CN113877532B - 一种氧化石墨烯强化固废无机球形吸附剂、制备方法及其应用 - Google Patents
一种氧化石墨烯强化固废无机球形吸附剂、制备方法及其应用 Download PDFInfo
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Abstract
本发明公开了一种氧化石墨烯强化固废无机球形吸附剂、制备方法及其应用,采用分散良好的氧化石墨烯水溶液辅助固废无机聚合物反应成型,并采用有机溶剂辅助机械搅拌的成球工艺,实现氧化石墨烯强化固废无机球形吸附剂的制备。制备的球形吸附剂粒径50μm‑2000μm,孔隙可控,吸附性能较佳。所述的制备方法包括氧化石墨烯分散液的配置、碱激发溶液的配置、氧化石墨烯与无机聚合物浆料的复合、水浴搅拌球形化、固化成型、清洗去碱。本发明利用氧化石墨烯的吸附特性,结合无机聚合物的低温制备及水浴搅拌成球的制备优势,获得了一种氧化石墨烯强化固废无机球形吸附剂,提高了吸附性能,有助于实现废水的高效处理。
Description
技术领域
本发明涉及一种氧化石墨烯强化固废无机球形吸附剂的制备及其方法,尤其涉及一种利用氧化石墨烯的吸附特性,采用有机溶剂辅助机械搅拌的成球工艺,实现氧化石墨烯强化固废无机球形吸附剂的低温制备及固废利用的方法。
制备的氧化石墨烯强化固废无机球形吸附剂,属于氧化石墨烯无机复合吸附材料的绿色制备技术领域。
背景技术
随着我国工业水平的发展,在工业生产过程中所排放的工业废弃物年产量巨大,这也是环境保护所关注的问题。在冶金能源工业中,粉煤灰、矿渣等固废因其具有大量的硅、铝、氧,具有一定的吸附特性,常作为吸附材料。但在实际应用中,粉末状的吸附剂虽然比表面积大,但不容易从污水中分离去除,因此,颗粒吸附剂随之也受到应用。常用的吸附剂主要有活性炭、硅藻土、活性氧化铝等,生产成本也较高。利用固废的反应活性,通过碱激发作用,可获得无机聚合物材料,也可用于吸附处理,环保绿色,工艺简单。
氧化石墨烯拥有高比表面积外,表面含有大量的活性基团,如羟基、羰基、羧基等,使其具有良好的亲水性,能稳定地分散在水溶液中,是一种潜在的优质吸附剂,且容易与重金属离子发生络合。同时,氧化石墨烯结构中的π电子共轭键可以高效吸附带有苯环的有机物。氧化石墨烯在环境修复领域中的应用具有广阔的发展前景。现有研究表明,氧化石墨烯对重金属及阳离子染料废水的处理效果明显优于广泛应用的传统吸附剂,氧化石墨烯对污染物的吸附性能与其比表面积及表面含氧量密切相关,更高的比表面及更多的含氧官能团均能显著增加氧化石墨烯的吸附位点。
固体吸附剂的形状有纤维状、粉末状、微球状等,其中,球形吸附剂具有最大的比表面积、流动性好、吸附均匀等优点,常在实际污水处理中被选用。常用的球形吸附剂的制备方法一般有溶胶-凝胶法、沉淀法等,对原料纯度要求较高,而利用水浴条件下搅拌的方式更为简单。
因此,利用氧化石墨烯的吸附特性,采用有机溶剂辅助机械搅拌的成球工艺,实现氧化石墨烯强化固废无机球形吸附剂的制备,实现无机球形吸附剂的低温绿色制备及对特定废水的吸附效果。氧化石墨烯价格适中,吸附性能较佳,将其与无机固废结合,利用其功能优势,获得的无机球形吸附材料,孔隙可调,吸附效果较佳,可应用于大规模生产,以及有毒有害废水处理。
发明内容
本发明涉及一种氧化石墨烯强化固废无机球形吸附剂的制备及其方法,其特征在于:利用氧化石墨烯的吸附特性,采用分散良好的氧化石墨烯水溶液辅助固废无机聚合物反应成型,并采用有机溶剂辅助机械搅拌的成球工艺,实现氧化石墨烯强化固废无机球形吸附剂的制备,获得的氧化石墨烯强化固废无机球形吸附剂球形完整,粒径在50-2000微米区间可控可调,物相以非晶为主,对多种污水中污染物具有高效吸附特性,吸附速度快,效率高,可适用于应用生产。为实现上述目的,本发明提供如下技术方案:
一种氧化石墨烯强化固废无机球形吸附剂的制备方法,具体步骤如下:
步骤一、氧化石墨烯分散液的配置:称取一定量氧化石墨烯,加入一定量的去离子水,其中氧化石墨烯与去离子水的质量比为(0.001-0.25):1,超声分散,获得分散均匀的氧化石墨烯分散液。
步骤二、碱激发溶液的配置:在质量分数为20-50%的硅胶溶液中按照摩尔比(0.7-1.2):(0.7-1.2)加入氢氧化钾,使用磁力搅拌器搅拌得到碱激发溶液。
步骤三、氧化石墨烯与无机聚合物浆料的复合:将一定量的粉煤灰和矿渣混合,其中粉煤灰与矿渣质量比为(1-2):1,混合后加入步骤二得到的碱激发溶液中,其中混合粉体与碱激发溶液的质量比为(2-6):(4-5)。
混合粉体与碱激发溶液的搅拌过程中逐渐滴入步骤一获得的氧化石墨烯分散液,其中氧化石墨烯分散液与碱激发溶液的质量比为(1-4):(20-25)。加入过程中伴随不断的机械搅拌,直到浆料颜色逐渐加深为止,搅拌20-50分钟后,实现氧化石墨烯与无机聚合物浆料的复合。
步骤四、水浴搅拌球形化:提前加热聚乙二醇溶液至60-90℃,并采用机械搅拌器对其搅拌使其受热均匀,将步骤三中所得氧化石墨烯与无机聚合物浆料滴入少许,滴入后搅拌并取出,得到球形的无机复合颗粒。
步骤五、固化成型:将步骤四获得的复合颗粒并置于60-90℃烘箱中干燥固化1-3天,取出用去离子水和无水乙醇进行清洗,之后继续置于60-90℃烘箱中干燥固化3-7天,得到固化后的球形的氧化石墨烯强化固废无机材料。
步骤六、清洗去碱:将步骤五中获得的氧化石墨烯强化固废无机材料置于去离子水中,加入少量盐酸溶液中和多余的碱金属离子等,浸泡1-10天至pH达到7时为止,取出后用无水乙醇清洗1-3次,之后置于25-90℃干燥0.5-5天,即可获得氧化石墨烯强化固废无机球形吸附剂。
所述的步骤一中,超声分散时间为10-120min。
所述的步骤二中,磁力搅拌器搅拌时间为15-360min。
所述的步骤三中搅拌时间为20-50分钟。
所述的步骤四中每次取氧化石墨烯与无机聚合物的量1-30g,滴入后搅拌2-10min球形化后取出,再加入下一次氧化石墨烯与无机聚合物。
一种氧化石墨烯强化固废无机球形吸附剂是由上述的制备方法制得的。
一种氧化石墨烯强化固废无机球形吸附剂用于对实际固废的治理和工业废水中重金属离子铅、镉的去除,以及有色亚甲基蓝溶液的去除。
与已有技术相比,本发明的优异效果体现在:本发明利用氧化石墨烯具有大的比表面积、表面有丰富的官能团和优异的吸附特性,将其与无机聚合物材料的低温制备相结合,利用了氧化石墨烯的结构优势,以及其水溶液的分散性,利用其水溶液辅助参与无机聚合物材料的合成中,既充当了促进反应和调节浆料粘度的成分,在反应的碱激发溶液的碱性条件下,氧化石墨烯可实现部分原位还原成石墨烯,实现了同步还原和与基体的复合,并在水浴搅拌的有机溶剂作用下,液滴短时间形成球形颗粒,并在短时间反应聚合和固化可收集,实现球形吸附剂的低温制备。此外,氧化石墨烯强化固废无机球形吸附剂的无机部分采用含有硅、铝氧化物的无机固废作为反应物参与聚合反应,固废粉体中活性硅铝氧成分参与聚合反应,也实现了典型工业固废的增值利用,获得的固废无机球形吸附剂材料球形容易控制和操作,球形化的粒径在50-2000微米区间,通过调节水浴搅拌的搅拌速度和温度直接可控,简单容易操作。
本发明获得的氧化石墨烯强化固废无机球形吸附剂具有丰富孔隙结构,比表面积大,可实现对重金属离子铅、镉和铜的去除,吸附效率高,效果好,稳定性好,可实现大规模的生产,成本低,可用于实际固废的治理及工业废水的去除。
附图说明
图1为本发明实施例1所得的氧化石墨烯强化固废无机球形吸附剂的XRD图。
图2为本发明实施例1所得的氧化石墨烯强化固废无机球形吸附剂的SEM图。
具体实施方式
下面结合附图和实施例,对本发明进一步详细说明。
实施例1
本发明涉及一种氧化石墨烯强化固废无机球形吸附剂的制备及其方法,利用氧化石墨烯的吸附特性,采用分散良好的氧化石墨烯水溶液辅助固废无机聚合物反应成型,并采用有机溶剂辅助机械搅拌的成球工艺,实现氧化石墨烯强化固废无机球形吸附剂的制备,获得的氧化石墨烯强化固废无机球形吸附剂。制备过程按照如下步骤进行:
步骤一、氧化石墨烯分散液的配置:称取一定量氧化石墨烯,加入一定量的去离子水,其中氧化石墨烯与去离子水的质量比为1:20,超声分散30min,获得分散均匀的氧化石墨烯分散液。
步骤二、碱激发溶液溶液的配置:在质量分数为40%的硅胶溶液中按照摩尔比1:1加入氢氧化钾,使用磁力搅拌器搅拌30min得到碱激发溶液。
步骤三、氧化石墨烯与无机聚合物浆料的复合:通过天平称取一定量的粉煤灰、矿渣,将两者混合,其中粉煤灰与矿渣质量比为1.5:1,混合后加入步骤二得到的碱激发溶液中,其中混合粉体与碱激发溶液的质量比为20:17。
混合粉体与钾溶液的搅拌过程中逐渐滴入步骤一获得的氧化石墨烯水溶液,其中氧化石墨烯水溶液与钾溶液的质量比为84:850。加入过程中伴随不断的机械搅拌,直到浆料颜色逐渐加深为止,搅拌30min后,实现氧化石墨烯与无机聚合物浆料的复合。
步骤四、水浴搅拌球形化:提前加热聚乙二醇溶液至80℃,并采用机械搅拌器对其搅拌使其受热均匀,将步骤三中所得浆料用小勺滴入少许,小勺每次取量约3g,滴入后搅拌3min后取出,得到球形的无机复合颗粒。
步骤五、固化成型:将步骤四获得的复合颗粒并置于60℃烘箱中干燥固化1天,取出用去离子水和无水乙醇进行清洗,之后继续置于60℃烘箱中干燥固化6天,得到固化后的球形的氧化石墨烯强化固废无机材料。
步骤六、清洗去碱:将步骤五中获得的氧化石墨烯强化固废无机材料置于去离子水中,加入少量盐酸溶液中和多余的钾,浸泡5天至pH达到7时为止,取出后用无水乙醇清洗3次,之后置于60℃烘箱中干燥5天,即可获得氧化石墨烯强化固废无机球形吸附剂。
图1为实施例1步骤六后获得的氧化石墨烯强化固废无机球形吸附剂的物相XRD图谱。从图中可以看出,氧化石墨烯强化固废无机球形吸附剂以非晶结构为主,符合典型无机聚合物材料特征峰。
图2为实施例1所得的氧化石墨烯强化固废无机球形吸附剂的SEM图;从图中可以看到复合球形吸附材料的球形均匀,球表面可见微、纳米孔隙结构。本实施例得到的氧化石墨烯强化固废无机球形吸附剂的吸附性能良好,当球形吸附剂用量为6g/L时,对100mg/L铅离子溶液的吸附量达到约17mg/g,去除率达到约100%。当球形吸附剂用量为4g/L时,对100mg/L镉离子溶液的吸附量达到约13mg/g,去除率达到约52%。当球形吸附剂用量为4g/L时,对100mg/L铜离子溶液的吸附量达到约12mg/g,去除率达到约47%。
实施例2
与实施例1不同在于步骤三中氧化石墨烯水溶液与钾溶液的质量比为83:850。
本实施例也可获得的具有微米、纳米孔隙结构的石墨烯/无机聚合物复合球形吸附材料,当球形吸附剂用量为2g/L时,对100mg/L铅溶液的吸附量达到约42mg/g,去除率达到约85%。
实施例3
与实施例1不同在于步骤三中氧化石墨烯水溶液与钾溶液的质量比为82:850。
本实施例也可获得的具有微米、纳米孔隙结构的碳纳米管强化无机聚合物球形吸附剂,当球形吸附剂用量为2g/L时,对100mg/L铅溶液的吸附量达到约42mg/g,去除率达到约84%。
综合以上各数据分析,说明本方法可以成功制备出氧化石墨烯强化固废无机球形吸附剂。
Claims (6)
1.一种氧化石墨烯强化固废无机球形吸附剂的制备方法,其特征在于,具体步骤如下:
步骤一、氧化石墨烯分散液的配置:称取一定量氧化石墨烯,加入一定量的去离子水,其中氧化石墨烯与去离子水的质量比为(0.001-0.25):1,超声分散,获得分散均匀的氧化石墨烯分散液;
步骤二、碱激发溶液的配置:在质量分数为20-50%的硅胶溶液中按照摩尔比(0.7-1.2):(0.7-1.2)加入氢氧化钾,使用磁力搅拌器搅拌得到碱激发溶液;
步骤三、氧化石墨烯与无机聚合物浆料的复合:将一定量的粉煤灰和矿渣混合,其中粉煤灰与矿渣质量比为(1-2):1,混合后加入步骤二得到的碱激发溶液中,其中混合粉体与碱激发溶液的质量比为(2-6):(4-5);
混合粉体与碱激发溶液的搅拌过程中逐渐滴入步骤一获得的氧化石墨烯分散液,其中氧化石墨烯分散液与碱激发溶液的质量比为(1-4):(20-25);加入过程中伴随不断的机械搅拌,直到浆料颜色逐渐加深为止,搅拌20-50分钟后,实现氧化石墨烯与无机聚合物浆料的复合;
步骤四、水浴搅拌球形化:提前加热聚乙二醇溶液至60-90℃,并采用机械搅拌器对其搅拌使其受热均匀,将步骤三中所得氧化石墨烯与无机聚合物浆料滴入少许,滴入后搅拌后取出,得到球形的无机复合颗粒;
步骤五、固化成型:将步骤四获得的复合颗粒并置于60-90℃烘箱中干燥固化1-3天,取出用去离子水和无水乙醇进行清洗,之后继续置于60-90℃烘箱中干燥固化3-7天,得到固化后的球形的氧化石墨烯强化固废无机材料;
步骤六、清洗去碱:将步骤五中获得的氧化石墨烯强化固废无机材料置于去离子水中,加入少量盐酸溶液中和多余的碱金属离子,浸泡1-10天至pH达到7时为止,取出后用无水乙醇清洗1-3次,之后置于25-90℃干燥0.5-5天,即可获得氧化石墨烯强化固废无机球形吸附剂。
2.根据权利要求1所述的一种氧化石墨烯强化固废无机球形吸附剂的制备方法,其特征在于,所述的步骤一中,超声分散时间为10-120min。
3.根据权利要求1所述的一种氧化石墨烯强化固废无机球形吸附剂的制备方法,其特征在于,所述的步骤二中,磁力搅拌器搅拌时间为15-360min。
4.根据权利要求1所述的一种氧化石墨烯强化固废无机球形吸附剂的制备方法,其特征在于,所述的步骤四中每次取氧化石墨烯与无机聚合物浆料的量1-30g,滴入后搅拌2-10min球形化后取出,再加入下一次氧化石墨烯与无机聚合物浆料。
5.一种氧化石墨烯强化固废无机球形吸附剂,其特征在于,是由权利要求1-4任一所述的制备方法制得的。
6.权利要求1-4任一所述的制备方法制得的一种氧化石墨烯强化固废无机球形吸附剂的应用,其特征在于,用于对实际固废的治理和工业废水中重金属离子铅、镉和铜的去除。
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104529382A (zh) * | 2015-01-14 | 2015-04-22 | 哈尔滨工业大学 | 一种利用氧化石墨烯原位还原制备的石墨烯/铝硅酸盐聚合物复合材料及其制备方法 |
WO2016113321A1 (en) * | 2015-01-14 | 2016-07-21 | Synthos S.A. | Geopolymer composite and expandable vinyl aromatic polymer granulate and expanded vinyl aromatic polymer foam comprising the same |
CN105800972A (zh) * | 2016-03-07 | 2016-07-27 | 青海大学 | 一种粉煤灰地质聚合物多孔材料及其制造工艺 |
CN109626364A (zh) * | 2019-01-29 | 2019-04-16 | 东北大学 | 一种氮硫双掺杂三维石墨烯的制备方法 |
CN110342605A (zh) * | 2019-07-30 | 2019-10-18 | 苏州飞辉环境科技有限公司 | 一种用于吸附焚烧飞灰浸出液中重金属的污泥基活性炭复合材料及其制备方法 |
CN110963551A (zh) * | 2019-11-26 | 2020-04-07 | 西安建筑科技大学 | 一种石墨烯无机聚合物复合电极制备方法 |
WO2021030368A1 (en) * | 2019-08-12 | 2021-02-18 | The Regents Of The University Of Colorado, A Body Corporate | Synthetic aluminosilicate material and methods of forming and using same |
CN113102477A (zh) * | 2021-03-16 | 2021-07-13 | 江苏亿金环保科技有限公司 | 一种铬污染土的治理方法 |
CN113213825A (zh) * | 2021-04-29 | 2021-08-06 | 哈尔滨工程大学 | 一种高开孔率多级孔结构的球形地质聚合物的制备方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11135565B2 (en) * | 2018-10-25 | 2021-10-05 | Uti Limited Partnership | Metal organic framework (MOF) composite materials, methods, and uses thereof |
-
2021
- 2021-11-15 CN CN202111345842.7A patent/CN113877532B/zh active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104529382A (zh) * | 2015-01-14 | 2015-04-22 | 哈尔滨工业大学 | 一种利用氧化石墨烯原位还原制备的石墨烯/铝硅酸盐聚合物复合材料及其制备方法 |
WO2016113321A1 (en) * | 2015-01-14 | 2016-07-21 | Synthos S.A. | Geopolymer composite and expandable vinyl aromatic polymer granulate and expanded vinyl aromatic polymer foam comprising the same |
CN105800972A (zh) * | 2016-03-07 | 2016-07-27 | 青海大学 | 一种粉煤灰地质聚合物多孔材料及其制造工艺 |
CN109626364A (zh) * | 2019-01-29 | 2019-04-16 | 东北大学 | 一种氮硫双掺杂三维石墨烯的制备方法 |
CN110342605A (zh) * | 2019-07-30 | 2019-10-18 | 苏州飞辉环境科技有限公司 | 一种用于吸附焚烧飞灰浸出液中重金属的污泥基活性炭复合材料及其制备方法 |
WO2021030368A1 (en) * | 2019-08-12 | 2021-02-18 | The Regents Of The University Of Colorado, A Body Corporate | Synthetic aluminosilicate material and methods of forming and using same |
CN110963551A (zh) * | 2019-11-26 | 2020-04-07 | 西安建筑科技大学 | 一种石墨烯无机聚合物复合电极制备方法 |
CN113102477A (zh) * | 2021-03-16 | 2021-07-13 | 江苏亿金环保科技有限公司 | 一种铬污染土的治理方法 |
CN113213825A (zh) * | 2021-04-29 | 2021-08-06 | 哈尔滨工程大学 | 一种高开孔率多级孔结构的球形地质聚合物的制备方法 |
Non-Patent Citations (3)
Title |
---|
Emmanuel Christopher Umejuru et al..《ACS Omega》Coal Fly Ash Decorated with Graphene Oxide−Tungsten Oxide Nanocomposite for Rapid Removal of Pb2+ Ions and Reuse of Spent Adsorbent for Photocatalytic Degradation of Acetaminophen.2021,第6卷第11155−11172页. * |
Shu Yan et al..《Environmental Research》Geopolymer composite spheres derived from graphene-modified fly ash/ slag: Facile synthesis and removal of lead ions in wastewater.2022,第220卷第1-13页. * |
朱双 等.《环境工程学报》粉煤灰/氧化石墨烯复合材料吸附Hg( Ⅱ).2017,第11卷(第3期),第1857-1864页. * |
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