CN110818389A - 一种赤泥制备空心陶瓷微球回收钠的方法 - Google Patents
一种赤泥制备空心陶瓷微球回收钠的方法 Download PDFInfo
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Abstract
本发明涉及一种低密度高强度空心陶瓷微球的制备及钠回收的方法,该空心陶瓷微球是由氧化铝生产的残渣赤泥制得的,渣中含有二氧化硅、铁的氧化物、氧化钠、氧化钙、三氧化二铝。用改造过的火焰喷枪熔射添加了0‑15%的生物质的赤泥粉末;生物质改善赤泥的成球性及形成还原性气氛,促进空心陶瓷微球的形成及钠的分离回收;喷吹得到了粒径6‑30um空心微球,分离回收其中的钠。本发明充分利用赤泥制资源,以工艺简单、高效、节能的方法制得高强度低密度的陶瓷空心微球、分离回收钠。
Description
技术领域
本发明属于冶金二次资源利用及无机非金属功能材料技术领域,具体涉及一种制赤泥备空心陶瓷微球回收钠的方法。
技术背景
空心陶瓷微球是一种具有磁的性空心无机非金属球体,具有颗粒微细、中空、质轻、耐高温等优点。其具有广泛的应用前景:空心微球具有比表面积大、低密度、易于分散、形貌可控等优点, 应用广泛;在污水净化、催化剂、功能材料的载体、保温应运方面有广泛的前景。
国内申请的关于陶瓷空心微球的专利较多,如专利200810138749.7、2011201110145156.5、201510061293.5;但在专利200810138749.7中制备微球需要配料、熔化、水淬、磁性空心球化等10道工序,制备工艺复杂且需要在1400-1600℃的温度下重新熔化原料,能源消耗较高,在实际工业化生产过程不利于获得较高的经济效益。在专利201110145156.5中,其生产的微珠粒径为0.2-5mm,粒径变化范围大,最大和最小粒径相差25倍,不同粒径的微球强度、密度差异较大,所以该方法制得的陶瓷磁性空心微球在实际应用中性能有所欠缺。在专利201310613228.3中,制备微珠需要配料、球磨、加蔗糖等过程,其弊端在于人工配料无法保证各种物质均匀的分散到粉末上,最终将导致空心微球的结构不稳定且形貌变化较大。专利CN201410252280(一种可用于空心陶瓷微珠吸波材料的表面改性液)、专利CNIO2993781A(一种磁性纳米四氧化三铁改性空心玻璃微珠)和专利01127074.8(轻型复合空心金属微球的制备方法)制备的磁性空心微球的方法是在空心微球上通过化学沉积的方法得到的具有磁性的物质,是在原有的空心微球的基础上得到的。
上述专利从制备原理和制备技术上做了探索研究,取得了一定的进展,但这些制备方法不同程度存在以下问题:
1. 制备空心微球原料需要重熔,能耗高,制备成本高;2. 制备空心微球配料中所加的原料需熔炼成熔融状态,配料时加入的发气的物质在熔制过程中发生分解,造成成分不稳定,吹制会导致发气物质分布不均匀,影响球的空心结构及形状,空心球的生成率低;3.化学沉积工艺复杂,同时磁性沉积物粘结力较低,沉积不均匀,易脱落,性能不稳定,使成本进一步升高,工业化推广困难;4.由于熔制的原因,微珠粒径差较大。
因此,研发一种能满足实际应用的高强度低密度的磁性空心陶瓷球成为该领域迫切需要解决的问题。
发明内容
本发明针对上述已有技术的不足,提供一种高效节能、利用赤泥制备空心陶瓷微球回收钠的方法。
本发明是一种赤泥制备空心陶瓷微球回收钠的方法,其步骤为:
(1)以湿态赤泥为原始基料,将其烘干到一定的含水量;
(2)在一定的含水量的赤泥中加入不同比例的生物质原料,在湿态研磨混合均匀同时烘干,得到粒径在20-50 um的赤泥混合粉末;
(3)经混磨烘干混合均匀的赤泥混合粉末通过火焰喷熔装置喷吹;
(4)利用余热装置回收喷吹产生的热量并冷却喷吹物;
(5)用旋涡分离器分离收集空心陶瓷微球、实心陶瓷微球及富含钠的细粉;
(6)分离、收集的含钠返回氧化铝生产流程。
本发明的优点是:1.本发明将工业废渣、污染物转化为高附加值产品,有利于减少环境污染;2.本发明采用的原料为赤泥,其优点在于氧化铝生产过程中原料中氧化铝等物质焙烧溶出,残渣颗粒细小。3.添加的生物质原料在含有氧化钠的赤泥中有利于分解及转化,使其均匀分布在赤泥原料中。4.本发明所使用的原料中均匀分布着金属的硫化物、磷化物等发气物质,这些均匀分布的发气源有利于得到结构良好空心陶瓷微球。5.赤泥中存在大量的铁橄榄石、硫化物,熔点低、粘度低、流动性好,易于熔融,从而使熔滴在表面张力的作用下易形成球形。6.生物质原料在喷吹过程中有促进赤泥中钠的分解和还原。7.本发明利用工业废渣,工艺简单,低消耗,高效率,易于规模化用于赤泥处理利。
附图说明
图1为本发明制备空心陶瓷微球的工艺流程图;图2为制得空心陶瓷微球的SEM图。
具体实施方式
本发明是一种赤泥制备空心陶瓷微球回收钠的方法,其步骤为:
(1)以湿态赤泥为原始基料,将其烘干到一定的含水量;
(2)在一定的含水量的赤泥中加入不同比例的生物质原料,在湿态用球磨机研磨混合均匀同时烘干,得到粒径在20-50 um的赤泥混合粉末;
(3)经球磨烘干混合均匀的赤泥混合粉末通过火焰喷熔装置喷吹;
(4)利用余热装置回收喷吹产生的热量并冷却喷吹物;
(5)用旋涡分离器分离收集空心陶瓷微球、实心陶瓷微球及富含钠的细粉;
(6)分离、收集的含钠物质,经成分分析返回氧化铝生产过程;
其中步骤(1)的赤泥是指氧化铝生产残余的渣,经过提取氧化铝后的渣一般称为赤泥,含有SiO2的质量百分含量为15-30%;Al2O3的质量百分含量为15-25%;Fe的质量百分含量为23-30%;CaO的质量百分含量为5-15%;Na2O的质量百分含量为5-7.5%,含水7-9%。
其中步骤(2)的生物质是指农产品加工残渣、农作物秸秆、木材加工残料,根据生物质不同加入量控制在0-15%,粒径小于50 um。
其中步骤(2)中的生物质是在赤泥含水5-10%的湿态加入,赤泥的量是按干态计算。
其中步骤(3)的火焰喷熔装置用压缩空气送粉,压力为0.1-0.15MPa,助燃气体为氧气、燃料乙炔(天然气),压力为0.1-0.15MPa,送料速度为5-50k g/min,喷熔温度为2500℃-3000℃。
其中步骤(4)利用余热装置回收喷吹产生的热量并冷却喷吹物。
其中步骤(5)利用旋涡分离器分离收集空心陶瓷微球、实心陶瓷微球及富含钠的细粉。
其中步骤(6)钠是以碳酸钠或氧化钠的形式存在,经分析后返回到氧化铝的生产流程加以利用。
实施例1:
1)将赤泥烘干到含水5%,加入占赤泥总量5%的生物质原料;
2)将赤泥混合料通过球磨机混合研磨、烘干,粒径达到20 um;
3)通过火焰喷枪熔射赤泥混合料粉末,送粉气体为压缩空气,压力为0.15MPa,助燃气体为氧气,压力为0.14MPa,燃料为乙炔(天然气),压力为0.11MPa,送料速度为5kg/min,熔射温度为2500℃;
4)利用旋涡分离器将空心陶瓷微球与钠的化合物分离;
所得空心陶瓷微球的外径为10-20um,空心微球壁厚大约0.5-1um;空心陶瓷微球中氧化钠的含量小于0.5%。
实施例2:
1)将赤泥烘干到含水10%,加入占赤泥总量10%的生物质原料;
2)将赤泥混合料通过球磨机混合研磨、烘干,粒径达到35um;
3)通过火焰喷枪熔射赤泥混合料粉末,送粉气体为压缩空气,压力为0.1MPa,助燃气体为氧气,压力为0.15MPa,燃料为乙炔(天然气),压力为0.12MPa,送料速度为10kg/min,熔射温度为3200℃;
4)利用旋涡分离器将空心陶瓷微球与钠的化合物分离;
所得空心陶瓷微球的外径为16-25um,空心微球壁厚大约0.5-1um,空心陶瓷微球中钠的含量小于0.4%。
实施例3:
1)将赤泥烘干到含水7.5%,加入占赤泥总量15%的生物质原料;
2)将赤泥混合料通过球磨机混合研磨、烘干,粒径达到50 um;
3)通过火焰喷枪熔射赤泥混合料粉末,送粉气体为压缩空气,压力为0.1MPa,助燃气体为氧气,压力为0.13MPa,燃料为乙炔(天然气),压力为0.13MPa,送料速度为20kg/min,熔射温度为2350℃;
4)利用旋涡分离器将空心陶瓷微球与钠的化合物分离;
所得空心陶瓷微球的外径为15-25um,空心微球壁厚大约0.5-1um,空心陶瓷微球中钠的含量小于0.3%。
实施例4:
1)将赤泥烘干到含水5%,加入占赤泥总量1%的生物质原料;
2)将赤泥混合料通过球磨机混合研磨、烘干,粒径达到40um;
3)通过火焰喷枪熔射赤泥混合料粉末,送粉气体为压缩空气,压力为0.15MPa,助燃气体为氧气,压力为0.14MPa,燃料为乙炔(天然气),压力为0.14MPa,送料速度为30kg/min;
4)利用旋涡分离器将空心陶瓷微球与钠的化合物分离;
所得空心陶瓷微球的外径为17-30um,空心微球壁厚大约0.5-1um;空心陶瓷微球中钠的含量小于0.4%。
实施例5:
1)将赤泥烘干到含水8%,加入占赤泥总量10%的生物质原料;
2)将赤泥混合料通过球磨机混合研磨、烘干,粒径达到50um;
3)通过火焰喷枪熔射赤泥混合料粉末,送粉气体为压缩空气,压力为0.1MPa,助燃气体为氧气,压力为0.13MPa,燃料为乙炔(天然气),压力为0.15MPa,送料速度为40kg/min,熔射温度为3200℃;
4)利用旋涡分离器将空心陶瓷微球与钠的化合物分离;
所得空心陶瓷微球的外径为13-22um,空心微球壁厚大约0.5-1um;空心陶瓷微球中钠的含量小于0.4%。
实施例6:
1)将赤泥烘干到含水8%,加入占赤泥总量10%的生物质原料
2) 将赤泥用球磨机研磨、烘干,粒径达到20 um;
3) 通过火焰喷枪熔射赤泥混合料粉末,送粉气体为压缩空气,压力为0.15MPa,
助燃气体为氧气,压力为0.15MPa,燃料为乙炔(天然气),压力为0.1MPa,送料速度为5kg/min,熔射温度为2500℃;
4) 利用旋涡分离器将空心陶瓷微球与钠的化合物分离;
所得空心陶瓷微球的外径为15-24um,空心微球壁厚大约0.6-1um;空心陶瓷微球中钠的含量小于0.6%。
实施例7:
1)将赤泥烘干到含水6%,加入占赤泥总量7%的生物质原料
2) 将赤泥用球磨机研磨、烘干,粒径达到35 um;
3) 通过火焰喷枪熔射赤泥混合料粉末,送粉气体为压缩空气,压力为0.1MPa,
助燃气体为氧气,压力为0.15MPa,燃料为乙炔(天然气),压力为0.1MPa,送料速度为30kg/min,熔射温度为2750℃;
4) 利用旋涡分离器将空心陶瓷微球与钠的化合物分离;
所得空心陶瓷微球的外径为12-24um,空心微球壁厚大约0.5-0.9um;空心陶瓷微球中钠的含量小于0.6%。
实施例8:
1)将赤泥烘干到含水7%,加入占赤泥总量9%的生物质原料
2) 将赤泥用球磨机研磨、烘干,粒径达到50um;
3)通过火焰喷枪熔射赤泥混合料粉末,送粉气体为压缩空气,压力为0.15MPa,
助燃气体为氧气,压力为0.15MPa,燃料为乙炔(天然气),压力为0.1MPa,送料速度为50kg/min,熔射温度为2500℃;
4) 利用旋涡分离器将空心陶瓷微球与钠的化合物分离;
所得空心陶瓷微球的外径为14-24um,空心微球壁厚大约0.5-0.8um;空心陶瓷微球中钠的含量小于0.6%。
Claims (6)
1.一种利用赤泥制备空心陶瓷微球回收钠的方法,其特征在于包含以下步骤:
(1)以赤泥为基础原料,加入不同比例的生物质粉,通过球磨机混料研磨,使生物质与25-50um的赤泥粉末混合均匀;
(2)在球磨机混料研磨过程中通入水蒸气使两者充分接触,再通入高温空气,使生物质与赤泥中的钠的混合物反应并烘干;
(3)将球磨烘干的混合粉末通过火焰喷枪熔射;
(4)利用热回收装置冷却喷吹物,回收余热;
(5)利用旋涡除分离置分离空心陶瓷微球、实心陶瓷微球及富含钠的细粉;
(6)将分离的钠混合物返回氧化铝生产系统。
2.根据权利要求1所述的赤泥制备空心陶瓷微球回收钠的方法,其特征在于所述赤泥包含SiO2、Fe2O3、FeO、Na2O、CaO、Al2O3等;SiO2的质量百分含量为15-30%;Al2O3的质量百分含量为15-25%;Fe的质量百分含量为23-30%;CaO的质量百分含量为5-15%;Na2O的质量百分含量为5-7.5%,余其它。
3.根据权利要求1所述的赤泥制备空心陶瓷微球回收钠的方法,其特征在于经球磨机研磨混料后的赤泥生物质混合粉末粒度在20 -50 um。
4.根据权利要求1所述的空心陶瓷微球的制备方法,其特征在于生物质加入的质量百分比为0-15%。
5.根据权利要求1所述的赤泥制备空心陶瓷微球回收钠的方法,其特征在于火焰喷枪的送粉气体为压缩空气,压力为0.1-0.15MPa,助燃气体为氧气,燃料为乙炔或天然气,压力为0.1-0.15MPa,送料速度为5-50 kg/min,熔射温度为2500℃-3000℃。
6.根据权利要求1所述的赤泥制备空心陶瓷微球回收钠的方法,其特征在于分离收集得到的钠是以碳酸钠或氧化钠的形式存在。
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