CN114797792B - 一种磁性生物炭基复合吸附剂的制备方法及其应用 - Google Patents
一种磁性生物炭基复合吸附剂的制备方法及其应用 Download PDFInfo
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Abstract
一种磁性生物炭基复合吸附剂的制备方法及其应用，本发明的目的是为了解决现有生物炭吸附剂对有机污染物去除效率较低的问题。制备方法：一、将生物质粉末加入到含有FeCl3·6H2O的乙醇溶液中，制备掺杂铁的生物质粉末；二、制备铁掺杂生物炭；三、向高锰酸盐溶液中加入硅藻土，得到氧化剂‑硅藻土复合粉末；四、向腐殖酸溶液中加入膨润土粉末，得到腐殖酸复合膨润土；五、向壳聚糖凝胶中添加铁掺杂生物炭、氧化剂‑硅藻土复合粉末和腐殖酸复合膨润土，制备凝胶球，冷冻干燥得到磁性生物炭基复合吸附剂。本发明磁性生物炭基复合吸附剂对苯酚具有优异的吸附效率(98％～99％)，可用于水体中有机污染物的快速去除。
Description
技术领域
本发明涉及一种复合吸附剂的制备方法及其应用。
背景技术
生物炭是指在低氧环境下，通过高温裂解将木材、草、玉米秸秆或动物粪便等进行碳化，是以固定碳元素为目的的炭材料。生物炭制备方式通常有快速热解法、慢速热解法、水热法和微波法等。实际应用中，生物炭的生产一般采取慢速热解法，该方法通常会提高生物炭的产量和均匀性。生物炭丰富的结构特性为污染物的吸附提供大量活性位点。其吸附机制一般包括表面吸附、分配作用、π-π电子授受作用等。表面吸附作用包含物理吸附、化学吸附及孔填充效应，生物炭中的稠芳环结构与有机物之间通常还有π-π相互作用。
酚类有机污染物主要来源有生活来源、农业来源和工业来源。酚类有机物对环境的污染通常指其对水体造成的污染，酚类废水是目前工业中污染风险和规模极大的废水之一。酚类有机污染物中最常见的污染物为苯酚，苯酚的酚羟基中氧原子的一对非共用电子与苯环大π键组成P-π共轭系统，使苯环上的电子云密度增加，强化了其化学反应活性。此外，在酚羟基上引入取代基可得到多种取代酚，常见的取代基有硝基、卤素原子、烷基等。
卡马西平(简称CBZ)是第一代抗惊厥药物，已在全球范围内广泛作为精神类疾病治疗药物用于治疗癫痫类疾病，是土壤和水环境中最常被发现的药物之一。卡马西平药物在环境中具有较强的持久性、生物活性和生物累积性，是一种潜在的危险污染物。现有去除水体中药物类有机污染物方法主要有高级氧化技术、吸附剂吸附技术、膜处理技术、物化法和生物法。
生物炭基吸附剂能对有机污染物进行有效去除，但现有生物炭基吸附剂对有机污染物去除效率较低，存在吸附反应时间较长的问题。
发明内容
本发明的目的是为了解决现有生物炭吸附剂对有机污染物去除效率较低的问题，而提供一种磁性生物炭基复合吸附剂的制备方法及其应用。
本发明磁性生物炭基复合吸附剂的制备方法按照以下步骤实现：
一、将生物质粉末加入到含有FeCl3·6H2O的乙醇溶液中，混合液在40～60℃下搅拌至乙醇完全挥发后，干燥后得到掺杂铁的生物质粉末；
二、将掺杂铁的生物质粉末放入管式炉中进行限氧烧制或无氧烧制，得到铁掺杂生物炭；
三、向高锰酸盐溶液中加入硅藻土，搅拌反应后减压旋转蒸发，干燥后得到氧化剂-硅藻土复合粉末；
四、向腐殖酸溶液中加入膨润土粉末，恒温振荡处理，经过抽滤、洗涤和干燥后得到腐殖酸复合膨润土；
五、向壳聚糖凝胶中添加铁掺杂生物炭、氧化剂-硅藻土复合粉末和腐殖酸复合膨润土，搅拌均匀后得到复合反应液，复合反应液滴入NaOH溶液中，搅拌形成凝胶球，分离收集凝胶球，经过水洗和冷冻干燥，得到磁性生物炭基复合吸附剂；
其中步骤五中添加铁掺杂生物炭、氧化剂-硅藻土复合粉末和腐殖酸复合膨润土的质量比为(2～3)：(1～3)：(1～3)。
本发明磁性生物炭基复合吸附剂的应用是将该磁性生物炭基复合吸附剂投入水中去除有机污染物苯酚或者卡马西平。
本发明所述的磁性生物炭基复合吸附剂由生物炭、硅藻土、膨润土和壳聚糖复合而成，生物炭具有疏松多孔的结构，比表面积大，孔隙结构发达等特点，生物炭通过静电吸附作用和表面官能团的络合作用吸附水体中的污染物，生物炭作为良好的吸附材料能够去除水和土壤中的重金属和有机污染物，本发明通过铁掺杂改性生物炭，使生物炭具有较强的磁性，便于该复合吸附剂的固液分离，同时磁性生物炭相比生物炭具有更多的持久性自由基和更高的吸附能力。
本发明通过高锰酸盐溶液浸渍硅藻土，使高锰酸盐氧化剂负载到硅藻土上，形成吸附-氧化复合体系，高锰酸盐(钾)作为强氧化剂，在氧化降解有机污染物的过程中很少产生有毒有害的副产物，高锰酸钾对含有不饱和官能团的有机物如烯烃类、酚类、胺类降解速度较快，降解效能高。硅藻土表面及孔内表面分布有大量的硅羟基和氢键，使硅藻土具有较强表面活性、吸附性以及酸性，通过硅藻土的吸附作用(以物理吸附为主)吸附有机污染物，再通过高锰酸盐进行氧化降解。
本发明合成了腐殖酸复合膨润土，膨润土晶格中的负电荷具有吸附阳离子和极性有机分子的能力，对有机污染物有一定的吸附能力，膨润土表面和内部结构不会被强氧化剂破坏，无毒副作用，作为生物相容性好的载体复合腐殖酸，腐殖酸中的腐殖质可通过疏水作用、螯合作用和氢键作用吸附有机污染物，并且腐殖酸能使高锰酸钾氧化反应产生的中间价态锰的稳定性提高，强化高锰酸盐的氧化效能。
本发明最后将氧化剂-硅藻土复合粉末、腐殖酸复合膨润土、磁性生物炭与壳聚糖复合，通过冷冻干燥制备得到多孔复合吸附剂。壳聚糖是一种天然的高分子材料，对酚类有机物有较好的吸附作用，壳聚糖表面含有丰富的活性氨基、羟基官能团和糖苷键，结合生物炭上的持久性自由基或者含氧官能团能与高锰酸盐氧化反应产生的亚稳态氧化物产生络合作用，提高中间价态锰的稳定性，进一步强化高锰酸盐(钾)的氧化降解效能。
本发明制备得到的磁性生物炭基复合吸附剂在投加60min时，对苯酚的去除率为98％～99％，对卡马西平的去除率为75％以上；对卡马西平的最高去除率可到95％以上，显示出优异的吸附效率，可用于水体中有机污染物的快速去除。
具体实施方式
具体实施方式一：本实施方式磁性生物炭基复合吸附剂的制备方法按照以下步骤实施：
一、将生物质粉末加入到含有FeCl3·6H2O的乙醇溶液中，混合液在40～60℃下搅拌至乙醇完全挥发后，干燥后得到掺杂铁的生物质粉末；
二、将掺杂铁的生物质粉末放入管式炉中进行限氧烧制或无氧烧制，得到铁掺杂生物炭；
三、向高锰酸盐溶液中加入硅藻土，搅拌反应后减压旋转蒸发，干燥后得到氧化剂-硅藻土复合粉末；
四、向腐殖酸溶液中加入膨润土粉末，恒温振荡处理，经过抽滤、洗涤和干燥后得到腐殖酸复合膨润土；
五、向壳聚糖凝胶中添加铁掺杂生物炭、氧化剂-硅藻土复合粉末和腐殖酸复合膨润土，搅拌均匀后得到复合反应液，复合反应液滴入NaOH溶液中，搅拌形成凝胶球，分离收集凝胶球，经过水洗和冷冻干燥，得到磁性生物炭基复合吸附剂；
其中步骤五中添加铁掺杂生物炭、氧化剂-硅藻土复合粉末和腐殖酸复合膨润土的质量比为(2～3)：(1～3)：(1～3)。
本实施方式步骤四所述的腐殖酸溶液是将腐殖酸溶于碱性溶液中形成腐殖酸溶液。
具体实施方式二：本实施方式与具体实施方式一不同的是步骤一中含有FeCl3·6H2O的乙醇溶液中FeCl3和乙醇溶液的质量体积比为(1～3g)：(50～60mL)。
本实施方式乙醇溶液的质量浓度为30％～40％。
具体实施方式三：本实施方式与具体实施方式一或二不同的是步骤二向真空管式炉内通入氮气保持限氧条件，调整氮气速率：0.1～0.2L/min，在700℃的温度下烧制1.2h～1.8h。
具体实施方式四：本实施方式与具体实施方式一至三之一不同的是步骤三中高锰酸盐溶液的浓度为0.2mol/L～0.4mol/L。
具体实施方式五：本实施方式与具体实施方式一至四之一不同的是步骤三中所述的高锰酸盐为高锰酸钾。
具体实施方式六：本实施方式与具体实施方式一至四之一不同的是步骤四中腐殖酸溶液的浓度为15～50mg/L。
具体实施方式七：本实施方式与具体实施方式一至六之一不同的是步骤四中所述的膨润土粉末通过酸化活化法改性或者焙烧活化法改性。
具体实施方式八：本实施方式与具体实施方式七不同的是所述焙烧活化法是在400～450℃下焙烧膨润土粉末。
本实施方式通过焙烧改性膨润土，能够增大膨润土粉末的比表面积及孔隙率，减小吸附阻力，改善吸附性能。
具体实施方式九：本实施方式与具体实施方式一至八之一不同的是步骤五中所述的壳聚糖凝胶是将壳聚糖溶解在质量浓度为2％～4％的乙酸溶液中。
具体实施方式十：本实施方式与具体实施方式一至九之一不同的是步骤五中冷冻干燥是在-50℃～-80℃下冷冻干燥15～20h。
实施例一：本实施例磁性生物炭基复合吸附剂的制备方法按照以下步骤实施：
一、将干燥的玉米秸秆粉末加入到含有FeCl3·6H2O的乙醇溶液中，Fe与玉米秸秆的质量比为0.6，混合液在40～60℃下搅拌至乙醇完全挥发后，干燥后得到掺杂铁的生物质粉末；
二、将掺杂铁的生物质粉末放入管式炉中，调整氮气速率：0.15L/min，在700℃的温度下烧制1.5h，得到铁掺杂生物炭；
三、向饱和高锰酸钾溶液中加入硅藻土，搅拌反应后减压旋转蒸发，干燥后得到氧化剂-硅藻土复合粉末；
四、向浓度为20mg/L腐殖酸溶液中加入焙烧活化法改性的膨润土粉末，恒温振荡处理，经过抽滤、洗涤和干燥后得到腐殖酸复合膨润土；
五、将2g壳聚糖溶解在100mL质量浓度为2％的乙酸溶液中，得到壳聚糖凝胶，向壳聚糖凝胶中添加1g铁掺杂生物炭、1g氧化剂-硅藻土复合粉末和1g腐殖酸复合膨润土，搅拌均匀后得到复合反应液，复合反应液滴入浓度为2mol/L的NaOH溶液中，剧烈搅拌形成凝胶球，分离收集凝胶球，经过水洗和冷冻干燥，得到磁性生物炭基复合吸附剂A。
对比实施例二：本实施例磁性生物炭基复合吸附剂的制备方法按照以下步骤实施：
一、将干燥的玉米秸秆粉末加入到含有FeCl3·6H2O的乙醇溶液中，Fe与玉米秸秆的质量比为0.6，混合液在40～60℃下搅拌至乙醇完全挥发后，干燥后得到掺杂铁的生物质粉末；
二、将掺杂铁的生物质粉末放入管式炉中，调整氮气速率：0.15L/min，在700℃的温度下烧制1.5h，得到铁掺杂生物炭；
三、将2g壳聚糖溶解在100mL质量浓度为2％的乙酸溶液中，得到壳聚糖凝胶，向壳聚糖凝胶中添加1g铁掺杂生物炭、1g硅藻土粉末和1g膨润土粉末，搅拌均匀后得到复合反应液，复合反应液滴入浓度为2mol/L的NaOH溶液中，剧烈搅拌形成凝胶球，分离收集凝胶球，经过水洗和冷冻干燥，得到生物炭复合吸附剂B。
对比实施例三：本实施例与实施例一不同的是步骤四直接采用焙烧活化法改性的膨润土粉末，而不浸渍腐殖酸溶液。
对比实施例三制备得到生物炭复合吸附剂C。
实施例一制备得到的磁性生物炭基复合吸附剂A中的高锰酸钾具有缓释效果，12h依然能检测到溶出的锰酸根离子。
本实施例磁性生物炭基复合吸附剂对有机污染物苯酚的吸附试验：
在室温为25℃下，含有机污染物苯酚溶液的pH为7.0、初始浓度为10mg/L，20mL有机污染物苯酚溶液中吸附剂的投加量为0.05g，采用紫外可见分光光度法测定吸附后的苯酚浓度；所述的吸附剂分别为磁性生物炭基复合吸附剂A、生物炭复合吸附剂B和生物炭复合吸附剂C。
磁性生物炭基复合吸附剂A、生物炭复合吸附剂B和生物炭复合吸附剂C大约在80min左右吸附饱和，吸附速度较快，其中磁性生物炭基复合吸附剂A对苯酚的平衡吸附量为18.53mg/g。在20min时，磁性生物炭基复合吸附剂A对苯酚的去除率为88.5％，生物炭复合吸附剂B对苯酚的去除率为76.1％，生物炭复合吸附剂C对苯酚的去除率为80.2％；在40min时，磁性生物炭基复合吸附剂A对苯酚的去除率为94.6％，生物炭复合吸附剂B对苯酚的去除率为77.6％，生物炭复合吸附剂C对苯酚的去除率为84.7％；在60min时，磁性生物炭基复合吸附剂A对苯酚的去除率可达到98.8％。
本实施例磁性生物炭基复合吸附剂对有机污染物卡马西平的吸附试验：
在室温为25℃下，含有机污染物卡马西平溶液的pH为7.0、初始浓度为200μg/L，20mL有机污染物苯酚溶液中吸附剂的投加量为0.02g。
在20min时，磁性生物炭基复合吸附剂A对卡马西平的去除率为65.3％，生物炭复合吸附剂B对卡马西平的去除率为32.6％，生物炭复合吸附剂C对卡马西平的去除率为56.5％；在40min时，磁性生物炭基复合吸附剂A对卡马西平的去除率为70.5％，在60min时，磁性生物炭基复合吸附剂A对卡马西平的去除率为75.9％。
通过以上试验可知，本实施例制备得到的磁性生物炭基复合吸附剂对有机污染物苯酚和卡马西平的吸附去除效果优异，吸附效率高。
Claims (9)
1.一种磁性生物炭基复合吸附剂的制备方法，其特征在于，该制备方法按照以下步骤实现：
一、将生物质粉末加入到含有FeCl3·6H2O的乙醇溶液中，混合液在40~60 ℃下搅拌至乙醇完全挥发后，干燥后得到掺杂铁的生物质粉末；
二、将掺杂铁的生物质粉末放入管式炉中进行限氧烧制或无氧烧制，得到铁掺杂生物炭；
三、向高锰酸盐溶液中加入硅藻土，搅拌反应后减压旋转蒸发，干燥后得到氧化剂-硅藻土复合粉末；
四、向腐殖酸溶液中加入膨润土粉末，恒温振荡处理，经过抽滤、洗涤和干燥后得到腐殖酸复合膨润土；
五、向壳聚糖凝胶中添加铁掺杂生物炭、氧化剂-硅藻土复合粉末和腐殖酸复合膨润土，搅拌均匀后得到复合反应液，复合反应液滴入NaOH溶液中，搅拌形成凝胶球，分离收集凝胶球，经过水洗和冷冻干燥，得到磁性生物炭基复合吸附剂；
其中步骤五中添加铁掺杂生物炭、氧化剂-硅藻土复合粉末和腐殖酸复合膨润土的质量比为（2~3）：（1~3）：（1~3）；
步骤五中所述的壳聚糖凝胶是将壳聚糖溶解在质量浓度为2%~4%的乙酸溶液中。
2.根据权利要求1所述的磁性生物炭基复合吸附剂的制备方法，其特征在于，步骤一中含有FeCl3·6H2O的乙醇溶液中FeCl3和乙醇溶液的质量体积比为（1~3g）：（50~60mL）。
3.根据权利要求1所述的磁性生物炭基复合吸附剂的制备方法，其特征在于，步骤二向真空管式炉内通入氮气保持限氧条件，调整氮气速率：0.1~0.2L/min，在700 ℃的温度下烧制1.2h~1.8h。
4.根据权利要求1所述的磁性生物炭基复合吸附剂的制备方法，其特征在于，步骤三中高锰酸盐溶液的浓度为0.2mol/L~0.4mol/L。
5.根据权利要求1所述的磁性生物炭基复合吸附剂的制备方法，其特征在于，步骤四中腐殖酸溶液的浓度为15~50mg/L。
6.根据权利要求1所述的磁性生物炭基复合吸附剂的制备方法，其特征在于，步骤四中所述的膨润土粉末通过酸化活化法改性或者焙烧活化法改性。
7.根据权利要求6所述的磁性生物炭基复合吸附剂的制备方法，其特征在于，所述焙烧活化法是在400~450℃下焙烧膨润土粉末。
8.根据权利要求1所述的磁性生物炭基复合吸附剂的制备方法，其特征在于，步骤五中冷冻干燥是在-50℃~-80℃下冷冻干燥15~20h。
9.一种如权利要求1所述的磁性生物炭基复合吸附剂的制备方法得到的磁性生物炭基复合吸附剂的应用，其特征在于，将所述的磁性生物炭基复合吸附剂投入水中去除有机污染物苯酚或者卡马西平。
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