CN115155543B - 一步制备磁性镁铁ldh-生物炭复合材料的方法及应用 - Google Patents

一步制备磁性镁铁ldh-生物炭复合材料的方法及应用 Download PDF

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CN115155543B
CN115155543B CN202210543986.1A CN202210543986A CN115155543B CN 115155543 B CN115155543 B CN 115155543B CN 202210543986 A CN202210543986 A CN 202210543986A CN 115155543 B CN115155543 B CN 115155543B
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ldh
composite material
magnesium
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张进
边颢昊
刘万鹏
沈澄
单胜道
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Zhejiang Lover Health Science and Technology Development Co Ltd
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Abstract

本发明公开了一种一步制备磁性镁铁LDH‑生物炭复合材料的方法及应用，本发明以生物质为基底，置于三价铁盐溶液中，再加入氢氧化镁充分搅拌，并老化一定时间，干燥后得到了镁铁LDH‑生物质，经过热解后得到了磁性镁铁LDH‑生物炭复合材料。该方法改善了共沉淀法制备LDH中反应不可控，产物结晶度低的问题；且减少了药品用量，省去了用碱溶液调控pH的步骤，提高了产率，降低了成本。所得磁性镁铁LDH‑生物炭复合材料在吸附水中磷酸盐方面表现出了优异的性能，且可以通过外加磁场回收，为LDH及其复合材料的制备提供了重要方法。

Description

一步制备磁性镁铁LDH-生物炭复合材料的方法及应用
技术领域
本发明属于纳米功能材料和环境材料制备技术领域，具体涉及一种一步制备磁性镁铁LDH-生物炭复合材料的方法及应用。
背景技术
磷是生命必不可少的元素，但是含磷废水中的磷若不妥善处理进入水生系统后会产生负面影响，造成水生系统富营养化。因此，开发有效且可持续的方法来去除含磷废水中的磷并将其作为资源回收具有巨大的潜力。目前的研究涉及了生物处理，膜分离，化学沉淀，电解和吸附等各种方法。在这些技术中，吸附处理因其成本低，选择性高，生态友好和易于操作而被认为是一种有前景的方法。
生物炭在环境应用中具有生产能耗低、减少碳排放的明显优点。此外，大量的低成本废料作为生物炭生产的原料，使其成为水处理应用的理想的可持续吸附剂。生物炭的表面可以通过化学活化或制作生物炭基复合材料进行改性，进一步提高其吸附能力。水滑石，即层状双金属氢氧化物(Layered Double Hydroxide,LDH)由于其强大的离子交换能力，在水处理等多个领域得到了广泛的关注，LDH的一般形式为[M2+ 1-xM3+ x(OH)2]·[An- x/n·mH2O]，其中M2+和M3+是二价和三价的金属阳离子，x是三价金属阳离子的摩尔比，An-是中间层中的阴离子。LDH与生物炭的协同作用显著改善了生物炭/LDH复合材料的比表面积、表面官能团、结构异质性、稳定性和吸附特性等理化性质，并且其可持续性、低成本和能有效去除各种污染物的巨大潜力使越来越多的研究者关注于将LDH负载在生物炭上来去除污染物。
目前，LDH-生物炭复合材料制备方法主要有三种，分别是水热合成法、在生物炭表面共沉淀LDH盐和在生物质表面共沉淀LDH盐后共热解。共沉淀法因其经济实惠和高产率的优点成为了最常用的制备LDH-生物炭复合材料的方法。然而，共沉淀法通常需要较长的老化时间以及较为严格的pH控制步骤，大量结晶核的形成也导致了低结晶度的LDH颗粒，且LDH-生物炭复合材料的低成本是相对的，对于经济效益不高的环保行业来说难以真正应用推广。
Lee等，在2019年用硝酸镁和硝酸铝加入氢氧化钠调节pH，在稻壳粉表面共沉淀了镁铝LDH，然后共热解合成了镁铝LDH-稻壳生物炭复合材料：其具体制备步骤如下：1)将1g稻壳粉置于80ml含一定浓度六水硝酸镁合九水硝酸铝的溶液中，然后在室温下以300转 /分钟的转速震荡一小时；2)在震荡的过程中，通过滴入浓度为5M 的氢氧化钠，保持溶液pH恒定在10.0；3)将混合物置于50℃环境下老化72小时；4)收集样品，用去离子水冲洗，并在80℃下烘干过夜；5)将干燥的样品置于管状石英炉中热解，在不同的温度范围内(300-700℃)，加热速率为10℃/min，热解过程中持续通入氮气； 6)收集制得的生物炭，用去离子水冲洗；8)在80℃下干燥。该技术生物质原料使用了稻壳，通过加入硝酸镁和硝酸铝用氢氧化钠调节 pH在稻壳粉上预载镁铝水滑石再热解制得了镁铝LDH复合稻壳生物炭吸附材料，制备步骤较为复杂，对实验操作要求较高，且需要老化的时间较久(72小时)，吸附后的材料难以回收，不适宜在实际中应用。
发明内容
针对现有技术中存在的问题，本发明在预处理、药品使用等多个方面进行了一系列改进，从而提出了一种简便的一步制备LDH-生物炭复合材料的方法。本发明方法制备的材料前体镁铁LDH-生物质用更短的老化时间得到了更高的产量和结晶度的LDH，在一定温度下热解后得到了磁性镁铁LDH-生物炭复合材料，其表面含有镁铁LDH 颗粒，在吸附水中的磷酸盐后能重建其LDH层状结构，且用强磁石回收的回收率可达98％以上。该方法基于Mg(OH)2在水溶液中难溶及完全电离的特性，实现了可控的共沉淀过程与pH控制，无需进行长时间的晶化与pH控制步骤。
具体通过以下技术方案加以实现：
一步制备磁性镁铁LDH-生物炭复合材料的方法，包括以下步骤：
1)将生物质干燥、粉碎、作为负载LDH的基料；
2)配置三价铁盐溶液，三价铁盐的浓度为0.2M-1M；加入步骤 1)所得的生物质，超声处理，接着缓缓加入氢氧化镁，加入过程中不断搅拌，直至混合物颜色均匀并呈浆状，最后放入烘箱中静置老化，得老化后的浆状物；
3)将步骤2)制得的浆状物进行离心，离心后的固态物质进行干燥处理，制得前体材料镁铁LDH-生物质；
4)将步骤3)制得的前体材料镁铁LDH-生物质于惰性气体氛围下热解，得到磁性镁铁LDH-生物炭复合材料。
进一步地，生物质选用玉米秸秆，玉米秸秆干燥至含水率≤5％；粉碎至能过20-40目筛。
进一步地，步骤2)中，三价铁盐为FeCl3、Fe(NO3)3、Fe2(SO4)3中的一种或几种。
进一步地，步骤2)中，氢氧化镁与三价铁盐的摩尔比为2-4:1。
进一步地，步骤2)中，老化温度为60±10℃，老化时间为2-4 小时。
进一步地，步骤2)中，生物质与铁盐溶液的加入量按照每100 毫升铁盐溶液中加入生物质5-10g。
进一步地，步骤3)中，干燥处理采用烘箱干燥处理，干燥处理温度为50±5℃。
进一步地，步骤4)中，惰性气体为氮气，热解温度为500±200℃，热解时间为2±0.5小时。
上述任一方法制备的复合材料在水处理中对磷酸盐吸附的应用。
本发明中对吸附材料进行回收的步骤为：使用强磁石在5s内对废水中的吸附材料进行固液分离和回收。
本发明利用Mg(OH)2在水溶液中难溶及完全电离的特性，一步制备得到了磁性镁铁LDH-生物炭，其制备流程简便，原材料来源广，成本低；制备得到的材料由镁铁LDH和镁铁氧化物镶嵌(包裹)的生物炭构成，附着的镁铁LDH和镁铁氧化物能够有效地去除水溶液中的磷，同时具有磁性使得材料易于分离回收。
附图说明
图1为本发明制备方法与传统镁铁LDH-生物质复合材料的制备技术路线图对比；
图2为使用磁铁对吸附完成后的磁性镁铁LDH-生物炭复合材料进行分离；
图3为实施例1中所制备的磁性镁铁LDH-生物炭复合材料的扫描电子显微镜图；
图4为实施例1中所制备的磁性镁铁LDH-生物炭复合材料的 FT-IR光谱图；
图5为实施例1中所制备的磁性镁铁LDH-生物炭复合材料的 XRD图谱。
具体实施方式
实施例1
使用一步制备磁性镁铁LDH-生物炭复合材料：其具体制备路线及与传统制备路线的对比见图1所示，
1)将玉米秸秆干燥至含水率≤5％，然后粉碎至能过20目筛，作为生物质；
2)称取27.05g(0.25mol)FeCl3·6H2O置于250ml烧杯中，加入 100ml去离子水附以超声处理使其完全溶解，将完全溶解后的铁盐溶液洗入500ml容量瓶中定容，从而配置成0.5mol/L的三价铁盐溶液；
3)将步骤2)中所配置的三价铁盐溶液加入盛有50g生物质的 1L烧杯，加入过程中持续搅拌，然后置于超声中30min，最后缓缓加入29g(0.5mol)Mg(OH)2，即镁铁摩尔比为2：1，加入过程中持续搅拌，直至整个溶液呈颜色均匀的浆状物，烧杯置于60℃烘箱中老化2小时；
4)将步骤3)中所得物进行离心，50℃烘箱干燥12h，得干燥后固态物；
将上述干燥后固态物于氮气氛围下于500℃热解2小时，得到负载LDH生物炭的复合材料。
该实施例中制得的磁性镁铁LDH-生物炭复合材料的扫描电子显微镜图见图3，FT-IR光谱图见图4，XRD图谱见图5。
使用强磁石在水溶液中回收，证明该LDH-生物炭复合材料具有磁性。回收效果见图2所示。
利用本实施例方法制备的磁性镁铁LDH-生物炭复合材料进行去除水中磷酸根的吸附试验，具体操作如下：
储备液配置：1000mg/LPO4 3-溶液：称取1.4315gKH2PO4，溶解于1L去离子水中配置。
吸附溶液配置：用去离子水稀释PO4 3-储备液以配置相应浓度的吸附溶液。
称取0.04g磁性镁铁LDH-生物炭复合材料，置于50ml离心管，添加40ml浓度分别为50/100/200mg/L的PO4 3-溶液，在25℃、200rpm 的条件下震荡、吸附24h，抽取上清液用45μm微孔滤膜过滤后，利用紫外分光光度法测定上清液中磷酸根的浓度，并计算吸附量和去除率。
溶液中磷酸根的浓度采用国标法抗坏血酸-钼蓝显色法测定，采用抗坏血酸-钼酸盐作为显色剂，生成蓝色化合物，由紫外分光光度计在700nm波长处测定。
实施例2
将实施例1)中步骤2)中的“称取67.625g(0.25mol) FeCl3·6H2O”、“最后缓缓加入29g(0.5mol)Mg(OH)2”和步骤4) 中的“于氮气分为下于500℃热解2小时”分别做了不同的修改，来观察不同改性条件对磁性镁铁LDH-生物炭复合材料去除磷效果的影响，修改方式如表1所示。
表1
按实施例1所述方法和条件下进行实验，对50-200mg/L的PO4 3-溶液进行吸附试验，所得结果见表2。
表2
对比例1
将实施例1)中步骤2)中的氢氧化镁替换为氯化镁，其余同实施例1。
对比例2
镁铝LDH-生物炭复合材料。制备方法：通过向摩尔比为2：1 的六水硝酸镁(Mg(NO3)2·6H2O)和九水硝酸铝(Al(NO3)3·9H2O)加入氢氧化钠(NaOH)，在稻壳粉表面共沉淀生成镁铝LDH，然后在 500℃下共热解2小时。
将0.1g镁铝LDH-生物炭复合材料置于100ml锥形瓶中，加入 80ml浓度为50-100mg/L的磷酸盐溶液进行吸附实验。
对比例3
铁镁LDH材料。制备方法：通过向摩尔比为2：1的六水氯化镁 (MgCl2·6H2O)和氯化铁(FeCl3)溶液中加入氢氧化钠(NaOH)沉淀制得。
将0.025g实施例1制得的材料和对比例1-3制得的材料各取 0.025g，分别置于50ml锥形管中，往各锥形管中分别加入25ml浓度为50mg/L的磷酸盐溶液(pH＝7.4)，于相同的条件下进行吸附试验。试验结果见表3。
表3
由表3可知：本发明创新合成方法制备的磁性镁铁LDH-生物炭复合材料对浓度为50mg/L的磷酸盐溶液中磷的去除效率和吸附容量都是最大的。

Claims (5)

1.一种一步制备磁性镁铁LDH-生物炭复合材料的方法，其特征在于在含生物质的三价铁盐溶液中加入氢氧化镁一步制得前体材料镁铁LDH-生物质，热解后得到磁性镁铁LDH-生物炭复合材料，所述方法包括以下步骤：
1）将生物质干燥、粉碎，作为负载LDH的基料；所述生物质选用玉米秸秆，玉米秸秆干燥至含水率≤5%；粉碎至能过20-40目筛；
2）配置三价铁盐溶液，三价铁盐的浓度为0.2M-1M；加入步骤1）所得的生物质，超声处理，接着缓缓加入氢氧化镁，氢氧化镁与三价铁盐的摩尔比为2-4:1，加入过程中不断搅拌，直至混合物颜色均匀并呈浆状，最后放入烘箱中静置老化，老化温度为60±10℃，老化时间为2-4小时，得老化后的浆状物；
3）将步骤2）制得的浆状物进行离心，离心后的固态物质进行干燥处理，制得前体材料镁铁LDH-生物质；
4）将步骤3）制得的前体材料镁铁LDH-生物质于氮气氛围下热解，热解温度为400-500℃，热解时间为2±0.5小时，得到磁性镁铁LDH-生物炭复合材料。
2.如权利要求1所述的一种一步制备磁性镁铁LDH-生物炭复合材料的方法，其特征在于步骤2）中，三价铁盐为FeCl3、Fe(NO3)3、Fe2(SO4)3中的一种或几种。
3.如权利要求1所述的一种一步制备磁性镁铁LDH-生物炭复合材料的方法，其特征在于步骤2）中，生物质与铁盐溶液的加入量按照每100毫升铁盐溶液中加入生物质5-10g。
4.如权利要求1所述的一种一步制备磁性镁铁LDH-生物炭复合材料的方法，其特征在于步骤3）中，干燥处理采用烘箱干燥处理，干燥处理温度为50±5℃。
5.根据权利要求1-4任一所述的方法制得的复合材料在水处理中对磷酸盐吸附的应用。
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