Dissolution Kinetics of Magnesitic-Dolomite and Magnesite-Chrome Refractories in Secondary Steelmaking Slags

Dissolution kinetics of magnesitic-dolomite and magnesite-chrome refractories in secondary steelmaking slags was studied by means of the rotating cylinder method under forced convection. Materials investigated include four magnesitic-dolomite samples（MgO content 40% to 93%）and two magnesite-chrome samples （co-clinkered and semi-rebonded）.Synthetic slags simulative of VOD and AOD slags with varying basicity （0.6-2.68） are used.The experiments are carried out in Ar atmosphere at different temperatures （1 600 ℃-1 750 ℃） and revolution speeds （200 r·min^-1 to 500 r·min^-1）.The microstructure of specimens （before and after slag tests） are studied by optical microscopy, SEM and EPMA. Based on our experimental results the mechanism and kinetics of the dissolution process are discussed.

Slag Resistance of Magnesite-chrome Brick Impregnated with Chrome-bearing Sols

Cr2O3 has eminent slag corrosion resistance. So, the magnesite -chrome brick is thought as an important refractory material used in RH refining furnace in the process of steel-making around the world. After chromebearing sols being prepared by sol-gel method, single sol （ Cr（ OH）3） and mixed sol （ Mg（ OH）2 - Cr（ OH）3） were impregnated into magnesite - chrome bricks by vacuum impregnation. The corrosion resistance of the impregnated bricks to silicon steel slag was studied by porosimetric analysis and fractal dimension calculation. The results showed that the corrosion resistance of impregnated magnesite -chrome brick was better than that of the unimpregnated brick and the brick impregnated by MgSO4 solution, and the one which has surface-treated by Mg（ OH）2 -Cr（OH）3 sol was the best, mainly because of lower apparent porosity, smaller pores diameter and their smoother inner sarface.

Studies on Synthesis and Characterization of Magnesia Based Refractory Aggregates Developed from Indian Magnesite

The present work intends to study the properties of magnesia based refractory aggregates developed from Indian magnesite by changing lime/silica ratio. The material has been sintered in the temperature range of 1550C - 1700C. The sintered samples are characterized in terms of bulk density, apparent porosity, true density, percentage densification, mechanical, thermo-mechanical properties like cold modulus of rupture, hot modulus of rupture and thermal shock resistance and structural properties by XRD. The developed microstructures at different temperatures are studied through FESEM study and compositional analysis of the developed phases is done by EDX study.

Service Results and Analysis of Fully Co-clinkered Magnesite-Chrome Brick in Slagline Area of VOD Vessel

Operating condition and service results of several tested bricks in slagline area of the VOD vessel are described. It has been shown that the fully co-clinkered magnesite chrome brick is superior, followed by two-stage calcined magnesite-dolomite brick , prereacted magnesite-chrome brick and one-stage calcined magnesite-dolomite brick. Chemical and petrological examination were carried out by conventional analysis and optical microscope respectively. The reason of damage of the tested bricks are discussed and described as follows : (1) MgO in brick is erased and dissolved by slag to destroy structure of the direct bond ; (2) slag penetrating into the brick and then reacting with it to form various belts leading to spatting ; (3 ) reducing action of reducing agents ; (4) vaporization of some composition in the brick at high temperature under vacuum causes reducing weight and increasing porosity and (5 ) serious ma-chanic abrasion. Therefore, some opinions on increasing lining life of VOD vessels are suggested.

Chemical Corrosion Mechanisms of Magnesite-chrome Bricks by Converter Slag

The corrosion resistance of four kinds magnesitechrome bricks against converter salg was investigated by static crucible slag tests. The microstructures of the asdelivered and tested refractories were analyzed by means of SEM and EDS. The results showed that： Different magnesite-chrome bricks have different slag resistances. Generally, the slag resiantance sequence is as follows： rebounded fused magnesite-chrome brick 〉 semi-reboun- ded magnesite-chrome brick 〉 direct-bonded magnesitechrome brick 〉 silicate bonded magnesite-chrome brick. Slag reacts with the periclase of magnesite-chrome refractories, which results in the dissoving of periclase in fayalite slag. However, the complex spinels have superior slag resistance.

Development and Application of Chrome-free Refractory Materials for RH Degasser

The research progress and industrial application of chrome-free refractories for RH degasser were introduced in the paper.It is proved that unburned magnesia-spinel refractories used for RH throat and snorkel in Baosteel have longer service life compared with traditional direct bonded fused magnesia-chrome materials.The new developed chrome-free unburned magnesia-spinel composite can fully meet the present demand for RH operation and can be applied extensively for RH processing.At present,instead of chrome-containing materials,chrome-free refractories have been applied widely for RH in Baosteel.Super low carbon MgO-C material with high mechanical properties at mild and high temperatures can be an alternative chrome-free material for RH.

Characteristics and Problem of Chrome-containing Refractory

One of characteristics of Cr2O3-containing refractory is excellent corrosion resistance. However, there is a problem of hexavalent chromium, which is noxious to the human body, and easily formed by the reactions among the refractory and CaO, Na2O and/or K2O in slag. In this article, the reason why the Cr2O3-containing refractory has excellent corrosion resistance, the forming conditions of hexavalent compounds, and the methods for suppressing generation of the compound, are described as a base of further development of excellent refractories.

High Chrome Containing Refractories for Coal Slurry Gasifier

Water, oxygen and coal are converted into CO, H2, methane in the coal slurry gasifier. Under the condition of high temperature and high pressure, high chromecontaining refractories are used as hot face lining. The collapse of refractories from corrosion and spalling is mainly attributed to liquid deslagging. Refractories for coal slurry gasifier, destruction mechanism and solutions are analyzed.

High Temperature Interactions of Chrome Oxide Free Refractories with Coal Slag Under Simulated Gasification Conditions

Chrome oxide free refractories have significant economic benefits for the development of gasification technology.Spinel based and SiC based refractories are corroded by coal slag at 1500℃under reducing atmosphere.Moreover,interactions between refractory materials and molten slag are also predicted by thermodynamic calculations under the same conditions.The results indicate that spinel based refractories are corroded by dissolution of molten slag,while SiC based refractories are corroded by oxidation of CO and FeO.Both of the spinel and SiC based refractories show good corrosion resistance against coal slag by the present experimental tests.Finally,preliminary developed spinel-SiC composite materials are prepared and corroded by coal slag as well,the research of which shows great potential to be used in slagging gasifiers.

Magnesia-Chrome Refractories for Flash Furnace

The rapid development of our country' s heavy non-ferrous metallurgical technology and the revolution in new type of heavynon-ferrous metallurgical furnace have imposed more critical demand on the refractory materials ,i.e. high quality and long service life. This paper presents the domestic status of the refractories for flash furnace , briefly describes the wear of the refractory used, andit is considered that the domestic in refractories for flash-furnace can be surely realized.

Refractories for RH Degassers and Ways of Improving Their Lining Life

This paper attempts to clarify the systematic works of the refractories for the RH degassers and the ways of improving their lining life. It includes ： （ 1 ） types of RH degassers ; （2） the operating conditions of refining and the severely damaged areas in RH degassers ; （3） the reasons why side wall and bottom of lower vessel, throat and snorkels become the severe wear areas are analyzed, such as erosion and abrasion caused by the high circula- tion rate of treated molten steel, thermal and structural spalling by the violent temperature change, high corrosion by the Fe-oxides containing siliceous slag and CaF：riched desulfurization powders attack, degradation of texture by the vaporization of refractory components in vacuum and in oxygen blowing; besides the above men- tioned factors, what other reasons to make the snorkels become the most quick wear elements are also explained; （4） the studies of resistance to refining slags attack and slag penetration and its prevention ; the evaluation of va- rious refractory materials to withstand the attack of slags is based on the experimental results of rotating cylinder method, rotary drum test and induction furnace test, and the phase diagrams analyses; the measures to reduce the slag penetration are discussed, for example the deep of slag penetration can be decreased by reducing the size of brick pores ; （5） suitable refractory materials selection and recent developments for the different severe wear areas in RH, and lining maintenance; （6） refractories for RH to refine silicon steel; （7） the ways of improving RH lining life.

Thermodynamic Evaluation of Cr_2O_3-Al_2O_3 Refractory Corrosion by Smelting Reduction Ironmaking Slag

The interfacial reactions of Cr2O3- Al2O3 refractory materials with smelting reduction ironmaking slag were investigated by thermodynamic modeling. The calculation results indicated that different spinel phases were produced after the interactions between the slag and three types of refractory materials（ 10Cr2O3- 90Al2O3,50Cr2O3- 50Al2O3 and 90Cr2O3- 10Al2O3） at 1 500℃. Increased contents of Al2O3 and Cr2O3in the remained liquid slag after interaction implied the dissolution of refractory. Thermodynamic modeling predicted that the process of dissolution might lead to much deeper penetration into the refractory materials by the present compositional slag. Accordingly,corrosion testing was also conducted to validate the thermodynamic prediction.

Effect of Atmosphere on Sintering of High Cr_2O_3 Bearing Refractories Considered from Thermodynamic Calculation

Pure Cr2O3 refractories and high Cr2O3 bearing refractories are difficult to sinter in oxidizing atmosphere, but they can be sintered easily in carbon embedded conditions. In the latter case it is attributed to the formation of liquid CrO in reducing atmosphere. The thermodynamic calculation shows that the Cr2O3 is reduced by CO at 1 550 ℃ to chromium carbides, which disproves the existence of liquid CrO. This is confirmed by further sintering experiment of the Cr2O3 refractories. Effect of atmosphere on sintering of high Cr2O3 bearing refractories and measures to accelerate the sintering process are discussed based on the experiment and thermodynamic calculation.

Corrosion resistance evaluation of highly dispersed MgO–MgAl2O4–ZrO2 composite and analysis of its corrosion mechanism: A chromium-free refractory for RH refining kilns

The corrosion resistance behavior of a highly dispersed MgO-MgAl2O4-ZrO2 composite refractory material is examined by testing with high-basicity and low-basicity RH(Ruhrstahl-Hereaeus)slags.The composite material exhibits greater resistance to the RH slags than the traditional MgO-Cr2O3 composite,MgO-ZrO2 composite,and MgO-MgAl2O4-ZrO2 composite.On the basis of the microstructural analysis and mechanisms calculations,the corrosion resistance behavior of the MgO-MgAl2O4-ZrO2 composite is attributable to its highly dispersed structure,which helps protect the high activity of ZrO2.When in contact with the slag,ZrO2 reacts with CaO to form the stable phase CaZrO3,which protects MgAl2O4 against corrosion,thereby enhancing the corrosion resistance of the composite.

Reuse and Reproduction of Used Refractories

The paper analyzed the recycle condition and developing trend of used refractories China and other countries, irwluding research achievements of recycles of used refractories such as MgO-C bricks, Al2O3-MgO-C brics, Al2O3-SiC-C castable and MgO-Cr2O3 bricks. Recycled refractories exhibit the same or even better properties as compared with the original. In addition, prospects for recycle of used refractories are also discusseded.

Pollution of Chrome Bearing Materials and the Solutions

This paper summarizes the pollution, situation and solutions of chrome bearing materials used in high temperature industry. Hexavalent chromium compounds are readily soluble in water and associated with carcinogen. Therefore, serious environmental problems appeal for the study and application of chrome free materials. Chrome free products include： magnesia based materials, dolomite based materials, magnesia spinel materials, magnesia hercynite or magnesia galaxite materials and zirconia containing materials,and other substitutes. Although any product has its advantages and disadvantages, the trend to development of chrome free products is inevitable.

Progress of Environment-friendly Basic Refractories for Cement Industry

The chrome pollution from cement industry was introduced briefly,the research on chrome free basic refractories for cement kilns was reviewed,the production technologies of magnesia calcia,magnesium aluminate spinel,magnesia hercynite refractories,etc. were specified,the principles to improve thermal shock resistance and coating adhesiveness of refractories were analyzed,the measures to extend service life by improving production equipment and service conditions of refractories were put forward,the future of chrome free refractories was expected and some developing suggestions were given.

Suggestions for Sintering Technologies of High Cr_2O_3 Bearing Refractories Based on Thermodynamic Calculation

Cr2O3 can be sintered well at 1500℃ in carbonembedded condition or H2 atmosphere. But the high chrome bearing refractories can not reach densification when sintered at 1 700℃ .for 10 h in weak reducing atmosphere formed by the combustion of fuel, and its ap- parent porosity is about 18%. The high chrome bearing refractories are mainly used in coal gasifiers. The temperature in the furnace is about 1 500℃ and the products are H2 and CO, which are just the sintering conditions of the dense chrome refractories with apparent porosity less than 10%. The high chrome bearing refractories used in coal gasifiers may be sintered again and then shrink, destroying the gasifier lining. The thermodynamic calculation shows that it is safe about the high chrome bearing refractories used in gasifiers. It is also explained that the high chrome bearing refractories can＇t be sintered densely in weak reducing atmosphere formed by the combustion of fuel. The new sintering technologies can be used to improve the bulk density of the high chrome bearing refractories.

Review of Basic Refractories and Development History of Sinosteel Luonai Basic Refractories

The importance of basic refractories during the development of steel,non-ferrous and cement industries was introduced.The process of magnesia-chrome bricks was expounded.The development history of basic refractories of Sinosteel Luonai as well as the research and application of magnesia-chrome bricks and chrome free bricks for RH vacuum refining furnaces,heavy non-ferrous smelting furnaces,and cement kilns was emphasized.

Research on Refractories Technology to Meet the Demands of Steel-making Process

Based on the refractories research of Baosteel, the demands for refractories from the developing steel-making technology as high security, high efficiency, energy saving and environment .friendly are introduced.