CN111992177B - 一种非热活化赤泥颗粒吸附剂及其制备方法 - Google Patents

一种非热活化赤泥颗粒吸附剂及其制备方法 Download PDF

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CN111992177B
CN111992177B CN202010928009.4A CN202010928009A CN111992177B CN 111992177 B CN111992177 B CN 111992177B CN 202010928009 A CN202010928009 A CN 202010928009A CN 111992177 B CN111992177 B CN 111992177B
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李龙江
张覃
周童
卯松
李先海
沈智慧
黄小芬
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Guizhou University
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Abstract

本发明公开了一种非热活化赤泥颗粒吸附剂及其制备方法,该赤泥颗粒吸附剂是由内层和外层组成的双层结构,所述的内层为成核颗粒支撑体,外层为吸附活性包裹层。所述的赤泥颗粒吸附剂由粉体主料和活性黏结液组成。所述的粉体主料由赤泥、粉煤灰、铝酸盐水泥和二氧化锰组成。所述的活性黏结液由增强及抗粉化剂、非热发泡剂和活性改性剂组成。本发明以赤泥、粉煤灰、铝酸盐水泥和二氧化锰为主料制备赤泥颗粒吸附剂,制得得赤泥颗粒吸附剂为双层结构,具有低粉化率、高强度、可再生及优越的吸附性能等特点。

Description

一种非热活化赤泥颗粒吸附剂及其制备方法
技术领域
本发明涉及一种非热活化赤泥颗粒吸附剂及其制备方法,属于环境保护和水处理技术领域。
背景技术
赤泥是制铝工业提取氧化铝时排出的污染性废渣,每生产1吨氧化铝,平均产生0.3~2.0吨赤泥,每年全球赤泥产生量约为1.2亿吨。我国氧化铝厂大都采用露天筑坝的方式堆存赤泥,不仅占用大量土地,也对环境造成严重的污染,因此赤泥的资源化利用迫在眉睫。
磷矿浮选废水存在排放量大、含磷量高、成分复杂等问题,若不处理直接排入水体,会对矿山地区的水质产生恶劣影响。目前,含磷废水处理技术主要有凝固法、沉淀法、需氧和厌氧处理、微生物还原和活性污泥法等。然而,这些处理方法存在一些缺点或不足,主要包括污染物去除不充分、成本高、对试剂或能量的要求高,以及会产生需要做进一步安全处理的有毒残渣或其他废料。
赤泥中的胶结和结晶连接成分,使赤泥具有牢固的水稳性能连接强度,能够获得良好的工程性能,可以将赤泥用于水污染治理。目前,已有一些研究学者将赤泥制成粉末吸附剂用于处理含磷废水,但这些粉末赤泥基吸附剂在实际应用中存在一定的局限性。废水经过粉末赤泥基吸附剂处理后存在固液分离等问题。若将粉末赤泥基吸附剂填装在吸附柱中进行动态吸附,易造成吸附柱堵塞和水头损失增加,使吸附无法进行。为了改善赤泥在实际中的可利用性,将其颗粒化是必然的选择。
已知的文献中,Despland等人以中和赤泥粉末为原料制备了多孔颗粒赤泥吸附剂。Yue等人以焚烧法制铝工业产生的粉末赤泥为原材料制备了颗粒赤泥吸附剂,这些颗粒赤泥吸附剂吸附能力较低(磷酸盐吸附量低于10mg/g)。公开号为CN101143312A的中国发明专利在制备颗粒赤泥吸附剂的过程中需要通过梯度控温进行焙烧。公开号为CN1317548A的中国发明专利以赤泥、粉煤灰、粘土为原料,配以造孔剂制备陶瓷吸附剂,制备的陶瓷吸附剂强度和气孔率低,吸附性能差,不适合大规模的推广应用。因此需要开发新型高效的颗粒吸附剂制备方法。
发明内容
本发明的目的在于:提供了一种非热活化赤泥颗粒吸附剂及其制备方法,该颗粒吸附剂具有双层结构,内层为成核颗粒支撑体,外层为吸附活性包裹层,采用该颗粒吸附剂解决了单一成型时需要较长的吸附时间的问题,且加大了吸附剂颗粒的强度,其具有粉化率低、强度大、可再生、吸附性能好等优点。
为了解决上述技术问题,本发明提供如下技术方案:一种非热活化赤泥颗粒吸附剂,该赤泥颗粒吸附剂是由内层和外层组成的双层结构,所述的内层为成核颗粒支撑体,外层为吸附活性包裹层。
进一步,所述的赤泥颗粒吸附剂由粉体主料和活性黏结液组成。
进一步,所述的粉体主料由赤泥、粉煤灰、铝酸盐水泥和二氧化锰组成。
进一步,所述的活性黏结液由增强及抗粉化剂、非热发泡剂和活性改性剂组成,其中,所述增强及抗粉化剂是由KH-602、羟丙基甲基纤维素(HPMC)和Na2SiO4粉体组成,所述非热发泡剂为H2O2,所述活性改性剂是由HCl、瓜环和十二烷基苯磺酸钠(SDBS)组成。
同时,本发明还提供一种非热活化赤泥颗粒吸附剂的制备方法,包括以下步骤:
步骤一、将赤泥和铝酸盐水泥均匀混合后造粒成型,成型颗粒用1mm筛筛分,筛下颗粒置于干燥箱,得到成核颗粒支撑体;
步骤二、在加有成核颗粒支撑体的造粒机中加入粉体主料,并喷洒活性黏结液,最后养护干燥,即可得到赤泥颗粒吸附剂。
上述方法中,所述步骤一中的赤泥和铝酸盐水泥的质量比为6:4。
上述方法中,所述步骤二中的粉体主料按重量份计算,它是由赤泥60~80份、粉煤灰1.7~8.5份、铝酸盐水泥2~10份和二氧化锰10~20份组成。
上述方法中,所述步骤二中的活性黏结液是由按重量份计算,它是由KH-6020.1~0.4份、羟丙基甲基纤维素(HPMC)0.5~2.5份、Na2SiO4粉体2~4份、H2O20.4~2.0份、HCl0.25~1.2份、瓜环0.01~0.09份以及十二烷基苯磺酸钠(SDBS)0.05~0.25份组成。
与现有技术相比,本发明所达到的有益效果是:本发明以赤泥、粉煤灰、铝酸盐水泥和二氧化锰为主料制备赤泥颗粒吸附剂,制得的赤泥颗粒吸附剂为双层结构,具有低粉化率、高强度、可再生及优越的吸附性能等特点。本发明基于以“以废治废”的思想,用非热活化的方法提高赤泥的吸附活性并制备成颗粒吸附剂,对磷矿浮选含磷废水中的磷酸盐物质进行吸附,研究其吸附过程的基础问题,提高吸附性能。吸附后,废水中的磷酸盐、F离子和砷离子达标排放,赤泥因pH值减小而用作混凝土填料等。解决磷矿废水达标排放问题和赤泥堆存占地危害环境问题,研究成果将会产生明显的社会效益、环境效益和经济效益。
附图说明
图1是本发明中赤泥颗粒吸附剂的结构示意图。
附图标记说明:1-成核颗粒支撑体、2-吸附活性包裹层。
具体实施方式
下面将结合本发明实施例中的附图和实施例对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
本发明的实施例:参见图1,本发明的一种非热活化赤泥颗粒吸附剂,该赤泥颗粒吸附剂是由内层和外层组成的双层结构,所述的内层为成核颗粒支撑体1,外层为吸附活性包裹层2。所述的赤泥颗粒吸附剂由粉体主料和活性黏结液组成。所述的粉体主料由赤泥、粉煤灰、铝酸盐水泥和二氧化锰组成。所述的活性黏结液由增强及抗粉化剂、非热发泡剂和活性改性剂组成,其中,所述增强及抗粉化剂是由KH-602、羟丙基甲基纤维素(HPMC)和Na2SiO4粉体组成,所述非热发泡剂为H2O2,所述活性改性剂是由HCl、瓜环和十二烷基苯磺酸钠(SDBS)组成。
同时,本发明还提供一种非热活化赤泥颗粒吸附剂的制备方法,包括以下步骤:
步骤一、制备吸附剂粉体主料:在搅拌机中添加赤泥和铝酸盐水泥,其质量比为6:4,均匀混合后置于圆盘造粒机中,边旋转边喷入去离子水,直到成型,然后采用1mm筛筛分,筛下圆形颗粒置于40℃电热鼓风干燥箱中,至含水率<5%,制得成核颗粒支撑体;按重量份计算,在成核颗粒支撑体中添加赤泥70份、粉煤灰6份、铝酸盐水泥5份和二氧化锰15份,在搅拌机中均匀混合,制得吸附剂粉体主料;
步骤二、制备活性黏结液:按重量份计算,在水胶比为3:1的去离子水中添加增强及抗粉化剂:KH-6020.3份、羟丙基甲基纤维素(HPMC)2份和Na2SiO4粉体3份,磁力搅拌5分钟、静置;然后添加0.4~2.0份的非热发泡剂H2O2,磁力搅拌5分钟、静置;再分别添加活性改性剂:HCl 1份、瓜环0.05份以及十二烷基苯磺酸钠(SDBS)0.15份,磁力搅拌5分钟、静置,制得活性黏结液;
步骤三、制备赤泥颗粒吸附剂:在圆盘造粒机中添加15份的成核颗粒支撑体,边旋转边加入吸附剂粉体主料,缓慢喷洒活性黏结液,至吸附活性包裹层达一定厚度,继续旋转10min后筛分,置于水泥砼恒温恒湿标准养护箱养护3天,最后置于40℃电热鼓风干燥箱里干燥,即可得到赤泥颗粒吸附剂。
实验例1:原状赤泥对含磷废水的吸附效果
本实验中赤泥颗粒吸附剂制备方法如下:
取赤泥300g,添加0.1%~0.4%的KH-602,水灰比为1:3,混合搅拌均匀,置于造粒机中进行造粒,造粒成型的颗粒置于水泥砼恒温恒湿标准养护箱进行颗粒养护。
检测项目:
磷矿浮选的尾矿回水,其初始总P浓度为127.8mg/L。
检测结果如下:
当吸附温度为20℃~25℃,吸附时间为12h~14h时,磷酸盐的吸附量为20.53mg/g,去除率为40.16%,抗压强度为0.36KPa,浸水粉化率为87.40%。
实验例2:粉煤灰对吸附剂性能的影响
本实验中赤泥颗粒吸附剂制备方法如下:
在内掺总材料质量为300g、水灰比为1:3的条件下,添加赤泥、8.3%的粉煤灰、0.1%的KH-602,混合搅拌均匀,置于造粒机中进行造粒,造粒成型的颗粒置于水泥砼恒温恒湿标准养护箱进行颗粒养护。
检测项目:
磷矿浮选得尾矿回水,其初始总P浓度为127.8mg/g。
检测结果如下:
吸附剂对磷酸盐的去除率达到76.6%,但粉化率达到94.30%。
实验例3:非热造孔剂H2O2对吸附性能的影响
本实验中赤泥颗粒吸附剂制备方法如下:
在内掺总材料质量为300g、水灰比为1:3的条件下,添加赤泥、5.1%粉煤灰、8%~10%A2C、0.25%HPMC、2%Na2SiO4、0.1%KH-602、0.08%~0.4%MnO2和H2O2,按非热活化颗粒吸附剂的制备和养护方法进行造粒。
检测项目:
磷矿浮选的尾矿回水,其初始总P浓度为127.8mg/L。
检测结果如下:
当添加0.4%~2%H2O2后,吸附剂对磷酸盐的吸附量从35.13mg/g上升到44.67mg/g,去除率从68.72%上升到87.38%,但强度从1.32KPa下降到0.92KPa,浸泡粉化率从1.5%上升到4.2%。
实验例4:盐酸对吸附性能的影响
本实验中赤泥颗粒吸附剂制备方法如下:
在内掺总材料质量为300g、水灰比为1:3的条件下,添加5.1%粉煤灰、8%~10%A2C、0.25%HPMC、2%Na2SiO4、0.1%KH-602、1.6%~2.0%H2O2、0.32%~0.4%MnO2和0.75%HCl,按非热活化颗粒吸附剂的制备和养护方法进行造粒。
检测项目:
磷矿浮选的尾矿回水,其初始总P浓度为127.8mg/L。
检测结果如下:
吸附剂对磷酸盐的吸附量为47.44mg/g,去除率达到92.80%,强度为1.03KPa,24h浸泡粉化率4.16%。
随着HCl量的增加,吸附剂吸附能力先增加后减小。
实验例5:瓜环对吸附性能的影响
本实验中赤泥颗粒吸附剂制备方法如下:
在内掺总材料质量为300g、水灰比为1:3的条件下,添加5.1%粉煤灰、8%~10%A2C、0.25%HPMC、2%Na2SiO4、0.1%KH-602、1.6%~2.0%H2O2、0.32%~0.4%MnO2和瓜环,按非热活化颗粒吸附剂的制备和养护方法进行造粒。
检测项目:
磷矿浮选的尾矿回水,其初始总P浓度为127.8mg/L。
检测结果如下:
当瓜环加入量从0.01%~0.09%时,吸附剂对磷酸盐的吸附量从43.32mg/g下降到38.69mg/g,去除率从84.74%下降到75.68%,抗压强度和浸泡粉化率变化不大。
吸附剂除了对磷有吸附作用外,对其他金属离子如Cr2+、Pb2+等有较好的吸附能力。
实验例6:表面活性剂对吸附性能的影响
本实验中赤泥颗粒吸附剂制备方法如下:
在内掺总材料质量为300g、水灰比为1:3的条件下,添加5.1%粉煤灰、8%~10%A2C、0.25%HPMC、2%Na2SiO4、0.1%KH-602、1.6%~2.0%H2O2、0.32%~0.4%MnO2、0.75%HCl、0.05%瓜环和0.2%~0.25%SDBS,按非热活化颗粒吸附剂的制备和养护方法进行造粒。
检测项目:
磷矿浮选的尾矿回水,其初始总P浓度为127.8mg/L。
检测结果如下:
吸附剂的吸附量达到48.53mg/g,去除率达到94.93%,抗压强度变化不大,浸泡粉化率略有下降。
实验例7:本发明的非热活化赤泥颗粒吸附剂对吸附性能的影响本实验中非热活化赤泥颗粒吸附剂制备方法如下:
在内掺总材料质量为300g、水灰比为1:3的条件下,按质量比内掺添加95%赤泥和5.1%~6.8%的粉煤灰,外掺添加8%~10%铝酸盐水泥(A2C)、0.25%HPMC、2%Na2SiO4、0.01%KH-602、1.6%~2.0%H2O2、0.32%~0.4%MnO2、0.75%HCl、0.05%瓜环、0.2%~0.25%SDBS以及9%成核颗粒支撑体,按照非热活化颗粒吸附剂的制备和养护方法进行造粒,制备30Kg非热活化赤泥颗粒吸附剂待用。
制备出的非热活化赤泥颗粒吸附剂的pH=10.16,比表面积48.92m2.g-1,孔容积2.01cm3.g-1,抗压强度1.12KPa,24h浸泡粉化率为3.72%,真密度为1530kg/m3
检测项目:
磷矿浮选的尾矿回水,其初始总P浓度为127.8mg/L。
检测结果如下:
非热活化赤泥颗粒吸附剂的用量为25g/L,吸附时间为14h时,总P的吸附量和去除率分别为48.63mg/g和95.13%。
综上所述,根据实验例1~实验例7的检测结果可知,采用本发明的非热活化赤泥颗粒吸附剂(实验例7)的吸附量和去除率最佳。

Claims (3)

1.一种非热活化赤泥颗粒吸附剂,其特征在于:该赤泥颗粒吸附剂是由内层和外层组成的双层结构,所述的内层为成核颗粒支撑体,所述成核颗粒支撑体由赤泥和铝酸盐水泥组成,所述的外层为吸附活性包裹层,所述的吸附活性包裹层由粉体主料和活性黏结液组成;所述的粉体主料由赤泥、粉煤灰、铝酸盐水泥和二氧化锰组成;所述的活性黏结液由增强及抗粉化剂、非热发泡剂和活性改性剂组成,其中,所述增强及抗粉化剂是由KH-602、羟丙基甲基纤维素(HPMC)和Na2SiO4粉体组成,所述非热发泡剂为H2O2,所述活性改性剂是由HCl、瓜环和十二烷基苯磺酸钠(SDBS)组成。
2.一种非热活化赤泥颗粒吸附剂的制备方法,其特征在于包括以下步骤:
步骤一、将赤泥和铝酸盐水泥均匀混合后造粒成型,成型颗粒用1mm筛筛分,筛下颗粒置于干燥箱,得到成核颗粒支撑体;
步骤二、在加有成核颗粒支撑体的造粒机中加入粉体主料,并喷洒活性黏结液,最后养护干燥,即可得到赤泥颗粒吸附剂;所述粉体主料按重量份计算,它是由赤泥60~80份、粉煤灰1.7~8.5份、铝酸盐水泥2~10份和二氧化锰10~20份组成;所述活性黏结液是由按重量份计算,它是由KH-602 0.1~0.4份、羟丙基甲基纤维素(HPMC)0.5~2.5份、Na2SiO4粉体2~4份、H2O2 0.4~2.0份、HCl 0.25~1.2份、瓜环0.01~0.09份以及十二烷基苯磺酸钠(SDBS)0.05~0.25份组成。
3.根据权利要求2所述的非热活化赤泥颗粒吸附剂的制备方法,其特征在于:所述步骤一中的赤泥和铝酸盐水泥的质量比为6:4。
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