CN106423087B - 一种磁性壳聚糖碳球的制备及在吸附去除水中Cr(Ⅵ)上的应用 - Google Patents

一种磁性壳聚糖碳球的制备及在吸附去除水中Cr(Ⅵ)上的应用 Download PDF

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CN106423087B
CN106423087B CN201611202849.2A CN201611202849A CN106423087B CN 106423087 B CN106423087 B CN 106423087B CN 201611202849 A CN201611202849 A CN 201611202849A CN 106423087 B CN106423087 B CN 106423087B
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王诗生
刘齐齐
戴波
盛广宏
练建军
吴鉴衡
于冬冬
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Abstract

本发明公开了一种磁性壳聚糖碳球的制备及在吸附去除水中Cr(Ⅵ)上的应用,属于水污染控制技术领域。该磁性壳聚糖碳球的制备,首先利用水热法制备磁性铁酸钴,然后运用水热法将壳聚糖碳化负载在磁性铁酸钴的表面,得到磁性壳聚糖碳球。本发明提供吸附剂的制备方法简单、能耗低,易操作;制备得到的吸附剂物理化学稳定性强,在较宽的pH范围内可使用;具有较强磁性,采用磁铁即能够实现快速固液分离;表面富含—OH和—NH2等活性基团,可用于水中Cr(Ⅵ)的高效去除。

Description

一种磁性壳聚糖碳球的制备及在吸附去除水中Cr(Ⅵ)上的 应用
技术领域
本发明属于水污染控制技术领域,具体涉及到一种磁性壳聚糖碳球的制备方法,本发明还涉及利用上述制备的磁性壳聚糖碳球去除水中Cr(Ⅵ)的方法。
背景技术
重金属铬是我国优先控制的污染物之一,主要来源于电镀、冶金、制革、印染和化工等行业排放的三废。铬在水体中主要以Cr(Ⅲ)和Cr(Ⅵ)的形式存在。与Cr(Ⅲ)相比,Cr(Ⅵ)的毒性更强,被人体吸收会引起胃疼、恶习、腹泻、呕吐、肝癌等疾病。
目前,含铬废水的处理方法主要有化学沉淀法、离子交换法、膜分离法、光催化法、电化学法、生物化学法等。吸附法具有操作简单、成本较低、处理效果好等优点,已广泛用于处理含铬废水。然而,一些传统的吸附剂吸附去除Cr(Ⅵ)时,存在着吸附量偏低或者吸附达到平衡所需时间长的缺点。
壳聚糖是通过甲壳素脱乙酰基而制得的一种天然阳离子多聚糖,具有生物相容性、环境友好性等特点,其分子链上富含—OH和—NH2等活性基团,可以通过静电或络合作用从废水中吸附重金属离子等污染物。
中国专利“一种新型高效的除铬剂及其制备方法”(申请号200910053681.7,公开号101927153A,公开日2010年12月29日)以壳聚糖和壳聚精为主要反应剂,再辅以稳定剂、水等成分,制备出一种除铬剂。
中国专利“一种磁性壳聚糖微球处理剂及其制备方法”(申请号201310097557.7,公开号103127914A,公开日2013年6月5日)是将电气石和磁性壳聚糖微球混合粉加入海藻酸钠和聚乙烯醇中溶解、混匀,然后固化成球,用于吸附去除水中Cr(Ⅵ)。
中国专利“改性磁性壳聚糖微球重金属离子吸附剂的制备方法”(申请号201310189171.9,公开号103263895A,公开日2013年8月28日)首先以壳聚糖为原料制备磁性壳聚糖微球,然后对其进行化学接枝改性,得到一种Cr(Ⅵ)吸附剂。
中国专利“一种基于壳聚糖的吸附Cr(Ⅵ)的吸附剂的制备方法”(申请号201410199659.4,公开号103933951A,公开日2014年7月23日)以自然界广泛存在的壳聚糖为原材料,在高压水热反应釜中进行水热反应,得到富含—OH和—NH2而又耐酸的新型碳材料吸附剂。
中国专利“一种耐酸性磁性壳聚糖微球、制备方法及其应用”(申请号201410608653.8,公开号104437395A,公开日2015年3月25日)以壳聚糖粉末为原料,通过乳液交联法制备包覆磁性SiO2的壳聚糖微球。同时为了进一步提高微球的吸附量,以枝状聚乙烯亚胺为功能基团对吸附剂进行改性,得到改性壳聚糖微球,可用于吸附去除水中Cr(Ⅵ)。
中国专利“利用β-环糊精壳聚糖与核桃壳生物碳复合的吸附剂去除废水中的Cr(Ⅵ)的方法”(申请号201510585777.3,公开号105236507A,公开日2016年1月13日)先将β-环糊精壳聚糖进行复合,然后将晒干磨成粉末的核桃壳生物质进行高温煅烧,制得核桃壳生物炭,最后将β-环糊精壳聚糖复合到生物炭表面。
中国专利“一种壳聚糖与磁性生物碳复合的磁性吸附剂去除废水中Cr(Ⅵ)的方法”(申请号201510126324.4,公开号104787831A,公开日2015年7月22日)先利用FeCl3·6H2O对水葫芦生物质进行浸泡,然后对浸泡过的生物质进行热解煅烧,从而制得磁性生物炭,再将壳聚糖复合到磁性生物炭表面。
中国专利“一种去除水中重金属的磁性吸附剂及其制备方法”(申请号201610186666.X,公开号105664884A,公开日2016年6月15日)将磁性壳聚糖—聚乙烯醇微球依次经戊二醛交联改性和二硫化碳改性所得,制备一种去除水中Cr(Ⅵ)的磁性吸附剂。
上述专利中制备的吸附剂吸附去除Cr(Ⅵ)性能较好。但是,由于壳聚糖在酸性水溶液中容易发生溶解并形成胶体,通常无法直接在酸性条件下使用。但是对于Cr(Ⅵ)只能在酸性条件下才能有良好效果。为了提高在酸性条件下的稳定性,必须对壳聚糖进行改性,如和戊二醛、环氧氯丙烷和乙二胺等发生交联反应。这些交联改性的制备过程相当复杂,且需要大量的有机溶剂,易产生二次污染,有时还会导致吸附性能的下降。另外,在上述专利中部分吸附剂吸附后难以固液分离。因而需要寻找更为简便、绿色而又有效的壳聚糖吸附剂的制备方法,既保留壳聚糖的活性基团,又能实现简单快速固液分离。
发明内容
本发明旨在提供一种制备工艺简单、成本低、易操作、吸附容量大、较强化学稳定性且能够实现简单快速分离去除废水中Cr(Ⅵ)的吸附剂的制备方法和应用。
本发明的原理:首先利用水热法制备磁性铁酸钴,然后运用水热法将壳聚糖碳化负载在磁性铁酸钴的表面,得到磁性壳聚糖碳球。该吸附剂表面既富含—OH和—NH2等活性基团,内核铁酸钴具有一定磁性,采用磁铁即能够实现快速简单分离。
本发明所采用的技术方案是,磁性壳聚糖微球的制备方法,具体按照以下步骤实施:
Ⅰ磁性铁酸钴的制备
(1)按照铁盐和钴盐摩尔比为2:1分别称取FeCl3·6H2O和CoCl2·6H2O溶于50mL蒸馏水中;
(2)在磁力搅拌下,向由步骤(1)得到的溶液中滴加2mol/L氢氧化钠溶液至pH大于11,将溶液转移至水热反应釜中(装填度≤75%),置于高温炉中180℃水热反应24h;
(3)自然冷却后,对步骤(2)得到的固液进行磁分离,所得固体用0.1mol/LHCl和蒸馏水反复洗涤至中性,烘干、研磨过筛,即得到磁性铁酸钴。
Ⅱ磁性壳聚糖微球的制备
(1)按照壳聚糖和磁性铁酸钴质量比为1~4:1称取壳聚糖和铁酸钴,加蒸馏水后超声使之溶解分散;
(2)将步骤(1)得到的溶液转移到水热反应釜中(装填度≤75%),置于高温炉中180℃水热反应12~48h;
(3)自然冷却后,对步骤(2)得到的固液进行磁分离,所得固体用无水乙醇和蒸馏水反复洗涤至中性,烘干、研磨过筛,即得到磁性壳聚糖微球。
进一步的,上述制备方法得到的磁性壳聚糖碳球在吸附去除水中Cr(Ⅵ)上的应用。
更进一步的,上述应用的最佳条件是:在298K、150r/min条件下,Cr(Ⅵ)初始浓度为100~600mg/L,溶液pH为2,吸附时间为5min~48h,之后磁分离。此时Cr(Ⅵ)的最大吸附量为274.8mg/g。
与现有技术相比,本发明有如下优点:
(1)本发明提供的吸附剂采用水热法制备,该工艺简单,能耗低,易操作;制备得到的吸附剂物理化学稳定性强,在较宽的pH范围内可使用;具有较好的磁性,可在外加磁场条件下与水分离,达到固液分离效果。
(2)本发明提供的吸附剂表面富含—OH和—NH2等活性基团,可以利用这种吸附剂吸附去除水中Cr(Ⅵ),在298K、pH=2和150r/min的条件下,该吸附剂的最大理论吸附量为274.8mg/g,表明将本发明提供的磁性壳聚糖碳球用于吸附去除水中Cr(Ⅵ)具有良好的经济效益和环境效益。
附图说明
图1为本发明实施例4中磁性壳聚糖碳球的扫描电镜(SEM)图。
图2是本发明实施例4中磁性壳聚糖碳球的红外光谱(FTIR)图;
其中:A代表铁酸钴,B代表磁性壳聚糖碳球。
图3是本发明实施例4中磁性壳聚糖碳球的X射线衍射(XRD)图;
其中:A代表铁酸钴,B代表磁性壳聚糖碳球。
图4是本发明实施例4中磁性壳聚糖碳球的磁滞回线图;
其中:A代表铁酸钴,B代表磁性壳聚糖碳球。
具体实施方式
下面通过实例,对本发明作进一步详细的描述,但本发明不局限于下述实施例。
一、吸附剂的制备
实施例1
1、磁性铁酸钴的制备
(1)分别称取2.71g FeCl3·6H2O和1.19g CoCl2·6H2O溶于50mL蒸馏水中;
(2)在磁力搅拌下,向由步骤(1)得到的溶液中滴加2mol/L氢氧化钠溶液至pH大于11,将溶液转移至100mL水热反应釜中(装填度≤75%),置于高温炉中180℃水热反应24h;
(3)自然冷却后,对步骤(2)得到的固液进行磁分离,所得固体用0.1mol/LHCl和蒸馏水反复洗涤至中性,60℃烘干、研磨过筛,即得到磁性铁酸钴。
2、磁性壳聚糖碳球的制备
(1)按照壳聚糖和磁性铁酸钴质量比为1:1称取壳聚糖和铁酸钴,加50mL蒸馏水后超声15min后使之溶解分散;
(2)将步骤(1)得到的溶液转移到100mL水热反应釜中(装填度≤75%),置于高温炉中180℃水热反应24h;
(3)自然冷却后,对步骤(2)得到的固液进行磁分离,所得固体用无水乙醇和蒸馏水反复洗涤至中性,60℃烘干、研磨过筛,即得到磁性壳聚糖微球。
实施例2
1、磁性铁酸钴的制备
同实施例1。
2、磁性壳聚糖碳球的制备
同实施例1,所不同的是加入壳聚糖和磁性铁酸钴质量比为2:1。
实施例3
1、磁性铁酸钴的制备
同实施例1。
2、磁性壳聚糖碳球的制备
同实施例1,所不同的是加入壳聚糖和磁性铁酸钴质量比为3:1。
实施例4
1、磁性铁酸钴的制备
同实施例1。
2、磁性壳聚糖碳球的制备
同实施例1,所不同的是加入壳聚糖和磁性铁酸钴质量比为4:1。
实施例5
1、磁性铁酸钴的制备
同实施例1。
2、磁性壳聚糖碳球的制备
同实施例4,所不同的是水热反应时间应为12h。
实施例6
1、磁性铁酸钴的制备
同实施例1。
2、磁性壳聚糖碳球的制备
同实施例4,所不同的是水热反应时间应为48h。
二、磁性壳聚糖碳球吸附去除水中Cr(Ⅵ)的实施例
实施例7
称取0.050g实施例1中制备的吸附剂,加入到40mLK2Cr2O7溶液中(pH=2,300mg/L),在298K、150r/min的条件下振荡至吸附平衡,磁分离后测定上清液中Cr(Ⅵ)剩余浓度,计算结果列于表1中。
实施例8
同实施例7,所不同的是称取0.050g实施例2中制备的吸附剂。
实施例9
同实施例7,所不同的是称取0.050g实施例3中制备的吸附剂。
实施例10
同实施例7,所不同的是称取0.050g实施例4中制备的吸附剂。
实施例11
同实施例7,所不同的是称取0.050g实施例5中制备的吸附剂。
实施例12
同实施例7,所不同的是称取0.050g实施例6中制备的吸附剂。
表1各实施例制备的吸附剂对Cr(Ⅵ)的吸附性能比较
由表1可知,在相同条件下,实施例1~4中制备的吸附剂对水中Cr(Ⅵ)的去除率呈递增趋势,且均能通过外加磁场实现固液快速分离。另外,从表1还可以看出,磁性壳聚糖碳球制备实施例4中的吸附剂吸附性能最好。
实施例13
称取若干份0.050g实施例4中制备的吸附剂,分别加入到20mL重铬酸钾溶液中(pH=2,300mg/L),在298K、150r/min的条件下振荡,在预先设定时间点取样,磁分离后测定上清液中Cr(Ⅵ)剩余浓度,计算结果列于表2中。
表2吸附动力学
由表2可知,本发明提供的吸附剂对Cr(Ⅵ)吸附速率较快,在吸附2h后基本能达到平衡,去除率高达91.7%。
实施例14
称取0.050g实施例4中制备的吸附剂,加入到40mL不同pH值重铬酸钾溶液中(pH=2~8,300mg/L),在298K、150r/min的条件下振荡至吸附平衡,磁分离后测定上清液中Cr(Ⅵ)剩余浓度,计算结果列于表3中。
表3 pH的影响
由表3可知,本发明提供的吸附剂吸附去除水中Cr(Ⅵ)随pH的升高而降低,酸性越强越有利于Cr(Ⅵ)的去除,当pH=2,Cr(Ⅵ)去除率高达91.4%。
实施例15
称取若干份0.050g实施例4中制备的吸附剂,分别加入到40mL不同浓度(100~600mg/L)重铬酸钾溶液中(pH=2),在298K、150r/min的条件下振荡至吸附平衡,磁分离后测定上清液中Cr(Ⅵ)剩余浓度,计算结果列于表4中。
表4吸附等温线
对表4数据进行F和L型线性拟合,结果符合L型吸附。根据L型方程计算理论最大吸附量为274.8mg/g。

Claims (3)

1.一种磁性壳聚糖碳球的制备方法,其特征在包括以下步骤:
(1)磁性铁酸钴的制备:
按照铁盐和钴盐摩尔比为2:1分别称取FeCl3·6H2O和CoCl2·6H2O溶于50mL蒸馏水中,在磁力搅拌下滴加2mol/L氢氧化钠溶液至pH大于11,后将溶液转移至水热反应釜中,置于高温炉中180℃水热反应24h;自然冷却后,用0.1mol/L HCl和蒸馏水反复洗涤至中性,烘干、研磨过筛,即得磁性铁酸钴;
(2)磁性壳聚糖碳球的制备:
按照壳聚糖和铁酸钴的质量比为1~4:1分别称取壳聚糖和步骤(1)得到的磁性铁酸钴,加蒸馏水后超声使之溶解分散,后将溶液转移至水热反应釜中,置于高温炉中180℃水热反应12~48h;自然冷却后,对得到的固液进行磁分离,所得固体用无水乙醇和蒸馏水反复洗涤至中性,烘干、研磨过筛,即得到磁性壳聚糖微球。
2.如权利要求1所述制备方法得到的磁性壳聚糖碳球在吸附去除水中Cr(Ⅵ)上的应用。
3.如权利要求2所述磁性壳聚糖碳球在吸附去除水中Cr(Ⅵ)上的应用,其特征在于,该应用的条件是:在298K、150r/min条件下,Cr(Ⅵ)初始浓度为100~600mg/L,溶液pH为2,吸附时间为5min~48h,之后磁分离。
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