CN108218393B - 一种利用煤矸石制备Al2O3-SiC-C系炮泥耐火材料的方法 - Google Patents
一种利用煤矸石制备Al2O3-SiC-C系炮泥耐火材料的方法 Download PDFInfo
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Abstract
本发明公开了一种利用煤矸石制备Al2O3‑SiC‑C系炮泥耐火材料的方法，属于耐火材料的制备领域，涉及无机化学制备领域。本发明以煤矸石、碳质材料经埋碳高温碳热还原反应产生Al2O3‑SiC复相材料，再和棕刚玉、SiC粉、粘土、蓝晶石粉、焦炭粉、沥青粉、Fe‑Si3N4粉、焦油等原料，经配料、混合、睏料等工艺，制备得到Al2O3‑SiC‑C系炮泥耐火材料。本发明解决了煤矸石废弃物产量大，难处理、使用率低的社会、环境问题，同时解决了无水炮泥成本高的经济问题，为煤矸石固体废弃物的高值化利用开辟了新的途径。
Description
技术领域：
本发明属于耐火材料的制备领域，涉及无机化学制备领域，具体涉及一种利用煤矸石制备 Al2O3-SiC-C系炮泥耐火材料的方法。
技术背景：
煤研石作为煤矿开采的一种工业固体废弃物，其大量堆积排放不仅占用了大量的土地资源，而且严重影响地表景观及人的身体健康。煤研石含有大量的Al、Si等有用元素，如果能将其利用起来，将会变废为宝，不仅解决了煤研石的随意排放堆积问题，同时也节省其他资源的利用，具有可观的经济及社会价值。
无水炮泥一般由刚玉、碳化硅、焦粉为主要原料，在通过调配不同的外加剂和结合剂制备而成。这种炮泥多采用优质的高纯原料，其耐铁渣侵蚀性能与传统的有水炮泥相比大幅度提高，可以使出铁口出铁时间延长的同时降低出铁的次数，即减少了出铁口开口的次数，减少了炮泥的使用消耗。
利用固体废弃矿物合成高性能低成本材料是当今国内外发展循环经济和环境可持续发展道路的重要途径。以煤矸石碳热还原制备的Al2O3-SiC复相材料为主要原料来制备高性能低成本Al2O3-SiC-C 系炮泥耐火材料的技术方案，对于开展我国典型煤矸石的矿物组成特征、在不同温度下矿物组成演发明内容变规律的研究，和优化利用煤矸石碳热还原制备Al2O3-SiC复相材料的工艺参数，形成高性能低成本Al2O3-SiC-C系炮泥耐火材料的制备技术，有着重要意义。该方案不仅工艺简单，而且固体废弃矿物利用率较高，更有效地保护了环境。
发明内容：
本文主要针对煤矸石对环境带来的问题并着眼于它的潜在价值，同时也为解决无水炮泥高成本的问题。
本发明提出的一种利用煤矸石制备Al2O3-SiC-C系炮泥耐火材料的方法，先以煤矸石、碳质材料经埋碳高温碳热还原反应产生Al2O3-SiC复相材料，再和棕刚玉、SiC粉、粘土、蓝晶石粉、焦炭粉、沥青粉、Fe-Si3N4粉、焦油等原料，经配料、混合、睏料等工艺，制备得到Al2O3-SiC-C系炮泥耐火材料。
所述的制备方法，埋碳高温碳热还原反应中碳质材料包括焦炭、炭黑、无烟煤等，其理论用量按照煤矸石中SiO2被完全转化为SiC计算得到，其用量范围为理论值到过量100％；Al2O3-SiC-C系炮泥耐火材料原料混合后，睏料时间为12h。
本发明制备得到的Al2O3-SiC-C系炮泥耐火材料抗压强度明显高于传统无水炮泥，抗折强度也高于传统无水炮泥，有较好的抗侵蚀性能。
具体实施方式：
将煤矸石原矿和焦炭(或炭黑或无烟煤)分别进行粉碎，磨细后过100目筛备用。
按照焦炭(或炭黑或无烟煤)碳含量标准至过量100％称量碳源还原剂和煤矸石细粉，放入尼龙球磨罐中。
在尼龙球磨罐中，以不同粒径的玛瑙球为研磨介质，共混球磨24小时。
粉体经干燥后利用粉末压片机在20MPa下成型后在埋碳的碳热还原气氛下煅烧，制得 Al2O3-SiC复相粉体。
将棕刚玉、SiC粉、粘土、蓝晶石、焦炭粉、沥青粉、Fe-Si3N4与Al2O3-SiC复相粉体混合均匀待用。
外加质量分数10％的80℃焦油，搅拌和匀，分多次加入混合好的细粉，充分搅拌，80℃睏料12 小时。
下面结合三个实施例，对本发明提供的由煤矸石生产Al2O3-SiC-C系无水炮泥恼火材料进行详细的说明。然而应理解的是，本文所详述的本发明并非旨在受限于以下实施例的细节。
实施例1
将煤矸石原矿和焦炭分别利用颚式破碎机进行粉碎，利用振动磨磨细后过100目筛备用。取焦炭55g和煤矸石细粉20g，其中煤矸石中SiO2含量为58.6％，Al2O3含量为41.2％，及少量Fe2O3，焦炭过量10％放入尼龙球磨罐中。在尼龙球磨罐中，以不同粒径的玛瑙球为研磨介质，共混球磨24小时。将粉体经干燥，之后利用粉末压片机在20MPa下成型。再在埋碳的碳热还原气氛下，于1600℃煅烧保温2小时，制得Al2O3-SiC复相粉体。
选用3-1mm、1-0mm、200目的棕刚玉，质量分数分别为20％、23％、7％，和质量分数为10％的240目95SiC，并均匀混合。将质量分数为8％的2000目95SiC、10％的200目粘土、5％的蓝晶石、 5％的焦炭粉、2％的沥青粉、10％的Fe-Si3N4与外加质量分数为2％的Al2O3-SiC复相粉体混合均匀待用。外加质量分数10％的80℃焦油，搅拌和匀，分多次加入混合好的细粉，碾开大团聚体，充分搅拌。将混料放入80℃烘箱内保温20分钟，之后继续混合搅拌，再放入烘箱保温，重复3-4次，80℃睏料12小时。
将制备好的原料经压片机压制成柱状、条状、坩埚状，分别测量其抗压、抗折、抗铁渣侵蚀性能，结果为：在1400℃的使用温度下，平均抗压强度为13.00MPa；抗折强度为11.48MPa，切片观察抗侵蚀程度较好，表明都优于相同条件下传统炮泥的使用性能。
实施例2
将煤矸石原矿和无烟煤分别利用颚式破碎机进行粉碎，利用振动磨磨细后过100目筛备用。取焦炭90g和煤矸石细粉20g，其中煤矸石中SiO2含量为58.4％，Al2O3含量为41.8％，及少量Fe2O3，无烟煤过量90％放入尼龙球磨罐中。在尼龙球磨罐中，以不同粒径的玛瑙球为研磨介质，共混球磨24 小时。将粉体经干燥，之后利用粉末压片机在20MPa下成型。再在埋碳的碳热还原气氛下，于1300℃煅烧保温5小时，制得Al2O3-SiC复相粉体。
选用3-1mm、1-0mm、200目的棕刚玉，质量分数分别为20％、23％、7％，和质量分数为10％的240目95SiC，并均匀混合。将质量分数为8％的2000目95SiC、10％的200目粘土、5％的蓝晶石、 5％的焦炭粉、2％的沥青粉、10％的Fe-Si3N4与外加质量分数为20％的Al2O3-SiC复相粉体混合均匀待用。外加质量分数10％的80℃焦油，搅拌和匀，分多次加入混合好的细粉，碾开大团聚体，充分搅拌。将混料放入80℃烘箱内保温20分钟，之后继续混合搅拌，再放入烘箱保温，重复3-4次，80℃睏料12小时。
将制备好的原料经压片机压制成柱状、条状、坩埚状，分别测量其抗压、抗折、抗铁渣侵蚀性能，结果为：在1400℃的使用温度下，平均抗压强度为11.67MPa；抗折强度为7.894MPa，切片观察抗侵蚀程度较好，表明都优于相同条件下传统炮泥的使用性能。
实施例3
将煤矸石原矿和炭黑分别利用颚式破碎机进行粉碎，利用振动磨磨细后过100目筛备用。取焦炭75g和煤矸石细粉20g，其中煤矸石中SiO2含量为59.1％，Al2O3含量为42.0％，及少量Fe2O3，炭黑过量100％放入尼龙球磨罐中。在尼龙球磨罐中，以不同粒径的玛瑙球为研磨介质，共混球磨24 小时。将粉体经干燥，之后利用粉末压片机在20MPa下成型。再在埋碳的碳热还原气氛下，于1500℃煅烧保温4小时，制得Al2O3-SiC复相粉体。
选用3-1mm、1-0mm、200目的棕刚玉，质量分数分别为20％、23％、7％，和质量分数为10％的240目95SiC，并均匀混合。将质量分数为8％的2000目95SiC、10％的200目粘土、5％的蓝晶石、 5％的焦炭粉、2％的沥青粉、10％的Fe-Si3N4与外加质量分数为10％的Al2O3-SiC复相粉体混合均匀待用。外加质量分数10％的80℃焦油，搅拌和匀，分多次加入混合好的细粉，碾开大团聚体，充分搅拌。将混料放入80℃烘箱内保温20分钟，之后继续混合搅拌，再放入烘箱保温，重复3-4次，80℃睏料12小时。
将制备好的原料经压片机压制成柱状、条状、坩埚状，分别测量其抗压、抗折、抗铁渣侵蚀性能，结果为：在1400℃的使用温度下，平均抗压强度为18.33MPa；抗折强度为21.89MPa，切片观察抗侵蚀程度较好，表明都优于相同条件下传统炮泥的使用性能。
Claims (3)
1.一种利用煤矸石制备Al2O3-SiC-C系炮泥耐火材料的方法，其特征在于，该方法包括以下步骤：
将反应原料煤矸石和碳质材料共混、球磨并干燥，然后用粉末压片机进行成型，其中所述碳质材料理论用量按照煤矸石中SiO2被完全转化为SiC计算得到，其用量为过量100％；
然后进行高温碳热还原反应以产生Al2O3-SiC复相材料，所述碳热还原反应在埋碳气氛下进行；
将棕刚玉、SiC粉、粘土、蓝晶石粉、焦炭粉、沥青粉、Fe-Si3N4粉与外加质量分数为10％的所述Al2O3-SiC复相材料和外加质量分数为10％的焦油进行配料、混合、睏料，从而得到Al2O3-SiC-C系炮泥耐火材料，
所述反应原料煤矸石中，含有58-60％的二氧化硅、40-42％的氧化铝，还含有不足1％的氧化钛、氧化铁；
所述碳质材料选自焦炭、炭黑、无烟煤，含碳量均大于90％；
所述碳热还原反应的反应温度为1500℃，反应时间为4h。
2.根据权利要求1所述的方法，其特征在于：棕刚玉粒度为3-1mm、1-0mm、200目，SiC粉粒度为240目和2000目，粘土、蓝晶石粉、焦炭粉、沥青粉、Fe-Si3N4粉粒度为200目。
3.一种Al2O3-SiC-C系炮泥耐火材料，其特征在于，其通过根据权利要求1或2所述的方法制备得到。
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