CN105819892B - 一种利用废弃莫来石‑刚玉砖制备轻质耐火材料的方法 - Google Patents

一种利用废弃莫来石‑刚玉砖制备轻质耐火材料的方法 Download PDF

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CN105819892B
CN105819892B CN201610203967.9A CN201610203967A CN105819892B CN 105819892 B CN105819892 B CN 105819892B CN 201610203967 A CN201610203967 A CN 201610203967A CN 105819892 B CN105819892 B CN 105819892B
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corundum brick
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武杏荣
章守兰
冒爱琴
申星梅
吕辉鸿
李辽沙
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MAANSHAN AHUT INDUSTRIAL TECHNOLOGY RESEARCH INSTITUTE Co Ltd
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Abstract

本发明提供一种利用废弃莫来石‑刚玉砖制备轻质耐火材料的方法，属于耐火材料技术领域。该方法包括废弃莫来石‑刚玉砖的遴选、粗破碎后磁选除铁、细破碎成粒径小于1mm的细颗粒料、细颗粒料的化学分析等工序；通过在废弃的莫来石砖细颗粒料中添加碳酸钙、造孔剂制备混合料，通过加入成型剂并球磨制备浆料；最后经过胶凝成型、干燥和高温烧成制得轻质耐火材料。本发明制备的耐火材料以莫来石为主晶相，钙长石为次晶相，制品气孔率高，体积密度小，属轻质耐火材料。本发明不仅有效利用了废弃耐火材料，而且提供了一种成本较低、工艺简单的制备方法，降低了对环境的污染，制得的轻质耐火材料可广泛应用于保温隔热。

Description

一种利用废弃莫来石-刚玉砖制备轻质耐火材料的方法
技术领域：
本发明属于耐火材料技术领域，具体涉及一种利用废弃莫来石-刚玉砖制备莫来石-钙长石轻质耐火材料的方法，本发明适用于废弃莫来石-刚玉质耐火材料的再生利用。
背景技术：
莫来石一刚玉质耐火材料作为窑具被广泛的加以应用，例如：匣钵、棚板、砖、陶瓷辊棒，铁氧体材料和电子绝缘陶瓷烧成窑炉内衬、推板、承烧板等；市场对莫来石-刚玉砖用量逐年增加；相应地，在实际使用过程中莫来石-刚玉砖发生开裂、破碎、粘连和变形等，造成大量的废弃莫来石-刚玉砖，这些废砖除少量回收利用，大量被废弃堆存，由于使用后的砖表面含有Zn、Mn、Ni、Cd等金属氧化物，雨水冲刷发生金属离子浸出而环境了污染。另一方面，自然界中天然莫来石很少，需要人工高温合成，因此使用后莫来石-刚玉砖经过处置，进行回收再利用，既可以节约资源，又能减少对环境的污染。
对废旧耐火材料回收利用制备刚玉和莫来石已出现过报道。中国专利CN201310478688.X公开了将废旧高铝砖破碎成细粉，经过制浆、干燥造粒和压制成型；将压制成型所得的坯料1570～1620℃烧结，保温8～12小时合成刚玉。中国专利CN201310478542.5公开了将废旧粘土砖破碎成细粉，经过制浆、干燥造粒和压制成型；将压制成型所得的坯料1530～1560℃烧结，保温8～12小时制备合成莫来石。对于莫来石-钙长石复合材料也有报道，中国专利CN201110433179.6公开一种利用石灰石、石英粉和γ-氧化铝为原料制备钙长石-莫来石复相耐高温材料的方法。
发明内容：
本发明针对现有废弃莫来石-刚玉砖综合利用中存在的技术问题，提供一种利用废弃莫来石-刚玉砖制备轻质耐火材料的方法。
本发明所提供的一种利用废弃莫来石-刚玉砖制备轻质耐火材料的方法具体步骤如下：
(1)废弃莫来石‐刚玉砖的遴选，采用人工铁锤敲击与金刚石刀具机械切割相结合的方法清除废弃莫来石‐刚玉砖表面的反应层。
(2)将清除反应层后的废弃莫来石‐刚玉砖投入到颚式破碎机中进行破碎，对破碎后的废弃莫来石‐刚玉砖用磁选机进行磁选，清除废弃莫来石‐刚玉砖中夹带的含铁杂质，得到废弃莫来石‐刚玉砖颗粒物。
(3)将步骤(2)得到的废弃莫来石‐刚玉砖颗粒物投入对辊机中进行破碎，筛分得到粒径小于1mm以下的废弃莫来石‐刚玉砖颗粒物。
(4)对获得的小于1mm以下细颗粒料进行取样，利用X‐射线荧光光谱仪测定其中的化学成分：Al2O3、SiO2和Fe2O3。
(5)混合料的制备：
将步骤(3)得到的粒径小于1mm以下的废弃莫来石‐刚玉砖颗粒物与碳酸钙、造孔剂进行混合得到混合料，所述粒径小于1mm以下的废弃莫来石‐刚玉砖颗粒物与碳酸钙及造孔剂的质量比为：(10‐15)：1：5，所述造孔剂为淀粉。
(6)浆料的制备：
将步骤(5)得到的混合料与成型剂混合后装入球磨罐中，利用行星球磨机进行球磨5‐10h制得浆料，所述行星球磨机的转速为550rpm。
所述成型剂为有机单体丙烯酰胺(AM)和N,N‐亚甲基双丙酰胺(MBAM)混合物的水溶液，所述有机单体丙烯酰胺和N,N‐亚甲基双丙酰胺的混合物中有机单体丙烯酰胺与N,N‐亚甲基双丙酰胺的质量比为10：1，所述有机单体丙烯酰胺和N,N‐亚甲基双丙酰胺的混合物与水配制成质量分数为5％的溶液，所述成型剂与所述混合料的体积比为3：10。
(7)在步骤(6)得到的所述浆料中加入适量的引发剂过硫酸铵和催化剂四甲基乙二胺，搅拌均匀后注入钢模中，固化成型后脱模，脱模后坯体置于体积分数为80％的乙醇水溶液中脱水5h，脱水后坯体置于干燥箱中在110℃下干燥24h。
(8)将干燥后的坯体置于高温炉中，在1300-1500℃下保温5-10h进行烧制，制得所述轻质耐火材料。
本发明中废弃莫来石一刚玉质耐火材料的主要成分为Al2O3和SiO2，是一种复相材料，即Al2O3与SiO2在高温下反应形成莫来石相(3Al2O3+2SiO2＝3Al2O3·2SiO2)后，Al2O3仍有富余，以刚玉相析出，基于此原因，通过回收废弃莫来石一刚玉砖并加以处置，并向其中配加CaO以及造孔剂，保留其中的莫来石主晶相，同时使CaO与SiO2以及多余的Al2O3在高温下反应生成钙长石，从而制备轻质耐火材料：莫来石-钙长石材料。本发明方法具有制备成本较低、工艺简单以及降低了对环境的污染，制备的轻质耐火材料可广泛用作保温隔热材料。
附图说明：
图1为实施例1制得的莫来石-钙长石轻质耐火材料的XRD图谱；
图2为实施例2制得的莫来石-钙长石轻质耐火材料的XRD图谱。
具体实施方式：
实施例1：从磁性材料行业回收废弃莫来石-刚玉推板砖，人工拣选后，采用人工铁锤敲击和金刚石刀具机械切割相结合方法，清除废砖表面与磁性材料反应层；清除后的残砖投入到颚式破碎机进行破碎，对破碎后物料经过磁选机进行磁选，清除其中夹带的含铁杂质；将磁选后得到的残砖颗粒投入对辊机进行细破，筛分得到粒径小于1mm以下细颗粒，粒径大于等于1mm以上的颗粒返回对辊机中继续破碎；对获得的粒径小于1mm以下细颗粒料进行取样，进行化学分析，利用X-射线荧光光谱仪测定其中的化学成分；具体成分为Al2O388.20％，SiO28.48％，Fe2O30.83％。将获得的粒径小于1mm的废砖细颗粒料与碳酸钙、淀粉按照质量比为：15：1：5进行配料，得到混合料。成型剂为有机单体丙烯酰胺(AM)和N,N-亚甲基双丙酰胺(MBAM)的水溶液；AM和MBAM质量比为10：1，与水混合配制成质量分数为5wt％的溶液；将混合料与成型剂按照体积比为10：3进行配料并装入球磨罐中，利用行星球磨机进行球磨10h，转速为550rpm；球磨得到的浆料中加入适量的引发剂过硫酸铵和催化剂四甲基乙二胺，搅拌均匀后注入钢模中，固化成型后脱模；脱模后坯体置于体积分数为80％的乙醇水溶液中进行脱水，时间为5h；脱水后试样置于干燥箱中在110℃下干燥24h；将干燥后坯体置于高温炉中，在1400℃下进行烧制得到制品，烧成保温时间5h，制品的显气孔率为50.5％，体积密度为1.23g/cm3，图1为制品的X-射线衍射图谱，经分析：莫来石和刚玉为主晶相，钙长石为次晶相。
实施例2：从陶瓷行业回收废弃莫来石-刚玉匣钵，人工拣选后，采用人工铁锤敲击和金刚石刀具机械切割相结合方法，清除废砖表面与陶瓷反应层；清除后的匣钵投入到颚式破碎机进行破碎，对破碎后物料经过磁选机进行磁选，清除其中夹带的含铁杂质；将磁选后得到的残砖颗粒投入对辊机进行细破，筛分得到粒径小于1mm以下细颗粒，粒径大于等于1mm以上的颗粒返回对辊机中继续破碎；对获得的粒径小于1mm以下细颗粒料进行取样，进行化学分析，利用X-射线荧光光谱仪测定其中的化学成分；具体成分为Al2O378.65％，SiO220.86％，Fe2O30.57％。将获得的粒径小于1mm以下的废砖细颗粒料与碳酸钙、淀粉按照质量比为：10：1：5进行配料，得到混合料。成型剂为有机单体丙烯酰胺(AM)和N,N-亚甲基双丙酰胺(MBAM)的水溶液；AM和MBAM质量比为10：1，与水混合配制成质量分数为5wt％的溶液；将混合料与成型剂按照体积比为10：3进行配料并装入球磨罐中，利用行星球磨机进行球磨5h，转速为550rpm；球磨得到的浆料中加入适量的引发剂过硫酸铵和催化剂四甲基乙二胺，搅拌均匀后注入钢模中，固化成型后脱模；脱模后坯体置于体积分数为80％的乙醇水溶液中进行脱水，时间为5h；脱水后试样置于干燥箱中在110℃下干燥24h；将干燥后坯体置于高温炉中，在1300℃下进行烧制得到制品，烧成保温时间10h，制品的显气孔率为53.9％，体积密度为1.12g/cm3，图2为制品的X-射线衍射图谱，经分析：莫来石为主晶相，钙长石和刚玉为次晶相。

Claims (1)

1.一种利用废弃莫来石-刚玉砖制备轻质耐火材料的方法，其特征在于该方法具体步骤如下：
(1)废弃莫来石‐刚玉砖的遴选，采用人工铁锤敲击与金刚石刀具机械切割相结合的方法清除废弃莫来石‐刚玉砖表面的反应层；
(2)将清除反应层后的废弃莫来石‐刚玉砖投入到颚式破碎机中进行破碎，对破碎后的废弃莫来石‐刚玉砖用磁选机进行磁选，清除废弃莫来石‐刚玉砖中夹带的含铁杂质，得到废弃莫来石‐刚玉砖颗粒物；
(3)将步骤(2)得到的废弃莫来石‐刚玉砖颗粒物投入对辊机中进行破碎，筛分得到粒径小于1mm以下的废弃莫来石‐刚玉砖颗粒物；
(4)对获得的小于1mm以下细颗粒料进行取样，利用X‐射线荧光光谱仪测定其中的化学成分：Al2O3、SiO2和Fe2O3；
(5)混合料的制备：
将步骤(3)得到的粒径小于1mm以下的废弃莫来石‐刚玉砖颗粒物与碳酸钙、造孔剂进行混合得到混合料，所述粒径小于1mm以下的废弃莫来石‐刚玉砖颗粒物与碳酸钙及造孔剂的质量比为：(10‐15)：1：5，所述造孔剂为淀粉；
(6)浆料的制备：
将步骤(5)得到的混合料与成型剂混合后装入球磨罐中，利用行星球磨机进行球磨5‐10h制得浆料，所述行星球磨机的转速为550rpm；所述成型剂为有机单体丙烯酰胺和N,N‐亚甲基双丙酰胺混合物的水溶液，所述有机单体丙烯酰胺和N,N‐亚甲基双丙酰胺的混合物中有机单体丙烯酰胺与N,N‐亚甲基双丙酰胺的质量比为10：1，所述有机单体丙烯酰胺和N,N‐亚甲基双丙酰胺的混合物与水配制成质量分数为5％的溶液，所述成型剂与所述混合料的体积比为3：10；
(7)在步骤(6)得到的所述浆料中加入适量的引发剂过硫酸铵和催化剂四甲基乙二胺，搅拌均匀后注入钢模中，固化成型后脱模，脱模后坯体置于体积分数为80％的乙醇水溶液中脱水5h，脱水后坯体置于干燥箱中在110℃下干燥24h；
(8)将干燥后的坯体置于高温炉中，在1300‐1500℃下保温5‐10h进行烧制，制得所述轻质耐火材料。
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