十分必要。为此,本文测定了温度1623 K、氧分压10?7,10?6,和10?5 Pa时SiO₂饱和的MnO–SiO₂渣和Al₂O₃饱和的MnO–SiO₂–Al₂O₃渣中NiO的溶解度和活度系数。结果表明:在试验条件下,镍在MnO–SiO₂渣和MnO–SiO₂–Al₂O₃渣中主要以NiO形式存在,且渣中NiO的溶解度随着氧分压增加而增加;向MnO–SiO₂渣中加入Al₂O₃可以降低渣中镍的溶解度,增加NiO的活度系数。此外,SiO₂饱和的MnO–SiO₂渣和Al₂O₃饱和的MnO–SiO₂–Al₂O₃渣中NiO的活度系数（γ_NiO,以纯固体NiO为参考态）可分别按如下公式计算:γ_NiO = 8.58w(NiO) + 3.18; γ_NiO=11.06w(NiO) + 4.07, 其中,w(NiO)为渣中NiO的质量分数。     

Al2O3对高炉渣物化性能影响的理论分析

随着优质铁矿资源的消耗,钢铁企业可利用的铁矿原料品位逐渐降低。因此,高铝质铁矿资源越来越受到钢铁企业的关注,但高铝原料在高炉冶炼过程中会带来渣铁黏稠、炉温偏低、冶炼安全等一系列问题。本研究中采用FactSage热力学软件分析Al₂O₃质量分数对高炉渣平衡物相、熔化温度、相析出温度的影响以及高铝渣液相区变化和黏度变化,旨在为高炉冶炼高铝原料提供一定的基础支撑。研究发现：炉渣为低铝（5%～10%）含量时,随着Al₂O₃含量增加,炉渣熔化温度升高,析出相为黄长石相和纯物质相,高炉渣黏度变化不大,炉渣中SiO₂含量高,炉渣黏度过高,不适合高炉冶炼;炉渣为中铝（10%～15%）含量时,随着Al₂O₃含量增加,炉渣熔化温度升高,析出相为尖晶石相、黄长石相和纯物质相,高炉渣黏度增加幅度略有提高,Al₂O₃含量对高炉渣性质影响较小,增加炉渣二元碱度对炉渣黏度降低效果较明显;炉渣为高铝（15%～30%）含量时...     

w(CaO)/w(Al2O3)对钙铝基保护渣结晶性能的影响

利用热丝法测试技术,结合扫描电镜和能谱分析,研究了不同w(CaO)/w(Al₂O₃)条件下钙铝基保护渣的结晶性能.结果表明,较低w(CaO)/w(Al₂O₃)下,保护渣结晶物相为LiAlO₂和CaO·Al₂O₃.其析出由渣中的Li⁺离子和Ca²⁺离子分别对高聚合度铝氧四面体结构的电荷补偿所致.而且,Li⁺离子优先参与,LiAlO₂优先析出.较高w(CaO)/w(Al₂O₃)下,结晶物相转变为LiAlO₂和3CaO·Al₂O₃.其变化原因为,CaO相对质量分数提高,保护渣聚合度降低,Ca²⁺离子和低聚合度铝氧四面体结构单元Q²结合而形成3CaO·Al₂O₃并析出.随着w(CaO)/w(Al₂O₃)由1.13提高至1.82,钙铝基保护渣析晶能力先减弱然后增强.在w(CaO)/w(Al₂O₃)为1.50和1.82时分别具有最弱和最强的析晶能力.     

高炉炼铁工艺中超高TiO2炉渣:密度和表面张力

针对高炉冶炼超高（>80%）甚至全钒钛磁铁矿工艺流程，为了优化高炉造渣制度，进行了一系列关于高钛型炉渣（BFS）物理化学性质方面的研究。本工作分别利用阿基米德原理和最大气泡压力法研究了高钛型炉渣的密度和表面张力。系统探究了TiO₂含量和MgO/CaO质量比对CaO–SiO₂–TiO₂–MgO–Al₂O₃炉渣密度和表面张力的影响规律。结果发现，随着TiO₂含量从20wt%增加到30wt%，炉渣密度逐渐降低，但随着MgO/CaO质量比从0.32增加到0.73，熔渣密度略有增加。从硅酸盐网络结构角度来看，炉渣密度与结构聚合度（DOP）具有一致的变化规律。TiO₂的加入会降低炉渣体系中(Q3)2/(Q2)比值（其中，Q2和Q3分别代表桥氧数为2和3的网络结构单元），进而降低炉渣结构聚合度，导致炉渣密度降低。随着TiO₂含量从20wt%增加到30wt%，CaO–SiO₂–TiO₂–MgO–Al₂O₃炉渣的表面张力显著降低。相反，随着MgO/CaO质量比从0.32增加到0.73，表面张力增加。此外，利用基于Butler公式的Tanaka模型获得了1723 K下含钛炉渣等表面张力图，为高炉冶炼超高比例（>80%）甚至全钒钛磁铁矿工艺中造渣制度的优化提供了数据支撑。     

CaO-SiO2-Al2O3-Na2O-MgO系模铸保护渣微观结构解析

为明晰化学成分变化对模铸保护渣物性的影响机制,采用Raman光谱对CaO-SiO₂-Al₂O₃-Na₂O-MgO系熔融模铸保护渣的微观结构进行了解析.熔体结构解析结果表明,熔渣中存在Q_Si⁰,Q_Si¹,Q_Si²,Q_Si³,Q_Si⁴五种硅氧四面体结构和Q_Al²,Q_Al³,Q_Al⁴三种铝氧四面体结构,随着碱度升高和Al₂O₃质量分数减小,高聚合度四面体结构向低聚合度转变,熔渣非桥氧数增多,聚合程度降低.物理性质测试结果表明,黏度随Al₂O₃质量分数增大而升高,随碱度的升高...     

Al含量对Fe?10Mn?xAl (x = 0.035wt%, 0.5wt%, 1wt%, 2wt%)合金体系和CaO?SiO2?Al2O3?MgO精炼渣反应的影响

轻量化是世界汽车发展的方向,中高锰钢因高强、高塑、高加工硬化率等优异的力学性能引起了人们的很大关注。除Mn含量高外,该钢种通常含有较高的Al以降低材料密度、防止氢延迟断裂等。因合金含量高,钢液中的溶质元素和顶渣会发生较强的渣/钢反应,进而对钢液、顶渣、洁净度等产生重要影响。本文旨在研究不同Al含量的中锰钢与精炼渣的反应及其影响。本文采用渣/钢平衡的实验方法研究了不同Al 含量(0.035wt%, 0.5wt%, 1wt%, 2wt%)的Fe?10Mn?xAl 合金体系与CaO?SiO₂?20wt%Al₂O₃?6wt%MgO (CaO/SiO₂ = 4)精炼渣之间的反应,及其对钢液和炉渣成分、非金属夹杂物的影响;在实验基础上,对钢液和炉渣成分变化以及夹杂物转变进行了热力学分析与讨论。研究结果表明,渣/钢反应后,钢中Al含量显著降低,初始Al含量对反应后钢、渣的成分有重要影响。随着初始Al含量增加,钢中的Si和渣中的Al₂O₃逐渐增加,而渣中的SiO₂和MnO逐渐减少。造成该变化的原因是:随着初始Al含量增加,钢液中的Al逐渐替代Mn与渣中SiO₂反应,即渣/钢之间的主控反应由2[Mn] + (SiO₂) = 2(MnO) + [Si]转变为4[Al] + 3(SiO₂) = 2(Al₂O₃) + 3[Si]。随着初始Al含量增加,钢中夹杂物类型也发生很大变化,转变路线为:MnO → MnO?Al₂O₃?MgO → MgO → MnO?CaO?Al₂O₃?MgO 和 MnO?CaO?MgO,相应的夹杂物形状由球形变为不规则状,最后又变为类球形。其转变机理是:随着初始Al含量增加,钢中Al逐渐替代Mn与渣中SiO₂反应,且Mg、Ca依次从渣中还原进入钢液,故而夹杂物类型发生上述转变。     

18wt%Cr–8wt%Ni不锈钢中增塑性MnO–Al2O3–SiO2基非金属夹杂物的演变及其浸泡性能

The properties of MnO–Al₂O₃–SiO₂-based plasticized inclusion are likely to change during soaking  process due to its low melting point. In this study, the evolution of the MnO–Al₂O₃–SiO₂-based inclusion of 18wt%Cr?8wt%Ni stainless steel under isothermal soaking process at 1250°C for different times was investigated by laboratory-scale experiments and thermodynamic analysis. The results showed that the inclusion population density increased at the first stage and then decreased while their average size first decreased and then increased. In addition, almost no Cr₂O₃-concentrated regions existed within the inclusion before soaking, but more and more Cr₂O₃ precipitates were formed during soaking. Furthermore, the plasticity of the inclusion deteriorated due to a decrease in the amount of liquid phase and an increase in the high-melting-point-phase MnO–Cr₂O₃ spinel after the soaking process. In-situ observations by high-temperature confocal laser scanning microscopy (CLSM) confirmed that liquid phases were produced in the inclusions and the inclusions grew rather quickly during the soaking process. Both the experimental results and thermodynamic analysis conclude that there are three routes for inclusion evolution during the soaking process. In particular, Ostwald ripening plays an important role in the inclusion evolution, i.e., MnO–Al₂O₃–SiO₂-based inclusions grow by absorbing the newly precipitated smaller-size MnO–Cr₂O₃ inclusions.     

B2O3对无氟CaO-Al2O3-BaO基保护渣性能的影响

借助高温物性测试仪、黏度仪、原位热分析仪及傅里叶变换红外光谱仪等,研究了B₂O₃含量对无氟CaO-Al₂O₃-BaO基保护渣熔化温度、黏度和结晶性能的影响。结果表明,当B₂O₃含量为7%时,无氟CaO-Al₂O₃-BaO基保护渣熔化温度、黏度和结晶性能最佳。     

CaF2对CaO-Al2O3-CaF2熔体结构影响的分子动力学研究

采用分子动力学的方法研究了不同CaF₂含量下CaO-Al₂O₃-CaF₂三元渣系熔体结构的变化规律,包括熔渣的短程结构、中程结构和键角的变化.结果表明:Ca—F,Al—F,Ca—O,Al—O的平均键长分别为0.2345,0.1895,0.2325,0.1745nm.随着CaF₂的加入,Ca²⁺与配位的阴离子(O^2-,F^-)存在动态平衡现象,总配位数维持在6~7之间.研究体系中Al—O四面体结构存在由复杂(Q⁴和Q³)向简单(Q²和Q¹)的转变,同时还会发生Al—O四面体［AlO₄］^5-向［AlO₃F］^4-结构的转变,两种转变的综合作用使熔体的网络结构解聚,为CaF₂改善CaO-Al₂O₃-CaF₂熔渣的流动性提供了合理的微观解释.键角分析表明F^-在体系中更多的是替换原来O^2-的位置,以Al³⁺为核心的网络结构依然为四面体结构,没有引起大规模的原子重新排列.     

BaO和MgO含量对CaO–Al2O3系保护渣与钢基底之间润湿行为的影响

结晶器内的界面现象对连铸过程的顺行和铸件的质量有很大的影响,虽然钢–渣之间的界面特性已经被许多研究者研究过,但是这些研究大多是已钢或铁为研究对象。传统的CaO–SiO₂系保护渣在参与高铝钢连铸时会与钢中的Al发生化学反应,导致保护渣的成分和性能发生变化,从而影响连铸顺行。因此,性能稳定的非反应型CaO–Al₂O₃系保护渣,成为高铝钢连铸过程的一种潜在功能材料。本文采用卧滴法,研究了BaO和MgO含量对非反应型CaO–Al₂O₃系保护渣润湿行为的影响,测量了渣-钢之间的接触角,并计算了界面张力。此外,还利用XPS测定了钢-渣界面处的氧种类,以证明保护渣成分和界面之间的内在联系。研究结果表明:BaO和MgO对保护渣的润湿行为有着不同的影响,具体而言,当BaO含量从3wt%增加到7wt%时,渣与IF钢的接触角从62.4°增加到74.5°,界面张力也从1630.3 mN/m增加到1740.8 mN/m。 XPS的结果表明,随着BaO的加入,钢–渣界面处的熔体结构发生聚合,O?(非桥氧)和O2?（游离氧）的比例降低,而O0(桥氧)的比例增加,这说明BaO的加入会降低熔剂对IF钢的润湿性。而当MgO含量从3wt%增加到7wt%时,渣与IF钢基体的接触角从62.4°减少到51.3°,界面张力也从1630.3 mN/m降低到1539.7 mN/m。加入MgO时,钢–渣界面处的熔体结构发生解聚,由于部分O0分解为O?和O2?,导致O0的比例减少,这说明MgO提高了IF钢的润湿性,使熔剂更容易在IF钢表面浸润。引起这一结果的主要原因是,Mg2+离子半径小于Ba2+离子,Mg2+的静电势也高于Ba2+,较高的静电势导致O2?和Mg2+之间产生较强的极化效应,导致熔体中Mg–O键由离子键向共价键转变,从而使得Mg2+的电荷补偿效应远远小于Ba2+。     

Electrical conductivity optimization of the Na3AlF6-Al2O3-Sm2O3 molten salts system for Al-Sm intermediate binary alloy production

Metal Sm has been widely used in making Al-Sm magnet alloy materials. Conventional distillation technology to produce Sm has the disadvantages of low productivity, high costs, and pollution generation. The objective of this study was to develop a molten salt electrolyte system to produce Al-Sm alloy directly, with focus on the electrical conductivity and optimal operating conditions to minimize the energy consumption. The continuously varying cell constant (CVCC) technique was used to measure the conductivity for the Na₃AlF₆-AlF₃-LiF-MgF₂-Al₂O₃-Sm₂O₃ electrolysis medium in the temperature range from 905 to 1055℃. The temperature (t) and the addition of Al₂O₃ (W(Al₂O₃)), Sm₂O₃ (W(Sm₂O₃)), and a combination of Al₂O₃ and Sm₂O₃ into the basic fluoride system were examined with respect to their effects on the conductivity (κ) and activation energy. The experimental results showed that the molten electrolyte conductivity increases with increasing temperature (t) and decreases with the addition of Al₂O₃ or Sm₂O₃ or both. We concluded that the optimal operation conditions for Al-Sm intermediate alloy production in the Na₃AlF₆-AlF₃-LiF-MgF₂-Al₂O₃-Sm₂O₃ system are W(Al₂O₃) + W(Sm₂O₃)=3wt%, W(Al₂O₃):W(Sm₂O₃)=7:3, and a temperature of 965 to 995℃, which results in satisfactory conductivity, low fluoride evaporation losses, and low energy consumption.     

Activity coefficient of NiO in SiO2-saturated MnO–SiO2slag and Al2O3-saturated MnO–SiO2–Al2O3slag at 1623 K

As a part of the fundamental study related to the reduction smelting of spent lithium-ion batteries and ocean polymetallic nodules based on MnO–SiO₂slags,this work investigated the activity coefficient of NiO in SiO₂-saturated Mn O–Si O₂slag and Al₂O₃-saturated Mn O–SiO₂–Al₂O₃slag at 1623 K with controlled oxygen partial pressure levels of 10^-7,10^-6,and 10^-5Pa.Results showed that the solubility of nickel oxide in the slags increased with increasing oxygen partial pressure.The nickel in the Mn O–Si O₂slag and Mn O–Si O₂–Al₂O₃slag existed as Ni O under experimental conditions.The addition of Al₂O₃in the Mn O–Si O₂slag decreased the dissolution of nickel in the slag and increased the activity coefficient of Ni O.Furthermore,the activity coefficient of Ni O(γN_(i O)),which is solid Ni O,in the Si O₂saturated Mn O–Si O₂slag and Al₂O₃saturated Mn O–Si O₂–Al₂O₃slag at 1623 K can be respectively calculated asγN_(i O)=8.58w(Ni O)+3.18 andγN_(i O)=11.06w(Ni O)+4.07,respectively,where w(Ni O)is the Ni O mass fraction in the slag.     

Sintering Behavior and Microstructure of diphasic β-Sialon/Al2O3 Composites

Six compositions with different ratio of β-Sialon/Al₂O₃ were synthesized from Al₂O₃, Si₃N₄ and SiO₂ by sintering with 3%Y₂O₃(mass fraction) as addition under the cover with powders of SiC+C and at nitrogen atmosphere. Theeffects of atmosphere, sintering temperature and composition on the sintering behavior were studied. The results showedthat the composites reached the best sintering behavior with the highest density about 92% at 1 650℃ under the weakreduction atmosphere. Finally the relative density of diphasic β-Sialon and β-Sialon/Al₂O₃ composites were studied andpredicted using ANN (Artificial Neural Networks) method and the results were experimental examined by fore randomsamples.     

Al2O3/LiAlO2表面包覆改性LiNi1/3Co1/3Mn1/3O2三元正极材料研究

三元正极材料因比容量高、成本低和较为环保而备受研究者的关注和青睐,但其循环稳定性与倍率性能较差。通过固相包覆法制备了纳米Al₂O₃以及LiAlO₂包覆的LiNi_1/3Co_1/3Mn_1/3O₂材料,对所制备材料的结构及形貌进行系统表征,结果表明,两种包覆均在保持正极材料结构的基础上成功形成了表面包覆层。电化学性能测试表明,用质量分数为1%的Al₂O₃包覆时,其初始放电容量从原始材料的159 mA·h·g^-1提升至162.57 mA·h·g^-1,循环35次的容量保持率由74.38%提升至94.89%;用质量分数为3%的LiAlO₂包覆时,初始放电比容量提升至164.85 mA·h·g^-1,前35次的容量保持率较未包覆材料均有所提高。此外,经包覆后正极材料循环性能和倍率性能均有所提高,电压衰减和电化学阻抗降低,...     

In situ reaction mechanism of MgAlON in Al-Al2O3-MgO composites at 1700℃ under flowing N2

The Al-Al₂O₃-MgO composites with added aluminum contents of approximately 0wt%, 5wt%, and 10wt%, named as M₁, M₂, and M₃, respectively, were prepared at 1700℃ for 5 h under a flowing N₂ atmosphere using the reaction sintering method. After sintering, the Al-Al₂O₃-MgO composites were characterized and analyzed by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The results show that specimen M₁ was composed of MgO and MgAl₂O₄. Compared with specimen M₁, specimens M₂ and M₃ possessed MgAlON, and its production increased with increasing aluminum addition. Under an N₂ atmosphere, MgO, Al₂O₃, and Al in the matrix of specimens M₂ and M₃ reacted to form MgAlON and AlN-polytypoids, which combined the particles and the matrix together and imparted the Al-Al₂O₃-MgO composites with a dense structure. The mechanism of MgAlON synthesis is described as follows. Under an N₂ atmosphere, the partial pressure of oxygen is quite low; thus, when the Al-Al₂O₃-MgO composites were soaked at 580℃ for an extended period, aluminum metal was transformed into AlN. With increasing temperature, Al₂O₃ diffused into AlN crystal lattices and formed AlN-polytypoids; however, MgO reacted with Al₂O₃ to form MgAl₂O₄. When the temperature was greater than (1640 ±10)℃, AlN diffused into Al₂O₃ and formed spinel-structured AlON. In situ MgAlON was acquired through a solid-solution reaction between AlON and MgAl₂O₄ at high temperatures because of their similar spinel structures.     

Fabrication of Fe–TiC–Al2O3 composites on the surface of steel using a TiO2–Al–C–Fe combustion reaction induced by gas tungsten arc cladding

The aim of the present study was to fabricate Fe–TiC–Al₂O₃ composites on the surface of medium carbon steel. For this purpose, TiO₂–3C and 3TiO₂–4Al–3C–xFe (0 ≤ x ≤ 4.6 by mole) mixtures were pre-placed on the surface of a medium carbon steel plate. The mixtures and substrate were then melted using a gas tungsten arc cladding process. The results show that the martensite forms in the layer produced by the TiO₂–3C mixture. However, ferrite–Fe₃C–TiC phases are the main phases in the microstructure of the clad layer produced by the 3TiO₂–4Al–3C mixture. The addition of Fe to the TiO₂–4Al–3C reactants with the content from 0 to 20wt% increases the volume fraction of particles, and a composite containing approximately 9vol% TiC and Al₂O₃ particles forms. This composite substantially improves the substrate hardness. The mechanism by which Fe particles enhance the TiC + Al₂O₃ volume fraction in the composite is determined.     

Fluoride evaporation and crystallization behavior of CaF2–CaO–Al2O3–(TiO2) slag for electroslag remelting of Ti-containing steels

To elucidate the behavior of slag films in an electroslag remelting process, the fluoride evaporation and crystallization of CaF₂–CaO–Al₂O₃–(TiO₂) slags were studied using the single hot thermocouple technique. The crystallization mechanism of TiO₂-bearing slag was identified based on kinetic analysis. The fluoride evaporation and incubation time of crystallization in TiO₂-free slag are found to considerably decrease with decreasing isothermal temperature down to 1503 K. Fish-bone and flower-like CaO crystals precipitate in TiO₂-free slag melt, which is accompanied by CaF₂ evaporation from slag melt above 1503 K. Below 1503 K, only near-spherical CaF₂ crystals form with an incubation time of less than 1 s, and the crystallization is completed within 1 s. The addition of 8.1wt% TiO₂ largely prevents the fluoride evaporation from slag melt and promotes the slag crystallization. TiO₂ addition leads to the precipitation of needle-like perovskite (CaTiO₃) crystals instead of CaO crystals in the slag. The crystallization of perovskite (CaTiO₃) occurs by bulk nucleation and diffusion-controlled one-dimensional growth.     

V2O5/ZrO2-Al2O3催化甲醇选择性氧化合成二甲氧基甲烷

采用浸渍法制备了V₂O₅质量分数不同的V₂O₅/Al₂O₃催化剂,采用Zr对Al₂O₃载体进行改性并应用于催化甲醇选择性氧化制备二甲氧基甲烷(DMM)的反应中。经X-射线衍射(XRD)、扫描电子显微镜(SEM)、紫外-可见分光光谱(UV-Vis)、傅里叶变换红外光谱(FTIR)、拉曼光谱(Raman)、N₂吸附-脱附(BET)、H₂程序升温还原(H₂-TPR)和NH₃程序升温脱附(NH₃-TPD)表征分析,结果表明:与单一Al₂O₃负载的钒基催化剂相比,Zr改性提高了钒氧化物的分散性与稳定性,加强了催化剂中各组分间的相互作用,有效调变了催化剂的酸性和氧化性,进而提高了DMM的选择性。考察了反应条件对甲醇选择性氧化制备DMM的影响,最佳反应温度为175 ℃,经20%V₂O₅/12%ZrO₂-Al₂O₃催化氧化,甲醇转化率为27.9%,DMM选择性为99.9%。