CN114105536B - 一种低碳环保免烧陶粒滤料及其制备方法和用途 - Google Patents
一种低碳环保免烧陶粒滤料及其制备方法和用途 Download PDFInfo
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Abstract
本发明属于水处理技术领域,公开了一种低碳环保免烧陶粒滤料及其制备方法和用途。经过步骤:首先,将高纯度酸加水稀释后与硅酸盐或铝硅酸盐材料混合搅拌成酸激发材料;然后在酸激发材料中加入水、硅质粉体和膨胀珍珠岩,混合搅拌均匀制成基体;经发泡造孔,挤压成型,常压蒸汽养护和高压蒸汽养护,表面改性,形成最终陶粒滤料成品,滤料综合性能优异,具有粒型好,抗酸性能好、硬度高的优点。本发明无需传统1000℃以上的煅烧工艺,通过90~200℃水热合成工艺制备,生产能耗低,节约资源,制得的陶粒滤料成球型,滤料堆积孔隙率高,利于反冲洗,避免滤层积泥。
Description
技术领域
本发明属于水处理技术领域,具体涉及一种低碳环保免烧陶粒滤料的制备方法。
背景技术
随着社会的发展,城市规模不断扩大,生活和工业生产导致的污水处理问题愈发严峻,现有的天然滤料包括石英砂、无烟煤、活性炭、沸石等,造价成本高,而且形状多不规则,存在水流阻力大、容易引起滤池堵塞、造成冲刷破碎、反冲洗困难等问题。人造陶粒滤料,主要由粘土或页岩等天然材料煅烧制备而成,具有球形度高、过滤性能好、成本低等优势,但煅烧法生产陶粒存在建厂投资大、工艺技术复杂、生产能耗高的问题,不仅产生大量的碳排放,同时严重限制企业的发展,而且大量使用粘土会导致耕地毁坏,不利于国家可持续发展。
传统的免烧陶粒制备方法,主要依靠水泥等硅酸盐材料的水化反应,或者粉煤灰、矿粉等铝硅酸盐材料化学激发制备而得,由于其水化产物主要为氢氧化钙、水化硅酸钙或者水化铝酸钙凝胶等碱性产物,不具备抗酸侵蚀性能,不能满足人造陶粒滤料的盐酸溶出率指标要求,所以市场上还未有免煅烧工艺制备的陶粒滤料产品。而免烧滤料现有研究中,专利CN111018097A《一种适用于曝气生物滤池的陶粒滤料及其制备方法》,采用300℃高温蒸汽养护制备滤料,其制备工艺中没有针对盐酸可容率指标的耐酸技术手段,滤料抗酸侵蚀性能有待评估;CN109503207A《一种水处理的陶粒滤料制备方法》,采用污泥中掺加石墨烯和TiO2,400℃蒸养制备而得,采用非硅酸盐材料体系,价格昂贵,经济适应性差。
因此,基于硅酸盐或铝硅酸盐材料体系,采用免煅烧工艺制备抗酸侵蚀性能优良、高性价比的陶粒滤料,是对免烧陶粒技术的进一步拓展和人造陶粒滤料的工艺突破,具有显著的环境效益和社会效益。
发明内容
本发明的目的在于提供一种低碳环保免烧陶粒滤料的制备方法,在满足陶粒滤料高硬度、高孔隙率的基础上,具有显著的抗酸腐蚀性能,符合人造陶粒滤料各项性能指标。
为实现上述发明目的,本发明采用的技术方案为:
一种低碳环保免烧陶粒滤料的制备方法,包括如下步骤:
(1)酸激发:将高纯度酸加水稀释,然后与硅酸盐或铝硅酸盐材料混合搅拌成酸激发材料;
(2)基体制备:酸激发材料中加入水、硅质粉体和膨胀珍珠岩,混合搅拌均匀制备成基体;
(3)发泡造孔:基体中加入化学发泡材料或者物理泡沫制备多孔浆体;
(4)挤压成型:通过挤压成型工艺将多孔浆体制备成颗粒;
(5)养护:球型颗粒通过一定温度的常压蒸汽养护和高压蒸汽养护提高硬度,然后烘干;
(6)表面改性:养护结束后已冷却的球体,通过滚动在颗粒表面喷洒抗酸试剂,然后自然养护,形成最终陶粒滤料成品。
步骤(1)中,所述高纯度酸为浓盐酸、浓硫酸或者浓硝酸中的一种;稀释按高纯度酸与水质量比(1~2):(5~6)进行。
进一步地:所述硅酸盐或铝硅酸盐材料为水泥、矿粉、粉煤灰、沸石粉、偏高岭土中的一种或几种;
进一步地:所述高纯度酸的掺入比例为硅酸盐或铝硅酸材料质量的6%~10%;
步骤(2)中,
进一步地:所述硅质粉体的细度≥400目,膨胀珍珠岩颗粒大小为0.1~2mm;
进一步地:所述硅质粉体包含磨细砂、石英粉或者SiO2含量≥90%的高硅含量粉体材料;
进一步地:所述酸激发材料:硅质粉体:膨胀珍珠岩质量比例为(20~30):(60~70):(10~20),水的用量为:酸激发材料、硅质粉体材料和膨胀珍珠岩总质量的20%~40%。
步骤(3)中,
进一步地:所述化学发泡材料为铝粉、碳酸氢钠或者硅粉中的一种或几种;
进一步地:所述化学发泡材料掺量为硅酸盐或铝硅酸盐材料质量的0.5~1%;
进一步地:所述物理泡沫制备方法为,将发泡剂与水按质量比1:20混合,并掺入适量稳泡剂,通过发泡机制备成泡沫;
进一步地:所述物理泡沫掺量为基体质量的3~6%;
步骤(4)中,所述挤压成型工艺采用制丸机完成,颗粒大小为5~10mm;
步骤(5)中,所述养护工艺为:先进行常压90℃蒸汽养护,然后进行压力0.9~1MPa,温度180~200℃的高压蒸汽养护,最后在100℃下烘干。
进一步地:常压蒸汽养护工艺具体为:控制2h的时间从常温升温到90℃,然后90℃恒温保持4h,最后控制1h的时间从90℃降温到常温;
进一步地:高压蒸汽养护工艺具体为:在0.9~1MPa的压力下,控制2.5h的时间从常温升温到180~200℃,然后180~200℃下恒温3h、最后控制1h的时间从180~200℃降温到常温;
步骤(6)中,
进一步地:所述抗酸试剂为有机硅憎水剂或纳米硅铝涂料具有表面抗酸效果的液体试剂,喷洒比例为烘干颗粒堆积体积的(15~30)kg/m3;自然养护的时间为1~2d。
本发明制备的低碳环保免烧陶粒滤料,包括表面的耐酸层和内部的高连通孔隙基体结合多孔填料。
本发明制备的低碳环保免烧陶粒滤料,粒径5~10mm,破碎率与磨损率之和为2~5%,含泥量≤0.5%,盐酸可容率1~2%,孔隙率40~50%,比表面积(0.5~1.0)×104cm2/g,符合CJ/T 299-2008《水处理用人工陶粒滤料》指标要求。
将本发明制备的低碳环保免烧陶粒滤料用于污水的处理。
本发明的有益效果:
(1)环境效益好:无需传统1000℃以上的煅烧工艺,通过水热合成工艺(90~200℃)制备,生产能耗低,节约资源。
(2)粒型好:滤料成球型,堆积孔隙率高,利于反冲洗,避免滤层积泥。
(3)抗酸能力强:通过酸激发材料和大量硅质组分(石英粉、珍珠岩)的填充,显著降低基体水化产物与酸的反应活性(硅质组分抗酸能力强),同时辅助表面耐酸改性剂,在滤料表面形成类似于煅烧陶粒釉质层的耐酸结构,进一步提高抗酸性能。
(4)滤料综合性能优异:通过物理或化学发泡工艺引入气体,并结合膨胀珍珠岩的多孔构造,在陶粒内部形成高连通的孔隙结构,同时基于高硅含量粉体材料在高温高压蒸汽养护条件下与硅/铝酸盐材料的水化产物进一步反应生成高强度的托勃莫来石,提高陶粒滤料的硬度。
附图说明
图1为本发明免烧陶粒滤料的构造图。
具体实施方式
下面结合附图以及具体实施例对本发明作进一步的说明,但本发明的保护范围并不限于此。
实施例1:
称取水泥质量6%的浓硫酸,按照1:5(wt%)加水稀释,与水泥混合搅拌成酸激发材料;将酸激发材料、石英粉和膨胀珍珠岩按照20:70:10的质量比例混合搅拌,然后加入基体总质量35%的水搅拌成浆体;加入水泥质量0.8%的铝膏粉并搅拌均匀,然后将浆体倒入制丸机中挤压造粒成球(粒径8mm左右);成型后颗粒在常温条件下静置5~6h→90℃常压蒸汽养护(升温2h,恒温4h,降温1h)→1MPa/180℃高压蒸汽养护(升温2.5h、恒温3h、降温1h)→100℃烘干并冷却至室温。检测冷却后颗粒的堆积密度并置于圆盘造粒机中,基于颗粒的堆积体积称取15kg/m3的有机硅憎水剂在颗粒表面喷洒成壳,然后自然养护1d完成陶粒滤料成品制备,滤料的构造图如图1所示。
按照CJ/T 299-2008《水处理用人工陶粒滤料》进行检测,产品性能见表1。
实施例2:
称取矿粉和偏高岭土(铝硅酸盐材料)总质量8%的浓盐酸,按照2:5.5(wt%)加水稀释,与矿粉和偏高岭土(质量比7:3)混合搅拌成酸激发材料;将酸激发材料:磨细砂:膨胀珍珠岩按照30:60:10的质量比例混合搅拌,然后加入基体总质量25%的水搅拌成浆体;将生物蛋白类发泡剂与水1:20混合,加入适量稳泡剂,采用物理发泡机制备泡沫,然后在浆体中加入质量5%的泡沫搅拌均匀,倒入制丸机中挤压造粒成球(粒径8mm左右);成型后颗粒在常温条件下静置5~6h→90℃常压蒸汽养护(升温2h,恒温4h,降温1h)→1MPa/180℃高压蒸汽养护(升温2.5h、恒温3h、降温1h)→100℃烘干并冷却至室温。检测冷却后颗粒的堆积密度并置于圆盘造粒机中,基于颗粒的堆积体积称取20kg/m3的纳米铝硅涂料在陶粒表面喷洒成壳,然后自然养护1d完成陶粒滤料成品制备。
按照CJ/T 299-2008《水处理用人工陶粒滤料》进行检测,产品性能见表1。
实施例3:
称取水泥、粉煤灰和沸石粉总质量6%的浓硝酸,按照1:6(wt%)加水稀释,与水泥、粉煤灰和沸石粉(质量比5:3:2)混合搅拌成酸激发材料;将酸激发材料:磨细砂:膨胀珍珠岩按照30:50:20的质量比例混合搅拌,然后加入基体总质量40%的水搅拌成浆体;加入水泥质量1%的碳酸氢钠并搅拌均匀,然后将浆体倒入制丸机中挤压造粒成球(粒径8mm左右);成型后颗粒在常温条件下静置5~6h→90℃常压蒸汽养护(升温2h,恒温4h,降温1h)→1MPa/180℃高压蒸汽养护(升温2.5h、恒温3h、降温1h)→100℃烘干并冷却至室温。检测冷却后颗粒的堆积密度并置于圆盘造粒机中,基于颗粒的堆积体积称取25kg/m3的纳米铝硅涂料在陶粒表面喷洒成壳,然后自然养护1d完成陶粒滤料成品制备。
按照CJ/T 299-2008《水处理用人工陶粒滤料》进行检测,产品性能见表1。
表1免烧陶粒滤料产品性能
根据试验结果,自制的陶粒滤料采用蒸养蒸压等水热合成工艺制备,突破人造陶粒滤料的传统煅烧制备工艺,各项指标均符合标准要求,产品性能良好。
所述实施例为本发明的优选的实施方式,但本发明并不限于上述实施方式,在不背离本发明的实质内容的情况下,本领域技术人员能够做出的任何显而易见的改进、替换或变型均属于本发明的保护范围。
Claims (13)
1.一种低碳环保免烧陶粒滤料的制备方法,其特征在于,包括如下步骤:
(1)酸激发:将高纯度酸加水稀释,然后与硅酸盐或铝硅酸盐材料混合搅拌成酸激发材料;所述高纯度酸为浓盐酸、浓硫酸或者浓硝酸中的一种;
(2)基体制备:酸激发材料中加入水、硅质粉体和膨胀珍珠岩,混合搅拌均匀制备成基体;
(3)发泡造孔:基体中加入化学发泡材料或者物理泡沫制备多孔浆体;
(4)挤压成型:通过挤压成型工艺将多孔浆体制备成球型颗粒;
(5)养护:球型颗粒通过一定温度的常压蒸汽养护和高压蒸汽养护提高硬度,然后烘干;
常压蒸汽养护工艺为:控制2h的时间从常温升温到90℃,然后90℃恒温保持4h,最后控制1h的时间从90℃降温到常温;
高压蒸汽养护工艺为:在0.9~1MPa的压力下,控制2.5h的时间从常温升温到180~200℃,然后180~200℃下恒温3h、最后控制1h的时间从180~200℃降温到常温;
(6)表面改性:养护结束后已冷却的球体,通过滚动在颗粒表面喷洒抗酸试剂,然后自然养护,形成最终陶粒滤料成品。
2.如权利要求1所述的制备方法,其特征在于,步骤(1)中,所述稀释按高纯度酸与水质量比(1~2):(5~6)进行。
3.如权利要求1所述的制备方法,其特征在于,步骤(1)中,所述硅酸盐或铝硅酸盐材料为水泥、矿粉、粉煤灰、沸石粉、偏高岭土中的一种或几种;所述高纯度酸的掺入比例为硅酸盐或铝硅酸材料质量的6%~10%。
4.如权利要求1所述的制备方法,其特征在于,步骤(2)中,所述硅质粉体的细度≥400目,膨胀珍珠岩颗粒大小为0.1~2mm;所述硅质粉体包含磨细砂、或者SiO2含量≥90%的高硅含量粉体材料。
5.如权利要求1所述的制备方法,其特征在于,步骤(2)中,所述硅质粉体为石英粉。
6.如权利要求1所述的制备方法,其特征在于,步骤(2)中,所述酸激发材料:硅质粉体:膨胀珍珠岩质量比例为(20~30):(60~70):(10~20),水的用量为:酸激发材料、硅质粉体材料和膨胀珍珠岩总质量的20%~40%。
7.如权利要求1所述的制备方法,其特征在于,步骤(3)中,所述化学发泡材料为铝粉、或者碳酸氢钠中的至少一种;所述化学发泡材料掺量为硅酸盐或铝硅酸盐材料质量的0.5~1%。
8.如权利要求1所述的制备方法,其特征在于,步骤(3)中,所述物理泡沫制备方法为,将发泡剂与水按质量比1:20混合,并掺入适量稳泡剂,通过发泡机制备成泡沫;所述物理泡沫掺量为基体质量的3~6%。
9.如权利要求1所述的制备方法,其特征在于,步骤(4)中,所述挤压成型工艺采用制丸机完成,颗粒大小为5~10mm。
10.如权利要求1所述的制备方法,其特征在于,步骤(5)中,烘干的温度为100℃。
11.如权利要求1所述的制备方法,其特征在于,步骤(6)中,所述抗酸试剂为有机硅憎水剂或纳米硅铝涂料,喷洒比例为烘干颗粒堆积体积的15~30kg/m3;自然养护的时间为1~2d。
12.一种低碳环保免烧陶粒滤料,其特征在于,是通过权利要求1~11任一项所述制备方法得到的,包括表面的耐酸层和内部的高连通孔隙基体结合多孔填料。
13.将权利要求12所述的低碳环保免烧陶粒滤料用于污水的处理的用途。
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