水泥回转窑烧成带用耐火材料的最新研究

对水泥回转窑烧成带用耐火材料的使用条件和要求进行了分析,并对近年来水泥窑用镁铬砖、镁尖晶石砖、镁钙锆砖的应用进行了探讨,指出所存在的缺点及改进措施。认为其发展方向为镁钙锆砖及尖晶石砖,并对其应用前景进行了展望,希望实现水泥回转窑的无铬化。     

水泥窑用高性能镁铬砖的研制及应用

分析了普通镁铬砖在水泥窑上使用存在的不足之处。在原来普通镁铬砖工艺基础上引入特制的合成料,使制品的性能得到改善。高性能镁格砖在水泥窑上使用,寿命远远超过普通镁铬砖。     

Corrosion and adherence properties of cement clinker on porous periclase-spinel refractory aggregates with varying spinel content

The corrosion and adherence properties of cement clinker on porous periclase-spinel refractory aggregates with varying spinel content were examined using a static crucible test and a sandwich test, respectively. The reaction characteristics of porous periclase-spinel aggregates and cement clinker and the effects of spinel content on the adherence property were investigated through scanning electron microscope (SEM), energy dispersive spectrometer (EDS), and FactSage^® thermo-chemical software. It was observed that the spinel content and pore characteristics strongly affected the corrosion results and thus affected the adherence ability of cement clinker on porous periclase-spinel aggregates. With an increase in the spinel content, the amount of glass phase formed from the reaction of the refractory and cement clinker increases because the rate of the spinel dissolution into the cement clinker is higher than that of periclase. The glass phase acts as a bridge between the cement clinker and the aggregate to enhance the adherence property, which depends on the amount, area distribution and viscosity of the glass phase and its penetration in aggregates. When the spinel content is 15–40 wt%, the refractory aggregate not only has a high cement clinker resistance but also a high adherence property. Once the spinel content exceeds 50 wt%, the skeletal structure of the aggregate will be destroyed, which will lead to a substantial decline in the cement clinker resistance.     

水泥回转窑用含ZrO2耐火材料

含ZrO2耐火材料在水泥窑上的应用不断增加,水泥窑用含ZrO2耐火材料包括含锆白云石砖、含锆镁砖、含锆镁尖晶石砖、含锆高铝砖等.本文从材料的抗化学侵蚀性、热震稳定性、导热性和力学性能等方面讨论了ZrO2的引入对耐火材料使用性能的影响.     

活性石灰套筒窑煅烧带的材质选择

本文主要通过对几种耐火材料的热震稳定性、抗石灰侵蚀性和耐磨性能的实验和分析,以及对本钢活性石灰套筒窑煅烧带坍塌原因的分析,最终得出应该选择镁铝尖晶石材质的制品代替原来所用的纯镁质制品作为活性石灰套筒窑煅烧带的砌筑材料的结论。     

Hercynite and magnesium aluminate spinels acting as a ceramic bonding in an electrofused MgO–CaZrO3 refractory brick for the cement industry

Innovative chrome-free basic refractory bricks have been design based on electrofused magnesia–calcium zirconate (MgO-CaZrO₃) technology using as ceramic bonding magnesium aluminate spinel (MgAl₂O₄) and hercynite spinel (FeAl₂O₄) in order to improve their properties. Industrial refractory bricks have been manufactured by solid state sintering of magnesium and calcium zirconate aggregates with MgAl₂O₄ and FeAl₂O₄ spinels at 1650 °C in a tunnel kiln. Physical and microstructural characteristics of new refractory bricks have been characterised in terms of density, porosity, crystalline phases, phase distribution and morphology. X-ray diffraction (XRD) analyses and scanning electron microscopy (SEM) with microanalysis (using energy dispersive spectroscopy analysis -EDS) have been used. The mechanical behaviour has been evaluated in terms of cold crushing strength (CCS) at room temperature and three point bending modulus of rupture (MOR) at 25 and 1260 °C. Static and dynamic resistance test by chemical attack of clinker raw meal constituents have been carried out at 1450 °C. Results have shown that thermo-mechanical properties of new refractory bricks significantly improved with increasing both type of spinel in content. Microstructural analysis revealed that spinel phases aided to develop a strong bond between the magnesia and calcium zirconate refractory aggregates. Finally, these refractory matrixes exhibit a good thermal stability and an excellent chemical resistance against clinker raw meal.     

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.     

Bonding of Cement Clinker onto Doloma-Based Refractories

Adherence ability of cement clinker on doloma refractories was investigated using a specially designed sandwich test conducted at 1550°C for 30 min, under a load of 5.3 kPa. Fractional factorial experiments determined that silica ratio, particle size, and alumina ratio of raw meal had significant effects on the reactions between the clinker and the refractory. Silica ratio was found to be the most prominent factor influencing the adherence strength of the clinker on the surface of doloma bricks. Doloma refractory, having an excess of free lime, reacts with clinker to form additional C₃S at the interface, which is greatly beneficial to adherence strength. The interface of doloma/clinker with low silica ratio is covered with a continuous MgO-enriched layer, which is formed from the CaO reacting with the raw meal in presence of a large amount of liquid phase generated in the clinker. This layer reduced the adherence strength of clinker on doloma. With high silica-ratio raw meal, clinker and doloma form a C₃S-rich layer at the interface, improving strongly the adherence strength of clinker on the brick.     

Effects of Chrome Oxide Concentrate Powder on Properties of Magnesia Composite Materials

The magnesia composite materials were prepared using fused magnesia,used magnesia chrome bricks, magnesium aluminate spinel, alumina powder and chrome oxide powder as starting materials. In order to improve the performance of magnesia composite material,the influence of chrome oxide concentrate powder on the properties of magnesia composite material was researched. The apparent porosity,bulk density,cold crushing strength,linear expansion and thermal shock resistance of the specimens were determined. The results show that adding chrome oxide concentrate promotes the formation of the composite phases of three kinds of spinel,which is beneficial to the thermal shock resistance. The magnesia chrome spinel can not be formed at high temperatures theoretically,but can dissolve in the magnesia composite material. Comprehensively,the optimal addition of chrome oxide concentrate is 10. 0 mass% for the magnesia composite materials.     

水泥回转窑用碱性耐火材料显微结构的控制

根据显微结构特征分析研究了水泥回转窑用无铬碱性耐火材料的性能和发展。这些氧化镁基或白云石基材料,引入低膨胀性且抗侵蚀的加入物改善其显微结构。镁铝尖晶石砖是从直接加入粒状氧化铝、烧成过程中生成原生尖晶石,到直接加入预合成的尖晶石,发展至细粒晶型尖晶石再增强的含电熔尖晶石镁质砖;白云石砖以其良好的对水泥熟料的粘着性而被广泛用于水泥回转窑烧结带,加入氧化镁粉和氧化锆改善其基质增强了抗侵蚀性及抗热震稳定性;新发展的氧化镁-铁铝尖晶石和氧化镁-锰铝尖晶石耐火材料以其优越的柔性而被用于轮箍部位。     

Reaction Characteristics of Magnesia–Spinel Refractories with Cement Clinker

The adherence ability of cement clinker on magnesia–spinel refractories is investigated, using a sandwich test, at 1550°C for 30 min under a load of 5.3 kPa. Fractional factorial experiments determine that the silica ratio (SR)—SiO₂/(Al₂O₃+Fe₂O₃) and particle size of raw meal, as well as heating rate, have a significant effect on adherence ability. Microstructural analyses indicate that the adherence ability depends upon reactions between clinker and refractories at high temperature. Only spinel reacts with CaO and 3CaO·SiO₂ from clinker to form n -calcium aluminate (such as 3CaO·Al₂O₃, 12CaO·7Al₂O₃, CaO·Al₂O₃), but there is no reaction between MgO and the clinker. Fine crystalline spinel, evenly distributed in magnesia-based brick, is prone to reacting with lime-containing phases from clinker to form low melting phases and a belite-enriched zone at the clinker/brick interface. This reaction positively contributes to the high adherence on a magnesia−spinel brick. The high content of liquid in clinker with low SR accelerates reactions between spinel and clinker, while a limited reaction occurs at the brick/clinker interface with high silica.     

Effect of Fused MgO-ZrO_2 Clinker Addition on Thermal Shock Resistance of MgO-ZrO_2 Unfired Bricks

MgO-ZrO2 unfired bricks with ZrO2 content up to 8% at the interval of 2% were prepared,using fused magnesia(MgO:97%)and fused MgO-ZrO2 clinker(ZrO2:14.33%)as starting materials and phenolic resin as binder.The effects of ZrO2 content on thermal shock resistance(TSR)and other properties such as cold and hot modulus of rupture have been investigated.Residual cold modulus of rupture ratio after heating at 1 000 ℃ and quenching by air blowing was adopted to characterize TSR.Addition of the MgO-ZrO2 clinker impr...     

水泥工业用无铬碱性砖的发展情况

消除铬公害和在水泥窑内应用代用燃料促使白云石砖、尖晶石砖和镁锆砖组成的系列无铬碱性砖成功地替代着镁铬砖。当前无铬碱性砖还在不断开发和更新之中。     

The production and service testing of magnesia wares from Rapna magnesia

Conclusions Magnesite refractories from Rapna magnesia are of high quality.Tests on periclase — spinel wares from Rapna magnesia in the crowns of Marten's furnaces working under intensified conditions showed that their wear was 15 to 17% lower than that of regular periclase — spinel bricks.It was shown that, by the use of periclase — spinel bricks from Rapna magnesia in the crown of a Marten's furnace working with an oxygen jet, it will be possible to lengthen the run of the furnace by 16–21%.Translated from Ogneupory, No. 7, pp. 1–6, July, 1969.     

Reactions of Secondary Phases with Carbon in Magnesia‐Carbon Bricks

Despite the excellent thermochemical properties of magnesia carbon bricks, these exhibit one weak characteristic during their use: their carbothermally induced wear. Carbon has a high affinity to oxygen, which leads to a reaction between magnesia and carbon, forming gaseous products at very low oxygen partial pressures in the surrounding atmosphere. When magnesia carbon material is furthermore applied at negative pressures, the precited carbothermic reduction processes effect an internal decomposition or even degradation of the bricks. Mostly, high‐purity magnesia varieties (MgO ≥ 96 wt%) are used for the production of magnesia carbon bricks because the low‐melting calcium silicate secondary phases in magnesia impair the high‐temperature resistance of these bricks. The fundamental question if and to which extent secondary phases react with carbon and which impact they have on the carbothermally induced wear of bricks has been unsolved so far. The following paper presents which influence the mineral secondary phases, monticellite, merwinite, and belite that are most commonly occurring in magnesia, have on the carbothermally induced wear. The respective studies were conducted by means of thermogravimetric and microstructural analyses. The results of these studies show that monticellite in the MgO–C microstructure brings about an increase in weight loss on account of carbothermic reduction processes. On the contrary, belite and merwinite in the MgO–C structure do not exhibit any negative impact on the thermal stability of the microstructure.     

中国耐火原料的新近发展

介绍了过去几年中国几种主要耐火原料,如矾土基原料(包括电熔刚玉、尖晶石、莫来石)、镁质原料(包括大结晶98电熔镁砂、高铁高钙镁砂、电熔或烧结镁铬砂)和非氧化物材料(包括氮化硅铁、氮化硅)的最新发展,同时讨论了非氧化物结合的新型材料在未来几年的发展趋势.     

Thermodynamic assessment and experimental validation of clinker formation from blast furnace slag through lime addition

In the present study thermodynamic simulation of chemistry modification of blast furnace slag by lime addition to obtain clinker composition has been carried out. The effects of lime addition on each mineralogical phase under the equilibrium are simulated using FactSage 6.4 thermodynamic software. The critical value of lime addition in slag for each mineralogical phases and its effect on liquidus temperature of the slag has been reported. The desired cementitious phase namely belite has been observed beyond 14.4% of lime addition. A decreasing trend is observed in the liquidus temperature of the mixture from 1530?°C to 1497?°C for the lime addition of 15–24%. The simulation results were further validated by experiments conducted on blast furnace slag in the laboratory. Energy-Dispersive X-ray Spectroscopy analysis were used to qualitatively estimate the mineralogical phases formed after melting of the slag mixtures in the laboratory followed by air cooling.     

添加浮选镁砂颗粒和Al2O3细粉对方镁石-尖晶石砖性能的影响

以烧结镁砂、浮选镁砂、电熔镁铝尖晶石和煅烧Al₂O₃细粉为主要原料,以木质素磺酸钙为结合剂,经混练、成型、1 650℃烧成制备了方镁石-尖晶石砖,主要研究了以浮选镁砂颗粒替代普通烧结镁砂颗粒以及在此基础上外加不同量煅烧Al₂O₃细粉（质量分数分别为0、3%和5%）对方镁石-尖晶石砖性能的影响。结果表明：1)以浮选镁砂颗粒替代普通烧结镁砂颗粒制备的方镁石-尖晶石砖,显气孔率和常温耐压强度降低,体积密度、抗热震性、高温强度和高温韧性提高。2)在以浮选镁砂颗粒替代普通烧结镁砂颗粒制备的方镁石-尖晶石砖中,随着煅烧Al₂O₃细粉引入量的增多,显气孔率和常温耐压强度降低,体积密度、抗热震性、高温强度和高温韧性提高。     

不同类型镁钙砂对MgO-CaO-C砖抗渣性的影响

分别以30%(w)的烧结镁钙砂A、烧结镁钙砂B、电熔镁钙砂3种镁钙砂原料与62%(w)的电熔镁砂、8%(w)的鳞片石墨制备了3种CaO质量分数均为6%的MgO-CaO-C砖.利用回转抗渣法对比了3种MgO-CaO-C砖抗CaO-SiO2渣的侵蚀性能,并对残砖进行了SEM分析.结果表明:(1)Mgo-CaO-C砖抗CaO-SiO2渣侵蚀的能力与镁钙砂的致密度成正比,电熔镁钙砂抗渣侵蚀性能及挂渣性能皆优于烧结镁钙砂.(2)镁钙砂的CaO的分布影响Mgo-CaO-C砖的抗渣性能:电熔镁钙砂的CaO形成连续相而将MgO与渣隔离开来,更有利于抗CaO-SiO2渣侵蚀;烧结镁钙砂的CaO分布不均匀,会导致Mgo-CaO砂的不均匀熔损,进而加速渣对其侵蚀.     

Chemical corrosion mechanisms of magnesia–chromite and chrome-free refractory bricks by copper metal and anode slag

The penetration and corrosion resistance to copper and anode slag of six magnesia–chromite and six chrome-free refractory brick types were tested using static finger tests at a typical copper-refining temperature (1300 °C). The microstructures of the as-delivered and tested refractory types were investigated by means of electron-probe micro-analysis (EPMA) and scanning electron microscopy (SEM) techniques. The results showed that the overall wear rate of the fingers was very low, with the exception of the alumina-based brick made of fused corundum and magnesia–alumina spinel, and the magnesia-based brick made of sintered magnesia and zircon addition. In all refractory types new phases were formed as a result of slag-refractory interactions. Apart from the samples recovered from the copper zone of the latest generation of direct-bonded magnesia–chromite bricks, all the rest were completely infiltrated by copper and slag components (copper oxide, iron oxide, alumina and silica). However, the amount of infiltrated liquid in the chrome-free types was higher than in the magnesia–chromite bricks. Explanations are provided for the distinct infiltration behaviour. The results show that economically viable chrome-free refractory alternatives are still elusive for anode furnace linings.