利用高炉渣制备微晶玻璃的研究
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摘要
随着工业的迅速发展,大量的废渣被排放到环境中。而高炉渣是冶金工业中排放量很大的一种废渣,也是宝贵的可再生资源。目前,大部分高炉渣用作矿渣水泥的原料,但附加值较低,不能满足目前国家提出的节能减排、节约资源的要求。
高炉渣主要化学成分为CaO、Al2O3和Si02,它们是CaO-Al2O3-MgO-SiO2系微晶玻璃的重要组成。同时高炉渣中富含的Fe2O3(FeO)也可以作为微晶玻璃的有效晶核剂。以高炉渣为主要原料制备微晶玻璃为高炉渣的回收利用找到了新的、有效的途径,同时对于提高钢铁废渣的利用率、增加企业经济效益、减轻环境污染具有重要的意义。
本文以云南某大型钢铁企业排放的高炉渣和废玻璃为主要原料,不添加晶核剂,采用一次烧结法制备了CaO(MgO)-Al2O3-SiO2系高炉渣微晶玻璃,其主晶相为透辉石(CaMgSi2O6).运用DSC和XRD等现代检测分析手段对高炉渣微晶玻璃的核化晶化温度和物相组成进行了分析,探讨了试样成型压力的选择、高炉渣加入量以及热处理工艺制度对微晶玻璃性能和晶相组成的影响。
本文采用半干半湿成型法将试样压制成型。试样的成型压力对微晶玻璃的制备有一定的影响。经过研究讨论,选取压力范围在110-150MPa之间变动,随着成型压力的增大,微晶玻璃各项性能都得到改善。但是成型压力在110-130MPa范围时内单位压力对微晶玻璃性能的贡献率比在130-150MPa范围内的要大,同时考虑到模具寿命、能耗等因素,不是压力越大越好,而是要选择一个最佳点。综合各方面因素,选取成型压力为、130MPa。
高炉渣的加入量对微晶玻璃的制备同样有一定的影响。不同高炉渣加入量所制备的微晶玻璃,其晶相组成不同,甚至主晶相都发生了变化。高炉渣加入量为35wt%时,微晶玻璃的主晶相为透辉石(CaMgSi2O6)；高炉渣加入量为55wt%时,微晶玻璃的主晶相为镁黄长石(Ca2MgSi2O7).微晶玻璃的各项性能随高炉渣含量的变化而不同,35%高炉渣加入量得到的微晶玻璃各项性能最好,但是高炉渣利用率较低。在满足微晶玻璃性能要求前提下,为了最大限度地提高高炉渣的利用率,本文选择高炉渣的加入量为45wt%。
优化高炉渣玻璃的热处理工艺参数也可以有效的提高微晶玻璃的综合性能。本文经优化后最佳的热处理工艺参数为：核化温度750℃,保温1.5h；晶化温度880℃,保温2.5h。升温速率为：5～10℃/min。
With the rapid development of industry, plenty of slag is ejected into environment. The blast slag is a waste which is emitted in large quantities in metallurgical industry. And it is also a valuable renewable resource. At present, the majority of blast slag is used as a raw material for slag cement. But it is not the most effective way, and it can not reach the requirements of saving energy, reducing emission and saving resource.
The blast slag is mostly composed of CaO、Al2O3和SiO2,which are the important component of the CaO-Al2O3-MgO-SiO2 System glass-ceramics. Furthermore, Fe2O3(FeO) in the blast slag is an effective nucleation agent in the glass-ceramics system. So it is a new, effective way to prepare glass-ceramics materials by using the blast slag. It is the great significance for improving the utilization of steel slag, increasing the economic efficiency of enterprises and reducing the environmental pollution.
In this paper, the glass-ceramics of CaO-MgO-Al2O3-SiO2 system had been initially prepared by direct sintering method using the blast slag produced by a certain steel corporation in Yunnan province and wasted glass. The major crystalline of the glass-ceramics was diopside (CaMgSi2O6). DSC was used to ascertain the heat-treatment temperature system, and XRD to characterize the phase composition. The effect of forming pressure, heat-treatment parameters and the content of the blast slag in raw material was discussed.
In this paper, the sample was suppressed by semi-dry molding method. Along with the increase of the forming pressure, the properties of the glass-ceramics also changed. Through research, the pressure was changed between 110MPa and 150MPa. And along with the increase of the forming pressure, the performance of the glass-ceramics also was improved. It is faster to improve the performance of the glass-ceramics when the forming pressure increased from 110MPa to 130MPa than increasing from 130MPa to 150MPa. Taking into account the die life and energy consumption, not the greater pressure was the better, but we should choose the best points. Taking all factors, we determined that the pressure was 130MPa.
Along with the increase of the content of the blast slag, the content of the crystal phase in the glass-ceramics was different, or even was changed. When the content of the blast slag was 35wt%, the major crystalline of the glass-ceramics was diopside (CaMgSi2O6). And when the content of the blast slag was 55wt%, the major crystalline of the glass-ceramics was akermanite (Ca2MgSi2O7). Along with the increase of the content of the blast slag, the properties of glass-ceramics were different. When the content of the blast slag was 35wt%, the properties of glass-ceramics were best. However, the utilization of blast slag was low. For meeting the performance requirements of glass-ceramics and maximizing the utilization of blast slag, we the content of the blast slag was 45wt%.
The properties of the glass-ceramics can also be promoted by optimizing the heat-treatment parameters. The optimal heat-treatment parameters in this paper are: nucleated at 750℃for 1.5h, then crystallized at 880℃for 2.5h. The proper rate for heating is:5～10℃/min.
高炉渣主要化学成分为CaO、Al2O3和Si02,它们是CaO-Al2O3-MgO-SiO2系微晶玻璃的重要组成。同时高炉渣中富含的Fe2O3(FeO)也可以作为微晶玻璃的有效晶核剂。以高炉渣为主要原料制备微晶玻璃为高炉渣的回收利用找到了新的、有效的途径,同时对于提高钢铁废渣的利用率、增加企业经济效益、减轻环境污染具有重要的意义。
本文以云南某大型钢铁企业排放的高炉渣和废玻璃为主要原料,不添加晶核剂,采用一次烧结法制备了CaO(MgO)-Al2O3-SiO2系高炉渣微晶玻璃,其主晶相为透辉石(CaMgSi2O6).运用DSC和XRD等现代检测分析手段对高炉渣微晶玻璃的核化晶化温度和物相组成进行了分析,探讨了试样成型压力的选择、高炉渣加入量以及热处理工艺制度对微晶玻璃性能和晶相组成的影响。
本文采用半干半湿成型法将试样压制成型。试样的成型压力对微晶玻璃的制备有一定的影响。经过研究讨论,选取压力范围在110-150MPa之间变动,随着成型压力的增大,微晶玻璃各项性能都得到改善。但是成型压力在110-130MPa范围时内单位压力对微晶玻璃性能的贡献率比在130-150MPa范围内的要大,同时考虑到模具寿命、能耗等因素,不是压力越大越好,而是要选择一个最佳点。综合各方面因素,选取成型压力为、130MPa。
高炉渣的加入量对微晶玻璃的制备同样有一定的影响。不同高炉渣加入量所制备的微晶玻璃,其晶相组成不同,甚至主晶相都发生了变化。高炉渣加入量为35wt%时,微晶玻璃的主晶相为透辉石(CaMgSi2O6)；高炉渣加入量为55wt%时,微晶玻璃的主晶相为镁黄长石(Ca2MgSi2O7).微晶玻璃的各项性能随高炉渣含量的变化而不同,35%高炉渣加入量得到的微晶玻璃各项性能最好,但是高炉渣利用率较低。在满足微晶玻璃性能要求前提下,为了最大限度地提高高炉渣的利用率,本文选择高炉渣的加入量为45wt%。
优化高炉渣玻璃的热处理工艺参数也可以有效的提高微晶玻璃的综合性能。本文经优化后最佳的热处理工艺参数为：核化温度750℃,保温1.5h；晶化温度880℃,保温2.5h。升温速率为：5～10℃/min。
With the rapid development of industry, plenty of slag is ejected into environment. The blast slag is a waste which is emitted in large quantities in metallurgical industry. And it is also a valuable renewable resource. At present, the majority of blast slag is used as a raw material for slag cement. But it is not the most effective way, and it can not reach the requirements of saving energy, reducing emission and saving resource.
The blast slag is mostly composed of CaO、Al2O3和SiO2,which are the important component of the CaO-Al2O3-MgO-SiO2 System glass-ceramics. Furthermore, Fe2O3(FeO) in the blast slag is an effective nucleation agent in the glass-ceramics system. So it is a new, effective way to prepare glass-ceramics materials by using the blast slag. It is the great significance for improving the utilization of steel slag, increasing the economic efficiency of enterprises and reducing the environmental pollution.
In this paper, the glass-ceramics of CaO-MgO-Al2O3-SiO2 system had been initially prepared by direct sintering method using the blast slag produced by a certain steel corporation in Yunnan province and wasted glass. The major crystalline of the glass-ceramics was diopside (CaMgSi2O6). DSC was used to ascertain the heat-treatment temperature system, and XRD to characterize the phase composition. The effect of forming pressure, heat-treatment parameters and the content of the blast slag in raw material was discussed.
In this paper, the sample was suppressed by semi-dry molding method. Along with the increase of the forming pressure, the properties of the glass-ceramics also changed. Through research, the pressure was changed between 110MPa and 150MPa. And along with the increase of the forming pressure, the performance of the glass-ceramics also was improved. It is faster to improve the performance of the glass-ceramics when the forming pressure increased from 110MPa to 130MPa than increasing from 130MPa to 150MPa. Taking into account the die life and energy consumption, not the greater pressure was the better, but we should choose the best points. Taking all factors, we determined that the pressure was 130MPa.
Along with the increase of the content of the blast slag, the content of the crystal phase in the glass-ceramics was different, or even was changed. When the content of the blast slag was 35wt%, the major crystalline of the glass-ceramics was diopside (CaMgSi2O6). And when the content of the blast slag was 55wt%, the major crystalline of the glass-ceramics was akermanite (Ca2MgSi2O7). Along with the increase of the content of the blast slag, the properties of glass-ceramics were different. When the content of the blast slag was 35wt%, the properties of glass-ceramics were best. However, the utilization of blast slag was low. For meeting the performance requirements of glass-ceramics and maximizing the utilization of blast slag, we the content of the blast slag was 45wt%.
The properties of the glass-ceramics can also be promoted by optimizing the heat-treatment parameters. The optimal heat-treatment parameters in this paper are: nucleated at 750℃for 1.5h, then crystallized at 880℃for 2.5h. The proper rate for heating is:5～10℃/min.
引文
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