CN107282025A - 纳米纤维素基官能化气凝胶型重金属吸附材料的制备方法 - Google Patents
纳米纤维素基官能化气凝胶型重金属吸附材料的制备方法 Download PDFInfo
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Abstract
本发明公开了一种纳米纤维素基官能化气凝胶型重金属离子吸附材料的制备方法，其通过结合化学预处理和机械处理的方法制备一种表面功能化的纳米纤维，并对该纳米纤维进行化学修饰制备出官能化气凝胶作为重金属离子吸附材料，制得的官能化气凝胶的孔隙率达到99％以上，对重金属的移除率超过96％以上，可广泛适用于重金属污染处理。
Description
技术领域
本发明涉及一种有重金属吸附材料的制备方法，具体涉及一种纳米纤维素基官能化气凝胶的制备方法。
背景技术
随着我国经济的高速发展，近年来在金属采选及冶炼、金属表面处理及热处理加工、制革及电池制造等过程中带来的重金属工业废水污染问题日益恶化，这不仅给生态环境造成了严重危害，而且也威胁到人类的健康。由于重金属一般具有很大的毒性、高的移动性和低的中毒浓度，在水体中不能被生物降解，易在生物体内富集。人通过饮水及食物链的作用，可使重金属在人体内富集而中毒，甚至导致死亡。因此，重金属污染也已成为近些年来一直被人们提及的重大环境污染问题。
目前，工业重金属废水处理方法有很多，主要包括化学沉淀法、电解法、离子交换法、氧化还原法和吸附法等。较其他处理方法而言，吸附法具有高效节能、操作简单、试用性强、二次污染小、对低浓度污染去除能力较好等优点，是目前处理处理重金属污染废水最为有效且经济的方法之一。吸附法主要是利用吸附材料与污染物之间物理或化学作用达到移除效果，因此材料表面官能团类型和比表面积对吸附效果影响很大。粉末或颗粒状活性炭、生物质碳是目前最常用的处理工业重金属废水污染的吸附材料，虽然它们吸附效果较好，但是也普遍存在回收再生难、生物降解性差及成本偏高等缺点。综上所述，研制开发一种具有回收再生性好、且表面富有对重金属离子兼具有良好吸附能力化学基团的新型“绿色”吸附材料，具有非常重要的意义。
纳米纤维素基气凝胶(Aerogel)是一种由力学性能优异、直径为纳米级(1～100nm)的微纤组成的连续三维网络结构纳米多孔材料，其孔隙率可高达90％以上，密度最低可至0.001g/cm3，比表面积也较微米级的多孔材料更大，纤维素分子链上含有大量易化学改性的活性羟基，同时纳米来源广泛、可再生、易降解、化学和热稳定性好等。此外，与无机气凝胶(如石墨烯、硅气凝胶)和聚合物气凝胶相比，它们韧性更好且环境友好，因此是一种理想的吸附材料载体。
目前，纳米纤维素气凝胶用作重金属吸附材料研究较少，现有报道采用纳米纤维素基气凝胶作为吸附材料，虽然有一定吸附能力，但其吸附效果不太好，且该气凝胶的湿强度差，压缩回弹性不佳，不利于其吸附回收再利用，导致其实用性下降。因此，纳米纤维素基气凝胶对重金属的吸附性能和强度仍有待进一步提高。
发明内容
本发明所要解决的技术问题是通过结合化学预处理和机械处理的方法制备一种表面功能化的纳米纤维，以该纳米纤维素为基体制备出官能化气凝胶作为重金属吸附材料，其具有良好的吸附性能、和可再回收性、适应范围广的优点。
本发明解决其技术问题所采用的技术方案是：一种纳米纤维素基官能化气凝胶型重金属吸附材料的制备方法，包括如下步骤：
(1)表面带负电荷的纳米纤维素的制备：取竹浆或木浆在水中机械搅拌使其分散且固含量为0.1～2wt％，按每克竹浆或木浆加入0.01～0.3mmol的TEMPO和0.1～3mmol溴化钠，搅拌溶解后，按每克竹浆或木浆滴加1～20mmol/g的次氯酸钠到混合体系中，反应过程中用0.1～0.5mol/L NaOH稀溶液调控pH值在10，直到溶液的pH值不再改变，停止反应，抽滤并用蒸馏水将氧化后的纤维洗至中性，最后将纤维悬浮液通过高压均质机打磨后得到均匀透明的表面带负电荷的NFC分散液，电荷滴定后的微纤表面羧基电荷含量在0.4～2.3mmol/g；
(2)表面带正电荷的纳米纤维素的制备：将竹浆或木浆或经过打浆预处理后的竹浆或木浆分散于质量浓度1～10％NaOH溶液中，定量加入2,3-环氧丙基三甲基氯化铵，搅拌混匀后在25～70℃反应2-10h；反应完毕后，用质量浓度0.5～1％盐酸调pH至7，用蒸馏水抽滤洗涤至无剩余反应试剂；最后将纤维悬浮液通过高压均质机打磨，得到表面带正电荷的NFC分散液。电荷滴定结果显示微纤表面季铵盐基团含量为0.3～1.5mmol/g；
(3)官能化气凝胶的制备：将步骤1制得的表面带负电荷的纳米纤维素和官能化试剂按任意比例混合反应，得到第一混合溶液；将步骤2制得的表面带正电荷的纳米纤维素和官能化试剂在酸性条件下任意比例混合，得到第二混合溶液；将第一混合溶液、第二混合溶液溶液分别置于-70～-40℃预冷冻2～4h后再冷冻干燥48h，然后把冷冻干燥得到的气凝胶放入烘箱中85℃下干燥2～5h进行烘干固化，分别得到表面带负电荷兼官能化基团、表面带正电荷兼官能化基团的纳米纤维素基官能化气凝胶，将上述气凝胶作为重金属离子的吸附材料。
进一步地，所述步骤4中官能化试剂：半胱氨酸、乙二胺四乙酸、乙二胺三乙酸、聚丙烯酰胺、3-巯基丙基三甲氧基硅烷、3-氨丙基三甲氧基硅烷、双(三甲基硅烷基)氨基钾、N,O-双(三甲基硅烷基)乙酰胺、氨甲基三甲基硅烷。
本发明的有益效果是：本发明通过结合化学预处理和机械处理的方法制备一种表面功能化的纳米纤维，并将该纳米纤维与官能化试剂混合反应制备官能化气凝胶，制得的官能化气凝胶的孔隙率达到90％以上，在用于种重金属离子吸附时5小时的吸附率超过96％以上，可广泛适用于吸附各种重金属离子的水体污染，如汞离子、镉离子、铬离子、铜离子、铅离子等。
附图说明
图1为本发明实施例1、2和对比例1、2、3的吸附性能对比图；
图2为本发明实施例1和对比例4的吸附性能对比图；
图3为本发明实施例2和对比例2的对不同重金属的吸附性能对比图。
具体实施方式
本发明技术方案不局限于以下所列举具体实施方式，还包括各具体实施方式间的任意组合。
实施例1
高电荷阴离子纳米纤维素与3-巯基丙基三甲氧基硅烷1:0.5(w/w)的官能化气凝胶的制备如下：
取1g竹浆在50g水中机械搅拌使其分散，加入0.01mmol的TEMPO和1mmol溴化钠，搅拌溶解后，滴加2.5mmol/g的次氯酸钠到混合体系中，反应过程中用0.5mol/L NaOH稀溶液调控pH值在10，直到溶液的pH值不再改变，停止反应，抽滤并用蒸馏水将氧化后的纤维洗至中性，最后将纤维悬浮液通过高压均质机打磨后得到均匀透明的表面带负电荷的NFC分散液。
将阴离子纳米纤维素分散液pH调至4，加入3-巯基丙基三甲氧基硅烷(固体质量比＝1:0.5(w/w)搅拌反应3h，将其改性液置于-60℃冷冻4h后冷冻干燥，干燥好的气凝胶置于烘箱中(85℃)5h即可。其性能见表1及图1。
实施例2
高电荷阴离子纳米纤维素与3-巯基丙基三甲氧基硅烷1:1.5(w/w)的官能化气凝胶的制备如下：
取1g竹浆在50g水中机械搅拌使其分散，加入0.01mmol的TEMPO和1mmol溴化钠，搅拌溶解后，滴加2.5mmol/g的次氯酸钠到混合体系中，反应过程中用0.5mol/L NaOH稀溶液调控pH值在10，直到溶液的pH值不再改变，停止反应，抽滤并用蒸馏水将氧化后的纤维洗至中性，最后将纤维悬浮液通过高压均质机打磨后得到均匀透明的表面带负电荷的NFC分散液。
将阴离子纳米纤维素分散液pH调至4，加入3-巯基丙基三甲氧基硅烷(固体质量比＝1:0.5(w/w)搅拌反应3h，将其改性液置于-60℃冷冻4h后冷冻干燥，干燥好的气凝胶置于烘箱中(85℃)5h即可。其性能见表1及图1，见表3及图3。
实施例3
无电荷纳米纤维素制备如下：
取1g竹浆在50g水中机械搅拌使其充分散，将其置于细胞破碎机中超声破碎(1200w)1h，制备的NFC悬液。其性能见表3。
实施例4
低电荷纳米纤维素制备如下：
取1g竹浆在50g水中机械搅拌使其分散，加入0.01mmol的TEMPO和1mmol溴化钠，搅拌溶解后，滴加1.5mmol/g的次氯酸钠到混合体系中，反应过程中用0.5mol/L NaOH稀溶液调控pH值在10，直到溶液的pH值不再改变，停止反应，抽滤并用蒸馏水将氧化后的纤维洗至中性，最后将纤维悬浮液通过高压均质机打磨后得到均匀透明的表面带负电荷的NFC分散液。其性能见表3。
实施例5
高电荷纳米纤维素制备如下：
取1g竹浆在50g水中机械搅拌使其分散，加入0.01mmol的TEMPO和1mmol溴化钠，搅拌溶解后，滴加2.5mmol/g的次氯酸钠到混合体系中，反应过程中用0.5mol/L NaOH稀溶液调控pH值在10，直到溶液的pH值不再改变，停止反应，抽滤并用蒸馏水将氧化后的纤维洗至中性，最后将纤维悬浮液通过高压均质机打磨后得到均匀透明的表面带负电荷的NFC分散液。其性能见表3。
对比例1
无电荷纳米纤维素气凝胶的制备如下：
将纳米纤维素分散液置于-60℃冷冻4h后冷冻干燥即可。其性能见表1及图1。
对比例2
高电荷阴离子纳米纤维素气凝胶的制备如下：
将高电荷阴离子纳米纤维素分散液置于-60℃冷冻4h后冷冻干燥即可。其性能见表1及图1，见表3及图3。
对比例3
低电荷阴离子纳米纤维素与3-巯基丙基三甲氧基硅烷1:1.5(w/w)的官能化气凝胶的制备如下：
将低电荷阴离子纳米纤维素分散液pH调至4，加入3-巯基丙基三甲氧基硅烷(固体质量比＝1:0.5(w/w)搅拌反应3h，将其改性液置于-60℃冷冻4h后冷冻干燥，干燥好的气凝胶置于烘箱中(85℃)5h即可。其性能见表1及图1。
对比例4
商业化活性炭(200目)，比表面积1482.4g/m2。其性能见表2及图2
表1本发明阴离子纳米纤维素基官能化气凝胶实施例和对比例的吸附性能数据
| 孔隙率 | 27mg/L Hg2+吸附量 | 27mg/L Hg2+移除率 | |
| 实施例1 | 99.3％ | 123.3mg/g | 91.3％ |
| 实施例2 | 99.09％ | 129.6mg/g | 96.1％ |
| 对比例1 | 99.1％ | 3.7mg/g | 2.42％ |
| 对比例2 | 99.6％ | 32.5mg/g | 24.1％ |
| 对比例3 | 99.1％ | 121.1mg/g | 89.7％ |
表2本发明阴离子纳米纤维素基官能化气凝胶实施例和对比例的吸附性能数据
| 孔隙率 | 27mg/L Hg2+吸附量 | 27mg/L Hg2+移除率 | |
| 实施例2 | 99.09％ | 129.7mg/g | 96.1％ |
| 对比例4 | 102.3mg/g | 75.1％ |
表3本发明阴离子纳米纤维素基官能化气凝胶实施例和对比例的吸附性能数据
孔隙率计算公式：孔隙率P＝[(ρ-ρ0)/ρ]×100％
式中：ρ0材料的表观密度，g/cm3；ρ材料的真实密度，g/cm3。
移除率(％)计算公式为：[(Co-C)/Co]×100％；
式中，Co为吸附金属离子前的初始浓度，C为吸附金属离子后的平衡浓度；表4本发明实施例电荷数据
上述所述的实施例，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，凡在本发明的精神和原则之内所做的任何修改、等同替换。改进等，均应包括在本发明的保护范围之内。
Claims (2)
1.一种纳米纤维素基官能化气凝胶型重金属吸附材料的制备方法，其特征在于：包括如下步骤：
(1)表面带负电荷的纳米纤维素的制备：取竹浆或木浆在水中机械搅拌使其分散且固含量为0.1～2wt％，按每克竹浆或木浆加入0.01～0.3mmol的TEMPO和0.1～3mmol溴化钠，搅拌溶解后，按每克竹浆或木浆滴加1～20mmol/g的次氯酸钠到混合体系中，反应过程中用0.1～0.5mol/L NaOH稀溶液调控pH值在10，直到溶液的pH值不再改变，停止反应，抽滤并用蒸馏水将氧化后的纤维洗至中性，最后将纤维悬浮液通过高压均质机打磨后得到均匀透明的表面带负电荷的NFC分散液，电荷滴定后的微纤表面羧基电荷含量在0.4～2.3mmol/g；
(2)表面带正电荷的纳米纤维素的制备：将竹浆或木浆或经过打浆预处理后的竹浆或木浆分散于质量浓度1～10％NaOH溶液中，定量加入2,3-环氧丙基三甲基氯化铵，搅拌混匀后在25～70℃反应2-10h；反应完毕后，用质量浓度0.5～1％盐酸调pH至7，用蒸馏水抽滤洗涤至无剩余反应试剂；最后将纤维悬浮液通过高压均质机打磨，得到表面带正电荷的NFC分散液。电荷滴定结果显示微纤表面季铵盐基团含量为0.3～1.5mmol/g；
(3)官能化气凝胶的制备：将步骤1制得的表面带负电荷的纳米纤维素和官能化试剂按任意比例混合反应，得到第一混合溶液；将步骤2制得的表面带正电荷的纳米纤维素和官能化试剂在酸性条件下任意比例混合，得到第二混合溶液；将第一混合溶液、第二混合溶液分别置于-70～-40℃预冷冻2～4h后再冷冻干燥48h，然后把冷冻干燥得到的气凝胶放入烘箱中85℃下干燥2～5h进行烘干固化，分别得到表面带负电荷兼官能化基团、表面带正电荷兼官能化基团的纳米纤维素基官能化气凝胶，将上述气凝胶作为重金属离子的吸附材料。
2.如权利要求1所述的纳米纤维素基官能化气凝胶型重金属离子吸附材料的制备方法，其特征在于：所述步骤3中的官能化试剂选自半胱氨酸、乙二胺四乙酸、乙二胺三乙酸、聚丙烯酰胺、3-巯基丙基三甲氧基硅烷、3-氨丙基三甲氧基硅烷、双(三甲基硅烷基)氨基钾、N,O-双(三甲基硅烷基)乙酰胺、氨甲基三甲基硅烷。
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