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.     

Wear Mechanisms of Chromia Refractories in Slagging Gasifiers

The hot-face refractory lining is a key component of gasification systems. The refractory liner protects the gasification system from the high-temperature corrosive gaseous and from the molten slag environment associated with the conversion of carbon feedstocks. This paper will discuss the effect of gasifier operating conditions and carbon feedstock slag/ash chemistry on the refractory service life. Particular attention is focused on the wear mechanism of chromia refractories, determined through postmortem analysis of spent refractory bricks from service in gasifiers. Also presented is the behavior of a phosphate-containing chromia refractory with improved resistance to structural spalling.     

Post-mortem analysis of MgO–Al2O3–C bricks containing bauxite used in steel ladle walls

A serious problem with integrated masonry linings ladle was that the ladle wall bricks were difficult to be partially replaced. Thus, the service life of the ladle was determined by the properties of ladle wall bricks. In this study, the new generation of MgO–Al₂O₃–C bricks with bauxite aggregates was tested in a ladle lining of an integrated steel ladle for 103 cycles, and the corroded microstructure of the used brick was investigated. A multilayered structure of bauxite aggregates could be observed in the used brick, which inhibited the slag penetration along the boundary of the magnesia aggregates and reduced the degree of the aggregates fall off from the used bricks. Besides, during the process of slag penetration, bauxite aggregates could melt into the slag, which increased the viscosity of the slag and weakened the penetration ability of the slag. The MgO–Al₂O₃–C bricks with bauxite addition could improve the service life of the ladle to a certain extent.     

锆英石对铝铬锆砖抗侵蚀性能及六价铬形成的影响

铝铬锆砖因具有优异的抗渣侵蚀性能,被作为炉衬材料广泛应用于工作环境恶劣的危废焚烧炉。然而,铝铬锆砖在制备和服役过程中可能形成有毒的水溶性Cr(VI),相关研究工作却未见报道。本研究分别以单斜氧化锆和锆英石为氧化锆源制备了两种铝铬锆砖,研究了铝铬锆砖在四种不同组成危废焚烧炉渣中的侵蚀行为及熔渣侵蚀前后砖中Cr(VI)的含量。结果表明,锆英石高温下分解形成单斜氧化锆和无定形的二氧化硅,促进化学稳定性较好的(Al,Cr)₂O₃固溶体的形成,提高了铝铬锆砖的致密化程度,同时改善了铝铬锆砖的抗渣侵蚀性能。此外,生成的二氧化硅可以还原砖中Cr(VI)化合物,降低铝铬锆砖中的Cr(VI)含量。熔渣侵蚀后,铝铬锆砖渗透层中Cr(VI)含量与熔渣成分密切相关。在被高碱性氧化物含量的熔渣侵蚀后,铝铬锆砖渗透层中的Cr(VI)含量较高,但锆英石作为氧化锆源的铝铬锆砖在不同熔渣中侵蚀前后的原砖层和渗透层内的Cr(VI)含量均低于欧盟限制标准。     

水煤浆加压气化炉用高铬耐火材料的显微结构及损毁机理

采用扫描电镜和能谱分析方法 ,分析了水煤浆加压气化炉用高铬砖渣蚀前后的显微结构和相组成 ,探讨了主要损毁机理。结果表明 :煤熔渣与砖反应和渗透引起砖组成的改变 ,从而导致砖的结构剥落和强度弱化是砖损毁的主要原因 ;LIRR -HK90砖的显微结构呈网络状镶嵌结构 ,直接结合程度高 ,与渣反应可生成 (Mg ,Fe) (Al,Cr,Fe) 2 O4 复合尖晶石致密带 ,阻止了渣的进一步渗透 ,减缓渣蚀速度和结构剥落 ,其使用效果优于进口的同类产品     

Slag Resistance of Refractories for Direct Reduction of Laterite Nickel Ores in Rotary Kilns

Aiming at prolonging the service life of refractories for direct reduction of laterite nickel ores in rotary kilns, the slag resistance of ten materials(corundum bricks, chrome corundum bricks, silicon nitride bonded silicon carbide bricks, high alumina silicon carbide bricks, high alumina bricks, magnesia chrome bricks, magnesium aluminate spinel bricks, spinel chrome corundum bricks, chrome corundum castables and magnesia alumina chrome composite spinel bricks) was evaluated by rotary slag tests, which simulate the service conditions in rotary kilns. The corroded residual bricks were analyzed by SEM and EDS. The results show that the magnesia alumina chrome composite spinel brick possesses the advantages of magnesium aluminate spinel bricks and chrome corundum bricks; MgO-rich spinel can absorb the penetrated ferric oxide, and forms a dense zeylanite layer, which prevents the penetration of the molten laterite nickel ores; therefore, it is an ideal lining of rotary kilns for direct reduction of laterite nickel ores.     

镁硅质防粘渣涂料的防粘渣试验及其应用

为了验证以菱镁矿、石英、黏土、氧化铬微粉及磷酸盐为原料制成的镁硅质防粘渣涂料的防粘渣性能,采用静态坩埚法(1 600℃3 h,空气气氛)对比研究了转炉钢包渣线用普通镁碳砖和VOD钢包渣线用低碳镁碳砖在涂覆该涂料前后的防粘渣性能,分析了试验后涂料的显微结构,探讨了涂料的防粘渣机制,并在宝钢进行了实际使用试验。结果表明:防粘渣涂料在熔渣与镁碳砖之间形成了明显的隔离层,起到了较好的防粘渣作用。这是由于,防粘渣涂料在1 600℃的平衡物相为MgO、M2S及MA与MK的固溶体,无液相出现,隔离了镁碳砖与熔渣的接触,不易被钢渣溶解,也不与镁碳砖发生烧结反应,还在一定程度上保护炭素不被氧化,加之其较大的体积收缩和排气反应,使其容易与粘附在其表面的熔渣一起脱落,从而起到防粘渣的作用。实际使用表明,该涂料大大减轻了钢包的粘渣程度,并延长了渣线和包口镁碳砖的使用寿命,得到了钢厂的认可。     

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.     

Degradation mechanism of Cr2O3-Al2O3-ZrO2 refractories in a coal-water slurry gasifier: Role of stress cracks

Durability and corrosion behavior of refractory lining, a core part of a commercial water-coal slurry gasifier, largely determine its gas yield rate and carbon conversion rate. In this work, corrosion behavior of high chromite-containing refractory served for 4200 hours in a water-coal slurry gasifier was studied, and the role of generated stress cracks on its degradation behavior was elucidated. The results demonstrated that the depth of penetration under the assistance of the cracks was up to 2.60 cm, which was much deeper than that in the case free from stress crack. The sub-surface, accompanied by cracking, provided a pathway for slag penetration and resulted in more severe corrosion. Furthermore, the isolation layer of (Cr, Fe, Al)₂O₃ solid solution on the refractory’ surface trapped most of the iron oxides. As a result, a further attack from other main corrosive species was controlled by their diffusion through it.     

4喷嘴对置式气化炉耐火砖蚀损影响因素浅析

简述了4喷嘴对置式气化炉耐火砖的结构形式和蚀损情况;分析介绍了其使用寿命短的影响因素及相应的技改措施：①气化炉烧嘴空间偏小,应增加气化炉长径比;②烧嘴物料喷入速度偏高,应控制其喷入速度;③拱顶耐火砖预制块结构不合理,则应改造其结构;④熔渣侵蚀,则砖壁应保留一定量的固态渣;⑤热应力破坏,则应保持稳定操作。结果表明：技改后气化炉拱顶砖的使用寿命由最初的780h提高到超过4300h。     

Discussion on Wear Mechanism of High Chrome Brick Used in Coal Slurry Gasifier

The microstructure and phase composition of high chrome brick used in coal slurry gasifier has been analyzed by means of SEM and Energy Spectrum. The results indicate that the used brick can be divided into different zones as slag-adhered zone, reaction zone, penetration zone and unaltered zone. The phase composition and microstructure are different and cracks occurred in different degree at these zones. A dense ring belt was formed with complex spinel ( Mg, Fe)( Cr,Al, Fe2O4) in the reaction zone near the hot face. The wear mechanism of the brick during its employment has been discussed. It is considered that the reaction and penetration of coal slag and strong reduetant bring about the composition change of the brick and destroys its original network inlayed structure and consequently result in its structure spalling and weakening strength, which is the main wear mechanism of the brick and followed by temperature fluctuation and high mechanical im-pact of flowing fluid with high-speed.     

铝铬砖和镁铬砖抗艾萨炉炉渣蚀损的模拟研究

采用回转抗渣法模拟研究了试验温度、保温时间和熔渣加入量等因素对铝铬砖和镁铬砖抗艾萨炉炉渣侵蚀能力的影响。用SEM、EDAX及XRD等方法,对抗渣试样的显微结构和矿物组成进行了分析研究。结果表明:随着侵蚀温度的升高、保温时间的延长及炉渣加入量的增加,铝铬砖和镁铬砖的侵蚀面积增大;熔渣渗入铝铬砖后,形成铁铝尖晶石和铁铬尖晶石保护层,阻止了熔渣的侵蚀;三种耐火材料抗艾萨炉炉渣侵蚀能力由强到弱为:铝铬砖>电熔再结合镁铬砖>直接结合镁铬砖。     

使用后铝镁炭砖的显微结构分析

对宝钢电炉盛钢桶用铝镁炭砖使用后的显微组成和结构进行了分析 ,研究了用后铝镁炭砖的相组成和显微结构变化。结果表明 ,铝镁炭砖在使用过程中组成相的烧结反应产物产生的微膨胀使制品结构进一步致密 ,尤其是越靠近工作面 ,尖晶石晶粒尺寸越大 ,最终在工作面与蚀变铝酸钙一起形成致密层 ,有效地减缓和阻止了铁水和熔渣向砖内的侵蚀与渗透。     

不锈钢冶炼用铁水包Al2O3-SiC-C内衬砖的性能与侵蚀机理

铁水包内衬材料长期服役于间隔周期较长的高、低温交替环境,极易发生剥落与侵蚀损毁。为了探索影响铁水包内衬材料使用寿命的主要因素,对市面上四种铁水包Al₂O₃-SiC-C内衬砖的化学成分、物相组成、物理性能和微观结构进行了分析,并以高炉渣为侵蚀介质,重点研究了不锈钢冶炼用铁水包Al₂O₃-SiC-C内衬砖的侵蚀机理。结果表明:铁水包Al₂O₃-SiC-C内衬砖中Al₂O₃含量越高,高温下制品的液相量越低,越有利于提高耐火砖的高温力学性能;随着含碳量的增加,铁水包Al₂O₃-SiC-C内衬砖的抗渣性得到明显改善,但抗氧化性及高温抗折强度呈下降趋势;高炉渣中CaO、MgO向耐火砖中渗透,与耐火砖中的Al₂O₃、SiO₂发生反应形成高熔点的镁铝尖晶石及低熔点的钙长石等,生成的低熔相会加剧耐火砖的侵蚀。     

钢包粘渣与包衬耐火材料

阐明了钢包粘渣与包衬耐火材料存在一定的关系 ,抗渣渗透性差、容易出现开裂的包衬耐火材料容易粘渣。为防止钢包粘渣 ,适于采用抗侵蚀性和抗渣渗透性优良的尖晶石砖、铝尖晶石 (或铝镁 )浇注料、低密度浇注料以及抗剥落性好的刚玉 -锆英石浇注料作包衬耐火材料     

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。     

水煤浆气化炉用Cr2O3-ZrO2-Al2O3砖的蚀变过程

利用扫描电镜及能谱仪对水煤浆气化炉用进口铬锆铝砖的蚀变过程进行了显微观察与分析.结果表明此砖在水煤浆气化炉环境条件下的侵蚀主要由熔渣中的SiO2、CaO和P2O5引起;Cr2O3对这种渣蚀表现出很强的化学惰性,溶蚀很小,其使用过程中的主要变化是高温蒸发和在砖内蚀变液相作用下的溶蚀、溶析;而氧化锆蚀变生成的系列产物不仅在蚀变初期有利于保持砖结构致密,并且对蚀变后期基质连续网络结构的形成和保持也起了重要的作用.     

德士古气化炉渣堵机理探讨

介绍了造成德士古冰煤浆加压气化炉渣堵的几个影响因素，并分析了产生原因，从选用优质耐火砖，稳定气化炉运行，严格控制炉温，使用破渣机等几个方面提出了预防气化炉渣堵的有效措施。     

Corrosion of high chromia refractory materials by basic coal slag under simulated coal gasification atmosphere

In this paper, dynamic corrosion experiment of a high chromia refractory interaction with basic coal slag under slagging gasifier conditions was conducted by using rotary drum corrosion test with the FactSage thermodynamic analysis. The microstructures and chemical compositions of the corroded samples were analyzed by scanning electron microscopy (BEI and EDS), and the corrosion mechanism was investigated by combining thermodynamic simulation and SEM analysis. The results show that the simulation results were consistent with the results of corrosion test. Reaction layer and penetration layer are formed from the surface to the interior of the sample after corrosion. The (Mg, Fe) (Al, Cr)₂O₄ spinel solution was formed in the reaction layer, which make the matrix structure become dense and change the overall structure of the particles’ uniformity. Corrosion of Cr₂O₃ aggregate is relatively weak by slag. The Cr₂O₃ dissolves into the slag through the formed spinel solution layer on the surface of aggregates. While, Cr₂O₃ and Al₂O₃ dissolve into molten slag through the spinel solution layer formed in the matrix. ZrO₂ in the matrix directly dissolved into molten slag and penetrates inner the matrix with the penetration of the slag to form a ZrO₂-free region. The liquid sintering of the matrix has happened in the melt, causes the structure of the penetration layer become dense, which is different from that of the original sample.     

Corrosion mechanism of magnesia-chrome refractory bricks with FetO-SiO2-Cr2O3 copper converter slag

The paper investigates the effect of Cr₂O₃ on the resistance of magnesia-chrome refractory bricks to copper converter slag. The static crucible method was employed to carry out the slag resistance experiment. The corrosion of magnesia-chrome refractory bricks under the action of Fe_tO-SiO₂-xCr₂O₃ (x = 0–5 wt%) slag at 1300 °C was discussed. The microstructure of the corroded sample was analyzed by XRD and SEM-EDS to elucidate the corrosion mechanisms of magnesia-chrome refractory bricks with Fe_tO-SiO₂-Cr₂O₃ slag. The results indicated that the permeability index of the slag-resistant samples gradually decreased with increasing Cr₂O₃ content in the Fe_tO-SiO₂-Cr₂O₃ slag. Combined with SEM and XRD characterization, the MgO in the refractory reacted with FeO and SiO₂ in the molten slag, leading to dissolution and reaction corrosion of the refractories. Meanwhile, forming a (Mg, Fe)O solid solution layer in corroded samples can prevent further chemical reactions and high-temperature dissolution between the Fe_tO-SiO₂-Cr₂O₃ slag and refractories. With the addition of Cr₂O₃ in the Fe_tO-SiO₂-Cr₂O₃ slag, the corrosion effect of slag on refractories was weakened, and the (Mg, Fe)O solid solution layer became thinner. The magnesia-chrome refractory bricks showed excellent slag resistance when the Cr₂O₃ content in the copper converter slag was 5 wt%.