CN113832297B - 一种赤泥基复合铁酸钙及其制备方法和应用 - Google Patents

一种赤泥基复合铁酸钙及其制备方法和应用 Download PDF

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CN113832297B
CN113832297B CN202111215491.8A CN202111215491A CN113832297B CN 113832297 B CN113832297 B CN 113832297B CN 202111215491 A CN202111215491 A CN 202111215491A CN 113832297 B CN113832297 B CN 113832297B
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red mud
calcium ferrite
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composite calcium
calcium
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CN113832297A (zh
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张延玲
赵峥
张威风
余阚
张尧
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University of Science and Technology Beijing USTB
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Abstract

本发明提供了一种赤泥基复合铁酸钙及其制备方法和应用，属于冶金技术领域。本发明中复合铁酸钙的制备方法包括以下步骤：将赤泥与钙源进行混合，将所得混合料在含氧气氛下进行焙烧，得到赤泥基复合铁酸钙；所述钙源包括石灰或碳酸钙。本发明利用固体废弃物赤泥制备复合铁酸钙，原料成本大幅降低，另一方面，所制备得到的复合铁酸钙与传统铁酸钙相比，物相结构主要为CaFe2O4、Ca2FeAlO5和Ca2Fe2O5，其熔点更低、石灰溶解效率更高，在钢水初炼及精炼流程中应用时助熔和脱磷效果更优，具有广阔的工业应用前景。

Description

一种赤泥基复合铁酸钙及其制备方法和应用
技术领域
本发明涉及冶金技术领域，尤其涉及一种赤泥基复合铁酸钙及其制备方法和应用。
背景技术
铁酸钙是一种众所周知的优异的炼钢助熔剂和脱磷剂。铁酸钙熔点低、石灰溶解效率高，为炼钢脱磷提供了优异的热力学和动力学条件。
目前市场上的铁酸钙通常由铁精矿粉和石灰烧制而成，价格昂贵，造成炼钢成本过高。
发明内容
本发明的目的在于提供一种赤泥基复合铁酸钙及其制备方法和应用，本发明制备的赤泥基复合铁酸钙成本低，且在炼钢过程助熔和脱磷效果更优。
为了实现上述发明目的，本发明提供以下技术方案：
本发明提供了一种赤泥基复合铁酸钙的制备方法，包括以下步骤：
将赤泥与钙源进行混合，将所得混合料在含氧氛围下进行焙烧，得到赤泥基复合铁酸钙；所述钙源包括石灰或碳酸钙。
优选的，所述赤泥的用量以Fe2O3的摩尔含量计，所述钙源的用量以CaO的摩尔含量计，所述Fe2O3与CaO的摩尔比为1:0.8～1。
优选的，所述焙烧的温度为1000～1200℃；保温时间为0.5～2h。
优选的，所述焙烧前，还包括将所述混合料压制成团。
优选的，所述赤泥中Fe2O3的含量>40wt％，Al2O3的含量为10～15wt％。
优选的，所述石灰中有效氧化钙含量大于80wt％，所述碳酸钙中有效氧化钙含量大于50wt％。
优选的，所述含氧氛围包括空气氛围或氧气氛围。
本发明提供了上述方案所述制备方法制备得到的赤泥基复合铁酸钙，包括CaFe2O4、Ca2FeAlO5和Ca2Fe2O5。
优选的，以质量百分含量计，所述赤泥基复合铁酸钙包括5～15％CaFe2O4、5～15％Ca2FeAlO5和70～90％Ca2Fe2O5。
本发明提供了上述方案所述赤泥基复合铁酸钙在炼钢中的应用。
本发明提供了一种赤泥基复合铁酸钙的制备方法，包括以下步骤：将赤泥与钙源进行混合，将所得混合料在含氧氛围下进行焙烧，得到赤泥基复合铁酸钙；所述钙源包括石灰或碳酸钙。本发明利用固体废弃物赤泥制备复合铁酸钙，原料成本大幅降低，所制备得到的赤泥基复合铁酸钙的熔点为1050～1100℃，物相结构主要为CaFe2O4、Ca2FeAlO5和Ca2Fe2O5，与熔点为1150～1250℃的普通铁酸钙相比，本产品的熔点更低、石灰溶解效率提高约25％，在炼钢过程中应用时助熔和脱磷效果更优。
附图说明
图1为实施例1所用的赤泥原料、实施例1～2制备的复合铁酸钙和对比例1制备的铁酸钙的XRD图；
图2为测试例1脱磷试验的结果图，分别加入三种脱磷剂Fe2O3+CaO、Fe2O3+CaO+纯铁酸钙及Fe2O3+CaO+复合铁酸钙所得脱磷效果。
具体实施方式
本发明提供了一种赤泥基复合铁酸钙的制备方法，包括以下步骤：
将赤泥与钙源进行混合，将所得混合料在含氧氛围下进行焙烧，得到赤泥基复合铁酸钙；所述钙源包括石灰或碳酸钙。
本发明将赤泥与钙源进行混合，得到混合料。
在本发明中，所述赤泥优选为铝业生产产生的工业固废赤泥；所述赤泥中Fe2O3的含量优选>40wt％，Al2O3的含量优选为10～15wt％。进一步的，所述赤泥的化学组成优选包括Fe2O3：>40wt％，Al2O3：10～15wt％，SiO2：2～5wt％，TiO2：4～5wt％，Na2O：1～2wt％。在本发明中，所述赤泥的含水率优选小于8wt％。所述赤泥的粒径优选小于200目。
在本发明中，所述钙源包括石灰或碳酸钙；所述石灰中有效氧化钙含量优选大于80wt％，所述碳酸钙中有效氧化钙含量优选大于50wt％。在本发明中，所述石灰和碳酸钙的含水率优选小于1wt％。在本发明中，所述钙源的粒径优选小于200目。
本发明控制赤泥和钙源的含水率在上述范围，可以防止质量配比失衡，同时防止对设备产生不利影响。
在本发明中，所述赤泥的用量以Fe2O3的摩尔含量计，所述钙源的用量以CaO的摩尔含量计，所述Fe2O3与CaO的摩尔比优选为1:0.8～1，更优选为1:0.85～0.95，进一步优选为1:0.9。本发明通过控制Fe2O3与CaO的摩尔比在上述范围，进一步确保生成物的主要物相是铁酸钙(CaFe2O4和Ca2Fe2O5)和铁铝酸钙(Ca2FeAlO5)。
本发明对所述混合的过程没有特殊要求，本领域熟知的能够混合均匀的方式均可。在本发明的实施例中，具体是采用搅拌机混匀2min。
得到混合料后，本发明优选将所述混合料压制成团，然后在含氧氛围下进行焙烧，得到赤泥基复合铁酸钙。
本发明对所述压制成团的方式没有特殊要求，本领域熟知的压制成团的方式均可。本发明对成团的尺寸和形状没有特殊要求，在本发明的实施例中，具体是压制成D10mm×H10mm的圆柱块。本发明通过压制成团使赤泥与钙源的混合料具有一定强度，方便烧结，结合更紧密，反应性更好。
在本发明中，所述焙烧的温度优选为1000～1200℃，更优选为1050～1150℃，进一步优选为1100℃；所述焙烧的保温时间优选为0.5～2h，更优选为1.0～1.5h。在本发明中，升温至所述焙烧的温度的升温速率优选为5℃/min。在本发明中，所述含氧氛围优选为空气氛围或氧气氛围。
本发明在所述焙烧过程中，赤泥中的Fe2O3、Al2O3与CaO发生反应，生成以CaFe2O4、Ca2FeAlO5和Ca2Fe2O5为主的物相。
本发明对所述焙烧设备没有特殊要求，本领域熟知的高温加热设备均可。在本发明的实施例中，所述焙烧优选在横式高温电阻炉中进行。
焙烧后，本发明优选将所得固相物进行冷却，得到赤泥基复合铁酸钙。
本发明在制备赤泥基复合铁酸钙的过程中，采用工业固废赤泥作为制备原料。拜耳法生产氧化铝过程中产生的赤泥，Fe2O3含量较高。这些拜耳赤泥经晾干(水分含量<8％)可直接作为原料制备复合铁酸钙，生产成本远低于市场上通用的铁酸钙产品。
本发明提供了上述方案所述制备方法制备得到的赤泥基复合铁酸钙，包括CaFe2O4、Ca2FeAlO5和Ca2Fe2O5。以质量百分含量计，所述复合铁酸钙优选包括5～15％CaFe2O4、5～15％Ca2FeAlO5和70～90％Ca2Fe2O5。在本发明的实施例中，所述复合铁酸钙包括12％CaFe2O4、10％Ca2FeAlO5和72％Ca2Fe2O5，或者包括15％CaFe2O4、10％Ca2FeAlO5和70％Ca2Fe2O5，余量为其他反应物。
本发明制备的赤泥基复合铁酸钙，其主要物相为CaFe2O4、Ca2FeAlO5和Ca2Fe2O5，与铁酸钙相比，其熔点更低、石灰溶解效率更高，炼钢过程中作为助熔剂和/或脱磷剂使用，可有效缩短冶炼周期、大幅提高脱磷效率。
本发明提供了上述方案所述复合铁酸钙在炼钢中的应用。在本发明中，所述复合铁酸钙优选作为炼钢过程中的助熔剂和/或脱磷剂使用。在本发明中，所述炼钢优选包括初炼和/或精炼。本发明对所述应用的方法没有特殊要求，采用本领域熟知的应用方法即可。
下面结合实施例对本发明提供的复合铁酸钙及其制备方法和应用进行详细的说明，但是不能把它们理解为对本发明保护范围的限定。
实施例1
a.将国内某企业的拜耳赤泥(其中，Fe2O3：65wt％，Al2O3：12wt％，SiO2：3wt％，TiO2：4wt％，Na2O：1.5wt％)、石灰粉磨细，过200目筛取筛下物；按照Fe2O3与CaO的摩尔比为1:1进行计算，称取赤泥100g、石灰粉30g，用搅拌机混匀2min后，压制成D10mm×H10mm的圆柱块。
b.将料块放入横式高温电阻炉，以5℃/min升温至1100℃，在空气气氛中，保温2h，固相经冷却后得到赤泥基复合铁酸钙，记为1100℃-30％CaO，包括12％CaFe2O4、10％Ca2FeAlO5和72％Ca2Fe2O5。
实施例2
a.将国内某企业的拜耳赤泥(其中，Fe2O3：65wt％，Al2O3：12wt％，SiO2：3wt％，TiO2：4wt％，Na2O：1.5wt％)、石灰粉磨细，过200目筛取筛下物；按照Fe2O3与CaO的摩尔比为1:0.8进行计算，称取赤泥100g、石灰粉25g，用搅拌机混匀2min后，无需压块，直接放入坩埚中。
b.将坩埚放入横式高温电阻炉，以5℃/min升温至1100℃，在空气气氛中，保温2h，固相经冷却后得到赤泥基复合铁酸钙，记为1100℃-25％CaO，包括15％CaFe2O4、10％Ca2FeAlO5和70％Ca2Fe2O5。
对比例1
采用纯物质Fe2O3和CaO制备铁酸钙，具体制备步骤如下：
将74.1g Fe2O3和25.9gCaO粉末搅拌2min充分混合，压制成D10mm×H10mm的圆柱块，将圆柱块放入横式高温电阻炉，以5℃/min升温至1200℃，在空气气氛中保温2h，固相经冷却后得到铁酸钙，记为1200℃-铁酸钙，包括25％CaFe2O4、75％Ca2Fe2O5。
结构表征：
对实施例1所用的赤泥原料、实施例1～2制备的赤泥基复合铁酸钙和对比例1制备的铁酸钙进行XRD表征，结果如图1所示。由图1可知，对比原料和纯铁酸钙，本发明利用赤泥与石灰煅烧的产物中除铁酸钙的同类物相外，还包含Ca2FeAlO5物相，不存在未反应的Fe2O3。
测试例1
取初始[P]含量为0.20～0.25wt％、[C]含量4.0wt％、[Si]含量0.4wt％的生铁块进行脱磷试验，温度1410℃，分三组分别加入Fe2O3+CaO、Fe2O3+CaO+纯铁酸钙、Fe2O3+CaO+实施例1赤泥基复合铁酸钙。其中，控制三组中所含初始Fe2O3与CaO总含量一致。具体的，脱磷剂Fe2O3+CaO占铁水质量20％，其中Fe2O3的含量为85％，CaO的含量为15％；Fe2O3+CaO+纯铁酸钙的总加入量占铁水质量的20％，其中Fe2O3的含量为67％，CaO的含量为8.4％，纯铁酸钙含量为24.6％；Fe2O3+CaO+实施例1赤泥基复合铁酸钙的加入量占铁水质量的20％，其中，Fe2O3的含量为66.5％，CaO的含量为7.8％，实施例1赤泥基复合铁酸钙的含量为25.7％；取反应0min、5min、10min时铁水样后，测铁水[P]含量，对比三种不同条件下脱磷效果。结果如图2所示。
由图2可知，在高磷条件下，第一种类型Fe2O3+CaO代表当前炼钢脱磷最常用的方法，10min内终点[P]含量0.123wt％。第二种类型加入部分纯铁酸钙，添加量控制为25％，10min内终点[P]含量0.0995wt％，脱磷效果优于第一种类型。第三种类型添加部分用实施例1制备的复合铁酸钙，10min内终点[P]含量0.0215wt％，脱磷效果优于前两种类型。综上，采用本发明制备的赤泥基复合铁酸钙脱磷效率高，效果优异。
测试例2
参照性能测试1的过程进行测试，取初始[P]含量为0.20～0.25wt％、[C]含量4.0wt％、[Si]含量0.4wt％的生铁块进行脱磷试验，温度1410℃，加入Fe2O3+CaO+实施例2赤泥基复合铁酸钙。其中，脱磷剂加入量占铁水质量的20％，其中，Fe2O3的含量为66.5％，CaO的含量为8.5％，实施例2赤泥基复合铁酸钙的含量为25％，反应10min后取铁水样，测铁水[P]含量，[P]含量为达到合格水平，为0.032wt％。
由以上实施例和对比例可知，本发明提供了复合铁酸钙的制备方法和应用，本发明制备的复合铁酸钙成本低，且在炼钢过程助熔和脱磷效果更优。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (6)

1.一种赤泥基复合铁酸钙的制备方法，包括以下步骤：
将赤泥与钙源进行混合，将所得混合料在含氧氛围下进行焙烧，得到赤泥基复合铁酸钙；所述钙源包括石灰或碳酸钙；
所述赤泥的用量以Fe2O3的摩尔含量计，所述钙源的用量以CaO的摩尔含量计，所述Fe2O3与CaO的摩尔比为1:0.8~1；
所述焙烧的温度为1000~1200℃；保温时间为0.5~2h；
所述赤泥中Fe2O3的含量>40wt%，Al2O3的含量为10~15wt%；
以质量百分含量计，所述赤泥基复合铁酸钙包括5~15%CaFe2O4、5~15%Ca2FeAlO5和70~90%Ca2Fe2O5；所述赤泥基复合铁酸钙的熔点为1050~1100℃。
2.根据权利要求1所述的制备方法，其特征在于，所述焙烧前，还包括将所述混合料压制成团。
3.根据权利要求1所述的制备方法，其特征在于，所述石灰中有效氧化钙含量大于80wt%，所述碳酸钙中有效氧化钙含量大于50wt%。
4.根据权利要求1所述的制备方法，其特征在于，所述含氧氛围包括空气氛围或氧气氛围。
5.权利要求1~4任一项所述制备方法制备得到的赤泥基复合铁酸钙，包括CaFe2O4、Ca2FeAlO5和Ca2Fe2O5；以质量百分含量计，所述赤泥基复合铁酸钙包括5~15%CaFe2O4、5~15%Ca2FeAlO5和70~90%Ca2Fe2O5。
6.权利要求5所述赤泥基复合铁酸钙在炼钢中的应用。
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