CN113087496A - 一种以磷尾矿为主要原料的镁钙材料及其制备方法 - Google Patents
一种以磷尾矿为主要原料的镁钙材料及其制备方法 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 74
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 60
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 title claims abstract description 60
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 60
- 239000010452 phosphate Substances 0.000 title claims abstract description 60
- 239000002994 raw material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000843 powder Substances 0.000 claims abstract description 49
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 48
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000011574 phosphorus Substances 0.000 claims abstract description 47
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 23
- 235000012245 magnesium oxide Nutrition 0.000 claims abstract description 23
- 239000000292 calcium oxide Substances 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 13
- 235000014380 magnesium carbonate Nutrition 0.000 claims abstract description 13
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract description 6
- 239000011819 refractory material Substances 0.000 abstract description 16
- 230000036571 hydration Effects 0.000 abstract description 14
- 238000006703 hydration reaction Methods 0.000 abstract description 14
- 239000000919 ceramic Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 20
- 239000011575 calcium Substances 0.000 description 14
- 229910052791 calcium Inorganic materials 0.000 description 10
- 238000010586 diagram Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 239000002699 waste material Substances 0.000 description 6
- 239000001506 calcium phosphate Substances 0.000 description 5
- 229910000389 calcium phosphate Inorganic materials 0.000 description 5
- 235000011010 calcium phosphates Nutrition 0.000 description 5
- 239000010459 dolomite Substances 0.000 description 5
- 229910000514 dolomite Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005188 flotation Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 5
- 230000004584 weight gain Effects 0.000 description 5
- 235000019786 weight gain Nutrition 0.000 description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011469 building brick Substances 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000004137 magnesium phosphate Substances 0.000 description 2
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 2
- 229960002261 magnesium phosphate Drugs 0.000 description 2
- 235000010994 magnesium phosphates Nutrition 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910004762 CaSiO Inorganic materials 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 229940077441 fluorapatite Drugs 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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Abstract
本发明涉及一种以磷尾矿为主要原料的镁钙材料及其制备方法。其技术方案是:先将磷尾矿粉在1050~1150℃条件下保温2~4小时,冷却,得到轻烧粉;再将90~98wt%的所述轻烧粉与2~10wt%的镁砂粉混合,成型;然后于1600~1700℃条件下保温2~5小时,冷却,制得以磷尾矿为主要原料的镁钙材料。所述磷尾矿粉的粒径为1~200μm;所述磷尾矿粉:P2O5含量≤2wt%,MgO含量≥18wt%,CaO含量≥28wt%。所述镁砂细粉的粒径为1~200μm;所述镁砂细粉的MgO含量≥96wt%。本发明能提高资源化利用、工艺简单、成本低和环境友好,所制备的以磷尾矿为主要原料的镁钙材料抗水化性能好、耐火度高、磷含量低和体积密度大,是制备高温陶瓷和耐火材料的优质原料。
Description
技术领域
本发明属于镁钙材料技术领域。尤其涉及一种以磷尾矿为主要原料的镁钙材料及其制备方法。
背景技术
磷尾矿是磷矿企业通过浮选磷矿石后产生的固体废料,每万吨磷矿石浮选会产生30-40%的磷尾矿,每年产生的磷尾矿总量很大(黎继永,童雄,韩彬等.磷尾矿综合利用研究进展.矿产保护与利用,2015,(5):5-11)。浮选后的磷尾矿中主要成分为白云石、方解石及氟磷灰石等,如果直接丢弃会造成资源的巨大浪费。目前对磷尾矿的回收利用已经有很多研究,总体来说有以下几个方面:(1)磷尾矿再浮选;(2)制备水泥;(3)制备建筑用砖;(4)制备微晶玻璃;(5)制备植物复合肥;(6)回填矿山。
目前对磷尾矿的回收利用主要为再次浮选回收其中的MgO和P2O5,或者用于直接回填矿山、制备水泥、建筑用砖、复合肥和微晶玻璃等,虽然达到了一定程度的回收利用效果,但大部分还处于实验室研究阶段,并不能进行大规模的工业化使用;且主矿相白云石仍未得到有效利用,磷尾矿直接用于填充矿山并没有达到资源循环利用的效果,这会导致资源的浪费。近年来,随着对磷产品的需求与日俱增,导致大量磷尾矿的产生和堆积,不仅占用土地且易造成环境污染,因而磷尾矿的回收利用是亟需解决的一大问题。
镁钙质耐火材料作为一种碱性耐火材料,在不锈钢和洁净钢生产过程中起到非常重要的作用,而镁钙质耐火材料的主要原料就是镁钙砂。磷尾矿的主要成分就是白云石,煅烧后可以得到镁钙砂,但是直接采用磷尾矿一步煅烧制备镁钙砂,得到的材料往往孔径较大,结构疏松,同时,由于其中磷元素的存在导致材料在高温下出现过多的液相。所以全部采用一步煅烧磷尾矿制备的镁钙砂不能作为耐火材料基质部分用的原料,而只能用作耐火材料制备的颗粒材料,限制了磷尾矿的再利用效能。
发明内容
本发明旨在克服现有技术缺陷,目的在于提供一种能提高磷尾矿资源化利用、工艺简单、成本低和环境友好的以磷尾矿为主要原料的镁钙材料的制备方法,用该方法所制备的以磷尾矿为主要原料的镁钙材料耐火度高、磷含量低和抗水化性能好,不仅用作制备耐火材料的颗粒材料,且能作为耐火材料基质部分用料。
为实现上述目的,本发明所采用的技术方案是:
先将磷尾矿粉在1050~1150℃条件下保温2~4小时,冷却,得到轻烧粉;再将90~98wt%的所述轻烧粉与2~10wt%的镁砂粉混合,成型;然后于1600~1700℃条件下保温2~5小时,冷却,制得以磷尾矿为主要原料的镁钙材料。
所述磷尾矿粉的粒径为1~200μm;所述磷尾矿粉:P2O5含量≤2wt%,MgO含量≥18wt%,CaO含量≥28wt%。
所述镁砂细粉的粒径为1~200μm;所述镁砂细粉的MgO含量≥96wt%。
由于采用上述技术方案,本发明具有如下积极效果:
本发明先将磷尾矿粉轻烧,再与镁砂粉混合,成型,然后于1600~1700℃条件下烧成,冷却,制得以磷尾矿为主要原料的镁钙材料(以下简称镁钙材料),工艺简单;本发明以废弃物磷尾矿为主要原料,变废为宝,能有效降低镁钙材料的生产成本。
本发明以磷尾矿为主要原料制备镁钙材料,不仅能有效的回收利用固体废弃物磷尾矿,防止磷尾矿堆积对周边环境造成污染;也能回收利用磷尾矿中大量的镁钙元素降低对天然白云石矿的开采,从而节约资源,不仅实现了磷尾矿的资源化利用,且环境友好。
本发明利用了磷尾矿含磷的特性,在高温处理过程中,五氧化二磷和氧化钙、氧化镁在颗粒表面和颗粒之间形成性能稳定的新相,如磷酸钙和磷酸镁,将镁钙砂中游离的氧化钙与空气中的水蒸气隔离,极大地降低镁钙材料的水化速率,延长在空气中的存放时间,能显著提高镁钙材料的抗水化性能,有利于生产、运输和使用。再者,磷酸钙和磷酸镁等氧化物的形成在镁钙材料内形成了固-固结合形式,有利于提高镁钙材料的高温力学性能。本发明制备的镁钙材料抗水化性能好、耐火度高和体积密度大,不仅用作制备耐火材料的颗粒材料、且能作为耐火材料基质部分用料,是制备高温陶瓷和耐火材料的优质原料
本发明制备的镁钙材料经检测:P2O5含量≤3wt%;MgO含量≥40wt%;CaO含量≥48wt%;体积密度≥3.0g/cm3;耐火度>1800℃;在50℃和90%湿度条件下保持10h,再于110℃烘干,镁钙材料的水化增重率≤0.5%。
因此,本发明能提高磷尾矿资源化利用、工艺简单、成本低和环境友好,所制备的以磷尾矿为主要原料的镁钙材料抗水化性能好、耐火度高、磷含量低和体积密度大,不仅能作为制备耐火材料的颗粒材料,且能作为耐火材料基质部分用料,是制备高温陶瓷和耐火材料的优质原料。
附图说明
图1为本发明制备的一种以磷尾矿为主要原料的镁钙材料X射线衍射分析结果图;
图2是图1所示以磷尾矿为主要原料的镁钙材料的某区域Ca元素分布扫描图;
图3是图1所示以磷尾矿为主要原料的镁钙材料的某区域Mg元素分布扫描图;
图4是图1所示以磷尾矿为主要原料的镁钙材料的某区域Si元素分布扫描图;
图5是图1所示以磷尾矿为主要原料的镁钙材料的某区域P元素分布扫描图;
图6是图1所示以磷尾矿为主要原料的镁钙材料的某区域O元素分布扫描图;
图7为镁砂粉的加入量对以磷尾矿为主要原料的镁钙材料中液相量的影响。
图2~图6所述的某区域均为某同一区域。
具体实施方式
下面结合附图和具体实施方式对本发明做进一步的描述,并非对其保护范围的限制。
本具体实施方式中:
所述磷尾矿粉的粒径为1~200μm;所述磷尾矿粉:P2O5含量≤2wt%,MgO含量≥18wt%,CaO含量≥28wt%。
所述镁砂细粉的粒径为1~200μm;所述镁砂细粉的MgO含量≥96wt%。
实施例中不再赘述。
实施例1
一种以磷尾矿为主要原料的镁钙材料及其制备方法。本实施例所述制备方法是:
先将磷尾矿粉在1050~1080℃条件下保温3~4小时,冷却,得到轻烧粉;再将90~93wt%的所述轻烧粉与7~10wt%的镁砂粉混合,成型,然后于1600~1640℃条件下保温4~5小时,冷却,制得以磷尾矿为主要原料的镁钙材料。
本实施例制备的以磷尾矿为主要原料的镁钙材料经检测:P2O5含量为2.32~2.49wt%;MgO含量为42.50~45.20wt%;CaO为含量48.00~49.51wt%;体积密度为3.05~3.10g/cm3;耐火度>1800℃;在50℃和90%湿度条件下保持10h,再于110℃烘干,以磷尾矿为主要原料的镁钙材料的水化增重率为0.3~0.43%。
实施例2
一种以磷尾矿为主要原料的镁钙材料及其制备方法。本实施例所述制备方法是:
先将磷尾矿粉在1080~1120℃条件下保温2.5~3.5小时,冷却,得到轻烧粉;再将93~96wt%的所述轻烧粉与4~7wt%的镁砂粉混合,成型,然后于1640~1680℃条件下保温3~4小时,冷却,制得以磷尾矿为主要原料的镁钙材料。
本实施例制备的以磷尾矿为主要原料的镁钙材料经检测:P2O5含量为2.75~3.0wt%;MgO含量为40.00~43.50wt%;CaO含量为49.01~50.02wt%;体积密度为3.0~3.05g/cm3;耐火度>1800℃;在50℃和90%湿度条件下保持10h,再于110℃烘干,以磷尾矿为主要原料的镁钙材料的水化增重率为0.4~0.5%。
实施例3
一种以磷尾矿为主要原料的镁钙材料及其制备方法。本实施例所述制备方法是:
先将磷尾矿粉在1120~1150℃条件下保温2~3小时,冷却,得到轻烧粉;再将96~98wt%的所述轻烧粉与2~4wt%的镁砂粉混合,成型,然后于1680~1700℃条件下保温2~3小时,冷却,制得以磷尾矿为主要原料的镁钙材料。
本实施例制备的以磷尾矿为主要原料的镁钙材料经检测:P2O5为含量2.40~2.65wt%;MgO含量为44.51~46.52wt%;CaO含量为50.02~51.20wt%;体积密度为3.03~3.09g/cm3;耐火度>1800℃;在50℃和90%湿度条件下保持10h,再于110℃烘干,以磷尾矿为主要原料的镁钙材料的水化增重率为0.2~0.34wt%。
本具体实施方式具有如下积极效果:
本具体实施方式先将磷尾矿粉轻烧,再与镁砂粉混合,成型,然后于1600~1700℃条件下烧成,冷却,制得以磷尾矿为主要原料的镁钙材料(以下简称镁钙材料),工艺简单;本具体实施方式以废弃物磷尾矿为主要原料,变废为宝,能有效降低镁钙材料的生产成本。
本具体实施方式以磷尾矿为主要原料制备镁钙材料,不仅能有效的回收利用固体废弃物磷尾矿,防止磷尾矿堆积对周边环境造成污染;也能回收利用磷尾矿中大量的镁钙元素降低对天然白云石矿的开采,从而节约资源,不仅实现了磷尾矿的资源化利用,且环境友好。
本具体实施方式利用了磷尾矿含磷的特性,在高温处理过程中,五氧化二磷和氧化钙、氧化镁在颗粒表面和颗粒之间形成性能稳定的新相,如磷酸钙和磷酸镁,将镁钙砂中游离的氧化钙与空气中的水蒸气隔离,极大地降低镁钙材料的水化速率,延长在空气中的存放时间,能显著提高镁钙材料的抗水化性能,有利于生产、运输和使用。再者,磷酸钙和磷酸镁等氧化物的形成在镁钙材料内形成了固-固结合形式,有利于提高镁钙材料的高温力学性能。
本具体实施方式制备的以磷尾矿为主要原料的镁钙材料抗水化性能好、耐火度高、体积密度大,是制备高温陶瓷和耐火材料的优质原料。本具体实施方式制备的以磷尾矿为主要原料的镁钙材料如附图所示,图1为实施例3制备的一种以磷尾矿为主要原料的镁钙材料X射线衍射分析结果图;图2~图6为图1所示以磷尾矿为主要原料的镁钙材料的某同一区域的Ca、Mg、Si、P、O元素分布扫描图;图7为镁砂粉的加入量对以磷尾矿为主要原料的镁钙材料在高温下液相量的影响图。
从图1(由90wt%的磷尾矿粉和10wt%的镁砂粉混合后,在1700℃烧成的镁钙材料的X-射线衍射分析结果)可以看出,材料中的主要矿物为方钙石(CaO)、方镁石(MgO)和硅酸钙(CaSiO3),没有检测出含磷化合物,说明含磷化合物的含量很低。
从图2~图6可可以看出,磷元素、硅元素的分布主要和钙元素的区域重合,即,材料中存在磷酸钙类矿物和硅酸钙类矿物,且二者存在于同一区域。
从图7可以看出:5wt%左右的镁砂加入量是较为合适的,此时材料在高温下产生的液相数量最少,这也是本具体实施方式中镁砂加入量的依据。
本具体实施方式制备的镁钙材料经检测:P2O5含量≤3wt%;MgO含量≥40wt%;CaO含量≥48wt%;体积密度≥3.0g/cm3;耐火度>1800℃;在50℃和90%湿度条件下保持10h,再于110℃烘干,镁钙材料的水化增重率≤0.5%。
因此,本具体实施方式能提高磷尾矿资源化利用、工艺简单、成本低和环境友好,所制备的以磷尾矿为主要原料的镁钙材料抗水化性能好、耐火度高、磷含量低和体积密度大,不仅能作为制备耐火材料的颗粒材料,且能作为耐火材料基质部分用料,是制备高温陶瓷和耐火材料的优质原料。
Claims (4)
1.一种以磷尾矿为主要原料的镁钙材料制备方法,其特征在于:先将磷尾矿粉在1050~1150℃条件下保温2~4小时,冷却,得到轻烧粉;再将90~98wt%的所述轻烧粉与2~10wt%的镁砂粉混合,成型;然后于1600~1700℃条件下保温2~5小时,冷却,制得以磷尾矿为主要原料的镁钙材料。
2.根据权利要求1所述以磷尾矿为主要原料的镁钙材料的制备方法,其特征在于所述磷尾矿粉的粒径为1~200μm;所述磷尾矿粉:P2O5含量≤2wt%,MgO含量≥18wt%,CaO含量≥28wt%。
3.根据权利要求1所述以磷尾矿为主要原料的镁钙材料的制备方法,其特征在于所述镁砂细粉的粒径为1~200μm;所述镁砂细粉的MgO含量≥96wt%。
4.一种以磷尾矿为主要原料的镁钙材料,其特征在于所述以磷尾矿为主要原料的镁钙材料是根据权利要求1~3项中任一项所述以磷尾矿为主要原料的镁钙材料的制备方法所制备的以磷尾矿为主要原料的镁钙材料。
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