CN114177884A - 三维整体型纤维状多孔碳材料、制备方法及应用 - Google Patents
三维整体型纤维状多孔碳材料、制备方法及应用 Download PDFInfo
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- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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Abstract
本发明涉及一种三维整体型纤维状多孔碳材料、制备方法及应用。将棉基原料浸入去离子水、无机碱溶液、含杂原子M的无机盐或无机酸溶液中,超声以除去粘附于棉基原料表面的气泡,在一定的温度和时间下浸渍,干燥,在惰性气氛下煅烧碳化处理,得到三维整体型纤维状多孔碳材料。本发明制备工艺简单,原料涉及面广,能够变废为宝,制备的材料除了具有比表面积大,孔道丰富,导电性导热性好,耐高温,耐酸碱的优点外,还兼有密度低,结构松散且整体型好,能够有效吸附水体中水溶性有机物,水体中重金属离子等。
Description
技术领域
本发明属于从天然的线、棉或纤维制造碳纤维技术领域,具体涉及一种利用棉基材料制备三维整体型纤维状多孔碳材料、制备方法及应用。
背景技术
中国是世界公认的化工大国,化工行业的快速发展大大提高了对各类化学品的需求,提高了国民生活水平。
吸附法被认为是脱除水体中污染物的有效方法。吸附法是利用吸附剂的活性使周围介质中的污染物富集到其表面,从而达到分离的效果,主要通过污染物和吸附剂之间的相互作用完成吸附,包括物理吸附和化学吸附。物理吸附由范德华力引起,为单分子层或多分子层吸附,反应过程可逆且没有选择性,吸附热较小,吸附速度快,所需的活化能较小。化学吸附则由化学键引起,为单分子层吸附,反应不可逆且有选择性,吸附热较大,吸附速度慢,需要一定的活化能。由于吸附法具有操作安全简单、无需添加化学试剂、选择性好、吸附剂可循环再生等优点,己被广泛地应用在工业废水处理中,该方法的核心技术是吸附能力强、化学性质稳定的高效吸附剂的开发。
活性碳材料具有孔道结构丰富,比表面积大,吸附性强等特点,能够脱除各种有机或无机污染物,并且具有较大的吸附容量。不仅如此,碳材料还具备价格低廉,环境友好的特点,在工业废水处理领域极具应用前景。但是,活性碳材料作为吸附剂也存在一定的缺点,这就是大多数活性碳材料都是粉体材料,易随着排水流失而进入外界环境中,流失的活性碳材料会释放之前吸附的污染物,重新污染环境。另一方面,流失的碳材料将会极大地增加吸附剂的成本,影响其经济效益。其结果是,以活性碳材料作为工业废水吸附剂时,粉体特性使得回收和再生该类材料时,需消耗极大的时间和经济成本,给工业生产造成极大的经济和环境压力。所以,开发和制备新型的整体型碳材料,实现碳材料在水处理过程中的连续操作和快速回收,成为最大改进这类材料工业价值的有效措施。同时,可以在制备过程中,对碳材料进行改性,以保证碳材料的高吸附容量。
发明内容
本发明针对现有制备工艺得到的三维多孔碳纤维多为粉体材料,不易回收和再生的不足,提供一种操作简单、成本低廉的以棉基原料制备不同吸附特性的三维整体型纤维状多孔碳材料的方法。本发明方法获得碳材料不仅比表面积大,孔道丰富,性质稳定,而且具有整体型结构,在水处理污染物吸附中表现出优异的应用潜力。
为了实现上述目的,本发明所采用的技术方案为:
一种三维整体型纤维状多孔碳材料的制备方法,包括以下步骤:
(1)化学改性:将棉基原料浸入下述一种浸渍溶液中,超声处理以除去粘附于棉基原料表面的气泡,继续浸渍改性处理,浸渍时间为0.5-24 h,温度为25-100 °C,然后将改性后的材料取出,在不超过100 °C的条件下干燥,得到改性棉纤维材料;
所述浸渍溶液为去离子水溶液,无机碱溶液,含杂原子M的无机盐或无机酸溶液,所述杂原子为N、S、P、B、Cl、Br、I、Si或F;
(2)碳化处理:将经过步骤(1)改性后的材料放入管式炉中,通入惰性气体,在惰性气氛下进行煅烧处理,煅烧温度为600~1000 °C,煅烧时间为1-4 h,得到三维整体型纤维状多孔碳材料。
优选地,所述棉基材料为天然棉花、棉纤维编织物、回收棉布、回收涤棉布、莫代尔布、棉基滤纸或莱赛尔布。
优选地,所述浸渍溶液按1 g 棉基原料与10~500 mL浸渍溶液的配比使用,无机碱溶液、含杂原子M的无机盐或无机酸溶液的浓度为0.01~1 mol/L。
优选地,所述含杂原子M的无机盐溶液为硝酸铵、磷酸铵、醋酸铵、氯化铵或硫酸铵水溶液,所述含杂原子M的无机酸溶液为硝酸、盐酸、硫酸、磷酸、硼酸、氢氟酸、硅酸、氢溴酸或氢碘酸水溶液,所述无机碱溶液为尿素、氨水、氢氧化钠、氢氧化钾、氢氧化钙或氢氧化镁水溶液。
优选地,所述煅烧处理的升温速率在1~10 °C/min,煅烧处理的升温速率可以根据材料的功能及性质进行调整,如2 °C/min,5 °C/min,10 °C/min等。
优选地,所述惰性气氛是氮气或氩气。不同的煅烧气氛会对产物三维多孔碳纤维材料的石墨化度产生影响,同时将会影响产物的机械性能、物理化学性质以及导电性和导热性等性能。
一种通过三维整体型纤维状多孔碳材料的制备方法获得的材料,所述杂原子M通过接枝或掺杂方式留在纤维状碳材料的结构中。
一种通过三维整体型纤维状多孔碳材料的制备方法获得的材料在水处理中的应用。
与现有技术相比,本发明具有以下优越性:
1. 以棉基原料为制备原料,原料涉及的面广,能够变废为宝;
2. 通过简单的浸渍工艺,原有的纤维素结构得以修饰或改变,再经过高温煅烧,棉纤维会转变为活性碳纤维,而浸渍溶液中的N、S、P、B、F、Cl、Si、I或Br杂原子则会通过接枝或掺杂方式留在碳纤维的结构中,形成杂原子修饰或掺杂的三维整体型纤维状多孔碳材料,杂原子在所得到的碳纤维结构中的结构均一性和分散性均较高;
3. 所制得的三维多孔碳材料的整体性保持较好,结构稳定,非常适合用于对各种流动体系中的有机分子或重金属离子进行吸附,吸附剂不会产生二次污染,易回收;
4. 可以通过调控杂原子种类、载量、存在状态等条件达到控制三维多孔整体型碳材料对不同污染物吸附性能。
附图说明
图1为实施例1所得的三维碳纤维气凝胶的外观图片。
图2为实施例1所得的三维碳纤维气凝胶的扫描电镜图。
图3为实施例1所得的三维碳纤维气凝胶的XRD谱图。
图4为实施例1所得的三维碳纤维气凝胶对不同有机污染物的饱和吸附能力图。
图5为棉基滤纸的外观图片。
图6为棉基滤纸磷改性后得到的黑色的三维多孔磷改性碳纤维材料的外观图片。
具体实施方式
下面结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整的描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。
实施例1
称取0.5 g的天然棉花,将其完全浸入到50 mL的去离子水中,超声处理以除去粘附于棉花表面的气泡。将该混合物于室温下静置24 h,使棉纤维上的官能团与去离子水中的H+离子达到交换平衡,然后将棉纤维取出,放于75 °C的烘箱中干燥过夜。完全烘干后再将此样品放入管式炉内,室温下通氩气30 min,然后在继续通氩气的条件下开始以5 °C /min的速率升温到1000 °C,并在该温度下恒温4 h,然后自然冷却至室温。待高温反应完全结束,收集得到的黑色的三维多孔碳纤维材料,如图1所示,材料结构松散且整体型好,机械性能好,耐压,抗弯曲,抗折皱。
对材料进行饱和吸附能力测试,制备0.005 g催化剂,分别倒入50 mL浓度为40mg/L的有机物溶液中,超声分散使其混合均匀。然后将混合物置于黑暗环境下,在不断磁力搅拌的情况下,在室温条件下吸附0.5 h。最终得到材料对不同有机污染物的饱和吸附能力如图4所示,去离子水改性的天然棉花,对孔雀石绿的吸附能力最强,四环素的吸附能力最弱。
实施例2
称取0.1 g的天然棉花,将其完全浸入到50 mL的浓度为0.1 mol/L的尿素溶液中,超声处理以除去粘附于棉花表面的气泡。将该混合物于室温下静置0.5h,使棉纤维上的官能团与溶液中的尿素分子充分结合,然后将棉花纤维取出,放于75 °C的烘箱中干燥过夜。完全烘干后再将此改性棉花样品放入管式炉内,室温下通氩气30 min,然后在继续通氩气的条件下开始以5 °C /min的速率升温到900 °C,并在该温度下恒温4 h,然后自然冷却至室温。待高温反应完全结束,收集得到黑色的三维多孔氮改性碳纤维材料。
实施例3
称取0.5 g的回收棉布,将其完全浸入到20 mL的浓度为0.1 mol/L的氨水溶液中,超声处理以除去粘附于棉布表面的气泡。将该混合物于室温下静置24 h,使棉纤维上的官能团与溶液中的铵根离子充分结合,然后将棉布取出,放于80 °C的烘箱中干燥过夜。完全烘干后再将此改性棉布样品放入管式炉内,室温下通氮气60 min,然后在继续通氮气的条件下开始以2 °C /min的速率升温到800 °C,并在该温度下恒温4 h,然后自然冷却至室温。待高温反应完全结束,收集得到黑色的三维多孔氮改性碳纤维布。
除尿素或氨水外,浸渍溶液可更换成氢氧化钠、氢氧化钠钾、氢氧化钙、氢氧化钠镁的水溶液。
实施例4
称取1 g的天然棉花,将其完全浸入到50 mL的浓度为1 mol/L的磷酸铵溶液中,超声处理以除去粘附于棉花表面的气泡。将该混合物于室温下静置24 h,使棉纤维上的官能团与溶液中的铵根离子和磷酸根充分结合,然后将棉花纤维取出,放于50 °C的烘箱中干燥过夜。完全烘干后再将此改性棉花样品放入管式炉内,室温下通氩气90 min,然后在继续通氩气的条件下开始以1 °C /min的速率升温到850 °C,并在该温度下恒温2 h,然后自然冷却至室温。待高温反应完全结束,收集得到黑色的三维多孔氮磷改性碳纤维材料。
实施例5
将边长为7.5 cm的正方形棉基滤纸,如图5所示,将其完全浸入到20 mL的浓度为0.05 mol/L的磷酸溶液中,超声处理以除去粘附于滤纸表面的气泡。将该混合物于室温下静置4 h,使棉纤维上的官能团与溶液中的磷酸根充分结合,然后将滤纸取出,放于90 °C的烘箱中干燥过夜。完全烘干后再将此改性滤纸样品放入管式炉内,室温下通氮气20 min,然后在继续通氮气的条件下开始以1 °C /min的速率升温到1000 °C,并在该温度下恒温4 h,然后自然冷却至室温。待高温反应完全结束,收集得到黑色的三维多孔磷改性碳纤维材料,如图6所示,材料结构完整且整体型保持较好,仍保持原有滤纸的形状,边长约为3cm。
实施例6
称取5 g的回收棉布,将其完全浸入到50 mL的浓度为0.01 mol/L的硫酸溶液中,超声处理以除去粘附于棉布表面的气泡。将该混合物于室温下静置12 h,使棉纤维上的官能团与溶液中的硫酸根充分结合,然后将棉布取出,放于100 °C的烘箱中干燥过夜。完全烘干后再将此改性棉布样品放入管式炉内,室温下通氩气40 min,然后在继续通氮气的条件下开始以10 °C /min的速率升温到600 °C,并在该温度下恒温1 h,然后自然冷却至室温。待高温反应完全结束,收集得到黑色的三维多孔硫改性碳纤维布。
实施例7
可以按照实施例1-6的方法,以天然棉花、棉纤维编织物、回收棉布、回收涤棉布、莫代尔布、棉基滤纸或莱赛尔布为棉基原料,重复实验,为了在三维碳纤维中引入其他杂原子,浸渍溶液可更换为含N、S、P、Cl、I、Br、F、B、Si的无机盐或无机酸水溶液,所述含杂原子M的无机酸溶液为硝酸、盐酸、硼酸、氢氟酸、硅酸、氢溴酸、醋酸或氢碘酸的水溶液,无机盐如硝酸铵、醋酸铵、氯化铵或硫酸铵的水溶液。通过调控杂原子种类、载量、存在状态等条件达到控制三维多孔碳材料吸附性能的目的。
对比例1
称取0.5 g的天然棉花,放入管式炉内,室温下通氩气30 min,然后在继续通氩气的条件下开始以5 °C /min的速率升温到1000 °C,并在该温度下恒温4 h,然后自然冷却至室温。待高温反应完全结束,收集得到黑色的三维多孔碳纤维材料。
对比例2
称取0.5 g的天然棉花,放于75 °C的烘箱中干燥过夜,完全烘干后,收集得到白色的三维棉花纤维。
实施例8
按实施例1、对比例1和对比例2的方法制备0.005 g催化剂,分别编号为I、II、III,倒入50 mL浓度为40 mg/L的甲基橙溶液(MO),超声分散使其混合均匀。然后将混合物置于黑暗环境下,在不断磁力搅拌的情况下,在室温条件下吸附0.5 h。最终得到不同样品对MO的饱和吸附能力如下表所示:
样品 | 对甲基橙饱和吸附能力(mg/g) |
I | 745.8 |
II | 642.2 |
III | 13.3 |
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (8)
1.一种三维整体型纤维状多孔碳材料的制备方法,其特征在于,包括以下步骤:
(1)化学改性:将棉基原料浸入下述一种浸渍溶液中,超声处理以除去粘附于棉基原料表面的气泡,继续浸渍改性处理,浸渍时间为0.5-24 h,温度为25-100 °C,然后将改性后的材料取出,在不超过100 °C的条件下干燥,得到改性棉纤维材料;
所述浸渍溶液为去离子水溶液,无机碱溶液,含杂原子M的无机盐或无机酸溶液,所述杂原子为N、S、P、B、Cl、Br、I、Si或F;
(2)碳化处理:将经过步骤(1)改性后的材料放入管式炉中,通入惰性气体,在惰性气氛下进行煅烧处理,煅烧温度为600~1000 °C,煅烧时间为1-4 h,得到三维整体型纤维状多孔碳材料。
2.根据权利要求1所述的三维整体型纤维状多孔碳材料的制备方法,其特征在于,所述棉基原料为天然棉花、棉纤维编织物、回收棉布、回收涤棉布、莫代尔布、棉基滤纸或莱赛尔布。
3.根据权利要求1所述的三维整体型纤维状多孔碳材料的制备方法,其特征在于:所述浸渍溶液按1 g 棉基原料与10~500 mL浸渍溶液的配比使用,无机碱溶液、含杂原子M的无机盐或无机酸溶液的浓度为0.01~1 mol/L。
4.根据权利要求1所述的三维整体型纤维状多孔碳材料的制备方法,其特征在于:所述含杂原子M的无机盐溶液为硝酸铵、磷酸铵、醋酸铵、氯化铵或硫酸铵水溶液,所述含杂原子M的无机酸溶液为硝酸、盐酸、硫酸、磷酸、硼酸、氢氟酸、硅酸、氢溴酸或氢碘酸水溶液,所述无机碱溶液为尿素、氨水、氢氧化钠、氢氧化钾、氢氧化钙或氢氧化镁水溶液。
5.根据权利要求1所述的三维整体型纤维状多孔碳材料的制备方法,其特征在于,所述煅烧处理的升温速率在1~10 °C/min。
6.根据权利要求1所述的三维整体型纤维状多孔碳材料的制备方法,其特征在于,所述惰性气氛是氮气或氩气。
7.权利要求1至6任一权利要求所述三维整体型纤维状多孔碳材料的制备方法获得的材料,其特征在于,所述杂原子M通过接枝或掺杂方式留在纤维状碳材料的结构中。
8.权利要求1至6任一权利要求所述三维整体型纤维状多孔碳材料的制备方法获得的材料在水处理中的应用。
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