CN104258817B - 三聚氰胺修饰的磁性壳聚糖、制备方法及其应用 - Google Patents

三聚氰胺修饰的磁性壳聚糖、制备方法及其应用 Download PDF

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CN104258817B
CN104258817B CN201410370954.1A CN201410370954A CN104258817B CN 104258817 B CN104258817 B CN 104258817B CN 201410370954 A CN201410370954 A CN 201410370954A CN 104258817 B CN104258817 B CN 104258817B
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CN104258817A (zh
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吴占超
刘杰
王召占
匡少平
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Qingdao University of Science and Technology
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

Abstract

本发明提出了三聚氰胺修饰磁性壳聚糖的制备方法及其应用，首先将壳聚糖用2％乙酸溶液溶胀，然后与环氧氯丙烷反应，之后将四氧化三铁引入到产物当中，最后与三聚氰胺反应，从而得到目标吸附剂。本发明吸附剂可连续合成，不用分离中间产物，制备过程简单，主要用于对重金属离子污染的废水进行吸附处理，它既可以对单一的重金属离子进行吸附回收，也可以对多种重金属离子污染的废水进行吸附处理，而且具有成本低、吸附效果好、易分离、可多次重复使用等优点，是一种潜在的重金属废水处理剂。

Description

三聚氰胺修饰的磁性壳聚糖、制备方法及其应用
技术领域
本发明涉及一种三聚氰胺修饰磁性壳聚糖及其制备方法和应用，制备的产品主要用于对重金属离子污染的废水进行吸附处理，是潜在的废水处理剂，属于重金属离子废水处理领域。
背景技术
水对生命体起着至关重要的作用，它是生命的源泉，是人类赖以生存和发展的最重要的资源之一。随着近代工业的发展，产生了各种各样的污染物，水体的污染也越来越严重，这给人类的健康造成了很大的威胁。尤其是采矿、冶炼、电镀、化工、制革、电子等行业的发展造成的重金属污染，它对人类的危害逐渐呈现出来。近年来出现的“血铅事件”、“毒大米”、“痛痛病”以及一些癌症村的出现，包括2005年广东北江韶关段镉严重超标事件，2006年湘江湖南株洲段镉污染事故，2009年湖南省浏阳市镉污染事件，这些都是重金属污染的实例。
目前用于处理含重金属废水的方法很多，由于成本高、耗能大、易产生二次污染以及对重金属离子有选择性等缺点，因此大部分都不能用于实际的废水处理。壳聚糖是甲壳素脱乙酰基后的产物，其表面含有大量的羟基和氨基，使得它能和很多重金属离子发生螯合作用，形成具有网状结构的螯合物。其来源广泛、价格低廉，并且属可再生资源。此外，壳聚糖还具有无毒、生物可降解性、生物相容性、多功能性以及高化学反应性等特点。壳聚糖虽然有很多优点，但其对金属离子的吸附量仍不是很高，因此，对壳聚糖进行改性，增加其分子中配位原子的数量，使其具有更大的吸附能力成为了人们研究的热点。目前高含氮、氧和硫的化合物是壳聚糖修饰物的首选，例如三乙烯四胺、乙二胺、硫脲、氯乙酸和2-Thioglyceraldehyde等。三聚氰胺为价廉易得的化工原料,含有三个自由氨基和三个芳香氮原子,对重金属离子具有很大的吸附潜力,如果将其接枝到壳聚糖分子上,有望得到价廉、高效的天然基质吸附剂。由于三聚氰胺的溶解性很差，导致其反应活性很低，因此，目前还很少研究与三聚氰胺相关的重金属离子吸附剂。
发明内容
基于以上考虑,本研究用三聚氰胺对壳聚糖进行了修饰，得到了三聚氰胺修饰的磁性壳聚糖，提供了三聚氰胺修饰磁性壳聚糖吸附剂的制备方法。
所述吸附剂的结构示意图见说明书附图(图1)。
本发明吸附剂制备方法的大体过程如下：
取1.0g壳聚糖溶于100ml 2％(体积百分数)的乙酸溶液中，溶胀20min；搅拌下将其加入到100ml 0.25mol/L NaOH溶液中沉淀，抽滤，用丙酮洗涤3次，将其转入到100ml丙酮中，搅拌成悬浊液，滴入5ml环氧氯丙烷，于25℃下反应24h。之后加入1.0g Fe3O4，超声20min。之后加入5.5g三聚氰胺(先溶于50mlDMSO中)，回流7h。之后再加入10g三聚氰胺(先溶于50mlDMSO中)、50ml 1mol/L NaOH溶液和0.05g KI，再回流5h。冷却至室温，抽滤，依次用去离子水、丙酮充分洗涤，60℃真空干燥，之后通过外加磁场将没有磁性的部分分离掉，即得到三聚氰胺修饰的磁性壳聚糖。
本发明吸附剂的优点：
第一，可连续合成，不用分离中间产物，制备过程简单，而且制备成本低。
第一，吸附位点多，吸附量大，吸附速度快，25分钟即可达到吸附平衡；
第二，吸附效果好、无二次污染而且原料廉价易得；
第三，对重金属离子没有选择性，既可以对单一的重金属离子进行吸附回收，也可以对多种重金属离子污染的废水进行吸附处理。
第四，吸附完之后，两分钟之内即可从溶液中快速分离出来；之后可通过解吸使吸附剂 再生，即可重复使用；
附图说明
图1、吸附剂的结构示意图。
图2、吸附剂的制备过程。
图3、壳聚糖(a)、三聚氰胺修饰的磁性壳聚糖(b)和三聚氰胺(c)的红外光谱。
图4、四氧化三铁(a)、壳聚糖(b)、三聚氰胺修饰的磁性壳聚糖(c)和三聚氰胺(d)的X-射线衍射分析。
图5、三聚氰胺修饰的磁性壳聚糖的扫描电镜图片。
图6、磁分离效果图片。
具体实施方式
所用壳聚糖的脱乙酰度大于90％，购于上海蓝季科技发展有限公司。
取1.0g壳聚糖溶于100ml 2％(体积百分数)的乙酸溶液中，溶胀20min；搅拌下将其加入到100ml 0.25mol/L NaOH溶液中沉淀，抽滤，用丙酮洗涤3次，将其转入到100ml丙酮中，搅拌成悬浊液，滴入5ml环氧氯丙烷，于25℃下反应24h。之后加入1.0g Fe3O4，超声20min。之后加入5.5g三聚氰胺(先溶于50mlDMSO中)，回流7h。之后再加入10g三聚氰胺(先溶于50mlDMSO中)、50ml 1mol/L NaOH溶液和0.05g KI，再回流5h。冷却至室温，抽滤，依次用去离子水、丙酮充分洗涤，60℃真空干燥，之后通过外加磁场将没有磁性的部分分离掉，即得到三聚氰胺修饰的磁性壳聚糖。
用本发明吸附剂对Cu2+进行了吸附试验。
最佳吸附条件为:pH＝5.5、温度为25℃、吸附时间为25min以及Cu2+的初始浓度为5mmol/L。
实验结果:在最优实验条件下对Cu2+的吸附量为2.58mmol/g；本发明吸附剂再生5次后的吸附量为2.05mmol/g。
分离效果：通过外加磁场可在2分钟内将吸附剂和溶液彻底分开。

Claims (2)

1.一种新型的重金属离子吸附剂，其结构示意图如下：
。
2.权利要求1中吸附剂的制备方法，其特征包含以下步骤：
取1.0g壳聚糖溶于100ml 2％(体积百分数)的乙酸溶液中，溶胀20min；搅拌下将其加入到100ml 0.25mol/L NaOH溶液中沉淀，抽滤，用丙酮洗涤3次，将其转入到100ml丙酮中，搅拌成悬浊液，滴入5ml环氧氯丙烷，于25℃下反应24h。之后加入1.0g Fe3O4，超声20min，之后加入50mL 0.11g/mL的三聚氰胺DMSO溶液，回流7h；之后再加入50mL 0.2g/mL的三聚氰胺DMSO溶液、50ml 1mol/L NaOH溶液和0.05g KI，再回流5h，冷却至室温，抽滤，依次用去离子水、丙酮充分洗涤，60℃真空干燥，之后通过外加磁场将没有磁性的部分分离掉，即得到三聚氰胺修饰的磁性壳聚糖。
CN201410370954.1A 2014-07-30 2014-07-30 三聚氰胺修饰的磁性壳聚糖、制备方法及其应用 Expired - Fee Related CN104258817B (zh)

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Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104923169A (zh) * 2015-04-25 2015-09-23 青岛科技大学 L-精氨酸修饰磁性壳聚糖、制备方法及其应用
CN105195112B (zh) * 2015-10-26 2017-06-06 福建农林大学 三聚氰胺改性壳聚糖包裹磁性纳米纤维素吸附剂的制备方法及产品
CN105879913B (zh) * 2016-04-28 2018-07-17 东华大学 一种负载金属离子的壳聚糖膜催化材料及其制备方法
CN106311187B (zh) * 2016-09-07 2018-01-02 济南大学 一种三聚氰胺改性磁性椰子皮吸附剂的制备
CN106238004B (zh) * 2016-09-07 2018-02-09 济南大学 一种三聚氰胺改性磁性麻吸附剂的制备
CN106215881B (zh) * 2016-09-07 2018-02-09 济南大学 一种三聚氰胺改性多孔磁性葡聚糖微球的制备方法
CN108816198A (zh) * 2018-07-11 2018-11-16 安庆师范大学 一种镉离子吸附剂及其制备方法
CN111514870B (zh) * 2020-05-12 2021-08-13 西安交通大学 三聚氰胺修饰固相萃取剂及富集马兜铃酸的固相萃取方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4285819A (en) * 1980-01-28 1981-08-25 California Institute Of Technology Functional magnetic microspheres
CN101723499A (zh) * 2009-11-03 2010-06-09 燕山大学 二乙烯三胺五乙酸改性硅藻土的制备工艺
CN102079823A (zh) * 2010-12-06 2011-06-01 南华大学 一种乙二胺改性壳聚糖复合磁性微球的制备方法及其用途

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4285819A (en) * 1980-01-28 1981-08-25 California Institute Of Technology Functional magnetic microspheres
CN101723499A (zh) * 2009-11-03 2010-06-09 燕山大学 二乙烯三胺五乙酸改性硅藻土的制备工艺
CN102079823A (zh) * 2010-12-06 2011-06-01 南华大学 一种乙二胺改性壳聚糖复合磁性微球的制备方法及其用途

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Preparation of trithylene-tetramine grafted magnetic chitosan for adsorption of Pb(II) ion from aqueous solutions;Shaoping Kuang, et al;《Journal of Hazardous Materials》;20130518;第260卷;第211页左栏第2段至右栏第4段 *
羧、氨基修饰磁性壳聚糖纳米微球的制备与表征;张全丽，等;《青岛科技大学学报（自然科学版）》;20111231;第32卷(第6期);第573-576、579页 *

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