CN112321290A - 生产烧结镁橄榄石的方法 - Google Patents
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- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
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Abstract
本发明属菱镁矿尾矿资源利用领域，尤其涉及一种生产烧结镁橄榄石的方法，包括：（1）将菱镁矿尾矿粉、轻烧粉、纳米陶瓷结合剂及微米陶瓷结合剂按比例放到高速混砂碾中，混碾15～20分钟，得到混合料；（2）将所得的混合料，利用压球机，在2～6Mpa压力下制成直径40～60mm的球料；（3）将球料夏季自然环境下放置2～3天，冬季3～5天，自然风干；（4）将步骤（3）所得球料与宁夏煤和俄罗斯煤混合交替布料，利用1400～1800℃的重烧竖窑中，煅烧6～15小时，自然降温后出窑，即得到镁橄榄石。本发明生产成本低，目的产物致密度高、纯度高、含钙低、含铁低。
Description
技术领域
本发明属菱镁矿尾矿资源利用领域，尤其涉及一种生产烧结镁橄榄石的方法。
背景技术
镁橄榄石属于斜方晶系，一致熔融二元化合物，晶型稳定，具有较高的荷重软化温度、良好的热震稳定性和化学稳定性，被广泛应用于治金、建材、玻璃、陶瓷等领域。自然界也有镁橄榄石矿，如国内的河南、湖北等地具有相当储量的天然菱镁矿藏，然后天然镁橄榄石矿氧化铁含量较高，因此限制其使用范围，因此，工业上合成镁橄榄石的研究就成为行业内的热点之一。
目前，工业上镁橄榄石合成方法主要有煅烧法、电熔法、煅烧法所制得样品的体积密度为3.08g/cm³、气孔率为7.8%、氧化铁含量为1.1%、耐火度大于1650℃。电熔法所制得样品的体积密度3.11g/cm³、气孔率为6.4%、氧化铁含量为0.8%、耐火度大于1650℃。最常见的，也最为成熟的就是煅烧法。该方法是以天然镁橄榄矿石矿或天然菱镁矿、轻烧氧化镁、硅石矿、蛇纹石矿、滑石矿等作为原料，利用高温竖窑、回转窑等煅烧设备进行生产。此外，也可以采用电熔法制备合成镁橄榄石，然而不论是电熔法还是烧结法，原料成本高、产品质量不稳定、工艺复杂、操作繁琐等因素，致使合成镁橄榄石产品价格普遍偏高，大大限制了镁橄榄石在耐火材料行业使用。因此，探索一种生产成本低、致密度高、纯度高、耐火性好的镁橄榄石制备方法已经迫在眉睫。
现在生产的镁橄榄石质耐火材料，大多数采用天然铁镁橄榄石原料，属于弱碱性耐火材料，主要化学组成为氧化镁、氧化硅和氧化铁，以镁橄榄石（2MgO·SiO2)为主晶相，并含有一定数量的铁酸镁。镁橄榄石质耐火材料具有一定的抗碱性熔渣能力，较高的耐火度和荷重软化温度，较强的抗氧化铁侵蚀能力。但是，由于材料中含有5%以上的氧化铁，在玻璃窑蓄热室内等部位使用时受气氛影响极大，特别是在还原气氛下氧化镁将置换砖中的氧化铁、氧化铝生成铁酸镁、镁铝尖晶石、顽火辉石（MgO·SiO2)和FeO,这些反应伴随24.3%的体积膨胀。含氧化铁的镁橄榄石耐火材料在使用过程中若经历气氛变化，材料体积发生急变，造成结构疏松，强度下降，从而导致材料过早损毁。
随着菱镁矿资源开采力度的加大，优质镁资源不断减少，菱镁矿在浮选时产生大约30%的尾矿，导致尾矿不断堆积。大量堆积的菱镁矿尾矿不仅占用土地资源、破坏地貌植被，其含有的重金属铅、锌以及有害元素和化学药剂更会造成对地表水、地下水及大气环境的污染。此外，尾矿堆积还潜伏着泥石流、山体滑坡、垮坝等地质灾害，威胁着下游群众的生命财产安全。
发明内容
本发明旨在克服现有技术的不足之处而提供一种生产成本低，目的产物致密度高、纯度高、含钙低、含铁低的生产烧结镁橄榄石的方法，所得目的产物镁橄榄石晶粒长、耐火度高、抗震性好，有利于实现菱镁矿尾矿的大规模生产利用。
为解决上述技术问题，本发明是这样实现的：
生产烧结镁橄榄石的方法，可按如下步骤实施：
（1）将菱镁矿尾矿粉、轻烧粉、纳米陶瓷结合剂及微米陶瓷结合剂按比例放到高速混砂碾中，混碾15～20分钟，得到混合料；
（2）将步骤（1）所得的混合料，利用压球机，在2～6Mpa压力下制成直径40～60mm的球料；
（3）将球料夏季自然环境下放置2～3天，冬季3～5天，自然风干；
（4）将步骤（3）所得球料与宁夏煤和俄罗斯煤混合交替布料，利用1400～1800℃的重烧竖窑中，煅烧6～15小时，自然降温后出窑，即得到镁橄榄石。
作为一种优选方案，本发明以重量百分含量计，菱镁矿尾砂：80～85%；轻烧粉：10～15%；纳米陶瓷结合剂：1～2%；微米陶瓷结合剂：3～5%；宁夏煤和俄罗斯煤2～4块粒占球料总量：10～20%。
进一步地，本发明所述菱镁矿尾砂的MgO含量≥30%，SiO2含量≥15%；轻烧粉MgO含量≥80%，SiO2含量≥12%。
进一步地，本发明所述步骤（4）中，球料与宁夏煤和俄罗斯煤混合交替布料中，各层厚度配比为球料厚度110～120mm，煤的厚度25～50mm。
菱镁矿尾矿，解决了堆积贮存菱镁矿尾矿和资源浪费的问题，可防止尾矿堆积对环境产生的危害，真正的变废为宝。本发明生产成本低，致密度高、纯度高、含钙低、含铁低的镁橄榄石合成的新方法，得到的镁橄榄石晶粒长、耐火度高、抗震性好，有利于实现菱镁矿尾矿的大规模生产利用。采用宁夏煤和俄罗斯煤，热值高在7000～8000卡之间，含C85%以上，能快速实现高温烧结，保证产品质量。加入的纳米陶瓷结合剂与微米陶瓷结合剂，作用是低温快速烧结，增加晶粒长度，形成镁橄榄石结合相，增加镁橄榄石的体积密度。生产出的成品镁橄榄石化学性质和物理特性都非常稳定镁橄榄石的化学成分为：MgO≥60%；SiO2≥35%；CaO≤1.5%；Fe2O3≤1.2%；Al2O3≤0.8%。
附图说明
下面结合附图和具体实施方式对本发明作进一步说明。本发明的保护范围不仅局限于下列内容的表述。
图1为本发明生产方法流程框图。
具体实施方式
实施例1
本实施例生产的镁橄榄石成型方法为压球，生产配方中各组重量百分比如下：
菱镁矿尾矿：85%；
轻烧粉：11%；
纳米陶瓷结合剂：1%；
微米陶瓷结合剂：3%。
宁夏煤和俄罗斯煤2～4块粒占球料总量：15%。
其中所述的菱镁矿尾矿细粉MgO≥30%，SiO2含量15～18%，Fe2O3含量低于0.5%，烧碱50%左右，粒度＜0.088mm，优先加入量为85%。
其中所述轻烧粉（80%）的MgO含量在80%，SiO2含量在17%左右。
其中纳米陶瓷结合剂：1%；微米陶瓷结合剂：3%；按照该配方配料，进行批量生产，配好料后放到高速混砂碾中，混碾15～20分钟，得到混合料，通过压球机成球，球的直径Φ60mm，然后进行自然风干。
自然干燥的时间夏季2～3天，冬季3～5天就可以自然烘干了。
其中所述烧结部分就是用重烧竖窑煅烧，将干燥的球料和煤进行窑中布料，球料的厚度在110～120mm之间，煤的厚度在25～50mm之间。控制球料和煤的比例范围在1：0.7左右。窑温在1400～1800℃之间，烧结时间在6～15小时左右，随窑自然降温后出窑，即得到高纯镁橄榄石。
实施例2
本实施例生产的镁橄榄石成型方法为压球，生产配方中各组重量百分比如下：
菱镁矿尾矿：83%；
轻烧粉：12%；
纳米陶瓷结合剂：2%；
微米陶瓷结合剂：3%。
宁夏煤和俄罗斯煤2～4块粒占球料总量：16%。
其中所述的菱镁矿尾矿细粉MgO≥35%，SiO2含量17～18%，Fe2O3含量低于0.5%，烧碱50%左右，粒度＜0.087mm。
其中所述轻烧粉（80%）的MgO含量在80%，SiO2含量在18%左右。
上述实施例中纳米陶瓷结合剂为硅溶胶。微米陶瓷结合剂为氧化硅微粉。
镁橄榄石作为耐火材料被广泛应用于冶金、热工以及铸造行业。在热工领域，镁橄榄石主要用于加热炉炉底、热风炉炉衬以及各种工业窑炉蓄热室的格子砖。在铸造领域，由于镁橄榄石不含游离态，而被公认为是绿色环保型铸造材料，主要用于铸件造型材料使用。在冶金领域，镁橄榄石主要作为连铸中间包的内衬材料使用，少部分作为转炉和钢包修补材料使用。
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。
Claims (4)
1.一种生产烧结镁橄榄石的方法，其特征在于，按如下步骤实施：
（1）将菱镁矿尾矿粉、轻烧粉、纳米陶瓷结合剂及微米陶瓷结合剂按比例放到高速混砂碾中，混碾15～20分钟，得到混合料；
（2）将步骤（1）所得的混合料，利用压球机，在2～6Mpa压力下制成直径40～60mm的球料；
（3）将球料夏季自然环境下放置2～3天，冬季3～5天，自然风干；
（4）将步骤（3）所得球料与宁夏煤和俄罗斯煤混合交替布料，利用1400～1800℃的重烧竖窑中，煅烧6～15小时，自然降温后出窑，即得到镁橄榄石。
2.根据权利要求1所述生产烧结镁橄榄石的方法，其特征在于：以重量百分含量计，菱镁矿尾砂：80～85%；轻烧粉：10～15%；纳米陶瓷结合剂：1～2%；微米陶瓷结合剂：3～5%；宁夏煤和俄罗斯煤2～4块粒占球料总量：10～20%。
3.根据权利要求2所述生产烧结镁橄榄石的方法，其特征在于：所述菱镁矿尾砂的MgO含量≥30%；SiO2含量≥15%；轻烧粉MgO含量≥80%；SiO2含量≥12%。
4.根据权利要求3所述生产烧结镁橄榄石的方法，其特征在于：所述步骤（4）中，球料与宁夏煤和俄罗斯煤混合交替布料中，各层厚度配比为球料厚度110～120mm，煤的厚度25～50mm。
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