CN113307332B - 一种用于电Fenton技术的活性炭纤维改性阴极的制备方法及应用 - Google Patents
一种用于电Fenton技术的活性炭纤维改性阴极的制备方法及应用 Download PDFInfo
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Abstract
一种用于电Fenton技术的活性碳纤维改性阴极的制备方法及应用属于环境功能材料领域。本发明在ACF电极的基础上,将60~200mg预处理后碳纳米管和20~60mg氮化碳以及22.5~67.5mg/L聚四氟乙烯(PTFE)溶于15mL水溶液中,利用超声浸渍法将CNTs和g‑C3N4吸附到ACF电极表面并在350℃条件下焙烧1小时,制成CNTs/g‑C3N4‑ACF复合电极。负载到活性炭纤维阴极表面的CNTs和g‑C3N4进一步提高了电极的氧气两电子还原活性,增多了电极的活性点位和比表面积,提高了电极的电流效率,大幅度增加了ACF阴极在电Fenton体系内的双氧水产量,进一步提升电Fenton体系对污染物的降解效果。
Description
技术领域
本发明提供一种负载碳纳米管和石墨相氮化碳的活性炭纤维改性阴极的制备及应用方法,属于环境功能材料技术领域,化学与环境工程的交叉领域。
背景技术
垃圾渗滤液是一种成分复杂的高浓度有机废水,在2010年,环保部发布的《生活垃圾填埋场渗滤液工程技术规范(试行)》中,把膜技术纳滤(NF) 工艺和反渗透(RO)工艺作为推荐的垃圾填埋场的垃圾渗滤液深度处理工艺,该工艺被大量采用。膜滤浓缩液的各类特征共性较多,指标也存在在相对集中的范围。膜浓缩液可占垃圾渗滤液总体积的8%~20%,部分甚至可达40%。膜截留浓缩液COD高,COD约在200~10000mg/L之间,无机盐类含量高且成分复杂,废水TDS多在20000~60000mg/L之间,氨氮浓度在50~1000mg/L之间,氯离子浓度在4000-50000mg/L之间,色度在500~1500倍之间。如何有效处理膜截流浓缩液,是维持膜处理系统长期稳定运行的关键因素,也是垃圾渗滤液处理的一个难点问题。
电Fenton法是利用电子作催化剂同位产生Fe2+和H2O2,并进一步生成高氧化活性的羟基自由基(·OH),来实现污染物的降解,其实质是电解过程生成 Fenton反应所需试剂,Fenton反应所生成的羟基自由基(·OH),其氧化还原电位高达2.80V,具有十分高的氧化活性。电Fenton技术适用于处理高浓度难生化降解的有机废水,在垃圾渗滤液膜滤浓缩液处理领域成为研究热点。
活性炭纤维(ACF)是一种新型的环保材料,因为其大的比表面积(1000 m2·g-1~3000m2·g-1)和占据总体孔容90%的微孔,具有很好的吸附特性。并且具有高析氢电位,导电性强,有利于氧气的两电子还原,无毒,廉价便于获取,化学特性稳定和抗腐蚀性的特点,在电Fenton中作为阴极材料被广泛使用。
通过浸渍煅烧的方法引入活性炭纤维的碳纳米管(CNTs)和氮化碳 (g-C3N4),因其特殊的物理化学特性,提升了活性炭纤维的导电性,增大了比表面积,改变了孔径结构,并且提升了氧气的两电子还原活性,加快了Fe2+的还原,提升了过氧化氢的生成速率。同时,浸渍过程中加入适量的聚四氟乙烯(PTFE),可以更好地将碳纳米管和氮化碳结合到活性炭纤维上,并且能够保持氧气在活性炭纤维电极表面传递过程中的气液固三相平衡,提高传递效率。通过该种方法的活性炭纤维阴极地改性,有效提高了电Fenton系统对污染物地降解效率。
发明内容
本发明为了提高过氧化氢的生成效率,提供了一种电Fenton体系内,对活性炭纤维阴极的一种改性方法。该方法制备步骤简单,成本低廉,在较为泛的pH环境下均能发挥良好的电催化效果,易于实现工业化。
电极的改性过程,包括以下步骤:
(1)活性炭纤维碳布预处理:将活性炭纤维碳布浸入10wt%NaOH溶液中并超声处理0.5h,用超纯水洗涤3次后浸入5wt%HCl溶液中2h,再用超纯水冲洗至中性,然后在80℃的烘箱中干燥24h待用。
(2)碳纳米管预处理:将多壁碳纳米管(MWCNTs)置于体积比1:1的硝酸水溶液中,超声处理4小时,用超纯水水洗至中性,冻干48小时备用。
(3)氮化碳制备:将适量的尿素置于培养皿中在50℃烘箱中干燥24h,将干燥好的尿素置于带盖坩埚中,在通氮气的气氛炉中焙烧,以4℃/min升温,达到550℃后保持4小时,冷却至室温取出。
(4)将预处理好的多壁碳纳米管和氮化碳溶于蒸馏水中,超声10分钟后加入聚四氟乙烯,继续超声10分钟,混合液中多壁碳纳米管浓度为4g/L~20g/L、氮化碳浓度为1g/L~6g/L和聚四氟乙烯的浓度为22.5~67.5mg/L。
(5)将预处理好的活性炭纤维碳布平铺在培养皿中,将超声好的混合液倾倒在碳布上,再次超声20分钟,超声结束后静置3分钟,将碳布翻面,共超声 80分钟。
(6)超声结束后将培养皿内剩余的糊状物均匀的涂在碳布表面,置于80℃烘箱内干燥2小时。
(7)将干燥好的碳布置于马弗炉中,以5℃/min的速率升温,达到350℃后保持1小时,冷却至室温取出,即制得改性活性炭纤维阴极。
所述方法制备的活性炭纤维电极,在电Fenton体系内作为阴极处理富里酸配水和混凝预处理后的垃圾渗滤液膜滤浓缩液,其条件为:阳极采用钌铱钛电极,阴极采用本专利改性的活性炭纤维电极,pH值为3~9,电流为0.1~0.5A,体系内投加FeCl2,令体系内Fe2+浓度为0.1~0.6mM,反应时间为150min,极板间距为1cm,采用空气泵连接电解槽底部曝气条曝气,曝气速率为0.3L/min,富里酸配水投加电解质为0.05M硫酸钠。
本发明中,碳纳米管增加了活性炭纤维的导电性,改善了电极表面的孔径结构和增大了电极的比表面积,并且和氮化碳均增强了氧气的两电子还原催化特性,增加了电极的活性点位,有利于O2和Fe3+吸附还原,适量的PTFE有利于固定碳纳米管和氮化碳,并且有利于氧气在电极表面的传输,以上因素均使电极过氧化氢生成速率大幅提高,进一步与体系内Fe2+发生Fenton反应,产生高氧化性的·OH,无选择地将污染物氧化成小分子有机物或直接矿化成CO2和H2O。整个系统易于操作,电流密度低,电流效率高,在广泛pH范围内,对多种难降解污染物均有良好地降解效果,是一种有工业应用前途的活性炭纤维阴极。
附图说明
图1为碳纳米管、氮化碳改性活性炭纤维电极的表观图
图2为碳纳米管、氮化碳改性活性炭纤维电极的X射线衍射图
图3为实例1中碳纳米管、氮化碳改性活性炭纤维电极过氧化氢产量随时间变化的关系图
图4为实例2中碳纳米管、氮化碳改性活性炭纤维电极处理富里酸模拟废水浓度随时间变化的关系图
图5为实例3中碳纳米管、氮化碳改性活性炭纤维电极重复使用6次稳定性的效果图
具体实施方式
为了更好的解释本发明的精神及内容,进一步的阐述本发明的用途,下面给出本发明的几个非限定性实例,即本发明的内容包括但不限于下述几个实例。
实例1
将活性炭纤维碳布裁成5cm×5cm规格,首先将其浸入10wt%NaOH溶液中并超声处理0.5h,用超纯水洗涤3次,然后浸入5wt%HCl溶液中2h,用超纯水冲洗至中性,然后在80℃的烘箱中干燥24h待用。
将碳纳米管置于体积比1:1的硝酸水溶液中,超声处理4小时,用超纯水稀释后,采用微孔膜过滤,用超纯水水洗至中性,放入真空箱中80℃干燥备用。将适量的尿素置于培养皿中在50℃烘箱中干燥24h,将干燥好的20g尿素置于带盖坩埚中,在通氮气的气氛炉中焙烧,升温速率4℃/min,达到550℃后保持4小时,冷却至室温取出,及得到氮化碳。将180mg碳纳米管和30mg氮化碳溶于15ml蒸馏水中,超声10分钟后加入0.7mg聚四氟乙烯,继续超声10分钟。将预处理好的活性炭纤维碳布平铺在培养皿中,将超声好的混合液倾倒在碳布上,再次超声20分钟,超声结束后静置3分钟,将碳布翻面,此步骤一共翻面3次,共超声80分钟。超声结束后将培养皿内剩余的糊状物均匀的涂在碳布表面,置于80℃烘箱内干燥2小时。将干燥好的碳布置于马弗炉中,以5℃/min 的速率升温,达到350℃后保持1小时,冷却至室温取出,即制得改性活性炭纤维阴极。
将上述制备成的电极应用于下述电解体系中,在100ml电解池中加入 80ml0.05M硫酸钠电解液,加入阳极采用钌铱钛电极,阴极采用制备电极,阴阳极接入0.2A恒流输出模式电源,极板间距1cm,空气通气速率为0.2L/min,用硫酸和氢氧化钠调节pH为3,测量体系内过氧化氢生成量。将80ml电解液替换成80ml混凝预处理后的垃圾渗沥液纳滤浓缩液,COD为1226mg/L,体系内投加0.4mM硫酸亚铁,电流大小、极板间距、通气速率、体系内的酸碱度保持与测量过氧化氢时的条件不变,反应150min内,过氧化氢最高生成量为130mg/L,150min 后,预处理后的纳滤浓缩液COD下降到160mg/L。
实例2
将活性炭纤维碳布裁成5cm×5cm规格,首先将其浸入10wt%NaOH溶液中并超声处理0.5h用超纯水洗涤3次,然后浸入5wt%HCl溶液中2h,用超纯水冲洗至中性,然后在80℃的烘箱中干燥24h待用。
将碳纳米管置于体积比1:1的硝酸水溶液中,超声处理4小时,用超纯水稀释后,采用微孔膜过滤,用超纯水水洗至中性,放入真空箱中80℃干燥备用。将适量的尿素置于培养皿中在50℃烘箱中干燥24h,将干燥好的20g尿素置于带盖坩埚中,在通氮气的气氛炉中焙烧,升温速率4℃/min,达到550℃后保持4小时,冷却至室温取出,及得到氮化碳。将247mg碳纳米管和45mg氮化碳溶于15ml蒸馏水中,超声10分钟后加入0.9mg聚四氟乙烯,继续超声10分钟。将预处理好的活性炭纤维碳布平铺在培养皿中,将超声好的混合液倾倒在碳布上,再次超声20分钟,超声结束后静置3分钟,将碳布翻面,此步骤一共翻面3次,共超声80分钟。超声结束后将培养皿内剩余的糊状物均匀的涂在碳布表面,置于80℃烘箱内干燥2小时。将干燥好的碳布置于马弗炉中,以5℃/min 的速率升温,达到350℃后保持1小时,冷却至室温取出,即制得改性活性炭纤维阴极。
将上述制备成的电极应用于下述电解体系中,在100ml电解池中加入 80ml0.05M硫酸钠电解液,加入阳极采用钌铱钛电极,阴极采用制备电极,阴阳极接入0.1A恒流输出模式电源,极板间距1cm,空气通气速率为0.2L/min,用硫酸和氢氧化钠调节pH为7,测量体系内过氧化氢生成量。将80ml电解液替换成80ml的300mg/L富里酸配水,投加0.05M硫酸钠,体系内投加0.6mM硫酸亚铁,电流大小、极板间距、通气速率、体系内的酸碱度保持与测量过氧化氢时的条件不变,反应150min内,过氧化氢最高生成量为114mg/L,150min后富里酸去除率为88%。
实例3
将活性炭纤维碳布裁成5cm×5cm规格,首先将其浸入10wt%NaOH溶液中并超声处理0.5h,用超纯水洗涤3次,然后浸入5wt%HCl溶液中2h,再用超纯水冲洗至中性,然后在80℃的烘箱中干燥24h待用。
将碳纳米管置于体积比1:1的硝酸水溶液中,超声处理4小时,用超纯水稀释后,采用微孔膜过滤,用超纯水水洗至中性,放入真空箱中80℃干燥备用。将适量的尿素置于培养皿中在50℃烘箱中干燥24h,将干燥好的20g尿素置于带盖坩埚中,在通氮气的气氛炉中焙烧,升温速率4℃/min,达到550℃后保持4小时,冷却至室温取出,及得到氮化碳。将120mg碳纳米管和40mg氮化碳溶于15ml蒸馏水中,超声10分钟后加入0.3mg聚四氟乙烯,继续超声10分钟。将预处理好的活性炭纤维碳布平铺在培养皿中,将超声好的混合液倾倒在碳布上,再次超声20分钟,超声结束后静置3分钟,将碳布翻面,此步骤一共翻面3次,共超声80分钟。超声结束后将培养皿内剩余的糊状物均匀的涂在碳布表面,置于80℃烘箱内干燥2小时。将干燥好的碳布置于马弗炉中,以5℃/min 的速率升温,达到350℃后保持1小时,冷却至室温取出,即制得改性活性炭纤维阴极。
将上述制备成的电极应用于下述电解体系中,在100ml电解池中加入80ml0.05mol/L硫酸钠电解液,加入阳极采用钌铱钛电极,阴极采用制备电极,阴阳极接入0.4A恒流输出模式电源,极板间距1cm,空气通气速率为0.3L/min,用硫酸和氢氧化钠调节pH为5,测量体系内过氧化氢生成量。将80ml电解液替换成80ml的300mg/L富里酸配水,投加0.05M硫酸钠,体系内投加0.2mM硫酸亚铁,电流大小、极板间距、通气速率、体系内的酸碱度保持与测量过氧化氢时的条件不变,反应150min内,过氧化氢最高生成量为108mg/L,150min后富里酸去除率为83%。
Claims (2)
1.一种用于电Fenton技术的活性炭纤维改性阴极的制备方法,其特征在于包括以下步骤:(1)将多壁碳纳米管置于体积比1:1的硝酸水溶液中,超声处理4小时,用超纯水稀释后,采用微孔膜过滤,用超纯水水洗至中性,放入真空箱中80℃干燥备用;(2)将尿素置于培养皿中在50℃烘箱中干燥24h,将干燥好的尿素置于带盖坩埚中,在通氮气的气氛炉中焙烧,升温速率4℃/min,达到550℃后保持4小时,冷却至室温取出,得到氮化碳粉末;(3)将活性炭纤维碳布浸入10wt%NaOH溶液中并超声处理 0.5 h,用超纯水洗涤3次,然后浸入5wt%HCl溶液中2h,再此用超纯水冲洗至中性,然后在 80°C 的烘箱中干燥 24h 待用;(5) 将预处理好的多壁碳纳米管和氮化碳溶于蒸馏水中,超声10分钟后加入聚四氟乙烯,继续超声10分钟,混合液中多壁碳纳米管浓度为4g/L~20g/L、氮化碳浓度为1g/L~6g/L和聚四氟乙烯的浓度为22.5~67.5mg/L;(6) 将预处理好的活性炭纤维碳布平铺在培养皿中,将超声好的混合液倾倒在碳布上,再次超声20分钟,超声结束后静置3分钟,将碳布翻面,此步骤一共翻面3次,共超声80分钟;(7) 超声结束后将培养皿内剩余的混合液底部的糊状物均匀的涂在碳布表面,置于80℃烘箱内干燥2小时;(8) 将干燥好的碳布置于马弗炉中,以5℃/min的速率升温,达到350℃后保持1小时,冷却至室温取出,即制得活性炭纤维改性阴极。
2.根据权利要求1的所述方法制备出的活性炭纤维改性阴极在电Fenton系统中作为阴极使用,其特征在于:
阳极采用钌铱钛电极,阴极采用制备的活性炭纤维电极改性阴极,pH值为3~9,电流为0.1~0.5A,投加FeCl2,使体系内Fe2+的浓度为0.1~0.6mmol/L,反应时间为150min,极板间距为1cm,采用空气曝气,曝气速率为0.2L/min,富里酸配水投加电解质为0.05mol/L硫酸钠。
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