CN115178235A - 一种改性生物炭高效吸附去除水体中Cr（Ⅵ）的方法 - Google Patents
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Abstract
本发明公开一种改性生物炭高效吸附去除水体中Cr（Ⅵ）的方法，属于生物炭及污染水体处理应用技术领域。本发明所述方法以玉米秸秆为原生质制备生物炭，并采用氯化锌活化制备ZnCl2活化改性生物炭；将其加入到Cr（Ⅵ）污染的水体中并振荡一段时间，通过离心将ZnCl2活化改性生物炭与处理后的水体分离，进而实现水体中Cr（Ⅵ）的去除；ZnCl2活化改性过程显著提升了玉米秸秆生物炭吸附Cr（Ⅵ）的能力；本发明方法中的改性生物炭表现出优于其他吸附剂的吸附性能，且操作简单，处理成本低，吸附效果显著，对实现废物资源化利用具有重要的意义，具有良好的经济和环境效应以及广阔的研究及应用前景。
Description
技术领域
本发明涉及一种改性生物炭高效吸附去除水体中Cr（Ⅵ）的方法，属于生物炭及污染水体处理应用技术领域。
背景技术
铬（Chromium）广泛应用于电镀、皮革鞣制加工、纺织、工业颜料、橡胶和陶瓷原料等行业，是一种典型的重金属污染物，具有致癌、致突变和致畸作用，含Cr废水排放入水体中，对水环境造成了巨大污染，对水生生物有致死作用。其中，Cr（Ⅵ）的毒性最高，可溶解且迁移能力强，在污水处理厂中无法完全去除，容易通过食物链积累于各种生物体内，引发过敏性皮炎、湿疹、支气管炎、肺结核等疾病，危害人和动物的健康，破坏生态平衡。
目前，从水相中去除Cr（Ⅵ）的技术很多，例如化学沉淀法、离子交换法、生物吸附、膜分离法等，这些方法处理过程较复杂并且成本较高。与之相比，吸附法由于效果好，操作简单，成本低，无二次污染而被广泛采用。生物炭作为一种新型吸附材料，是生物质在缺氧条件下热解转化而成的副产物，其性质稳定，具有发达的孔隙结构和丰富的表面官能团，可以通过表面络合、静电吸引、氢键结合、阳离子交换、化学还原以及π-π相互作用吸附污染物，因此在重金属污染修复方面受到了广泛关注。
生物质直接热解得到的炭质材料吸附效果有限，需要通过改性处理来提高对重金属的吸附效果。为提高生物炭的吸附性能，研究人员研究了众多生物炭活化的方法，主要包括物理改性（蒸汽改性、紫外辐射、球磨、气体吹扫等）、化学改性（酸改性、碱改性、氧化剂改性、电化学改性、金属盐及金属氧化物改性等）和新型碳质材料改性（碳纳米管、石墨烯复合材料）。生物炭改性方法的选择取决于生物炭在环境中的应用。基于上述若干问题，本发明提供一种ZnCl2活化改性生物炭高效吸附去除水体中Cr（Ⅵ）的方法。
发明内容
本发明的目的在于提供一种ZnCl2活化改性生物炭高效吸附去除水体中Cr（Ⅵ）的方法，能有效去除水体中的Cr（Ⅵ），具有操作简单、制备成本低、吸附容量大等优势，对实现废物资源化利用具有重要的意义，并且具有较大的环境修复应用潜力，为水体中Cr（Ⅵ）的去除提供了一种新的方法。
本发明的技术方案如下：一种ZnCl2活化改性生物炭高效吸附去除水体中Cr（Ⅵ）的方法，具体包括以下步骤：
（1）将玉米秸秆生物质放入粉碎机中粉碎，过100目筛，放入恒温干燥箱中低温（55~65℃）烘6h至恒重，将生物质加入2 mol/L的氯化锌溶液中，浸渍12 h，烘干后取出样品用研钵研磨成粉末；
（2）将步骤（1）所得样品置于管式炉中，以5~15 ℃/min升温速率将温度升温至800℃进行热解，所得样品依次用去离子水、丙酮洗涤后滤干；滤干后用去离子水洗涤并抽滤，最后将其置于烘箱中烘干，待其冷却至室温后研磨，过100目筛，得到改性生物炭，置于密闭容器中保存备用；
（3）将步骤（2）所得改性活性炭加入Cr（Ⅵ）污染的水体中并振荡或搅拌一段时间，通过静置或离心将ZnCl2活化改性生物炭与处理后的水体分离，进而实现水体中Cr（Ⅵ）的吸附去除。
优选的，本发明步骤（1）和（2）中烘干条件为：浸渍生物质放入105 ℃的烘箱中烘干12 h，烘干过程中每隔1小时搅拌一次样品。
优选的，本发明步骤（2）中热解过程通入N2，N2的流速为0.8 L/min。
优选的，本发明步骤（2）中依次用去离子水、丙酮洗涤的具体过程为：用去离子水洗涤0.5 h，再加入丙酮洗涤5 h。
优选的，本发明所述的ZnCl2活化改性生物炭的投加量为1g·L-1。
优选的，本发明振荡或搅拌时间不低于24 h，振荡或搅拌的温度为25 ℃。
优选的，本发明离心转速为4000 r·min-1，离心时间为10 min。
本发明的有益效果：
（1）本发明使用ZnCl2活化改性生物炭，操作简单、制备成本低、具高比表面积和高微孔体积、吸附容量大，实现了对水体中Cr（Ⅵ）的高效吸附去除；ZnCl2活化改性生物炭吸附Cr（Ⅵ）后可通过离心分离，利于吸附剂的循环利用，降低了经济成本，对实现废物资源化利用具有重要的意义，具有良好的经济和环境效应以及广阔的研究及应用前景。
（2）本发明通过对比实验验证了ZnCl2活化改性过程在生物炭改性中的作用，即ZnCl2活化改性过程可在高温下抑制碳重排，阻止生物炭孔道坍塌，增强生物炭内部孔道结构的稳定性，促进微孔形成，使得生物炭在高温条件下也可以达到较高的比表面积以及较大的孔容，极大提高对Cr（Ⅵ）的吸附量。
（3）在800 ℃、15 ℃/min升温速率下ZnCl2活化改性生物炭比原始玉米秸秆生物炭比表面积提升445.98倍，微孔体积提升1656.89倍，最大的吸附量约为130.69 mg·L-1，本发明所述吸附剂的吸附机理为孔填充作用，ZnCl2活化改性生物炭比表面积为1,618.36m2·g-1。
具体实施方式
下面结合具体实施例对本发明作进一步详细说明，但本发明的保护范围并不限于所述内容。
本发明所述实施例以ZnCl2活化改性生物炭对含Cr（Ⅵ）的水体进行处理，吸附采用动态连续过程或静态间歇过程；将ZnCl2活化改性生物炭加入到含Cr（Ⅵ）水溶液的密闭容器中，并通过搅动或振荡使其充分吸附，达到吸附平衡后，测定水溶液中Cr（Ⅵ）的浓度，并计算ZnCl2活化改性生物炭吸附量大小。相同条件下，考察不同升温速率制备的ZnCl2活化改性生物炭以及原始未改性玉米秸秆对水体中Cr（Ⅵ）的吸附能力，并通过最大吸附量来评价吸附剂的吸附效果。
实施例1
一种改性生物炭高效吸附去除水体中Cr（Ⅵ）的方法，具体包括以下步骤：
（1）将玉米秸秆生物质放入粉碎机中粉碎，过100目筛，放入恒温干燥箱中低温（60℃）烘至恒重，置烘箱中干燥24 h，将140 g生物质加入560 ml的2 mol/L的氯化锌溶液中，浸渍12 h。
（2）步骤（1）所得样品放入105 ℃的烘箱中烘干12 h，烘干过程中每隔1小时搅拌一次样品，烘干后取出样品用研钵研磨成粉末，装进干燥皿中进行称量，每份40 g，将其放入石英舟，置于管式炉SK-G15123K-610内，在0.8 L/min的N2流速下，以15 ℃/min的升温速率加热到800 ℃，热解1 h，所得样品用去离子水洗涤0.5 h，再加入丙酮洗涤5 h后滤干；滤干后用去离子水洗涤并抽滤，最后将其置于105 ℃的烘箱中烘干，待其冷却至室温后研磨，过100目筛，ZnCl2活化改性得到的样品命名为ZB800-15（在800 ℃、15 ℃/min升温速率下ZnCl2活化改性生物炭），将制备所得的改性生物炭置于密闭容器中保存备用；经上述步骤所制得的ZnCl2活化改性生物炭ZB800-15的比表面积为1,618.36 m2·g-1，吸附效果明显。
以制得的ZnCl2活化改性生物炭ZB800-15为吸附剂，吸附水体中的Cr（Ⅵ）。称取10mg ZnCl2活化改性生物炭于15 mL棕色玻璃瓶中，加入10 mL不同浓度的Cr（Ⅵ）溶液（浓度范围为25~250 mg·L-1）。在25 ℃下于摇床中振荡24 h后，以4000 r·min-1离心10 min，取上清液于8mL色谱瓶中，经0.45μm水相滤膜过滤后，用火焰原子分光光度计测定上清液中Cr（Ⅵ）的浓度，结果如表1所示。
表1 实施例ZB800-15对Cr（Ⅵ）的吸附量对比表
由表1可见，当水体中Cr（Ⅵ）的初始浓度为250mg·L-1时，ZnCl2活化改性生物炭ZB800-15比表面积为1,618.36 m2·g-1，微孔体积为0.66607 cm³/g，对水体中Cr（Ⅵ）的最大吸附量可达130.69 mg·g-1，有较好的吸附效果。
实施例2
本实施例制备方法和实施例1相同，不同在于在800℃、5 ℃/min 升温速率下制备ZnCl2活化改性生物炭ZB800-5为吸附剂。
本实施例制备的ZB800-5吸附剂用于吸附水体中的Cr（Ⅵ）；称取10 mg ZnCl2活化改性生物炭于15 mL棕色玻璃瓶中，加入10 mL不同浓度的Cr（Ⅵ）溶液（浓度范围为25~250mg·L-1）；在25 ℃下于摇床中振荡24 h后，以4000 r·min-1离心10 min，取上清液于8mL色谱瓶中，经0.45μm水相滤膜过滤后，用火焰原子分光光度计测定上清液中Cr（Ⅵ）的浓度，结果如表2所示。
对比例一
以在800 ℃、15 ℃/min 升温速率下制备玉米秸秆生物炭B800-15为吸附剂，吸附水体中的Cr（Ⅵ）；称取10mg玉米秸秆生物炭B800-15于15mL棕色玻璃瓶中，加入10mL不同浓度的Cr（Ⅵ）溶液（浓度范围为25~250 mg·L-1）。在25 ℃下于摇床中振荡24 h后，以4000r·min-1离心10 min，取上清液于8mL色谱瓶中，经0.45μm水相滤膜过滤后，用火焰原子分光光度计测定上清液中Cr（Ⅵ）的浓度，结果如表2所示。
对比例二
以在800 ℃、5 ℃/min 升温速率下制备玉米秸秆生物炭B800-5为吸附剂，吸附水体中的Cr（Ⅵ）；称取10 mg 玉米秸秆生物炭B800-5于15 mL棕色玻璃瓶中，加入10 mL不同浓度的Cr（Ⅵ）溶液（浓度范围为25~250 mg·L-1）；在25 ℃下于摇床中振荡24 h后，以4000r·min-1离心10 min，取上清液于8mL色谱瓶中，经0.45μm水相滤膜过滤后，用火焰原子分光光度计测定上清液中Cr（Ⅵ）的浓度，结果如表2所示。
表2实施例及对比例比表面积、微孔体积、对Cr（Ⅵ）的最大吸附量对比表
由表2可见：
（1）ZnCl2活化改性生物炭ZB800-15比原始玉米秸秆生物炭B800-15比表面积提升445.98倍，微孔体积提升1656.89倍，证明ZnCl2活化改性过程可在800 ℃、15 ℃/min升温速率下抑制碳重排，阻止生物炭孔道坍塌，增强生物炭内部孔道结构的稳定性，促进微孔形成，使得生物炭在高温条件下也可以达到较高的比表面积以及较大的孔容，极大提高对Cr（Ⅵ）的吸附量。
（2）ZnCl2活化改性生物炭ZB800-5比表面积为1,464.01 m2·g-1，微孔体积为0.63758 cm³/g，比原始玉米秸秆生物炭B800-5比表面积提升29.19倍，微孔体积提升33.21倍，当水体中Cr（Ⅵ）的初始浓度为250mg·L-1时，ZB800-5对水体中Cr（Ⅵ）的最大吸附量约为65.43 mg·g-1，低于ZB800-15。
（3）玉米秸秆生物炭B800-15比表面积为3.63 m2·g-1，微孔体积为0.00040 cm³/g，当水体中Cr（Ⅵ）的初始浓度为250mg·L-1时，Z800-15对水体中Cr（Ⅵ）的最大吸附量约为4.23 mg·g-1，远低于ZB800-15。
（4）玉米秸秆生物炭B800-5比表面积为50.16 m2·g-1，微孔体积为0.01920 cm³/g，当水体中Cr（Ⅵ）的初始浓度为250mg·L-1时，Z800-15对水体中Cr（Ⅵ）的最大吸附量约为9.09 mg·g-1，远低于ZB800-15。
以上所述仅是本发明的优选条件，应当指出，在不脱离本发明原理的前提下，还可以做出若干改进，这些改进也应视为本发明的保护范围。
Claims (7)
1.一种改性生物炭高效吸附去除水体中Cr（Ⅵ）的方法，其特征在于，具体包括以下步骤：
（1）将玉米秸秆生物质放入粉碎机中粉碎，过100目筛，放入恒温干燥箱中低温烘至恒重，将生物质加入2 mol/L的氯化锌溶液中，浸渍12 h，烘干后取出样品用研钵研磨成粉末；
（2）将步骤（1）所得样品置于管式炉中，以5~15 ℃/min升温速率将温度升温至800 ℃进行热解，所得样品依次用去离子水、丙酮洗涤后滤干；滤干后用去离子水洗涤并抽滤，最后将其置于烘箱中烘干，待其冷却至室温后研磨，过100目筛，得到改性生物炭，置于密闭容器中保存备用；
（3）将步骤（2）所得改性活性炭加入Cr（Ⅵ）污染的水体中并振荡或搅拌一段时间，通过静置或离心将ZnCl2活化改性生物炭与处理后的水体分离，进而实现水体中Cr（Ⅵ）的吸附去除。
2.根据权利要求1所述改性生物炭高效吸附去除水体中Cr（Ⅵ）的方法，其特征在于：步骤（1）和（2）中烘干条件为：放入105 ℃的烘箱中烘干12 h，烘干过程中每隔1小时搅拌一次样品。
3.根据权利要求1所述改性生物炭高效吸附去除水体中Cr（Ⅵ）的方法，其特征在于：步骤（2）中热解过程通入N2，N2的流速为0.8 L/min。
4.根据权利要求1所述改性生物炭高效吸附去除水体中Cr（Ⅵ）的方法，其特征在于：步骤（2）中依次用去离子水、丙酮洗涤的具体过程为：用去离子水洗涤0.5 h，再加入丙酮洗涤5 h。
5.根据权利要求1所述改性生物炭高效吸附去除水体中Cr（Ⅵ）的方法，其特征在于：所述的ZnCl2活化改性生物炭的投加量为1g·L-1。
6.根据权利要求1所述改性生物炭高效吸附去除水体中Cr（Ⅵ）的方法，其特征在于：振荡或搅拌时间不低于24 h，振荡或搅拌的温度为25 ℃。
7.根据权利要求1所述改性生物炭高效吸附去除水体中Cr（Ⅵ）的方法，其特征在于：离心转速为4000 r·min-1，离心时间为10 min。
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