纺织学报 ›› 2019, Vol. 40 ›› Issue (03): 109-117.doi: 10.13475/j.fzxb.20171202310

• 染整与化学品 • 上一篇    下一篇

光催化剂负载酰肼基活性炭除甲醛材料的制备

张义安1, 狄剑锋1,2()   

  1. 1.江南大学 纺织服装学院, 江苏 无锡 214122
    2.五邑大学 纺织服装学院, 广东 江门 529020
  • 收稿日期:2017-12-11 修回日期:2018-11-05 出版日期:2019-03-15 发布日期:2019-03-15
  • 通讯作者: 狄剑锋
  • 作者简介:张义安(1982—),男,博士生。主要研究方向为纺织功能材料和新技术。

Preparation of photocatalyst loaded activated carbon grafted with polyhydrazide for removing formaldehyde

ZHANG Yian1, DI Jianfeng1,2()   

  1. 1. College of Textile and Clothing, Jiangnan University, Wuxi, Jiangsu 214122, China
    2. College of Textile and Clothing, Wuyi University, Jiangmen, Guangdong 529020, China
  • Received:2017-12-11 Revised:2018-11-05 Online:2019-03-15 Published:2019-03-15
  • Contact: DI Jianfeng

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摘要：

为解决甲醛污染生活环境的问题,利用缩合反应将聚酰肼(PAH)接枝到硝酸改性的活性炭上制备聚酰肼接枝活性炭(ACm-g-PAH),为消除其可能存在的二次污染,负载锰银掺杂纳米二氧化钛可见光光催化剂 (Mnx/Agy-TiO2)于ACm-g-PAH表面,进一步组装了自净化除甲醛材料锰银掺杂纳米二氧化钛负载聚酰肼接枝活性炭(Mnx/Agy-TiO2-l-ACm-g-PAH)。借助扫描电子显微镜、红外光谱仪对Mnx/Agy-TiO2-l-ACm-g-PAH的外观形貌和化学成分进行分析;通过软件Originpro 8.5将其催化甲醛数据与动力学方程进行拟合,并研究了其催化甲醛的动力学规律;对比分析了活化时间、活化温度和N,N-二环己基碳二亚胺(DCC)浓度对Mnx/Agy-TiO2-l-ACm-g-PAH材料甲醛移除率的影响机制。结果表明:当活化时间为2 h,活化温度为650 ℃,DCC用量为活性炭质量的2%,PAH浓度为11 mmol/L时,所制备材料Mnx/Agy-TiO2-l-ACm-g-PAH的甲醛移除率为99.6%;甲醛质量浓度在5~28.2 mg/g的范围内,Mnx/Agy-TiO2-l-ACm-g-PAH的甲醛移除率呈现衰减趋势;经过10次清洗后,材料的自净化能力减少为原来的12%。

关键词: 可见光, 除甲醛材料, 活性炭, 动力学, 光催化

Abstract:

In order to solve the problem of pollution due to formaldehyde, PAH grafted activated carbon (ACm-g-PAH)was prepared by the condensation reaction of grafting polyhydrazide onto nitric acid-modified activated carbon. Then, the self-purifying removal formaldehyde material of Mnx/Agy-TiO2-l-ACm-g-PAH (photocatalyst Mnx/Agy-TiO2 loaded PAH grafted activated carbon) was further assembled to eliminate the possibly secondary pollution by loading Mnx/Agy-TiO2(Mn and Ag co-doped nano-TiO2) on the surface of ACm-g-PAH. The morphology and chemical composition of Mnx/Agy-TiO2-l-ACm-g-PAH were characterized by scanning electron microscopy. And then the catalytic formaldehyde data was fitted to the kinetic equation by software Originpro 8.5 and the dynamic law of catalytic formaldehyde for Mnx/Agy-TiO2-l-ACm-g-PAH was studied. The influences of activation time, activation temperature and N,N-Dicyclohexylcarbodiimide(DCC) concentration on the formaldehyde removal rate of Mnx/Agy-TiO2-l-ACm-g-PAH materials were compared . The test results show that when the activation time is 2 h, the activation temperature is 650 ℃, DCC is 2% of the mass of activated carbon, and PAH is 11 mmol/L, its removal formaldehyde rate of the Mnx/Agy-TiO2-l-ACm-g-PAH is 99.6%. When the formaldehyde concentration loading is in the range of 5-28.2 mg/g, the formaldehyde removal rate of Mnx/Agy-TiO2-l-ACm-g-PAH show a tendency to decrease. After cleaning for 10 cycles, the self-purifying capability of the material is reduced to 12%.

Key words: visible light, formaldehyde removing material, activated carbon, kinetics, photocatalysis

中图分类号: 

  • TS194.5

图1

反应器结构示意图 1—循环泵;2—阀门;3—流量仪;4—载物管(活性炭滤网);5—循环进气口;6—白炽灯;7—紫外灯;8—开关;9—甲醛测试仪;10—进样口;11—循环出气口;12—载物台;13—加热环;14—温湿度仪;15—加湿器;16—圆底烧瓶;17—水浴锅;18—输气软管;19—夹子(阀门作用)。"

图2

活化温度对Mnx/Agy-TiO2-l-ACm-g-PAH除甲醛的影响"

图3

活化时间对Mnx/Agy-TiO2-l-ACm-g-PAH除甲醛的影响"

表1

ACm与Mnx/Agy-TiO2质量比对Mnx/Agy-TiO2-l-ACm-g-PAH除甲醛的影响"

ACm与Mnx/Agy-TiO2的质量比 甲醛移除率/%
60∶1 57.2
50∶1 62.6
40∶1 72.8
30∶1 75.5
20∶1 78.8
10∶1 79.7
5∶1 79.3

图4

PAH浓度对Mnx/Agy-TiO2-l-ACm-g-PAH除甲醛的影响"

图5

DCC质量分数对Mnx/Agy-TiO2-l-ACm-g-PAH除甲醛的影响"

图6

温度对除甲醛的影响"

图7

甲醛浓度对除甲醛的影响"

图8

洗涤次数对除甲醛的影响"

图9

不同材料的甲醛移除率"

图10

Mnx/Agy-TiO2-l-ACm-g-PAH与ACm 的扫描电镜照片"

图11

PAH和Mnx/Agy-TiO2-l-ACm-g-PAH的红外光谱图"

图12

ACm 与Mnx/Agy-TiO2-l-ACm-g-PAH的XPS曲线"

表2

ACm和Mnx/Agy-TiO2-l-ACm-g-PAH样品表面元素组成"

样本 元素相对含量/% 原子比 结合能/eV
C N O N与C O与C N1s O1s
ACm 97.92 0.12 1.96 0.001 23 0.020 01 418.11 532.44
Mnx/Agy-TiO2-l-ACm-g-PAH 96.38 2.21 1.41 0.022 93 0.014 62 392.16 532.10

图13

活化温度为650 ℃的Mnx/Agy-TiO2-l-ACm材料的XRD图谱"

表3

不同湿度条件下Mnx/Agy-TiO2-ACm-g-PAH光催化的动力学特性"

时间/
h		 甲醛浓度/(mg·g-1)
相对湿度65% 相对湿度74% 相对湿度82%
0 15.80 15.80 15.80
1 13.20 13.00 13.20
3 13.60 12.60 12.10
5 12.41 11.91 11.43
7 10.78 11.20 10.72
9 10.53 10.53 10.19
10 9.91 9.63 9.23
12 9.14 8.84 8.18
14 8.32 7.52 7.12
16 7.21 6.81 6.16
18 5.84 4.92 4.53
20 4.63 3.63 3.23
22 3.31 2.21 2.03
24 2.72 2.02 1.28

表4

Mnx/Agy-TiO2-l-ACm-g-PAH除甲醛的动力学拟合结果"

相对湿度/% k R2
45 0.053 75 0.928 2
65 0.059 19 0.961 2
80 0.063 91 0.995 5
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