CN1176875C - A kind of anti-hydration MgO-CaO series refractory material and its preparation method - Google Patents
A kind of anti-hydration MgO-CaO series refractory material and its preparation methodInfo
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- 239000011819 refractory material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 230000036571 hydration Effects 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 12
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- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 abstract description 15
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
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- 238000000746 purification Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
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- 238000001000 micrograph Methods 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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Abstract
本发明涉及一种用于冶金行业的抗水化MgO-CaO系耐火材料及其制备方法，以颗粒状MgO-CaO系耐火材料为原料，用CO2和水蒸气的混合气体对该材料表面进行轻水化碳化处理，使耐火材料表面生成一层致密的CaCO3抗水化膜层。该膜层能有效隔绝其内部CaO与外界水分的接触，因而显著地提高了MgO-CaO系耐火材料的抗水化性能。本发明的只对表面CaO进行处理而很好保留了其内部的活性CaO，从而对MgO-CaO系耐火材料所具有的洁净钢液的性能不会造成损害，同时，该材料在使用过程中表面的CaCO3会重新分解为CaO和CO2，重新分解出的CaO将具有更高的活性，更有利于净化钢水中的杂质；本发明生成速率快、处理时间短，生产成本低。The invention relates to a hydration-resistant MgO-CaO refractory material used in the metallurgical industry and a preparation method thereof. The granular MgO-CaO refractory material is used as a raw material, and the surface of the material is treated with a mixed gas of CO2 and water vapor. The light hydration carbonization treatment makes a dense CaCO 3 anti-hydration film on the surface of the refractory material. The film layer can effectively isolate the internal CaO from contact with external moisture, thus significantly improving the hydration resistance of the MgO-CaO-based refractory material. The present invention only treats the surface CaO and well retains the active CaO inside, so that the performance of the clean molten steel of the MgO-CaO refractory material will not be damaged. At the same time, the surface of the material will not be damaged during use CaCO 3 will be re-decomposed into CaO and CO 2 , and the re-decomposed CaO will have higher activity and be more conducive to purifying impurities in molten steel; the invention has fast generation rate, short processing time and low production cost.
Description
本发明涉及一种用于冶金行业的抗水化MgO-CaO系耐火材料及其制备方法，该耐火材料可制成抗水化性能优良的各种耐火制品。The invention relates to a hydration-resistant MgO-CaO series refractory material used in the metallurgical industry and a preparation method thereof. The refractory material can be made into various refractory products with excellent hydration resistance.
由于MgO-CaO系耐火材料具有熔点高、储量大、抗碱性渣侵蚀能力强等特点，早在十六世纪MgO-CaO系耐火材料就已应用在冶金行业中。尤其是近几年来，随着炼钢技术的发展，对钢铁的质量要求不断提高，因此要求钢铁工业应尽可能的减少钢杂质成分，但是对于大部分耐火材料通常没有吸附钢水中的Si、S、P等杂质的能力。MgO-CaO系耐火材料由于吸附杂质能力较强而具有独特的净化钢液的作用，以及良好的高温使用性能，较好的热力学稳定性，而被认为是一种较理想的炼钢用耐火材料，可广泛用作钢包和中间包衬材，以及炉外精炼用耐火材料。但是该材料由于含有的游离CaO极易与水发生反应，造成制品的破坏。因此，对于广泛在炼钢行业中使用的不定形耐火制品由于在生产过程中需要加入较高比例的水分，使MgO-CaO系耐火材料很难应用于不定形耐火制品，从而大大限制了其在钢铁工业中的使用。Because MgO-CaO refractory materials have the characteristics of high melting point, large reserves, and strong resistance to alkaline slag erosion, MgO-CaO refractory materials have been used in the metallurgical industry as early as the sixteenth century. Especially in recent years, with the development of steelmaking technology, the quality requirements of steel have been continuously improved. Therefore, the steel industry is required to reduce steel impurities as much as possible. However, most refractory materials usually do not adsorb Si and S in molten steel. , P and other impurities. MgO-CaO series refractory materials are considered to be an ideal refractory material for steelmaking due to their strong ability to adsorb impurities and have a unique role in purifying molten steel, as well as good high-temperature performance and good thermodynamic stability. , can be widely used as ladle and tundish lining materials, as well as refractory materials for refining outside the furnace. However, the free CaO contained in this material is very easy to react with water, causing damage to the product. Therefore, for the monolithic refractory products widely used in the steelmaking industry, due to the need to add a high proportion of water in the production process, it is difficult for MgO-CaO-based refractory materials to be applied to monomorphic refractory products, which greatly limits its use. Use in the steel industry.
为改善MgO-CaO系耐火材料抗水化性问题，主要有以下途径：In order to improve the hydration resistance of MgO-CaO refractories, there are mainly the following ways:
(a)通过加入各种添加物，使MgO-CaO系耐火材料中的CaO晶粒被包覆；(a) by adding various additives, the CaO grains in the MgO-CaO refractory material are coated;
(b)对MgO-CaO系耐火原料表面进行无机盐包覆；(b) coating the surface of the MgO-CaO refractory raw material with inorganic salt;
(c)对MgO-CaO系耐火原料表面进行有机物包覆；(c) Coating the surface of the MgO-CaO refractory material with organic matter;
对于(a)方法人们研究的较多，中国专利1156710是采用通过在ZrO2-CaO材料中加入0-3％CeO、0-2％Fe2O3、1-8％SiO2等添加剂并通过热处理的方法使材料的抗水化性有所提高；《硅酸盐学报》1991(2)曾报道过添加Al2O3对MgO-CaO系耐火熟料的烧结性和抗水化性的影响，结果认为加入3％Al2O3对MgO-CaO系耐火熟料的抗水化性能具有明显的提高作用。但是这种方法通常会使制品高温性能受到一定程度上的损害，同时添加剂中存在的某些物质易于扩散进钢液中，会对钢液造成一定程度的污染。For (a) method people research more, Chinese patent 1156710 adopts by adding additives such as 0-3% CeO, 0-2% Fe 2 O 3 , 1-8% SiO 2 in ZrO 2 -CaO material and pass The method of heat treatment improves the hydration resistance of the material; "Journal of Silicates" 1991 (2) reported the effect of adding Al 2 O 3 on the sintering and hydration resistance of MgO-CaO refractory clinker , the results suggest that the addition of 3% Al 2 O 3 can significantly improve the hydration resistance of MgO-CaO based refractory clinker. However, this method usually damages the high-temperature performance of the product to a certain extent, and at the same time, some substances in the additives are easy to diffuse into the molten steel, which will cause a certain degree of pollution to the molten steel.
对于(b)方法，《国外耐火材料》1996(3)报道臼井皓司等人将MgO-CaO系耐火原料浸渍在5％浓度的磷酸溶液中进行表面处理。发现处理过的熟料表面普遍覆盖上磷，特别是在CaO存在的地方，生成了以磷酸钙为主的磷酸盐化合物，使熟料的抗水化性程度有较大程度上的提高。但是，这种改善MgO-CaO系耐火熟料抗水化性能的方法往往会带来一定的有害杂质，如P、S等，对钢水造成一定程度的污染，而且在施工过程中包裹层容易脱落，造成熟料的抗水化性能降低。日本专利昭61-256961通过用CO2气体对纯CaO材料表面进行处理，但因
对于(c)方法，中国专利1245479采用一种含有水浆状的基体处理剂、液态基体补强剂及着色剂的三液型表面处理剂，顺序涂布上述混合物等，可在短时间内在钙基无机质部件表面形成无龟裂、平滑、高强度及高耐火性、有光泽的着色涂膜。无水有机物进行表面处理的方法，虽然有利于改善CaO的耐水化性，但是该方法也存在有机成分不稳定，包覆不均匀的缺点，从而影响了抗水化效果。For (c) method, Chinese patent 1245479 adopts a kind of three-liquid type surface treatment agent that contains water-slurry matrix treatment agent, liquid matrix reinforcing agent and coloring agent, sequentially coats above-mentioned mixture etc., can be in calcium in a short time Forms a crack-free, smooth, high-strength, fire-resistant, and glossy colored coating on the surface of inorganic-based components. Although the method of surface treatment with anhydrous organic matter is beneficial to improve the hydration resistance of CaO, this method also has the disadvantages of unstable organic components and uneven coating, which affects the hydration resistance effect.
本发明所要解决的问题是针对上述现有技术存在的不足而提供一种制作简便、抗水化性能优良和有利钢水净化的抗水化MgO-CaO系耐火材料及其制备方法。The problem to be solved by the present invention is to provide a hydration-resistant MgO-CaO refractory material that is easy to manufacture, has excellent hydration resistance and is beneficial to the purification of molten steel and its preparation method in view of the shortcomings of the above-mentioned prior art.
本发明的耐火材料由以下的技术方案来实现：以颗粒状MgO-CaO系耐火材料为原料，其不同之处在于在MgO-CaO系耐火材料表面包覆一层致密的CaCO3抗水化膜层。The refractory material of the present invention is realized by the following technical scheme: the granular MgO-CaO refractory material is used as a raw material, and the difference is that a dense CaCO hydration-resistant film is coated on the surface of the MgO-CaO refractory material layer.
本发明耐火材料的制备方法为：以颗粒状的MgO-CaO系耐火材料为原料，置于300-800℃的温度中进行处理，充入CO2和水蒸汽的混合气体，水蒸汽的温度为40-90℃，处理0.5-3小时。The preparation method of the refractory material of the present invention is as follows: the granular MgO-CaO series refractory material is used as a raw material, placed in a temperature of 300-800 ° C for treatment, and filled with a mixed gas of CO and water vapor, and the temperature of the water vapor is 40-90°C, treat for 0.5-3 hours.
本发明的特点在于以MgO-CaO系耐火材料为原料在CO2和水蒸汽的混合气体中经过一定温度和时间的处理，使该原料表面所存在的游离CaO先与H2O发生化学反应：The feature of the present invention is that the raw material of the MgO-CaO refractory is treated at a certain temperature and time in the mixed gas of CO2 and water vapor, so that the free CaO present on the surface of the raw material first reacts chemically with H2O :
生成的Ca(OH)2再与CO2发生反应：The generated Ca(OH) 2 then reacts with CO 2 :
从而在原料表面生成一层致密的CaCO3抗水化膜层。由于表面致密CaCO3的形成能有效隔绝CaCO3层内部CaO与外界水分的接触，因此显著的提高了MgO-CaO系耐火原料的抗水化性能。这种处理方法的优势在于只是对表面CaO进行了处理而很好的保留了镁钙砂内部的活性CaO，从而对MgO-CaO系耐火材料所具有的洁净钢液的性能不会造成损害；同时，在该材料使用的过程中表面所形成的CaCO3会重新分解为CaO和CO2，因此不会对钢水造成任何污染，而且重新分解出的CaO将会具有更高的活性，更有利于净化钢水中的杂质；另外，该方法由于引入了水蒸汽改变了CaCO3层的形成机理，使其生成速率比采用CaO直接与CO2反应生成CaCO3的速率快得多，因此大大缩短了处理时间，降低了生产成本。本发明的MgO-CaO系耐火材料可用来制成各种不定形耐火制品，具有优良的抗水化性能。Thus, a dense CaCO 3 anti-hydration film layer is formed on the surface of the raw material. Since the formation of dense CaCO 3 on the surface can effectively isolate the CaO inside the CaCO 3 layer from contact with external moisture, it significantly improves the hydration resistance of the MgO-CaO-based refractory material. The advantage of this treatment method is that only the surface CaO is treated and the active CaO inside the magnesia-calcium sand is well retained, so that the performance of clean molten steel possessed by MgO-CaO refractories will not be damaged; at the same time , the CaCO 3 formed on the surface of the material will be re-decomposed into CaO and CO 2 during the use of the material, so it will not cause any pollution to molten steel, and the re-decomposed CaO will have higher activity and be more conducive to purification Impurities in molten steel; in addition, because the introduction of water vapor changes the formation mechanism of the CaCO3 layer, the formation rate of this method is much faster than that of using CaO to directly react with CO2 to form CaCO3 , thus greatly shortening the processing time , reducing production costs. The MgO-CaO series refractory material of the invention can be used to make various unshaped refractory products, and has excellent hydration resistance.
图1为经本发明方法处理过的MgO-CaO系耐火材料表面断层的电子扫描显微照片和该区域成分分布分析，从C元素的分布可看出，在颗粒断层的边缘C元素呈密集分布，表明颗粒表面确存在一层致密的CaCO3。Fig. 1 is the electronic scanning micrograph of the MgO-CaO series refractory surface fault processed by the method of the present invention and the component distribution analysis in this area, it can be seen from the distribution of C element that the C element is densely distributed at the edge of the particle fault , indicating that there is indeed a layer of dense CaCO 3 on the particle surface.
图2为未经本发明方法处理的MgO-CaO系耐火材料表面电子探针的扫描照片及成分分析。Fig. 2 is a scanning photo and component analysis of an electron probe on the surface of a MgO-CaO refractory material that has not been treated by the method of the present invention.
图3为经本发明方法处理过的MgO-CaO系耐火材料表面电子探针的扫描照片及成分分析。Fig. 3 is a scanning photo and component analysis of an electron probe on the surface of the MgO-CaO refractory material treated by the method of the present invention.
从成分分析中可以看出，处理后的试样的碳含量大幅度提高，而未处理试样则几乎没有发现有C元素的存在，由此也可证明经本发明方法处理的MgO-CaO系耐火材料表面存在CaCO3。It can be seen from the composition analysis that the carbon content of the treated sample is greatly improved, while the untreated sample is hardly found to have the existence of C element, which also proves that the MgO-CaO system processed by the method of the present invention CaCO 3 exists on the surface of the refractory material.
以下进一步详细说明本发明的实施例。Embodiments of the present invention will be further described in detail below.
本发明采用的MgO-CaO系耐火材料为含10-59％CaO的烧结镁钙砂，其组分含量按重量计为：The MgO-CaO series refractory material used in the present invention is sintered magnesia-calcium sand containing 10-59% CaO, and its component content is by weight:
MgO 40-89％ CaO 10-59％ Fe2O3 ＜0.6％MgO 40-89% CaO 10-59% Fe 2 O 3 ＜0.6%
Al2O3 ＜0.4％ SiO2 ＜0.1％。Al 2 O 3 <0.4% SiO 2 <0.1%.
烧结镁钙砂的粒度为1-12mm，以2-5mm为佳，其表面形成有CaCO3抗水化膜层，CaCO3抗水化膜层的厚度为2-20um。厚度过小，容易受机械等外力的作用而受到损害，降低的制品的抗水化性能；厚度过大，一方面造成成本的增加，另一方面在使用过程中CaCO3分解使制品中残留较多的气孔，降低了制品的高温使用强度。因此，本发明经实施表面CaCO3层厚度在4-10um为佳，过薄和过厚对镁钙砂的抗水化性能和高温使用性能都有不利影响。The particle size of the sintered magnesia-calcium sand is 1-12mm, preferably 2-5mm, and a CaCO 3 anti-hydration film is formed on the surface, and the thickness of the CaCO 3 anti-hydration film is 2-20um. If the thickness is too small, it is easy to be damaged by external forces such as machinery, and the hydration resistance of the product is reduced; if the thickness is too large, on the one hand, it will increase the cost, and on the other hand, the decomposition of CaCO 3 in the process of use will cause more residues in the product. Many pores reduce the high temperature service strength of the product. Therefore, the thickness of the CaCO3 layer on the surface of the present invention is preferably 4-10um, and too thin or too thick will have a negative impact on the hydration resistance and high-temperature performance of the magnesia-calcium sand.
本发明的制备过程主要受处理温度、水蒸汽温度以及处理时间这几个因素的影响。处理所需的温度范围应在300-800℃之间，尤其在600-700℃为佳，这是因为在300℃以下反应进行的速率较慢，而在800℃以上由于接近CaCO3的分解温度而导致部分所形成的CaCO3分解，因此在此温度下要想得到较厚的CaCO3层较为困难。由于水蒸汽的分压与水蒸汽的温度有相对稳定的一一对应关系，因此混合气体中CO2和水蒸汽的成分比例可以主要通过调节水蒸汽的温度来控制，通常水蒸汽在混合气体中的比例为4-50％。水蒸汽的温度一般在40-90℃时处理结果较优，尤其在70℃-80℃之间效果最佳。这是因为在此温度下CO2和水蒸汽的比例较为合适，能够使CaO与水蒸汽反应生成的Ca(OH)2恰好与CO2充分反应完全，从而得到一定厚度的CaCO3薄膜。水蒸汽温度过低，使其在混合气体中所占有的比例小，从而导致镁钙砂表面的CaO不能与H2O充分反应，因此所形成的CaCO3层较薄。水蒸汽温度过高，混合气体中含有的H2O过多，从而造成先反应生成的Ca(OH)2不能与CO2充分反应，以致产生外层为致密CaCO3而内层为疏松Ca(OH)2的双层结构，而容易使CaCO3在使用过程中产生脱落。该方法的处理时间一般认为在1小时左右，已足够使镁钙砂表面形成所需厚度的CaCO3层，虽然随处理时间的延长，原料的抗水化效果仍在提高，但幅度已经很小。因为一定厚度的CaCO3形成之后，外界水分和CO2要想和CaCO3层内的CaO再继续反应，则需要通过扩散进入并通过已形成的CaCO3层。显然这一过程是非常缓慢的，因此一般情况下，处理1小时已可以达到大幅度提高原料抗水化能力的目的。The preparation process of the present invention is mainly affected by several factors such as treatment temperature, water vapor temperature and treatment time. The temperature range required for processing should be between 300-800°C, especially 600-700°C, because the reaction rate is slower below 300°C, and above 800°C is close to the decomposition temperature of CaCO 3 As a result, part of the formed CaCO 3 decomposes, so it is difficult to obtain a thicker CaCO 3 layer at this temperature. Since the partial pressure of water vapor has a relatively stable one-to-one correspondence with the temperature of water vapor, the composition ratio of CO2 and water vapor in the mixed gas can be mainly controlled by adjusting the temperature of water vapor, usually water vapor in the mixed gas The ratio is 4-50%. Generally, the temperature of water vapor is better when the temperature is 40-90°C, especially when the temperature is between 70°C-80°C. This is because the ratio of CO 2 and water vapor is more appropriate at this temperature, so that the Ca(OH) 2 formed by the reaction of CaO and water vapor can fully react with CO 2 to obtain a certain thickness of CaCO 3 film. The temperature of water vapor is too low, so that its proportion in the mixed gas is small, so that CaO on the surface of magnesia-calcium sand cannot fully react with H 2 O, so the formed CaCO 3 layer is relatively thin. The temperature of the water vapor is too high, and the mixed gas contains too much H 2 O, so that the Ca(OH) 2 formed by the first reaction cannot fully react with CO 2 , so that the outer layer is dense CaCO 3 and the inner layer is loose Ca( OH) 2 double-layer structure, and it is easy to cause CaCO 3 to fall off during use. The treatment time of this method is generally considered to be about 1 hour, which is enough to form a CaCO 3 layer with the required thickness on the surface of the magnesia-calcium sand. Although the anti-hydration effect of the raw material is still improving with the prolongation of the treatment time, the magnitude is already small . Because after a certain thickness of CaCO 3 is formed, if external moisture and CO 2 want to continue to react with CaO in the CaCO 3 layer, they need to diffuse into and pass through the formed CaCO 3 layer. Obviously this process is very slow, so in general, one hour of treatment can achieve the purpose of greatly improving the hydration resistance of raw materials.
本发明的实施例与比较例的抗水化性能的优劣对比，采用如下抗水化检测方法：用颗粒状的MgO-CaO系耐火材料，在0.15Mpa的蒸汽高压釜中强制水化2小时，然后称出其水化增重，由公式：The advantages and disadvantages of the anti-hydration performance of the embodiments of the present invention and the comparative examples are compared, and the following anti-hydration detection method is adopted: use granular MgO-CaO refractory materials to force hydration in a steam autoclave of 0.15Mpa for 2 hours , and then weigh its hydration weight gain, by the formula:
式中：W1-试样干熏；In the formula: W1-sample dry smoking;
W2-实验后试样和烧杯总重；W2- the total weight of the sample and the beaker after the experiment;
W0-烧杯重；W0-beaker weight;
计算得出增重率。Calculate the weight gain.
本发明的多个实施例及其抗水化性能如下各表所示：Multiple embodiments of the present invention and their anti-hydration properties are shown in the following tables:
表1所示的粒度为2-3mm的镁钙砂在水蒸汽温度为70℃时于300℃、400℃、500℃、600℃、700℃、800℃的不同处理温度下分别轻水化碳化处理1小时后，经抗水化检测后所得的增重率。比较例1是未处理的镁钙砂抗水化检测后的结果。The magnesia-calcium sands with a particle size of 2-3mm shown in Table 1 were lightly hydrated and carbonized at different treatment temperatures of 300°C, 400°C, 500°C, 600°C, 700°C, and 800°C when the steam temperature was 70°C After 1 hour of treatment, the weight gain rate obtained after the anti-hydration test. Comparative example 1 is the result after the anti-hydration test of untreated magnesia-calcium sand.
表1
实施例2Example 2
表2所示的粒度为2-3mm的镁钙砂在水蒸汽温度为700℃的处理温度下，水蒸汽温度分别为40℃、50℃、60℃、70℃、80℃、90℃的条件下分别轻水化碳化处理1小时后，经抗水化检测后所得的增重率。The magnesia-calcium sand with a particle size of 2-3 mm shown in Table 2 is treated at a steam temperature of 700 °C, and the steam temperature is 40 °C, 50 °C, 60 °C, 70 °C, 80 °C, and 90 °C. The following is the weight gain rate obtained after the hydration resistance test after the light hydration and carbonization treatment for 1 hour.
表2
实施例3Example 3
表3所示的粒度为2-3mm的镁钙砂在水蒸汽温度为700℃的处理温度下，水蒸汽温度为70℃的条件下，分别轻水化碳化处理0.5小时、1小时、2小时、3小时后，经抗水化检测后所得的增重率。The magnesia-calcium sands with a particle size of 2-3mm shown in Table 3 were lightly hydrated and carbonized for 0.5 hours, 1 hour, and 2 hours at a steam temperature of 700°C and a steam temperature of 70°C. , 3 hours later, the weight gain rate obtained after the anti-hydration test.
表3
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| CN100348536C (en) * | 2002-08-30 | 2007-11-14 | 武汉科技大学 | Antihydration MgO-CaO clinker and its preparation method |
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| CN107686340A (en) * | 2017-08-29 | 2018-02-13 | 浙江攀盛冶金材料有限公司 | A kind of calcareous dry materials of magnesium and preparation method thereof |
| PL3772500T3 (en) * | 2019-08-05 | 2022-12-27 | Refractory Intellectual Property Gmbh & Co. Kg | Method for treating magnesia carbon products |
| CN110668833A (en) * | 2019-10-28 | 2020-01-10 | 刘晓慧 | Preparation method of magnesium-calcium-carbon composite material |
| CN111217613A (en) * | 2020-02-17 | 2020-06-02 | 武汉科技大学 | A kind of magnesium calcium material and preparation method thereof |
| CN112830799B (en) * | 2021-01-21 | 2022-08-09 | 西安建筑科技大学 | CaCO (calcium carbonate) 3 Coated corundum aggregate and preparation method and application thereof |
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