CN115007121A - 一种垃圾飞灰基多孔地聚物制备方法及在重金属污染治理中的应用 - Google Patents
一种垃圾飞灰基多孔地聚物制备方法及在重金属污染治理中的应用 Download PDFInfo
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Abstract
本发明公开了一种垃圾飞灰基多孔地聚物制备方法,包括以下步骤:(1)、在搅拌罐中加入(质量份):垃圾飞灰30‑50份,矿土10‑30份,经功能化改性的生物基废弃纤维1‑10份,活性硅氧烷溶液1‑10份,碱激发剂1‑10份,发泡剂1‑10份,功能单体5‑15份,交联单体1‑5份,水30‑50份,密闭下搅拌混合均匀,形成浆料;(2)在上述浆料中加入1‑5质量份的引发剂溶液,搅拌均匀,倒入模具中,在20‑60℃情形下发泡10‑30分钟,养护24小时。本发明方法所制得的垃圾飞灰基多孔地聚物在碱激发条件下,飞灰中硅铝断键重组,形成坚硬地聚物,将飞灰中重金属“固锁”于矿化晶体笼中,实现飞灰中重金属永久稳定固封,避免其浸出造成的二次污染。
Description
技术领域
本发明涉及危险固体废弃物治理技术领域,尤其涉及一种垃圾飞灰基多孔地聚物制备方法及在重金属污染治理中的应用。
背景技术
垃圾焚烧飞灰作为垃圾焚烧发电过程中的副产物,一般占被焚烧垃圾量的3%~5%,以其中包含的多种重金属元素及二噁英等有机危害物而被列为固体废弃物之一。若对其不加妥善处理而随意堆积填埋,其中的有害物质会渗漏到自然环境中并造成极大危害。随着垃圾产量与日俱增,以及焚烧方式处理垃圾作为主流垃圾处置方式,垃圾飞灰产量也迅速攀升,大量产生的垃圾焚烧飞灰是城市危险废弃物管理面临的一重大棘手难题。。
垃圾飞灰安全处置技术有安全填埋、熔融固化、化学药剂稳定化、溶剂提取和水泥固化等技术。其中,经重金属螯合处理后填埋,是较多采用的垃圾飞灰处置方式。垃圾飞灰中重金属填埋前的螯合稳定,虽可相对稳定地防止重金属离子的流失,但其费用十分昂贵,且即使深埋地下,由于气候和人为因素,仍有造成二次污染的可能。随着土地资源日益溃乏和填埋可能导致的二次污染,垃圾填埋选址越来越困难。
另一方面,随着经济的迅速发展,特别是采矿、冶金、化工等行业的人为活动,重金属水体污染问题也日趋严重。
目前,化学吸附法是重金属污染治理和控制的主要技术手段,其具有成本较低、吸附脱除效率高优势,是一种较为经济、批量化高效处理重金属废水的方法,然而,现行所用重金属吸附剂存在重金属吸附位点较少和比表面积较小缺陷,导致其吸附容量和吸附效率不够理想。
发明内容
本发明的目的在于针对现有技术的不足,提供一种垃圾飞灰基多孔地聚物制备方法及在重金属污染治理中的应用。本发明方法所制得多孔地聚物,不仅强度高,对飞灰、矿渣的重金属实现永久固封,其多孔表面还具有丰富的重金属螯合位点,能快速、高效地螯合水体中重金属,用于治理重金属污染废水。
本发明的目的之一在于提供一种垃圾飞灰基多孔地聚物制备方法,所述的垃圾飞灰基多孔地聚物的制备方法包括以下步骤:
(1)、在搅拌罐中加入(质量份):垃圾飞灰30-50份,矿土10-30份,经功能化改性的生物基废弃纤维1-10份,活性硅氧烷溶液1-10份,碱激发剂1-10份,发泡剂1-10份,功能单体5-15份,交联单体1-5份,水30-50份,密闭下搅拌混合均匀,形成浆料;
(2)在上述浆料中加入1-5质量份的引发剂溶液(引发剂浓度为5-10%wt.),搅拌均匀,倒入模具中,在20-60℃情形下发泡10-30分钟,养护24小时。
优选地,所述矿土优选为海泡石、蒙脱土、沸石、硅藻土、泥碳土、凹凸棒土中的一种或多种组合物。
所述活性硅氧烷溶液,优选为氨基硅氧烷、羟基硅氧烷、环氧基硅氧烷、羧基硅氧烷、巯基硅氧烷中的至少一种。
优选地,所述生物基废弃纤维可为废弃的甘蔗渣纤维、木薯渣纤维、椰壳纤维、锯木纤维、秸秆纤维、稻壳纤维中的至少一种。废弃生物质基纤维预先经酸或碱浸泡处理,粉碎,过100目筛,成粉末状或颗粒状。然后将其置于高分子重金属螯合剂处理液中,浸泡5-10小时,过滤,得到经功能化改性的生物基废弃纤维。
优选地,所述高分子重金属螯合剂可为聚乙烯亚胺、二硫代胺基聚乙烯亚胺中的至少一种。
优选地,所述碱激发剂可为氢氧化钠、氢氧化钾、钾水玻璃、钠水玻璃、锂水玻璃;
优选地,所述发泡剂可为正己烷、正庚烷中的一种。
优选地,所述功能单体选自丙烯酰胺、甲基丙烯酸缩水甘油酯、乙烯基硅氧烷、甲基丙烯酸羟丙磺酸中的至少一种。
优选地,所述引发剂为自由基引发剂,选自过氧化苯甲酰、偶氮二异丁睛、过硫酸钠、过硫酸钾、Fe2+/过硫酸钠、Fe2+/过硫酸钾中的至少一种。
优选地,所述交联单体选自二甲基丙烯酸甘油酯、二丙烯酸乙二醇酯、聚乙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、二缩三丙二醇二丙烯酸酯、乙二醇二丙烯酸酯、乙二醇二丙烯酸酯、二丙二醇二丙烯酸酯、新戊二醇二丙烯酸酯、三环癸烷二甲醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、双酚A环氧二丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯中的至少一种或多种组合物。
一种垃圾飞灰基多孔地聚物,通过上述的方法制得。
本发明的另一目的在于提供所制得垃圾飞灰基多孔地聚物在重金属治理中应用。
本发明方法所制得的垃圾飞灰基多孔地聚物在垃圾飞灰重金属治理中的应用方法,即通过形成上述地聚物,将垃圾飞灰中重金属永久固封其中,该地聚物可运用于垃圾填埋场、矿山回填、公路路面筑基、生态护坡等,不会再造成二次污染。
本发明方法所制得的垃圾飞灰基多孔地聚物在重金属废水治理中的应用方法:将所制得的垃圾飞灰基多孔地聚物投放于重金属离子的废水中,浸泡一段时间,过滤收集,即能脱除该溶液中的重金属离子,吸除重金属的多孔地聚物用酸性溶液将所述多孔地聚物表面吸附的重金属离子洗脱出去,实现重金属的回收。经洗脱后的所述多孔地聚物可再多次置于所述废水溶液中,实现多次循环再生使用。最后经脱除表面吸附重金属,且不再用于废水处理的多孔地聚物,可运用于垃圾填埋场、矿山回填、公路路面筑基、生态护坡等,不会再造成二次污染。
本发明的有益效果是:
(1)在碱激发条件下,飞灰中硅铝断键重组,形成坚硬地聚物,将飞灰中重金属“固锁”于矿化晶体笼中,实现飞灰中重金属永久稳定固封,避免其浸出造成的二次污染。
(2)自由基聚合形成具有重金属螯合功能的高分子链,与功能化纤维表面的重金属螯合功能基一起,在多孔材料表面和孔隙构成了密集的重金属螯合位点,对水体中不同种类的重金属离子进行螯合,通过絮集和网捕作用,高效简便脱除废水中重金属,摆脱一般小分子重金属处理剂线性螯合所致的效率低下缺点。
(3)所制备的多孔地聚物可在重金属废水中多次循环再生利用,最终经简单脱除表面吸附的重金属处置后仍可再利用于建筑、护坡、路基等场景。
具体实施方式
下面将结合本发明实施例对本发明实施例中的技术方案进行清楚、完整地描述,但不构成对本发明保护范围的限制。
实施例1
在搅拌罐中加入(质量份):垃圾飞灰30份,硅藻土15份,聚乙烯亚胺功能化改性的木薯渣纤维10份,氢氧化钠5份,正己烷5份,丙烯酰胺10份,氨基硅氧烷、二缩三丙二醇二丙烯酸酯3份,水30份,密闭下搅拌混合均匀,形成浆料。
在上述浆料中加入5份Fe2+/过硫酸钠溶液(引发剂浓度为10%wt.),搅拌均匀,倒入模具中,在20-30℃室温情形下发泡30分钟,养护24小时,即得多孔地聚物。
实施例2
在搅拌罐中加入(质量份):垃圾飞灰50份,海泡石20份,二硫代胺基聚乙烯亚胺功能化改性的秸秆纤维8份,水玻璃10份,正己烷8份,丙烯酰胺10份,巯基硅氧烷5份、1,6-己二醇二丙烯酸酯5份,水50份,密闭下搅拌混合均匀,形成浆料。
在上述浆料中加入8份Fe2+/过硫酸钾溶液(引发剂浓度为5%wt.),搅拌均匀,倒入模具中,在20-30℃室温情形下发泡30分钟,养护24小时,即得多孔地聚物。
实施例3
在搅拌罐中加入(质量份):垃圾飞灰50份,硅藻土15份,聚乙烯亚胺功能化改性的木薯渣纤维10份,氢氧化钠5份,正己烷5份,丙烯酰胺10份,、环氧基硅氧烷、双酚A环氧二丙烯酸酯8份,水40份,密闭下搅拌混合均匀,形成浆料。
在上述浆料中加入6份偶氮二异丁睛、(引发剂浓度为8%wt.),搅拌均匀,倒入模具中,在60℃室温情形下发泡30分钟,养护24小时,即得多孔地聚物。
对比例1
垃圾原灰
将固封后的垃圾飞灰进行浸出实验,采用《危险废物鉴别标准浸出毒性鉴别》(GB5085.3-2007、GB18598-2001)
结果如下:单位:(mg/kg)
实施例4
采用实施例1-3所述制备方法制得多孔聚合物用于重金属废水治理,应用方法为:将多孔聚合物按3-10%wt投放于某电镀企业废水溶液中,调节pH值至8-13,浸泡一段时间,过滤,即实现废水中重金属离子的脱除;取出多孔地聚物,置于1-8%的盐酸溶液中浸泡30分钟,取出,用于生产建筑材料或筑路等。
对比例2
某电镀企业废水治理
某电镀企业废水治理实验,采用《电镀污染物排放标准》GB21900-2008单位:mg/L
以上所述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,这些改进和润饰也视为本发明的保护范围。
Claims (10)
1.一种垃圾飞灰基多孔地聚物制备方法,其特征在于,包括以下步骤:
(1)、在搅拌罐中加入(质量份):垃圾飞灰30-50份,矿土10-30份,经功能化改性的生物基废弃纤维1-10份,活性硅氧烷溶液1-10份,碱激发剂1-10份,发泡剂1-10份,功能单体5-15份,交联单体1-5份,水30-50份,密闭下搅拌混合均匀,形成浆料;
(2)在上述浆料中加入1-5质量份的引发剂溶液,搅拌均匀,倒入模具中,在20-60℃情形下发泡10-30分钟,养护24小时。
2.如权利要求1所述的制备方法,其特征在于:所述矿土为海泡石、蒙脱土、沸石、硅藻土、泥碳土、凹凸棒土中的一种或多种组合物;所述活性硅氧烷溶液,为氨基硅氧烷、羟基硅氧烷、环氧基硅氧烷、羧基硅氧烷、巯基硅氧烷中的至少一种。
3.如权利要求1所述的制备方法,其特征在于:所述生物基废弃纤维为废弃的甘蔗渣纤维、木薯渣纤维、椰壳纤维、锯木纤维、秸秆纤维、稻壳纤维中的至少一种;废弃生物质基纤维预先经酸或碱浸泡处理,粉碎,过100目筛,成粉末状或颗粒状,然后将其置于高分子重金属螯合剂处理液中,浸泡5-10小时,过滤,得到经功能化改性的生物基废弃纤维。
4.如权利要求1所述的制备方法,其特征在于:所述碱激发剂为氢氧化钠、氢氧化钾、钾水玻璃、钠水玻璃、锂水玻璃中的一种,所述发泡剂为正己烷、正庚烷中的一种。
5.如权利要求3所述的制备方法,其特征在于:所述高分子重金属螯合剂为聚乙烯亚胺、二硫代胺基聚乙烯亚胺中的至少一种。
6.如权利要求1所述的制备方法,其特征在于:所述引发剂为自由基引发剂,选自过氧化苯甲酰、偶氮二异丁睛、过硫酸钠、过硫酸钾、Fe2+/过硫酸钠、Fe2+/过硫酸钾中的至少一种。
7.如权利要求1所述的制备方法,其特征在于:所述功能单体选自丙烯酰胺、甲基丙烯酸缩水甘油酯、乙烯基硅氧烷、甲基丙烯酸羟丙磺酸中的至少一种。
8.如权利要求1所述的制备方法,其特征在于:所述交联单体选自二甲基丙烯酸甘油酯、二丙烯酸乙二醇酯、聚乙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、二缩三丙二醇二丙烯酸酯、乙二醇二丙烯酸酯、乙二醇二丙烯酸酯、二丙二醇二丙烯酸酯、新戊二醇二丙烯酸酯、三环癸烷二甲醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、双酚A环氧二丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯中的至少一种或多种组合物。
9.一种垃圾飞灰基多孔地聚物,其特征在于:如权利要求1-8任意一项所述的方法制得。
10.如权利要求9所述的圾飞灰基多孔地聚物在重金属治理中的应用。
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