水煤浆加压气化炉用Cr2O3-Al2O3-ZrO2砖的损毁模式

详细分析了陕西渭河煤化工集团有限责任公司的德士古(Texaco)水煤浆加压气化炉用Cr2O3-Al2O3-ZtO2砖的损毁模式及影响因素,并提出了降低耐火砖损毁的方法.认为块状剥落、烧蚀损伤、冲蚀损伤和机械损坏是造成耐火砖损毁的主要原因;提高耐火砖自身的抗侵蚀能力,改善炉衬砌筑结构和炉内工况气氛,控制适当的炉渣特性,以及采用正确的修理维护方法,是提高德士古水煤浆加压气化炉用Cr2O3-Al2O3-ZrO2砖使用寿命的主要途径.经过几年的反复试验和技术改进,特别是采用中钢集团洛阳耐火材料研究院生产的Cr2O3-Al2O3-ZrO2砖后,渭河煤化工集团有限责任公司的德士古水煤浆加压气化炉用Cr2O3-Al2O3-ZrO2砖的使用寿命已从原设计的8000 h提高到现在的23000 h.     

环境气氛对煤灰在Al2O3-Cr2O3-ZrO2材料上结渣的影响

以白刚玉、℃-Al2O3粉、锆英石和氧化铬为主要原料,在200 MPa油压机上压制成50 mm×50 mm×5 mm的试样,在空气气氛中于1 500 ℃煅烧5 h,制得Al2O3-Cr2O3-ZrO2试样.将0.6 g变形温度约为1 120℃的云贵煤灰平铺在Al2O3-Cr2O3-ZrO2试样上,然后放入马弗炉中分别在空气和弱还原性气氛下于1 250℃煅烧5 h,随炉冷却后观察煤灰在Al2O3-Cr2O3-ZrO2试样上的结渣情况,并进行SEM及EDS分析.结果表明:在弱还原气氛条件下,煤灰在Al2O3-Cr2O3-ZrO2上的结渣非常致密;而在空气气氛条件下,煤灰与Al2O3-Cr2O3-ZrO2材料间的粘接比较疏松,两者间没有明显的相互渗透.     

危废焚烧炉用Al2O3-Cr2O3-ZrO2砖抗渣侵蚀性及六价铬形成研究

Al2O3-Cr2O3-ZrO2砖具有较优良的抗渣侵蚀性能和力学性能,被作为内衬材料应用于危废垃圾焚烧炉.然而,危废垃圾来源广,成分复杂,其焚烧所产生的渣对砖的侵蚀程度及机理也必然不同.此外,砖中的Cr2O3在高温下可能氧化为含Cr(Ⅵ)的有害物质.为此,通过静态抗渣实验研究了四种不同组成危废灰渣对Al2O3-Cr2O3-ZrO2砖的侵蚀过程及机理,并通过浸出实验研究了熔渣对砖中Cr(Ⅵ)形成的影响.结果 表明:不同渣对Al2O3-Cr2O3-ZrO2砖的侵蚀程度及机理各不相同.高钙渣A侵蚀过程中,生成了高熔点的CA6、Ca2Al2SiO7和Ca2SiO4相,在一定程度上减缓了渣的侵蚀速度,砖体表现出最好的抗侵蚀性.高铁渣D侵蚀过程中生成熔点较低的CaFe2O4相,加之砖中Al2O3在Fe2O3-SiO2渣中的溶解度较高,因此高铁渣D对砖体的侵蚀程度最严重.高硅渣B和C侵蚀过程中主要生成钙铝黄长石新相,渣对砖体的侵蚀程度居中.不同的渣侵蚀后,渗透层中的Cr(Ⅵ)含量均增加,且渣的组成对Cr(Ⅵ)含量影响较大.由于CaO能显著促进Cr(Ⅲ)氧化为Cr(Ⅵ),高钙渣A侵蚀后,渗透层中的Cr(Ⅵ)含量最高,为84.7 mg/kg.SiO2可优先与CaO和Na2O等碱金属氧化物反应生成稳定化合物,高硅渣B和C侵蚀后,渗透层中的Cr(Ⅵ)含量较低,分别为9.9 mg/kg和13.6 mg/kg.对于高铁渣D,浸出过程会有含Cr(Ⅵ)的水化相(3CaO· Al2O3·CaCrO4·nH2O)形成,降低了Cr(Ⅵ)的浸出能力.     

不锈钢表面SiO2-ZrO2-Al2O3-Cr2O3陶瓷涂层性能的研究

将氧氯化锆、正硅酸乙脂、无水乙醇3种物质按物质的量比135放进烧杯搅拌均匀后,再放进微波炉加热10s取出,得到SiO2-ZrO2溶胶。然后,将100mL氨水、50mL硝酸铝溶液和50mL硝酸铬溶液混合均匀后,放进微波炉加热1min后取出,即制得Al2O3-Cr2O3溶胶。取SiO2-ZrO2溶胶和Al2O3-Cr2O3溶胶按n(SiO2)n(ZrO2)n(Al2O3)n(Cr2O3)=6211混合,搅拌2h,得到SiO2-ZrO2-Al2O3-Cr2O3复合溶胶。将打磨、除锈、除油处理后的不锈钢基体浸入SiO2-ZrO2-Al2O3-Cr2O3溶胶一定时间后,以浸渍提拉法得到均匀的溶胶涂层,真空干燥48h,经700℃热处理1h后便可得到SiO2-ZrO2-Al2O3-Cr2O3复合陶瓷涂层。采用XRD、IR和SEM对不同条件热处理的复合陶瓷涂层的物相组成、表面形貌进行分析,并对复合陶瓷涂层的性能进行了研究。结果表明(1)SiO2-ZrO2-Al2O3-Cr2O3复合溶胶热处理后为非晶态材料,且在凝胶中形成了三维的硅氧四面体网络骨架;(2)涂层试样不出现龟裂或脱落的循环次数(900℃,空冷)在15~30次范围内,涂层的抗热震性较好;(3)在700℃热处理1h条件下,涂层单位面积的质量损失最小,具有较好的抗腐蚀性;(4)有涂层试样较无涂层试样的氧化速率低,且以3次涂膜的氧化速率最低;涂层由粒径为2~3μm左右的微粒组成,涂层较致密,抗氧化性较好;(5)有涂层试样的耐磨性均优于无涂层试样,有涂层试样的以3次涂膜的耐磨性最好。     

Cr2O3-Al2O3-ZrO2高铬制品

介绍了Cr2O3-Al2O3-ZrO2制品的组成及各组成的作用、烧成气氛、制品的显微结构特征和性能指标.着重论述了影响制品性能的烧成工艺和以电熔、烧结两种Cr2O3颗粒生产的Cr2O3-Al2O3-ZrO2制品的显微结构差异,表明在还原气氛下烧成的Cr2O3-Al2O3-ZrO2制品性能优良,而采用电熔Cr2O3料生产的Cr2O3-Al2O3-ZrO2制品性能优于使用烧结Cr2O3料生产的.     

不同组成Al_2O_3-Cr_2O_3砖的抗熔融还原炼铁渣行为研究

为了研究Al2O3-Cr2O3砖对熔融还原炼铁(HIsmelt工艺)渣的抗渣性,选取市售Cr2O3含量(w)分别约为10%、30%、60%和90%的Al2O3-Cr2O3砖(试样编号依次为Cr10、Cr30、Cr60和Cr90),模拟SRV熔融还原炉中耐火材料的抗渣行为,在GB/T 8931—2007的回转渣蚀法试验基础上,人为制造200~1 600℃的温度波动进行抗渣性试验,以综合评价材料的抗渣性和抗热震性。结果表明:Cr10、Cr30、Cr60和Cr90砖的抗渣侵蚀性能和抗热震性能均优异,而Cr10、Cr30和Cr90砖的抗渣渗透性差,Cr60砖的抗渣渗透性好;Al2O3-Cr2O3砖与渣中Mg O、Fe O反应形成了致密的复合尖晶石层,提高了材料的抗侵蚀性能,基质中Cr2O3含量不同是造成试样抗侵蚀性差别的原因;Al2O3-Cr2O3砖的组成、结构和渗透层中固溶体的反应程度是影响材料抗热震性的主要因素。     

Cr2O3、Fe2O3对高炉渣粘熔特性的影响

以高炉渣为主要原料采用熔融法制备微晶玻璃,通过试验研究了晶核剂Cr2O3、Fe2O3对高炉渣粘度及熔化性能的影响规律.结果表明:晶核剂Cr2O3使高炉渣熔点升高,粘度增大,加入2％ Cr2O3作晶核剂时,炉渣浇注温度需要控制在1400℃以上;晶核剂Fe2O3能够降低高炉渣的熔点,但对粘度影响不大,加入2％ Fe2O3作晶核剂时,需要将炉渣温度控制在1325℃以上;加入2％ Cr2O3和2％ Fe2O3组成的复合晶核剂时,需要将温度控制在1375℃以上才能保证渣液的良好流动性,以实现顺利浇注、压延成型,为采用熔融高炉渣直接制备微晶玻璃工艺的研发提供了基础的工艺技术参数.     

锻烧工艺对α-Al_2O_3晶粒的影响

研究了煅烧温度,保温时间及矿化剂对α-Al2O3晶粒度的影响。试验表明,锻烧温度、硼类和氟类矿化剂都能使α-Al2O3晶粒度长大,煅烧时间在较低温度（1400℃）下有利于α-Al2O3晶粒度生长,在1500℃以上对晶粒度基本没有影响。     

α-Al2O3纳米粉对高纯刚玉砖烧结性能的影响

研究了在刚玉砖基质中分别引入0.5%,1%,2%和3%的α-Al2O3纳米粉及分别引入4%,8%和12%的α-Al2O3微粉时对高纯刚玉砖烧结性能的影响.检测试样于1100℃、1300℃、1400℃、1500℃、1600℃和1700℃保温5 h热处理后的体积密度和强度,并用扫描电镜观察其显微结构.结果表明同时加入α-Al2O3纳米粉和α-Al2O3微粉可以促进固相烧结,改善制品烧结性能,使烧结温度降低200～400℃;当α-Al2O3纳米粉加入量为1%～2%,α-Al2O3微粉加入量为4%～8%时,烧结温度可降到1400～1500℃,此时,试样的体积密度和强度达到最佳值.其烧结机理是以扩散传质为主的固相烧结.     

Cr_2O_3-Al_2O_3砖中不同组成Cr_2O_3-Al_2O_3电熔颗粒料的抗侵蚀研究

首先以不同比例的铬绿和氧化铝粉电熔制得Cr2O3质量分数分别为15%、40%、50%、60%、85%、99%的6种Cr2O3-Al2O3电熔颗粒料(其编号依次为CR15、CR40、CR50、CR60、CR85和CR99),然后采用回转渣蚀法研究了此电熔颗粒料(4~1 mm)的抗侵蚀性。结果显示:电熔颗粒料的抗侵蚀性随Cr2O3含量的增加及颗粒尺寸的增大而增强;高Cr2O3含量的CR99、CR85颗粒料在渣面层被侵蚀,主要是渣中的FeO和Al2O3对颗粒料的侵蚀,FeO与骨料中的Cr2O3反应,首先形成(Fe,Cr)3O4尖晶石,再与其他物相反应形成了复合尖晶石,当FeO耗尽后,渗入到颗粒内的Al2O3开始和Cr2O3反应,在颗粒表面形成铝铬固溶体;CR60颗粒料在渣面层和渗透层都存在侵蚀,渗透层的侵蚀主要是CaO、SiO2对颗粒料中铝铬固溶体中Al2O3的熔蚀,形成钙长石、钙黄长石以及玻璃相;Cr2O3含量较低的CR50、CR40、CR15颗粒料在渗透层内的侵蚀机制和CR60颗粒料的相同。     

钕-铝系稀土色料的研制

通过钕-铝系列色料合成实验,分析不同配比及不同矿化剂等对色料呈色效果的影响,确定最佳工艺方法。对实验结果进行XRD及色度分析,确定其主晶相为钕酸铝,试样的明度均在70以上,色彩鲜艳亮丽。     

Polycrystalline In2O3 and In2O3/Y2O3 photoanodes

Single crystal In₂O₃ shows promise as a photoanode for the decomposition of water. Because of various difficulties in the preparation of the single crystal material, two simple techniques were developed for the preparation of polycrystalline In₂O₃ anodes. One method involves the thermal decomposition of the nitrate while the other utilizes the chemical vapour deposition technique. Voltammograms and photoresponse spectra of these anodes are compared to the single crystal material. Among other observations, it is noted that the quantum efficiencies of the thermally decomposed films are comparable to the single crystal material. It is also shown that the on-set potential can be shifted to more negative values by forming the mixed oxide In₂O₃/Y₂O₃.     

Phase equilibrium in binary La2O3-Dy2O3 and ternary CeO2-La2O3-Dy2O3 systems

Cerium oxide doped with oxides of rare earth elements is a multifunctional material, a wide range of uses which is associated with its unique physicochemical properties. Phase diagrams of multicomponent systems are the physicochemical basis for the creation of new materials with improved characteristics.In this work, phase equilibria in ternary CeO₂–La₂O₃–Dy₂O₃ and binary La₂O₃–Dy₂O₃ systems in the whole concentration range were studied. No new phases have been identified in these systems. An isothermal section of the phase diagram of the CeO₂–La₂O₃–Dy₂O₃ system at a temperature of 1500 °С is constructed. No new phases have been detected in the system. It was found that in the studied ternary system solid solutions are formed on the basis of (F) modification of CeO₂ with structure of fluorite type, monoclinic (B), cubic (C) and hexagonal (A) modifications of Ln₂O₃.In the La₂O₃–Dy₂O₃ binary system (1500–1100 °С) three types of solid solutions are formed: based on hexagonal modification A-La₂O₃, monoclinic modification B-Dy₂O₃ and cubic modification C-Dy₂O₃ separated by two-phase fields (A+B) and (B+C), respectively. The boundaries of the regions of homogeneity of solid solutions based on A-La₂O₃ are determined by compositions containing 35–40, 20–25, 15–20 mol% Dy₂O₃ at 1500, 1250, 1100 °C, respectively. From the obtained data it follows that the solubility of Dy₂O₃ in the hexagonal modification of lanthanum oxide is 39 mol% at 1500 °C, 23 mol. % at 1250 °C and 16 mol% at 1100 °C. The limits of existence of solid solutions based on monoclinic B-modification are determined by compositions containing 30–35, 65–60 (1250 °С), 35–40, 55–60 (1100 °С) 40–45, 70–75 (1500 °C) mol% Dy₂O₃.In the studied system, with a decrease in temperature from 1500° to 1100°C, there is a decrease in the solubility of La₂O₃ in the crystal lattice of cubic solid solutions of C-type from 16 to 10 mol%.     

Na2O-Al2O3-Fe2O3系烧结过程中铝、铁的反应行为

以Al2O3, Fe2O3和Na2CO3为原料,对Na2O-Al2O3-Fe2O3系烧结过程中的反应行为进行了详细研究. 基于溶出率与时间、温度的关系,证明Na2O×Al2O3和Na2O×Fe2O3的生成反应动力学都服从Zhuralev-Lesokin-Tempelman模型,表观活化能分别为186.59和80.92 kJ/mol,表明Na2O×Fe2O3比Na2O×Al2O3在动力学上更易形成;Al2O3易与Na2O×Fe2O3反应形成Na2O×Al2O3和Fe2O3,在1273 K烧结30 min,所得熟料Al2O3溶出率达98.51%;Fe2O3对Na2O×Al2O3的形成有双重作用,在1273 K下可加速Na2O×Al2O3的形成,超过1323 K,促使Na2O×Al2O3分解成Na2O和b-Al2O3,且随着温度升高或时间延长,分解程度增高,从而导致熟料中Al2O3溶出率显著降低.     

Fe2O3-MnO-Cr2O3-La2O3系统紫色颜料的制备及表征

采用溶胶均匀共沉淀法于低温下合成了含少量稀土氧化物La2O3的紫色颜料，并采用颜色测定、SEM、XRD等手段对颜料的颜色、检度及结晶构造等进行了表征。     

Separation of Phases by Spinodal Decomposition in the Systems Al2O3−Cr2O3 and Al2O3−Cr2O3−Fe2O3

Separation of phases was investigated in the hexagonal (rhombohedral) systems Al₂O₃−Cr₂O₃ and Al₂O₃−Cr₂O₃−Fe₂O₃. The binary system shows a miscibility gap with a T_c of 950°C; the miscibility gap for the ternary system was determined for a constant Cr₂O₃ content of 16.6 mol%. Dark field transmission electron microscopy of solid solutions annealed within the miscibility gap showed dark and light lamellas ∼50 to 200 Å thick. X-ray diffraction results for the solid solutions in the ternary system indicated that, in the early stages of annealing, broadening occurred only on (hkl) reflections where l≠0. There was no major change in the X-ray diffraction patterns of the annealed solid solutions in the binary system. Electron diffraction results indicated, however, that phase separation in both systems proceeded in the [001] direction. Solid solutions in the binary system separated very slowly; the separation could be enhanced hydrothermally. The mechanism of the separation of phases in both systems is spinodal and proceeds as follows: solid solution→intermediate modulated phase→equilibrium phases.     

ß-Al2O3 synthesis from m-Al2O3

-Al₂O₃ formation fromm-Al₂O₃ was found by a new convenient technique. By thermal decomposition of a complex compound, trioxalatoaluminate Na _x (NH₄)_3–x [Al(C₂O₄)₃]yH₂O(0.091 x 0.333;y= 3), a very fine powder ofm-Al₂O₃ was formed. The decomposition process was examined by thermal analysis and X-ray diffraction and the phase relation of the system Na₂O-Al₂O₃ in the midtemperature region between 600 and 1200° C is discussed briefly. The tablet ofm-Al₂O₃ was fired at 1600° C for 30 min to prepare dense-Al₂O₃ ceramics, the apparent density of which was greater than 95% of the theoretical value. The sintered tablet was examined from the structural point of view and the electrical conductivity was measured by an a.c. method to verify that the procedure of the complex decomposition is a suitable technique for-Al₂O₃ synthesis.     

Bactericidal Effectiveness of O3, O3/H2O2 and O3/TiO2 on Clostridium perfringens

The purpose of this research is to evaluate the bactericidal capacity of different Advanced Oxidation Treatments (AOTs) based on ozone: ozone, ozone/hydrogen peroxide and ozone/titanium dioxide on a wild strain of Clostridium perfringens, a fecal bacterial indicator in drinking water. The dose of ozone consumed ranges from 0.6 mg L^?1 min^?1 to 5.13 mg L^?1 min^?1 depending on the process and on the sample. In the treatments combined with O₃, H₂O₂ dose utilized is 0.04 mM and TiO₂ dose, 1 g L^?1. In order to evaluate the influence of natural organic matter and suspension solids over the disinfection rate, treatments are performed with two types of water – natural water from Ebro River (Zaragoza, Spain) and NaCl solution 0.9%. To achieve 4 log units of inactivation, 3.6 mg O₃ L^?1 is necessary in O₃ treatment, 4.25 mg O₃ L^?1 in O₃/TiO₂ system and 2.7 mg O₃ L^?1 in O₃/H₂O₂ after processing the natural water. In NaCl solution, to get the same inactivation, 0.42 mg O₃ L^?1 is necessary in O₃ treatment, 1.15 mg O₃ L^?1 in O₃/TiO₂ system and 0.06 mg O₃ L^?1 in O₃/H₂O₂ process. Even though the three treatments studied have a high bactericidal activity due to the number of surviving bacteria decreases to non-detectable levels, O₃/H₂O₂ is the most effective system for eliminating C. perfringens cells in a lower contact time, followed by O₃ and finally O₃/TiO₂ system.     

Oxide/oxide composites in the system Cr2O3-Y2O3-Al2O3

Ceramic compacts in the systems Al₂O₃–Y₂O₃, Cr₂O₃–Y₂O₃ and Y₃(Cr_yAl_1-y)₅O₁₂ (Cr-doped YAG) were prepared by solid state reaction in calcined co-precipitated powder mixtures of appropriate compositions. Various solid-solution phases were formed, e.g. Y₃(Al_1-xCr_x)₅O₁₂, YAl_yCr_1-yO₃ and Al_2-xCr_xO₃. Composite materials in the pseudo-binary or ternary systems Al₂O₃–Y₃Al₅O₁₂, Cr₂O₃–Y₂O₃ and Y₃(Al_1–xCr_x)₅O₁₂–YAl_yCr_1–yO₃–(Al_zCr_1−z)₂O₃ were obtained by hot-pressing appropriate powder precursors at 1600–1650°C for 1 h. The microstructure of the prepared materials was studied in a scanning electron microscope with element analysis facilities. X-ray diffraction was used to reveal the phases present and their lattice parameters. The chemical compatibility of these phases was investigated. The results are discussed with a special emphasis on the solubility of Cr in the YAG structure, and on the compatibility relationship between Cr-doped YAG and its neighbouring phases. A gel-coating process for preparing Al₂O₃–YAG composites with tailored microstructures is also described.