CN114380617A - 一种磷尾矿-煤矸石基轻质隔热材料及其制备方法 - Google Patents

一种磷尾矿-煤矸石基轻质隔热材料及其制备方法 Download PDF

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CN114380617A
CN114380617A CN202210012993.9A CN202210012993A CN114380617A CN 114380617 A CN114380617 A CN 114380617A CN 202210012993 A CN202210012993 A CN 202210012993A CN 114380617 A CN114380617 A CN 114380617A
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coal gangue
tailings
based light
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phosphorus
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叶义成
黄洋
胡南燕
罗斌玉
柯丽华
张光权
王其虎
姚囝
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Wuhan University of Science and Engineering WUSE
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Abstract

一种磷尾矿‑煤矸石基轻质隔热材料及其制备方法。其技术方案是：以50～80wt％的磷尾矿和20～50wt％的煤矸石为原料，混匀，外加所述原料6～32wt％的水，搅拌，即得混合料；将所述混合料困料12～24h，浇注成型，自然干燥，90～110℃条件下烘干24～48h，即得预处理料；将所述预处理料先以4～6℃/min的速率从室温升温至360～400℃，再以2～4℃/min的速率升温至670～750℃，然后以10～12℃/min的速率升温至1100～1500℃，保温3～7h，随炉冷却，制得磷尾矿‑煤矸石基轻质隔热材料。本发明具有再利用率高、生产成本低和工艺简单的特点，所制备的磷尾矿‑煤矸石基轻质隔热材料耐压强度高、气孔率高和导热系数低。

Description

一种磷尾矿-煤矸石基轻质隔热材料及其制备方法
技术领域
本发明属于磷尾矿-煤矸石再利用技术领域。具体涉及一种磷尾矿-煤矸石基轻质隔热材料及其制备方法。
背景技术
磷尾矿是低品位磷矿石经选矿富集P2O5后产生的固体废物。目前磷尾矿的堆存量逐年攀升，不仅占用大量土地，而且存在植被破坏、水源污染等以及溃坝的安全风险。磷尾矿的主要矿物组成为白云石(CaMg(CO3)2)，主要由CaO和MgO组成，还包括约10wt％的易挥发性物质(P2O5、SO3)和30wt％左右的有机物。
煤矸石是成煤过程中与煤伴生的，存在于煤炭周围或者夹层中的黑灰色岩石，是煤炭采掘和洗选加工过程中产生的固体废物。煤矸石是排放量较大的大宗工业固体废物之一。大量的煤矸石堆存，不仅占用大量土地，而且还存在含有害物质浸出而污染土壤和淡水、自燃以及溃坝的安全问题。煤矸石的主要矿物组成为黏土类矿物和砂岩，主要由SiO2、Al2O3和C组成，还包括20wt％以上的烃系和萘系有机物。
目前，关于磷尾矿再利用的技术有：“一种地聚合物稳定磷尾矿路面基层及其制备方法”(CN113548843A)专利技术，公开了一种以磷尾矿为主要原料用于路面基层的技术，该技术很大程度上解决了磷尾矿的利用问题，但是技术中磷尾矿仅仅是代替砂石起到骨架的作用，其中石英、白云石等有用成分没有得到充分利用，没有体现可用成分的价值，磷尾矿的利用附加值不高；“一种利用钙镁质磷尾矿生产水泥窑用耐火材料”(CN111116175A)专利技术，公开了一种利用磷尾矿制备水泥窑用耐火材料的方法，但该技术是将磷尾矿进行再次浮选获得钙镁组分，需要经过一系列的洗涤、分离、脱药等过程，工艺复杂，生产周期长，大量试剂的添加显著增加了成本，并且磷尾矿不足以完全充当钙镁质的原料，因此加入量不大。
目前，关于煤矸石再利用的技术有：“一种利用煤矸石制备轻质保温墙体材料的方法”(CN104446628A)专利技术，公开了一种以煤矸石为主要原料添加助溶剂和添加剂制备轻质保温墙体材料的专利技术，虽解决了煤矸石的附加值不高的问题，但存在造粒、球磨和切割等繁琐的工艺过程，添加碳化硅和硫酸钙等发泡剂增加了成本，且制备的产品耐压强度不高；“一种轻质隔热耐火陶瓷材料的制备方法”(CN108033749A)专利技术，公开了一种以煤矸石为主要原料，添加莫来石纤维制备轻质隔热耐火陶瓷材料的专利技术，该技术制备的产品附加值虽较高，但是添加大量莫来石纤维占用了资源，增加了成本，并且制备工艺复杂，不适合工业化生产；“利用纯煤矸石生产自保温烧结砖的方法”(CN101672083A)专利技术，公开了一种以煤矸石、煤粉和煤灰等固体废物为原料，通过添加造孔剂制备自保温烧结砖的专利技术，该技术虽制备工艺简单，所制备的自保温烧结砖存在孔隙率较低和热导率较高的问题。
目前，关于磷尾矿的再利用主要为路面基层和耐火原料等领域，未见用于轻质隔热耐火材料的公开报道；煤矸石虽用于制备轻质隔热耐火材料，但技再利用率低、工艺复杂和生产成本高，制备的轻质隔热材料耐压强度低和导热系数高。
发明内容
本发明旨在克服现有的技术缺陷，目的在于提供一种磷尾矿和煤矸石再利用率高、生产成本低和工艺简单的磷尾矿-煤矸石基轻质隔热材料的制备方法，用该方法制备的磷尾矿-煤矸石基轻质隔热材料耐压强度高、气孔率高和导热系数低。
为实现上述目的，本发明采用的技术方案的步骤是：
步骤一、先以50～80wt％的磷尾矿和20～50wt％的煤矸石为原料，混合均匀，再加入占所述原料6～32wt％的水，搅拌，即得混合料。
步骤二、将所述混合料困料12～24h，浇注成型，自然干燥，90～110℃条件下烘干24～48h，即得预处理料。
步骤三、将所述预处理料先以4～6℃/min的速率从室温升温至360～400℃，再以2～4℃/min的速率升温至670～750℃，然后以10～12℃/min的速率升温至1100～1500℃，保温3～7h，随炉冷却，制得磷尾矿-煤矸石基轻质隔热材料。
所述磷尾矿中CaO+MgO含量≥50wt％，磷尾矿的平均粒度≤50μm。
所述煤矸石为黏土质煤矸石，所述煤矸石：Al/Si的摩尔比≥0.3，C含量≥10wt％；所述煤矸石的平均粒度≤75μm。
由于采用上述技术方案，本发明与现有技术相比，具有如下积极效果：
本发明以磷尾矿和煤矸石为原料进行固废回收利用，再利用率高，避免了直接堆放而带来的土地、环境和安全问题，节约了大量资源、降低了生产成本。本发明经混合、成型、烘干、烧结后即可应用于工业炉窑节能保温行业，生产工艺简单，适合工业化生产。
本发明采用直接加水浇注成型，磷尾矿中的MgO或CaO水化能提高强度，且煤矸石中的黏土类矿物有很好的胶凝作用，能替代结合剂充当胶黏材料，达到成型的目的。无需额外添加结合剂，无需模压成型，节约成本且操作简单。
本发明制备的磷尾矿-煤矸石基轻质隔热材料耐压强度高、气孔率高和导热系数低，具体理由是：
一方面，磷尾矿和煤矸石主要由CaO、MgO、Al2O3、SiO2等非金属氧化物组成，CaO、MgO、Al2O3和SiO2均为耐高温氧化物，在高温下：CaO+Al2O3+2SiO2→CaOAl2O32SiO2或2MgO+2Al2O3+5SiO2→2MgO2Al2O35SiO2。根据CaO-MgO-Al2O3-SiO2相图知，存在多种高熔点化合物，如镁橄榄石(2MgOSiO2)、莫来石(3Al2O32SiO2)、镁铝尖晶石(MA)、钙长石(CaOAl2O32SiO2)和堇青石(2MgO2Al2O35SiO2)等。因此，磷尾矿和煤矸石能制备CaO-MgO-Al2O3-SiO2等耐高温材料。其中，MA具有热导率低、耐磨损、高强度、高硬度和抗冲击等良好的理化性能，莫来石具有优良的高温力学机械性能，镁橄榄石热导率低，堇青石有很强的热稳定性，钙长石具有低的热导率。通过调节磷尾矿和煤矸石的比例，能实现在高温下反应生成上述高熔点化合物的一种或多种，因此，本发明制备的磷尾矿-煤矸石基轻质隔热材料具有耐压强度高、气孔率高和导热系数低等特点。
另一方面，磷尾矿主要矿物组成为白云石(CaMg(CO3)2)，还包括约10wt％的易挥发性物质(P2O5、SO3)和30wt％左右的有机物，煤矸石含有大量的C和有机物。在310～400℃时，C燃烧生成气体溢出；在710～800℃时，CaMg(CO3)2分解成CaCO3、MgO和CO2；在800～870℃时，CaCO3分解成CaO，放出CO2。由于C烧失和CaMg(CO3)2的分解，CO2的释放，原本由这些颗粒占据的空间变空了，进而产生相当水平的颗粒间的孔隙，增加了磷尾矿-煤矸石基轻质隔热材料的气孔率。
其次，磷尾矿中的P2O5与SO3在低温下相继挥发，同时，有机物在高温下分解，同时产生CO2和水蒸气等气体。物质的挥发和分解产生气体溢出，释放了原本占据的空间，使材料内部产生孔洞，进一步增加了磷尾矿-煤矸石基轻质隔热材料的孔隙率。
因此，磷尾矿和煤矸石中的有机物、P2O5、SO3以及C的烧失和CaMg(CO3)2的分解均能作为低温和高温成孔剂，显著提高了磷尾矿-煤矸石基轻质隔热材料的气孔率和降低了导热系数。
本发明制备的磷尾矿-煤矸石基轻质隔热材料经检测：耐压强度为4.1～13.9MPa，气孔率为57～90％，体积密度为0.47～0.85g/cm3，导热系数为0.13～0.23W/(m·K)(600℃)。
因此，本发明具有再利用率高、生产成本低和工艺简单的特点，所制备的磷尾矿-煤矸石基轻质隔热材料耐压强度高、气孔率高和导热系数低。
具体实施方式
下面结合具体实施方式对本发明作进一步的描述，并非对其保护范围的限制。
本具体实施方式中：
所述磷尾矿的平均粒度≤50μm；
所述煤矸石为黏土质煤矸石，所述煤矸石的平均粒度≤75μm。
实施例中不再赘述。
实施例1
一种磷尾矿-煤矸石基轻质隔热材料及其制备方法。本实施例所述制备方法的步骤是：
步骤一、先以50～57wt％的磷尾矿和43～50wt％的煤矸石为原料，混合均匀，再加入占所述原料25～32wt％的水，搅拌，即得混合料。
步骤二、将所述混合料困料12～15h，浇注成型，自然干燥，90～95℃条件下烘干42～48h，即得预处理料。
步骤三、将所述预处理料先以4～4.5℃/min的速率从室温升温至390～400℃，再以2～2.5℃/min的速率升温至670～690℃，然后以10～10.5℃/min的速率升温至1100～1200℃，保温3～4h，随炉冷却，制得磷尾矿-煤矸石基轻质隔热材料。
所述磷尾矿中CaO+MgO含量为50～52wt％。
所述煤矸石：Al/Si的摩尔比≥0.36，C含量≥13wt％。
本实施例制备的磷尾矿-煤矸石基轻质隔热材料经检测：耐压强度为4.1～10.6MPa；气孔率为71～90％；体积密度为0.47～0.73g/cm3；导热系数为0.13～0.17W/(m·K)(600℃)。
实施例2
一种磷尾矿-煤矸石基轻质隔热材料及其制备方法。本实施例所述制备方法的步骤是：
步骤一、先以57～65wt％的磷尾矿和35～43wt％的煤矸石为原料，混合均匀，再加入占所述原料18～25wt％的水，搅拌，即得混合料。
步骤二、将所述混合料困料15～18h，浇注成型，自然干燥，95～100℃条件下烘干36～42h，即得预处理料。
步骤三、将所述预处理料先以4.5～5℃/min的速率从室温升温至380～390℃，再以2.5～3℃/min的速率升温至690～710℃，然后以10.5～11℃/min的速率升温至1200～1300℃，保温4～5h，随炉冷却，制得磷尾矿-煤矸石基轻质隔热材料。
所述磷尾矿中CaO+MgO含量为52～54wt％。
所述煤矸石：Al/Si的摩尔比为0.34～0.36，C含量为12～13wt％。
本实施例制备的磷尾矿-煤矸石基轻质隔热材料经检测：耐压强度为5.9～11.9MPa；气孔率为66～87％；体积密度为0.53～0.76g/cm3；导热系数为0.16～0.19W/(m·K)(600℃)。
实施例3
一种磷尾矿-煤矸石基轻质隔热材料及其制备方法。本实施例所述制备方法的步骤是：
步骤一、先以65～72wt％的磷尾矿和28～35wt％的煤矸石为原料，混合均匀，再加入占所述原料12～18wt％的水，搅拌，即得混合料。
步骤二、将所述混合料困料18～21h，浇注成型，自然干燥，100～105℃条件下烘干30～36h，即得预处理料。
步骤三、将所述预处理料先以5～5.5℃/min的速率从室温升温至370～380℃，再以3～3.5℃/min的速率升温至710～730℃，然后以11～11.5℃/min的速率升温至1300～1400℃，保温5～6h，随炉冷却，制得磷尾矿-煤矸石基的CaO-SiO2-Al2O3-MgO质轻质隔热材料。
所述磷尾矿中CaO+MgO含量为54～56wt％。
所述煤矸石：Al/Si的摩尔比为0.32～0.34，C含量为11～12wt％。
本实施例制备的磷尾矿-煤矸石基轻质隔热材料经检测：耐压强度为7.2～12.8MPa；气孔率为61～80％；体积密度为0.60～0.81g/cm3；导热系数为0.18～0.22W/(m·K)(600℃)。
实施例4
一种磷尾矿-煤矸石基轻质隔热材料及其制备方法。本实施例所述制备方法的步骤是：
步骤一、先以72～80wt％的磷尾矿和20～28wt％的煤矸石为原料，混合均匀，再加入占所述原料6～12wt％的水，搅拌，即得混合料。
步骤二、将所述混合料困料21～24h，浇注成型，自然干燥，105～110℃条件下烘干24～30h，即得预处理料。
步骤三、将所述预处理料先以5.5～6℃/min的速率从室温升温至360～370℃，再以3.5～4℃/min的速率升温至730～750℃，然后以11.5～12℃/min的速率升温至1400～1500℃，保温6～7h，随炉冷却，制得磷尾矿-煤矸石基轻质隔热材料。
所述磷尾矿中CaO+MgO含量≥56wt％。
所述煤矸石：Al/Si的摩尔比为0.3～0.32，C含量为10～11wt％。
本实施例制备的磷尾矿-煤矸石基轻质隔热材料经检测：耐压强度为8.1～13.9MPa；气孔率为57～75％；体积密度为0.64～0.85g/cm3；导热系数为0.19～0.23W/(m·K)(600℃)。
本具体实施方式与现有技术相比，具有如下积极效果：
本具体实施方式能有效地结合磷尾矿和煤矸石进行固废回收利用，提高了固废利用率，避免了直接堆放而带来的土地、环境和安全问题，节约了大量资源、降低了生产成本。本具体实施方式经混合、成型、烘干、烧结后即可应用于工业炉窑节能保温行业，生产工艺简单，适合工业化生产。
本具体实施方式采用直接加水浇注成型，磷尾矿中的MgO或CaO水化能提高强度，且煤矸石中的黏土类矿物有很好的胶凝作用，能替代结合剂充当胶黏材料，达到成型的目的。无需额外添加结合剂，无需模压成型，节约成本且操作简单。
本具体实施方式制备的磷尾矿-煤矸石基轻质隔热材料耐压强度高、气孔率高和导热系数低，具体理由是：
一方面，磷尾矿和煤矸石主要由CaO、MgO、Al2O3、SiO2等非金属氧化物组成，CaO、MgO、Al2O3和SiO2均为耐高温氧化物，在高温下：CaO+Al2O3+2SiO2→CaOAl2O32SiO2或2MgO+2Al2O3+5SiO2→2MgO2Al2O35SiO2。根据CaO-MgO-Al2O3-SiO2相图知，存在多种高熔点化合物，如镁橄榄石(2MgOSiO2)、莫来石(3Al2O32SiO2)、镁铝尖晶石(MA)、钙长石(CaOAl2O32SiO2)和堇青石(2MgO2Al2O35SiO2)等。因此，磷尾矿和煤矸石能制备CaO-MgO-Al2O3-SiO2等耐高温材料。其中，MA具有热导率低、耐磨损、高强度、高硬度和抗冲击等良好的理化性能，莫来石具有优良的高温力学机械性能，镁橄榄石热导率低，堇青石有很强的热稳定性，钙长石具有低的热导率。通过调节磷尾矿和煤矸石的比例，能实现在高温下反应生成上述高熔点化合物的一种或多种，因此，本具体实施方式制备的磷尾矿-煤矸石基轻质隔热材料具有耐压强度高、气孔率高和导热系数低等特点。
另一方面，磷尾矿主要矿物组成为白云石(CaMg(CO3)2)，还包括约10wt％的易挥发性物质(P2O5、SO3)和30wt％左右的有机物，煤矸石含有大量的C和有机物。在310～400℃时，C燃烧生成气体溢出；在710～800℃时，CaMg(CO3)2分解成CaCO3、MgO和CO2；在800～870℃时，CaCO3分解成CaO，放出CO2。由于C烧失和CaMg(CO3)2的分解，CO2的释放，原本由这些颗粒占据的空间变空了，进而产生相当水平的颗粒间的孔隙，增加了磷尾矿-煤矸石基轻质隔热材料的气孔率。
其次，磷尾矿中的P2O5与SO3在低温下相继挥发，同时，有机物在高温下分解，同时产生CO2和水蒸气等气体。物质的挥发和分解产生气体溢出，释放了原本占据的空间，使材料内部产生孔洞，进一步增加了磷尾矿-煤矸石基轻质隔热材料的孔隙率。
因此，磷尾矿和煤矸石中的有机物、P2O5、SO3以及C的烧失和CaMg(CO3)2的分解均能作为低温和高温成孔剂，显著提高了磷尾矿-煤矸石基轻质隔热材料的气孔率和降低了导热系数。
本具体实施方式制备的磷尾矿-煤矸石基轻质隔热材料经检测：耐压强度为4.1～13.9MPa；气孔率为57～90％；体积密度为0.47～0.85g/cm3；导热系数为0.13～0.23W/(m·K)(600℃)。
因此，本具体实施方式具有磷尾矿和煤矸石再利用率高、生产成本低和工艺简单的特点，所制备的磷尾矿-煤矸石基轻质隔热材料耐压强度高、气孔率高和导热系数低。

Claims (4)

1.一种磷尾矿-煤矸石基轻质隔热材料的制备方法，其特征在于所述制备方法的步骤是：
步骤一、先以50～80wt％的磷尾矿和20～50wt％的煤矸石为原料，混合均匀，再加入占所述原料6～32wt％的水，搅拌，即得混合料；
步骤二、将所述混合料困料12～24h，浇注成型，自然干燥，于90～110℃条件下烘干24～48h，即得预处理料；
步骤三、将所述预处理料先以4～6℃/min的速率从室温升温至360～400℃，再以2～4℃/min的速率升温至670～750℃，然后以10～12℃/min的速率升温至1100～1500℃，保温3～7h，随炉冷却，制得磷尾矿-煤矸石基轻质隔热材料。
2.根据权利要求1所述的磷尾矿-煤矸石基轻质隔热材料的制备方法，其特征在于所述磷尾矿中CaO+MgO含量≥50wt％，磷尾矿的平均粒度≤50μm。
3.根据权利要求1所述的磷尾矿-煤矸石基轻质隔热材料的制备方法，其特征在于所述煤矸石为黏土质煤矸石，所述煤矸石：Al/Si的摩尔比≥0.3，C含量≥10wt％；所述煤矸石的平均粒度≤75μm。
4.根据权利要求1所述的磷尾矿-煤矸石基轻质隔热材料的制备方法，其特征在于所述磷尾矿-煤矸石基轻质隔热材料是根据权利要求1～3项中的任一项所述的一种磷尾矿-煤矸石基轻质隔热材料的制备方法所制备的磷尾矿-煤矸石基轻质隔热材料。
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