石墨含量对Al2O3-C材料物理化学性能的影响

Al2O3-C材料具有较好的高温性能,广泛应用于连铸功能性耐火材料.为满足洁净钢技术的发展要求,本文研究了石墨含量对Al2O3-C材料物理化学性能的影响.以不同粒度的电熔白刚玉为主要原料,加入SiC微粉和金属Al抗氧化剂,以酚醛树酯为结合剂,研究了石墨含量对不同温度下Al2O3-C材料物理性能及抗渣侵蚀性的影响.结果显示,碳含量的降低,材料的显气孔率下降,体积密度增大,冷态和高温强度增加.不同碳含量的Al2O3-C材料都显示出良好的抗渣侵蚀性能.     

复合添加剂对RH炉浸渍管用MgO-MgO·Al2O3砖性能的影响

为了提高RH炉浸渍管用MgO-MgO·Al2O3砖性能,以电熔镁砂、烧结镁铝尖晶石、板状刚玉为基础原料,添加不同含量的TiO2和ZrO2复合添加剂来制备MgO-MgO·Al2O3材料.研究了添加剂对材料体积密度、显气孔率、抗热震性、高温抗折强度和抗RH精炼渣侵蚀和渗透性的影响.结果表明:引入复合添加剂能促进MgO-MgO·Al2O3材料的烧结,提高材料的体积密度、高温抗折强度、抗热震性、抗渣侵蚀和渗透性,加入2％的TiO2和1％ ZrO2时烧结性能最好,加入1％的TiO2和2％ ZrO2时抗热震性最佳,加入2％的TiO2和2％ZrO2时高温抗折强度最大,抗渣侵蚀性和渗透性最好.     

埋炭热处理时Al_2O_3-SiC-TiO_2-C浇注料的物相演变

为了探明可否通过原位反应在Al2O3-SiC-TiO2-C浇注料中合成碳氮化钛,在Al2O3-SiC-C浇注料常规配方中直接加入6%质量分数的TiO2制备了Al2O3-SiC-TiO2-C浇注料,结合1 100~1 500℃下埋炭热处理后浇注料的物相组成分析结果及热力学计算,研究了Al2O3-SiC-TiO2-C浇注料的物相演变过程。结果表明:在热处理温度为1 100℃时,体系内的主要变化为锐钛矿向金红石的转变过程;加热至1 200℃后,体系内的单质硅则可以完全与碳反应生成SiC;当温度升至1 300℃时,体系内的金红石TiO2开始被还原而转变为Ti3O5,同时铝酸钙水泥的主要组分CaO、Al2O3与SiO2之间也开始相互反应生成钙铝石榴石相;温度升高至1 400℃后,莫来石相开始生成,同时Ti3O5继续被还原并氮化转变为碳氮化钛;1 500℃时,已经不再有新相生成,但莫来石和碳氮化钛的量明显增多,且晶格发育更加完善。     

排渣气化炉用定型氧化铝基耐火材料的研究

气化炉是用来将碳源与氧和水反应,制备合成气的装置。在气化过程中,耐火材料内衬保护气化炉外壳,免受高温、高压、渣侵蚀、热冲击和热循环破坏。然而,目前使用的高铬耐火材料性能不能满足工业使用要求,需要开发新的无铬材料。通过对比烧结气氛,评价了定型氧化铝基耐火材料的力学性能、相组成、抗热震性能和抗碱侵蚀性能。根据试验结果,能进一步研究的潜在材料包括还原烧结β-Al2O3、尖晶石、六铝酸钙和熔渣砖。     

镁锆砖和镁铬砖的抗RH炉渣侵蚀性对比

为取代RH炉用镁铬材料,以电熔镁砂为主原料,分别加入单斜锆、脱硅锆、单斜锆与脱硅锆的混合粉、锆英石制备了ZrO2质量分数分别为15%和20%的镁锆砖,并利用静态坩埚法对比研究了镁锆砖和镁铬砖的抗RH炉渣侵蚀性。结果表明:对于Al2O3含量高且碱度(CaO/SiO2比)大的RH炉渣,镁锆砖抗侵蚀性能优于镁铬砖的;镁锆砖的侵蚀机理是砖中的ZrO2与渣中的CaO迅速反应,形成高熔点物相CaZrO3,能堵塞砖中的孔隙而形成致密保护层,从而阻止钢渣对镁锆砖的进一步侵蚀;而镁铬砖的侵蚀机理是渣中的Al2O3、Fe2O3等R3 和镁铬尖晶石中Cr3 交换,渣与砖反应生成的镁铝尖晶石和镁铁尖晶石使得材料变性,同时由于体积效应使镁铬材料鼓胀开裂,从而导致镁铬砖的严重侵蚀。     

原位反应生成Sialon结合Al2O3-C材料的抗渣侵蚀机理

以电熔白刚玉、单质硅粉和石墨为主要原料,在氮气气氛下1450℃保温4h原位生成Sialon结合Al2O3-C材料,采用静态坩埚法对烧后的Sialon结合Al2O3-C材料在1600℃下进行抗渣实验.采用XRD分析氮化后Al2O3-C材料的物相组成,用SEM和EDS分别对渣蚀后材料的显微结构和成分进行分析.结果表明:Al2O3-C材料高温氮化后能够生成较多β-Sialon相和少量的SiC相;热力学分析表明,Sialon和SiC本身氧化产生的SiO2和Al2O3,溶解到渣中,降低渣的侵蚀和渗透;SEM结果表明,渣的渗透主要是沿刚玉颗粒边缘进行的,随着渗透的深入,CaO含量不断下降.     

金属-氮化物结合刚玉质滑板抗渣性研究

对Al-AlN-Al2O3滑板与Al2O3-C滑板在1 600 ℃×3 h及1 650 ℃×3 h条件下,进行了坩埚法抗钢渣侵蚀实验.抗渣试验表明Al-AlN-Al2O3滑板试样较之Al2O3-C滑板试样具有更优良的抗渣侵蚀能力.其原因可归于Al-AlN-Al2O3滑板的致密组织结构及金属Al和AlN的有益作用.AlN难以被钢渣润湿,可减缓钢渣的侵蚀和渗透;AlN的结合密实作用可阻碍金属铝的熔出.金属Al高温下氧化形成Al2O3,刚玉与熔渣中的MgO反应形成Al2O3-MgO尖晶石,均使熔渣粘度及反应层致密度提高,因此提高了Al-AlN-Al2O3滑板的抗渣侵蚀能力.     

炉渣组分对CaO-Al2O3-SiO2-TiO2-MgO-Na2O渣系粘度的影响

针对高碱度高氧化铝含氧化钠的CaO-Al2O3-SiO2-TiO2-MgO-Na2O六元渣系,采用有限制的混料均匀设计方法设计实验,在1773 K温度熔融还原条件下测定了该渣系的粘度. 利用偏最小二乘法回归分析,建立了炉渣组分与粘度的回归方程,利用回归方程分析了炉渣碱度[w(CaO)/w(SiO2)], MgO, TiO2, Al2O3及Na2O对炉渣粘度的影响. 结果表明,回归方程拟合的关联系数RC2为0.9945,方程可很好地预测该渣系的粘度. 在实验范围内,炉渣粘度随碱度的增加而增加. 碱度一定时,炉渣粘度随MgO, Al2O3, Na2O含量的增加而逐渐降低,随着TiO2的增加先降低后增加. 当炉渣碱度小于3.1、MgO质量含量大于4%、Al2O3大于20%、TiO2在3.1%~6.1%、Na2O大于0.75%时,1773 K温度下炉渣粘度均小于2 Pa×s,此时渣系粘度完全满足实际冶炼要求.     

在气化炉中由渗透煤渣引起高铬砖显微结构的改变

对气化条件下渗透的煤渣与耐火材料反应对添加Al2O3和ZrO2的高铬砖显微结构的影响进行了深入研究。氧化铬耐火材料是一种显微结构不均匀的混合体,包括晶粒形状及尺寸、化学成分、致密化程度等。Cr2O3抗渣侵蚀能力与颗粒尺寸和致密化程度有关,颗粒尺寸越大且致密化程度越高,材料的抗侵蚀能力越高。ZrO2没有发生化学变化但它可能会溶解在渣中。对实验室和小规模气化炉用后耐火材料进行分析,均发现相同的反应产物。化学成分和晶相分析同样可以证明在砖和渣界面生成铬的氧化物,Fe慢慢被耗尽。当温度和时间发生变化时,尽管显微结构的变化很难定量分析,但是渣渗透量会随着时间延长和温度升高而增加。     

气化炉用后高铬砖的渣蚀机理

采用扫描电镜和XRD等分析方法,对石油焦气化炉和水煤浆气化炉用后高铬砖及渣蚀试验砖的显微结构进行了观察与分析。根据高铬砖显微结构变化,研究了在不同气化炉内高铬砖受熔渣侵蚀损毁的机理。结果表明:石油焦气化炉用高铬砖中的Cr2O3与熔渣中的V2O5接触反应,在低温下形成液相而被熔蚀,是其蚀损的主要原因;水煤浆气化炉用高铬砖蚀损的主要原因是Cr2O3在熔渣里的溶解和ZrO2的熔蚀;LIRR-HK95砖由于成分和结构的优化,抗石油焦渣侵蚀性能好。     

Towards chrome-free of high-temperature solid waste gasifier through in-situ SiC whisker enhanced silica sol bonded SiC castable

Refractory containing Cr₂O₃ was widely used in solid waste gasifier due to its excellent slag resistance. However, hexavalent chrome compounds (formed during the preparation and the use of refractory containing Cr₂O₃) will give rise to detrimental effect on environment and human's health. In addition, the Al₂O₃-Cr₂O₃ materials acted as the lining materials. Serious exfoliation occurred after about twenty days. For the purpose of chrome-free and service longevity of lining materials for solid waste gasifier, in-situ SiC whisker enhanced SiC castable and spinel castable containing 20%wt of Cr₂O₃ were prepared. The mechanical properties and corrosion resistance after heat treatment in different temperature of the castables were determined. The strength of SiC castable rised with the increasing of the temperature. And the nano SiC/SiO₂ core-shell whiskers was formed at 1500 °C. In comparison to the spinel castable containing 20 wt% of Cr₂O₃, the better volume stability and the reinforcement of the nano whiskers led to excellent resistance to crack propagation at high temperature. In addition, SiC castable showed lower apparent porosity because of the forming of SiO₂ through the oxidation of SiC over 1300 °C, the viscosity of slag increased since that the SiO₂ dissolve into the slag, which caused excellent penetration resistance of SiC castable compared with spinel-Cr₂O₃ castable. Excellent mechanical properties and slag resistance at high temperature indicated that SiC castable had the application prospect for high-temperature solid waste gasifier.     

含钒渣对铝碳材料的侵蚀

为了探讨含矾渣对铝碳材料的侵蚀机制,用动态感应抗渣法研究了w(V2O5)=10%、碱度2.8,w(V2O5)=6%、碱度2.8,w(V2O5)=6%、碱度1.44的3种含钒渣对铝碳材料的侵蚀。结果表明:随着V2O5含量(w)由6%增加到10%,铝碳材料的熔损指数增加;随着碱度的增加,铝碳材料的熔损指数也增加;添加电熔镁砂有助于提高铝碳材料的抗侵蚀性能。显微分析表明:V、Ti元素渗透能力强,渗透深,而尖晶石可固溶少量V2O5、MnO及FeO。     

Ti3SiC2/Al2O3复合材料的制备与性能研究

以TiC／TiO2/Si／Al／Ti等为主要原料，采用热压法原位合成Ti2SiC2／Al2O3复合材料，分别探讨了Al掺入量和工艺制度对Ti3SiC2/Al2O3复合材料物相、显微结构以及性能的影响。结果表明：原位合成制备的Ti3SiC2/Al2O3复合材料与传统方法合成制备的纯Ti3SiC2材料相比，材料的硬度和致密度均有很大的提高。     

Modification of ash flow properties of coal rich in calcium and iron by coal gangue addition

Flow property of coal ash and slag is an important parameter for slag tapping of entrained flow gasifier.The viscosity of slag with high contents of calcium and iron exhibits the behavior of a crystalline slag,of which viscosity sharply increases when temperature is lowered than temperature of critical viscosity(Tcv).The fluctuation in temperature near the Tcv can cause an accumulation of slag inside the gasifier.In order to prevent slag blockage,it is necessary to adjust the ash composition by additive to modify the flow property of coal rich in calcium and iron.Main components of coal gangue are Al2O3 and SiO2,which is a potential additive to modify the ash flow properties of these coals.In this work,we inves-tigated the ash flow properties of a typical coal rich in calcium and iron by adding coal gangue with dif-ferent SiO2/Al2O3 ratio.The results showed that the ash fusion temperatures (AFTs) firstly decreased,and then increased with increasing amount of coal gangue addition.Chemical composition of coal ash rich in calcium and iron moved from gehlenite primary phase to anorthite,quartz and corundum primary phases.The slags with coal gangue addition behaved as a glassy slag,of which the viscosity gradually increased as temperature decreased.Besides,a high SiO2/Al2O3 ratio of coal gangue was beneficial to modify the slag viscosity behavior.Addition of coal gangue with a high SiO2/Al2O3 ratio impeded forma-tion of crystalline phases during cooling.This work demonstrated that coal gangue addition was an effec-tive way to improve the ash flow properties of the coal rich in calcium and iron for the entrained flow gasifier.     

Effect of coal slag on the wear rate and microstructure of the ZrO2-bearing chromia refractories

The typical properties of slag and refractories for slagging coal gasifier were investigated. In the range of 0–25% CaO/ash, the characteristic ash-fusion temperatures (AFTs) and viscosity of a coal-ash slag decreased with an increase of CaO additive. When the CaO/ash ratio was greater than 25% in the mixture of the coal and limestone, AFTs no longer reduced. The slag viscosity for limestone addition with CaO/ash = 25% was very low and in a narrow range (4–13 Pa.s) at coal gasification temperatures between 1300 °C and 1500 °C. However, corrosion resistance of the ZrO₂-bearing chromia refractories reduced with increasing CaO content in coal slag, especially for a slag with more than 30% CaO content. Increased chromia in three kinds of the ZrO₂-bearing chromia refractories resulted in increased corrosion resistance. The higher the Cr₂O₃ content and the lower the SiO₂ content, the less the deterioration of microstructures in the materials. Thermochemical spalling of the ZrO₂-bearing 80% Cr₂O₃ refractory after 807 operating hours of a coal gasifier was considered as the primary attack mechanism.     

Effect of in situ formation of Ti(C,N) on the properties of Al2O3–ZrO2–C slide plate material

Al₂O₃–ZrO₂–C slide plate was ordinarily used in sliding nozzle system because of its excellent mechanical properties and slag corrosion resistance. This study improved the slag corrosion resistance of the slide plate by the carbothermic reduction of TiO₂ and aluminothermic reduction of TiO₂ under high temperature in coke bed to generate Ti(C,N) phase in situ. The result revealed that TiC of the high melting point phase could enter into anorthite (CaAl₂Si₂O₈) of the low melting point phase, forming eutectic phase CaAl₂Si₂O₈–TiC, and improve the viscosity of the slag. Furthermore, TiC and CaAl₂Si₂O₈ captured FeO and MnO from the slag, resulting in the increase of the slag viscosity, inhibiting the penetration corrosion of the slag, and improving the slag corrosion resistance of the materials. In general, compared with the material without TiO₂ powder, the slag corrosion resistance of the material introduced 2 wt.% TiO₂ powder was increased by 24%. Meanwhile, the cold crushing strength of fired specimen at room temperature was increased by 35.6%.     

含β-SiAlON的MgO-Al2O3浇注料的抗渣侵蚀性

利用静态坩埚抗渣试验法研究了含β-SiAlON的MgO-Al2O3浇注料的抗渣性.结果表明β-SiAlON加入后,会引起玻璃相含N而使粘度增加,且由于含N物质与氧化物渣的润湿性差,有利于阻止渣侵蚀.但SiAlON在高温的氧化较剧烈,导致试样膨胀,当其加入量较高时,这种变化会显著影响浇注料的其他性能.当SiAlON较多时,浇注料基质中能形成由针状SiAlON多形体构成的网状结构.     

Corrosion Resistance of Fused Cr_2O_3-Al_2O_3 Grains with Different Compositions

Six kinds of Cr2O3 Al2O3 fused grains ( the mass percent of Cr2O3 was 15% ,40% ,50% ,60% ,85% and 99% ,respectively) were prepared using chrome green and Al2O3 powder as starting materials by electrofusion,named as CR15,CR40,CR50,CR60,CR85, and CR99,respectively. The corrosion resistance of the six kinds of Cr2O3 Al2O3 fused grains ( 4 1 mm) was studied using rotary slag corrosion method. The results show that: ( 1) the corrosion resistance of the fused grains increases with the Cr2O3 content and the grain size increasing; ( 2) the grains of CR99 and CR85 with higher Cr2O3 content are corroded at the slag surface layer,because FeO and Al2O3 in the slag corrode the grains; FeO reacts with Cr2O3 in the aggregates forming ( Fe,Cr) 3O4 spinel firstly,and the spinel reacts with other phases forming composite spinel; when FeO is fully consumed,Al2O3 penetrated into the grains reacts with Cr2O3 forming Al2O3 Cr2O3 solid solution on the grains surface; ( 3) for CR60,the corrosion exists both in the slag surface layer and in the penetration layer; in the penetration layer,CaO and SiO2 react with Al2O3 in Al2O3 Cr2O3 solid solution forming anorthite, gehlenite, and glass phase; the grains of CR50,CR40 and CR15 have the same corrosion mechanism with CR60 in the penetration layer.     

A Retrospective Review of Alumina-magnesia-carbon Refractories

The residual expansion of in-situ spinel formation in using of alumina-magnesia-carbon(AMC)bricks monolizes the lining of steel-making ladles with the closure of their joints,which has been an effective solution avoiding washing out of the joints in ladle lining by the reduction of the penetration of liquid slag and molten steel.Alumina-magnesiacarbon refractories are overall reviewed,in terms of major raw materials,thermal evolution,corrosion and oxidation,and thermomechanical behavior,as well as type,addition and fraction of magnesia used.General commercial products contain 5%-10%MgO and 5%-10%C with a certain amount of metallic aluminum powder,which is believed to facilitate spinel formation at early stage of heating-up,although high magnesia containing AMC bricks are studied and used sometimes.With low ratio of Al₂O₃/C=12.9 and the carbon content of 6.4%C,AMC brick exhibits the highest corrosion resistance.It is important to determine the type,addition and fraction of magnesia used in AMC refractories for demonstrating high corrosion resistance and superior thermomechanical behavior.