CN109277083A - 一种净化水体的铁磁性生物炭球及其制备方法与应用 - Google Patents
一种净化水体的铁磁性生物炭球及其制备方法与应用 Download PDFInfo
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Abstract
一种净化水体的铁磁性生物炭球及其制备方法与应用。是由壳聚糖溶液、生物炭、零价铁粉、中空玻璃微球和氢氧化钠溶液制成的一种粒度在5~6mm的漂浮于水面的球体。制法是在壳聚糖溶液中添加生物炭和零价铁粉,并加入中空玻璃微球,将混合液滴入氢氧化钠溶液中制成,由于吸附位点多,具有强还原性,可以同时或分别去除废水中的六价铬和染料亚甲基蓝,且对所述两种污染物的去除效率都在50%以上。本发明制成的铁磁性生物炭球,由于具有铁磁性且能漂浮于水面,因此不难通过外加磁场进行回收,不会对环境构成二次污染,是一种环境友好型吸附产品。且本发明的制备原材料来源广泛,制作方法简单,成本低,易于产业化,有望成为一种净化水的优良品。
Description
技术领域
本发明属于环境功能材料领域,具体涉及一种净化水体的铁磁性生物炭球及其制备方法与应用。
背景技术
目前,我国部分河流水体受到严重的染料和重金属污染,使得水体生境破坏。印染废水具有COD高、组成复杂、碱度高、温度高、色度大、难生化降解等特点,是最难处理的废水之一。亚甲基蓝是一种典型的水溶性阳离子染料,为杂原子化合物,释放到环境中易对水体造成污染,严重破坏水体生态环境,危害水生动物,如致癌、致畸等,还会对人类健康带来潜在危害。六价铬被大量应用于金属冶炼、印染纺织、皮革鞣制、木材加工和电镀电解等工业生产过程中,是一种危害严重的重金属离子,具有高毒性和很强的流动性,长期暴露在六价铬环境中会慢性中毒,甚至引发癌症。已有的治理亚甲基蓝和六价铬污染常采用的方法有吸附法、膜分离法、高级氧化法、电化学方法和生物法等,虽然吸附法具备操作简易、高效去除、成本较低等特点,但对于含有六价铬的染料废水至今并没有一种高效的去除方法。诸如一种高性能染料吸附材料的制备方法(201810376540.8)的中国发明专利,虽然能够有效的去除亚甲基蓝,但并不能去除六价铬;另有一种吸附剂的制备方法及其在重金属吸附中的应用(201810098182.9)的中国发利,对六价铬具有很好的去除效果,但该方法只单纯解决六价铬污染问题,并未涉及亚甲基蓝的去除。目前并没有一种同时去除废水中的亚甲基蓝和六价铬的有效方法,显然同时提供一种高效去除含有六价铬的染料废水是十分必要的。
生物炭具有比表面积大、富含碳素、离子交换量高,以及孔隙结构发达等独特的理化性质,是用来去除水体中污染物的有效吸附剂。相比于价格昂贵的活性炭,生物炭因其制备方法简单、成本较低,且原料来源广泛,具有广泛地应用前景。虽然生物炭是一种良好的吸附材料,但是生物炭粉末颗粒较细,很难从水中快速分离出来,且在长时间水流的作用下污染物会被解吸。所以,生物炭的回收是一个亟待解决的问题。为此,将生物炭制成球可以解决生物炭流失的问题,如一种生物炭球及其制备方法和应用(CN201510086309.1)的中国发明专利。是利用生物炭和粘土制备的生物炭球,对氨氮去除效率接近50%,但是该生物炭球不能回收而存在二次污染的可能性。显然提供一种方便回收的、不对自然环境构成二次污染,且制备方法简单的生物炭球对于水环境修复具有重要意义。
发明内容
本发明的目的在于提供一种净化水体的铁磁性生物炭球的制备方法,以弥补现有技术的不足。
本发明利用壳聚糖是一种无毒的天然高分子,滴入氢氧化钠中可以形成固体凝胶,利用作为生物炭的载体制备生物炭球;又考虑到对生物炭进行改性后可以去除生物炭的灰分,增大生物炭的比表面积,提高对污染物的去除率,因此用盐酸浸泡生物炭进行改性;并利用零价铁粉具有强的还原性,可以将具有高毒性的六价铁还原为三价铬以降低毒性,且零价铁粉又具有铁磁性,将其加入后可以通过外加磁场快速收集;进而为了实现之后构成的铁磁性生物炭球的快速回收,又在其中加入密度小、质量轻的功能化材料的中空玻璃微球,使终至制成的铁磁性生物炭球的密度小于水而漂浮于水面。
因此,本发明通过在壳聚糖溶液中添加生物炭和零价铁粉,并加入轻质材料中空玻璃微球,将混合液滴入氢氧化钠溶液中制成净化水体的铁磁性生物炭球,并用于去除同时含有六价铬和染料的废水,当然也可以用于治理分别含六价铬和亚甲基蓝的废水。
本发明的净化水体的铁磁性生物炭球,其特征是由壳聚糖溶液、生物炭、零价铁粉、中空玻璃微球和氢氧化钠溶液制成的一种粒度在5~6mm的漂浮于水面的球体。
本发明的制备方法包括如下步骤:
(1)用3mol/L的盐酸浸泡生物炭24h,过滤后用去离子水清洗至pH为中性,在60~80℃的恒温干燥箱中干燥8~12h,过100目筛,得到改性生物炭;
(2)将壳聚糖溶于浓度为1%的乙酸溶液中,待完全溶解后制备成壳聚糖溶液;
(3)将所述改性生物炭和零价铁粉以质量比为1:4~4:1的比例混入上述壳聚糖溶液,并加入中空玻璃微球得到混合液,中空玻璃微球的质量为改性生物炭和铁粉总质量的3/4;
(4)将上述混合液通过50mL注射器滴入质量分数为2%~4%的氢氧化钠溶液中,交联后用去离子水冲洗数遍至pH为中性,即得到铁磁性生物炭球。
上述步骤(1)中生物炭为浒苔生物炭、芦苇生物炭或松针生物炭。
上述步骤(1)中生物炭的质量与3mol/L的盐酸的体积比为1(g):10(mL)。
上述步骤(2)中壳聚糖溶液的质量浓度为2%~4%。
上述步骤(3)中壳聚糖溶液体积与加入改性生物炭和铁粉总质量的比例为20(mL):1(g)。
上述步骤(4)中交联的时间为8~12h。
上述方法制得的铁磁性生物炭球应用于同时处理含有重金属六价铬离子和染料亚甲基蓝的废水,也可以用于净化分别含有重金属六价铬离子的废水和含有染料亚甲基蓝的废水。
本发明具有如下优点和有益效果:
(1)本发明制成的净化水体铁磁性生物炭球吸附位点多,具有强还原性,可被应用于同时或者分别处理含有重金属六价铬和染料亚甲基蓝的废水,且对所述两种污染物的去除效率都在50%以上。
(2)本发明的净化水体的铁磁性生物炭球,由于具有铁磁性且能漂浮于水体表面,因此不难通过外加磁场进行聚集回收,因此不会对环境构成二次污染,是一种环境友好型吸附产品。
(3)本发明的的净化水体铁磁性生物炭球制备原材料来源广泛,制作方法简单,易于产业化,有望成为一种净化水体的优良品牌。
附图说明
图1为本发明的浒苔生物炭酸洗改性前后的SEM图,其中(a)为酸洗改性前浒苔生物炭SEM图,(b)为酸洗改性后的浒苔改性生物炭SEM图。
图2本发明的净化水体的铁磁性生物炭球SEM图。
图3为本发明的铁磁性生物炭球形态图(放于玻璃皿中,其中的白色为反光)。
具体实施方式
本发明用3mol/L的盐酸浸泡生物炭24h,过滤后用去离子水清洗至pH为中性,在60℃的恒温干燥箱中干燥12h,过100目筛,得到改性生物炭;又,将3g壳聚糖溶于100mL浓度为1%的乙酸溶液,待完全溶解后制成质量分数为3%的壳聚糖溶液;之后将改性生物炭、零价铁粉以质量比为2:1的比例混入上述壳聚糖溶液,并加入中空玻璃微球得到混合液,中空玻璃微球的质量为生物炭和铁粉总质量的3/4;将上述混合液通过50mL注射器滴入质量分数为3%的氢氧化钠溶液中,交联10h后,用去离子水冲洗数遍至pH为中性,即可得到铁磁性生物炭球。下面结合实施例对本发明进行详细的描述。
实施例1 以浒苔生物炭为例:
向10g浒苔生物炭中加入3mol/L的盐酸100mL,浸泡24h后过滤,用去离子水冲洗至pH为中性,在80℃的恒温干燥箱中干燥10h,过100目筛,得到改性浒苔生物炭。浒苔生物炭的扫描电镜图为图1(a)所示,改性浒苔生物炭扫描电镜图如图1(b)所示,用盐酸浸泡改性以后,浒苔生物炭的表面更加粗糙,比表面积增大,改性浒苔生物炭对污染物的吸附位点更多,去除污染物能力更强。
将0.6g壳聚糖置于20mL去离子水中,待完全溶解后制成质量分数为3%的壳聚糖溶液;
称取0.33g改性浒苔生物炭和0.67g零价铁粉混入上述壳聚糖溶液,并向其中加入0.75g中空玻璃微球,得到混合液;
将上述混合液通过50mL注射器滴入质量分数为3%的氢氧化钠溶液中,交联10h后用去离子水冲洗数遍至pH为中性,得到铁磁性生物炭球。其扫描电镜图如图2,其中的空心小球为中空玻璃微球,表面有褶皱的块状物为改性浒苔生物炭,表面较光滑块状物为铁粉。其形态图如图3的黑色球体。物理性质如表1所示。
表1,净化水体铁磁性生物炭球的基本物理性质(平均值)
名称 | 粒径(mm) | 密度(g/m<sup>3</sup>) | 质量(g/粒) |
铁磁性生物炭球 | 5.8 | 0.75 | 0.075 |
下面是上述制成的铁磁性生物炭球在处理同时含有六价铬和亚甲基蓝的废水中的应用。
称取上述铁磁性生物炭球1g置于50mL锥形瓶中,向其中加入20mL亚甲基蓝浓度为20mg/L、六价铬浓度为10mg/L的溶液,在温度为30℃,转速为150r/min的条件下震荡吸附20h,用外加磁场快速收集吸附饱和的铁磁性生物炭球后,测定溶液中亚甲基蓝和六价铬的剩余浓度,结果表明了亚甲基蓝的去除率为67.16%,六价铬的去除率为56.24%。
实施例2 以芦苇生物炭为例:
向15g芦苇生物炭加入3mol/L的盐酸150mL,浸泡24h后过滤,用去离子水冲洗至pH为中性,在80℃的恒温干燥箱中干燥10h,过100目筛,得到改性芦苇生物炭;
将0.4g壳聚糖置于20mL浓度为1%的乙酸溶液中,待完全溶解后制成质量分数为2%的壳聚糖溶液;
称取0.25g改性芦苇生物炭和0.75g零价铁粉混入上述壳聚糖溶液,并向其中加入0.75g中空玻璃微球,得到混合液;
再将上述混合液通过50mL注射器滴入质量分数为4%的氢氧化钠溶液中,交联10h后用去离子水冲洗数遍至pH为中性,即得到铁磁性生物炭球。
下面是上述制成的铁磁性生物炭球在处理同时含有六价铬和亚甲基蓝的废水中的应用。
称取上述铁磁性生物炭球1g至于50mL锥形瓶中,向其中加入20mL亚甲基蓝浓度为10mg/L、六价铬浓度为10mg/L的溶液,在温度为30℃,转速为150r/min的条件下震荡20h,用外加磁场快速收集吸附饱和的铁磁性生物炭球后,测定溶液中亚甲基蓝和六价铬的剩余浓度,结果表明该亚甲基蓝的去除率为70.24%,六价铬的去除率为50.12%。
实施例3 以松针生物炭为例:
向5g松针生物炭加入3mol/L的盐酸50mL,浸泡24h后过滤,用去离子水冲洗至pH为中性,在70℃的恒温干燥箱中干燥11h,过100目筛,得到改性松针生物炭;
又将0.8g壳聚糖置于20mL浓度为1%的乙酸溶液中,待完全溶解后制备成质量分数为4%的壳聚糖溶液;
称取0.75g改性松针生物炭和0.25g零价铁粉混入上述壳聚糖溶液,并向其中加入0.75g中空玻璃微球,得到混合液;
之后,将混合液通过50mL注射器滴入质量分数为2%的氢氧化钠溶液中,交联12h后用去离子水冲洗数遍至pH为中性,即得到铁磁性生物炭球。
下面是上述制成的铁磁性生物炭球在处理同时含有六价铬和亚甲基蓝的废水中的应用。
称取上述铁磁性生物炭球1g至于50mL锥形瓶中,向其中加入20mL亚甲基蓝浓度为10mg/L、六价铬浓度为10mg/L的溶液,在温度为30℃,转速为150r/min的条件下震荡20h,用外加磁场快速收集吸附饱和的铁磁性生物炭球后,测定溶液中亚甲基蓝和六价铬的剩余浓度,结果亚甲基蓝的去除率为65.3%,六价铬的去除率为51.2%。
显然,本发明的铁磁性生物炭球对同时含有六价铬和亚甲基蓝染料的废水具有明显的去除率,是一种有效的净化水质的产品。
Claims (9)
1.一种净化水体的铁磁性生物炭,其特征在于,是由壳聚糖溶液、生物炭、零价铁粉、中空玻璃微球和氢氧化钠溶液制成一种粒度在5~6mm的漂浮于水面的球体。
2.权利要求1所述的净化水体的铁磁性生物炭球的制备方法,其特征在于,包括如下步骤:
(1)用3mol/L的盐酸浸泡生物炭24h,过滤后用去离子水清洗至pH为中性,在60~80℃的恒温干燥箱中干燥8~12h,过100目筛,得到改性生物炭;
(2)将壳聚糖溶于浓度为1%的乙酸溶液中,待完全溶解后制备成壳聚糖溶液;
(3)将所述改性生物炭和零价铁粉以质量比为1:4~4:1的比例混入上述壳聚糖溶液,并加入中空玻璃微球得到混合液,中空玻璃微球的质量为生物炭和铁粉总质量的3/4;
(4)将上述混合液通过50mL注射器滴入质量分数为2%~4%的氢氧化钠溶液中,交联8~12h后用去离子水冲洗数遍至pH为中性,即得到铁磁性生物炭球。
3.根据权利要求2所述的制备方法,其特征在于,上述步骤(1)中生物炭为浒苔生物炭、芦苇生物炭和松针生物炭。
4.根据权利要求2所述的制备方法,其特征在于,上述步骤(1)中生物炭的质量与3mol/L的盐酸的体积比为1(g):10(mL)。
5.根据权利要求2所述的制备方法,其特征在于,上述步骤(2)中壳聚糖溶液的质量浓度为2%~4%。
6.根据权利要求2所述的制备方法,其特征在于,上述步骤(3)中壳聚糖溶液体积与加入生物炭和铁粉总质量的比为20(mL):1(g)。
7.权利要求1所述的净化水体的铁磁性生物炭球,其特征在于,应用于处理同时含有重金属六价铬离子和染料亚甲基蓝的废水。
8.权利要求1所述的净化水体的铁磁性生物炭球,其特征在于,用于净化分别含有重金属六价铬离子的废水和含有染料亚甲基蓝的废水。
9.根据权利要求7所述的应用方法,其特征在于,净化或去除步骤为将铁磁性生物炭球以50g/L的浓度投放于含有六价铬的染料水体中,吸附20h后,通过外加磁场,将吸附饱和的铁磁性生物炭球快速聚集回收。
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109759014A (zh) * | 2019-02-25 | 2019-05-17 | 大连理工大学 | 一种含持久性自由基的生物炭基环境修复材料的制备方法 |
CN111085540A (zh) * | 2019-12-19 | 2020-05-01 | 浙江碧岩环保科技有限公司 | 可分离土壤污染物的新材料及其制备工艺 |
CN111747596A (zh) * | 2020-06-10 | 2020-10-09 | 苏州华烯环保科技有限公司 | 一种废水絮凝装置 |
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CN114345304A (zh) * | 2021-12-30 | 2022-04-15 | 北京建工环境修复股份有限公司 | 一种负载零价铁的纤维素壳聚糖复合微球及其制备方法和应用 |
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103464102A (zh) * | 2013-09-23 | 2013-12-25 | 北京师范大学 | 一种用于去除河流底泥污染物的多孔复合吸附剂及其制备工艺 |
CN103801387A (zh) * | 2012-11-15 | 2014-05-21 | 中国海洋大学 | 一种用于光催化氧化半焦基烟气脱硫、脱硝剂及其制备方法 |
CN104587924A (zh) * | 2014-12-18 | 2015-05-06 | 昆明理工大学 | 低聚物预涂覆制备低密度无渗透性多孔或中空微球的方法 |
CN105597691A (zh) * | 2015-12-19 | 2016-05-25 | 中国海洋大学 | 一种复合微球的制备方法及其应用 |
CN105709699A (zh) * | 2016-04-18 | 2016-06-29 | 华中科技大学 | 一种土壤重金属吸附剂及其制备方法 |
CN106492714A (zh) * | 2016-10-28 | 2017-03-15 | 华中科技大学 | 海藻酸钙包裹型纳米铁微球的制备与应用 |
CN107930596A (zh) * | 2017-11-29 | 2018-04-20 | 烟台大学 | 一种改性磁性生物质炭吸附材料及其制备方法 |
CN108311117A (zh) * | 2018-02-05 | 2018-07-24 | 中南林业科技大学 | 一种用于重金属废水处理的磁性生物炭材料及其制备方法 |
-
2018
- 2018-10-26 CN CN201811254912.6A patent/CN109277083A/zh active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103801387A (zh) * | 2012-11-15 | 2014-05-21 | 中国海洋大学 | 一种用于光催化氧化半焦基烟气脱硫、脱硝剂及其制备方法 |
CN103464102A (zh) * | 2013-09-23 | 2013-12-25 | 北京师范大学 | 一种用于去除河流底泥污染物的多孔复合吸附剂及其制备工艺 |
CN104587924A (zh) * | 2014-12-18 | 2015-05-06 | 昆明理工大学 | 低聚物预涂覆制备低密度无渗透性多孔或中空微球的方法 |
CN105597691A (zh) * | 2015-12-19 | 2016-05-25 | 中国海洋大学 | 一种复合微球的制备方法及其应用 |
CN105709699A (zh) * | 2016-04-18 | 2016-06-29 | 华中科技大学 | 一种土壤重金属吸附剂及其制备方法 |
CN106492714A (zh) * | 2016-10-28 | 2017-03-15 | 华中科技大学 | 海藻酸钙包裹型纳米铁微球的制备与应用 |
CN107930596A (zh) * | 2017-11-29 | 2018-04-20 | 烟台大学 | 一种改性磁性生物质炭吸附材料及其制备方法 |
CN108311117A (zh) * | 2018-02-05 | 2018-07-24 | 中南林业科技大学 | 一种用于重金属废水处理的磁性生物炭材料及其制备方法 |
Non-Patent Citations (3)
Title |
---|
CHANGJIANG YU ET AL: ""Pyrolytic behavior of a zero-valent iron biochar composite and its Cu(II) removal mechanism"", 《RSC ADVANCES》 * |
ZHOU YUNMEI ET AL: ""Biochar-supported zerovalent iron for removal of various contaminants from aqueous solutions"", 《BIORESOURCE TECHNOLOGY》 * |
孟繁健等: ""改性生物炭负载nZVI对土壤Cr(VI)的修复差异研究"", 《环境科学学报》 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109759014A (zh) * | 2019-02-25 | 2019-05-17 | 大连理工大学 | 一种含持久性自由基的生物炭基环境修复材料的制备方法 |
CN112850836A (zh) * | 2019-11-27 | 2021-05-28 | 北京化工大学 | 一种壳聚糖稳定硫化亚铁复合生物炭材料的制备与应用 |
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Application publication date: 20190129 |