CN111116175A - 一种利用钙镁质磷矿尾矿生产水泥窑用耐火材料的方法 - Google Patents

一种利用钙镁质磷矿尾矿生产水泥窑用耐火材料的方法 Download PDF

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CN111116175A
CN111116175A CN201911376236.4A CN201911376236A CN111116175A CN 111116175 A CN111116175 A CN 111116175A CN 201911376236 A CN201911376236 A CN 201911376236A CN 111116175 A CN111116175 A CN 111116175A
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magnesium
calcium
refractory material
cement kiln
phosphate ore
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张晋
贺爱平
郭茂生
秦元奎
胡修权
尤大海
李国栋
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Hubei Metallurgy Geology Research Institute (central South Institute Of Metallurgical Geology)
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Abstract

本发明提供一种利用钙镁质磷矿浮选尾矿清洁制备水泥窑用耐火材料的方法，提高水泥窑烧成带耐火材料的挂窑皮性能、解决传统镁铬砖的铬污染问题、减少白云石资源的开采，并解决磷矿尾矿占地、环境污染、安全威胁等问题。该磷矿尾矿主要成分是钙镁的碳酸盐矿物，并含有少量的磷、硅、铝、铁等。先对尾矿进行浮选提纯，然后对钙镁质组分轻烧、消化处理，再与经煅烧处理后的菱镁矿均质化、困料，最后加入氧化锆、氧化钒、氧化钇等改性剂，深度煅烧，最终合成能运用于水泥窑烧成带的、能替代镁铬砖的耐火材料。本发明能够实现钙镁质磷矿尾矿的高附加值利用，为磷化工企业带来新的利润增长点，促进磷化工企业的可持续发展。

Description

一种利用钙镁质磷矿尾矿生产水泥窑用耐火材料的方法
技术领域
本发明涉及一种利用钙镁质磷矿尾矿生产水泥窑用耐火材料的方法，尤其经过是提纯、轻烧、水化、改性、二次煅烧的工艺处理后制备可用于水泥窑烧成带的耐火材料。
背景技术
磷矿尾矿是磷化工行业选矿提取精矿后产生的大宗矿业固体废弃物，每100万吨磷矿石入选后会产生30-40万吨磷尾矿，我国每年产出的磷尾矿逾1000万吨。目前我国磷尾矿的综合利用率不足10％，大多数堆存于尾矿库中。磷尾矿的堆存不仅会带来水源污染、土地退化、空气恶化等环境问题，磷资源浪费问题，同时也会给磷化工企业带来极大的资金压力和用地压力，严重制约企业的可持续发展。
镁钙系耐火材料不仅在冶金行业有重要的作用，也可用于水泥窑的烧成带等部位。目前水泥回转窑烧成带常用的是镁铬砖。镁铬砖有较高的耐火度，耐氧化硅侵蚀，且化学稳定性较好，同时有较好的高温力学性能以及结窑皮性能，但是在碱性或者含硫的环境中Gr3+易转化为重金属污染离子Gr6+，从而对环境和人体健康造成极大的危害。因此镁铬砖已经逐步被淘汰。镁钙砖具有优良的挂窑皮性能，且耐腐蚀，只是容易在非生产期吸潮水化，是砖体开裂剥落；此外如果环境中含硫过高，耐火材料中的氧化钙则会与S反应，生成硫酸钙，引起砖体的膨胀开裂。
本发明针对钙镁质磷矿尾矿的特点和镁钙质耐火材料的缺陷，针对性地予以提纯和改性，最终制得可用于水泥回转窑烧成带的耐火材料产品。
发明内容
本发明的目的在于提供一种利用钙镁质磷矿尾矿生产水泥窑用耐火材料的方法，实现对钙镁质磷矿尾矿的资源综合利用，同时是对该工业固废的一种高附加值利用。本发明技术方案包括以下几个步骤：
(1)将镁钙质磷矿尾矿经过洗涤、分离、脱药、脱泥后烘干经镁浮选得到钙镁质组分；
(2)将步骤(1)的钙镁质组分经煅烧、得到钙镁氢氧化物；
(3)将菱镁矿(MgCO3含量大于98％)进行煅烧(煅烧的温度为650℃-850℃，煅烧时间30min-60min)，得到氧化镁(纯度为98％以上)；
(4)将步骤(2)中的钙镁氢氧化物、步骤(3)中的氧化镁、改性剂(所述的改性剂包括氧化锆、氧化钛、氧化钇)混匀，然后在干燥气氛(干燥气氛环境的湿度为10-15RH％)中困料40-60h，得到干燥的混合物料；
(5)将步骤(4)中干燥的混合物料在1300-1700℃的环境中煅烧6h-10h，制成水泥窑成带的耐火材料。
步骤(1)中浮选镁过程中采用一粗一精一扫的方式，其中，粗选药剂制度：硫酸6000-10000g/t，捕收剂TG 1000-3000g/t；镁精选药剂制度：捕收剂TG 500-1000g/t；镁扫选药剂制度：硫酸500-1500g/t，捕收剂TG 500-1000g/t。
步骤(2)中钙镁质组分以20-50℃/min的升温速率生物至900-950℃，保温煅烧40min-90min，得到钙镁的氧化物其中钙镁质组分含量大于93％，P2O5≤2.0％，Al2O3+Fe2O3+SiO2+Mn3O4≤2.5％。
步骤(4)中钙镁氢氧化物、氧化镁的质量比为1：1——1：3；氧化锆、氧化钛、或氧化钇等的添加量为钙镁氢氧化物、氧化镁总质量的2-3％。
在本发明中，将钙镁质磷尾矿中经过精选的钙镁质组分，进行煅烧、消化、混合二次煅烧等处理后制成可用于水泥窑烧成带的耐火材料，实现了对磷尾矿的高附加值利用。相对于以往的利用技术，本发明配套技术没有二次污染，且大大提升了产品的附加值，可以激发企业的投资愿景。同时，为了避免镁钙质耐火材料使用中的易水化导致剥落的问题，本发明采用二次煅烧技术及添加氧化钛、氧化锆、氧化钇等改性剂的方法，实现了对耐火材料抗水化性和抗剥落性的优化。
附图说明
图1为钙镁质磷矿尾矿形貌特征。
图2为本发明工艺流程示意图。
具体实施方式
下面列举几个实施实例对本发明作进行一步说明，但不是对本发明的限制。
实施例1：
将镁钙质磷矿尾矿经过洗涤、分离、脱药、脱泥等处理后烘干；然后通过一粗一精一扫的镁浮选流程得到有一定纯度的钙镁质组分。
表1钙镁质磷矿尾矿XRF分析结果
Figure BDA0002341046830000021
一粗一精一扫的镁浮选过程中镁粗选药剂制度：硫酸6000g/t，捕收剂TG 1500g/t；镁精选药剂制度：捕收剂TG 500g/t；镁扫选药剂制度：硫酸1000g/t，捕收剂TG 500g/t。磷粗选药剂制度：碳酸钠8000g/t，捕收剂TP 2000g/t；磷扫选药剂制度：碳酸钠1000g/t。得到钙镁组分产率72％，MgO品位19％，CaO品位35％。
表2浮选处理后钙镁质组分化学多元素分析
Figure BDA0002341046830000031
将上述得到的钙镁质组分在950℃条件下煅烧40min，升温速率20℃/min，进一步纯化，得到钙镁的氧化物。其中钙镁质组分含量大于93％，P2O5≤2.0％，Al2O3+Fe2O3+SiO2+Mn3O4≤2.5％；然后然后以2:1的比例与水进行消化反应，反应时间10min。精选后得到MgO含量高于35％的钙镁氢氧化物(主料1)。将菱镁矿进行精选、煅烧之后得到高纯度氧化镁(主料2)。
表3菱镁矿多元素化学分析表
Figure BDA0002341046830000032
表4耐火材料基料配比表
Figure BDA0002341046830000033
按照表3配比，称取5kg基料加入高速混合改性机处理后，在干燥气氛中进行困料处理(48h)，然后造粒，在1500℃的环境中煅烧8h得到耐火材料制品。
经检测耐火材料性能为：堆积密度为3.28g/cm3、显气孔率13.1％、常温抗压强度60MPa、高温抗折强度5.1MPa、水化试验增重率3.20％。
实施例2：
将镁钙质磷矿尾矿(理化性质同实施例1)经过洗涤、分离、脱药、脱泥等处理后烘干；然后通过一粗一精一扫的镁浮选流程得到有一定纯度的钙镁质组分。
其中镁粗选药剂制度：硫酸7000g/t，捕收剂TG 2000g/t；镁精选药剂制度：捕收剂TG 800g/t；镁扫选药剂制度：硫酸800g/t，捕收剂TG 600g/t。磷粗选药剂制度：碳酸钠10000g/t，捕收剂TP 2500g/t；磷扫选药剂制度：碳酸钠1000g/t。得到钙镁组分产率60％，MgO品位22.3％，CaO品位36.61％。
表5浮选处理后钙镁质组分化学多元素分析
Figure BDA0002341046830000034
将上述得到的钙镁质组分在900℃条件下煅烧1h，升温速率25℃/min，进一步纯化，得到钙镁的氧化物其中钙镁质组分含量大于95％，P2O5≤2.0％，Al2O3+Fe2O3+SiO2+Mn3O4≤2.5％；然后然后以5:2的比例与水进行消化反应，反应时间8min，得到MgO含量38％的钙镁氢氧化物(主料1)。将菱镁矿(理化性质同实施例1)进行精选、煅烧之后得到高纯度氧化镁(主料2)。
表6耐火材料基料配比表
Figure BDA0002341046830000041
按照表6配比，称取5kg基料经高速混合改性机处理后，在干燥气氛中进行困料处理(48h)，然后造粒，在1480℃的环境中煅烧10h得到耐火材料制品。
经检测耐火材料性能为：堆积密度为3.65g/cm3、显气孔率12.1％、常温抗压强度57MPa、高温抗折强度4.9MPa、水化试验增重率2.87％。
实施例3：
将镁钙质磷矿尾矿(理化性质同实施例1)经过洗涤、分离、脱药、脱泥等处理后烘干；然后通过一粗一精一扫的镁浮选流程得到有一定纯度的钙镁质组分。
其中镁粗选药剂制度：硫酸7500g/t，捕收剂TG 2200g/t；镁精选药剂制度：捕收剂TG1000 g/t；镁扫选药剂制度：硫酸900g/t，捕收剂TG 500g/t。磷粗选药剂制度：碳酸钠12000g/t，捕收剂TP 2800g/t；磷扫选药剂制度：碳酸钠800g/t。得到钙镁组分产率63％，MgO品位23.76％，CaO品位37.07％。
表7浮选处理后钙镁质组分化学多元素分析
Figure BDA0002341046830000042
将上述得到的钙镁质组分在950℃条件下煅烧1h，升温速率20℃/min，进一步纯化，得到钙镁的氧化物其中钙镁质组分含量大于95％，P2O5≤1.8％，Al2O3+Fe2O3+SiO2+Mn3O4≤2.5％；然后以3:2的比例与水进行消化反应，反应时间8min，得到MgO含量40％的钙镁氢氧化物(主料1)。的钙镁氢氧化物(主料1)。将菱镁矿(理化性质同实施例1)进行精选、煅烧之后得到高纯度氧化镁(主料2)。
表8耐火材料基料配比表
Figure BDA0002341046830000043
按照表8配比，称取5kg基料高速混合改性机处理后，在干燥气氛中进行困料处理(48h)，然后造粒，在1500℃的环境中煅烧6h得到耐火材料制品。
经检测耐火材料性能为：堆积密度为3.40g/cm3、显气孔率11.2％、常温抗压强度63MPa、高温抗折强度5.7MPa、水化试验增重率2.61％。

Claims (6)

1.一种利用钙镁质磷矿尾矿生产水泥窑用耐火材料的方法，其特征在于，主要包括以下几个步骤：
（1）将镁钙质磷矿尾矿经过洗涤、分离、脱药、脱泥后烘干经镁浮选得到钙镁质组分，其中MgO品位19%，CaO品位35%；
（2）将步骤（1）的钙镁质组分经煅烧、消化处理得到钙镁氢氧化物（主料1）；
（3）将MgCO3含量大于98%的菱镁矿在温度为650℃-850℃下煅烧30min-60min，得到纯度为98%以上的氧化镁（主料2）；
（4）将步骤（2）中的钙镁氢氧化物、步骤（3）中的氧化镁、改性剂混匀，然后在湿度为10-15RH%中困料40-60h，得到干燥的混合物料；
（5）将步骤（4）中干燥的混合物料在1300-1700℃的环境中煅烧6h-10h，制成水泥窑成带的耐火材料。
2.根据权利要求1所述的利用钙镁质磷矿尾矿生产水泥窑用耐火材料的方法，其特征在于，步骤（1）中浮选镁过程中采用一粗一精一扫的方式，其中，粗选药剂制度：硫酸6000-10000g/t，捕收剂TG 1000-3000 g/t；镁精选药剂制度：捕收剂TG 500-1000 g/t；镁扫选药剂制度：硫酸500-1500g/t，捕收剂TG 500-1000g/t。
3.根据权利要求1所述的利用钙镁质磷矿尾矿生产水泥窑用耐火材料的方法，其特征在于，步骤（2）中钙镁质组分以20-50℃/min的升温速率生物至900℃-950℃，保温煅烧40min-90min。
4.根据权利要求1所述的利用钙镁质磷矿尾矿生产水泥窑用耐火材料的方法，其特征在于，所述改性剂包括氧化锆、氧化钛、或氧化钇。
5.根据权利要求1所述的利用钙镁质磷矿尾矿生产水泥窑用耐火材料的方法，其特征在于，步骤（4）中钙镁氢氧化物、氧化镁的质量比为1：1——1：3。
6.根据权利要求1所述的利用钙镁质磷矿尾矿生产水泥窑用耐火材料的方法，其特征在于，改性剂的添加量为钙镁氢氧化物、氧化镁总质量的2-3%。
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