纺织学报 ›› 2019, Vol. 40 ›› Issue (03): 125-132.doi: 10.13475/j.fzxb.20180102208

• 染整与化学品 • 上一篇    下一篇

铝酸钴/蜂窝陶瓷催化剂的制备及其在印染废水处理中的应用

张兰河1,2(), 张明爽1, 高伟围1, 李正1, 贾艳萍1, 高敏3, 凌良雄1   

  1. 1.东北电力大学 化学工程学院, 吉林 吉林 132012
    2.吉林建筑大学 松辽流域水环境教育部重点实验室,吉林 长春 130118
    3.北京农业生物技术研究中心, 北京 100089
  • 收稿日期:2018-01-10 修回日期:2018-11-08 出版日期:2019-03-15 发布日期:2019-03-15
  • 作者简介:张兰河(1971—),男,教授,博士。主要研究方向为水处理理论与工艺的研究。E-mail: zhanglanhe@163.com。
  • 基金资助:
    吉林省科技发展计划项目(20180201016SF);吉林省科技发展计划项目(20180101309JC);吉林省科技发展计划项目(20180101079JC);吉林省科技发展计划项目(220170519013JH)

Preparation of cobalt aluminate/ceramic honeycomb catalyst and application thereof in dye wastewater treatment

ZHANG Lanhe1,2(), ZHANG Mingshuang1, GAO Weiwei1, LI Zheng1, JIA Yanping1, GAO Min3, LING Liangxiong1   

  1. 1. College of Chemical Engineering, Northeast Electric Power University, Jilin, Jilin 132012, China
    2. Key Laboratory of Songliao Aquatic Environment, Ministry of Education, Jilin Jianzhu University,Changchun, Jilin 130118, China
    3. Beijing Agro-Biotechnology Research Center, Beijing 100089, China
  • Received:2018-01-10 Revised:2018-11-08 Online:2019-03-15 Published:2019-03-15

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摘要：

为提高污水深度处理的臭氧催化氧化效率,采用涂覆法制备铝酸钴(CoAl2O4)/蜂窝陶瓷(CH)催化剂,考察涂覆次数、催化剂投加量、焙烧时间和温度等因素对催化效率的影响,优化催化剂的制备条件;借助X射线衍射仪、场发射扫描电子显微镜和N2-吸附/脱附等手段分析催化剂的结构,通过对苯二酚的降解效果评价催化剂的催化性能,研究催化剂的使用寿命和催化机制。结果表明:在涂覆6次、700 ℃焙烧6 h、Co与Al的量比为0.4∶5的条件下,铝酸钴/蜂窝陶瓷(CoAl2O4/CH)催化剂的催化活性最高,比表面积和孔容最大(分别达到45.47 m2/g、0.05 cm2/g),对苯二酚和化学需氧量(COD)去除率分别达到84.51%和50.60%;制备的CoAl2O4/CH催化剂晶相属于尖晶石结构,蜂窝陶瓷涂层为海绵状结构;CoAl2O4/CH催化剂使用5次以上,仍保持较高的催化活性和稳定性,应用前景好。

关键词: 铝酸钴/蜂窝陶瓷, 催化剂, 印染废水, 催化氧化, 污水处理

Abstract:

In order to increase the catalytic efficiency of advanced wastewater treatment by catalytic ozonation, cobalt aluminate(CoAl2O4)/ceramic honeycomb (CH) catalyst was prepared by a coating method. The influence of coating times, the addition amount of catalyst, calcination time and temperature on the catalytic efficiency was investigated to optimize the preparation conditions. The structure of catalysts were analyzed by X-ray diffractometer, field emission scanning electron microscopy and N2-adsorption and desorption. The catalytic performance and mechanisms were evaluated by catalytic ozonation of hydroquinone. The results show that the catalytic efficiency of CoAl2O4/CH is the highest under the conditions of coating for 6 times, calcination temperature of 700 ℃, calcination time of 6 h and molar ratio of Co to Al of 0.4∶5. The specific surface area and pore volume are the highest and reach 45.47 m2/g and 0.05 cm2/g, respectively. Removal rate of hydroquinone is 84.51% and removal rate of COD is 50.60%. The prepared catalysts belong to the spinal structure and the coating has a sponge-like structure. The catalysts maintain high catalytic activity and stability after repeated use for more than 5 times. Therefore, the application is promising.

Key words: cobalt aluminate/ceramic honeycomb catalyst, catalyst, dye wastewater, catalytic ozonation, wastewater treatment

中图分类号: 

  • TQ426.64

图1

臭氧催化氧化对苯二酚废水流程"

表1

正交试验表"

水平 A B C D
焙烧
温度/℃		 焙烧
时间/h		 Co与Al
的量比		 涂覆次数
1 500 2 0.2∶5 2
2 600 4 0.4∶5 4
3 700 6 0.6∶5 6

表2

催化剂制备正交试验结果"

试验号 A B C D COD
去除率/%		 对苯二酚
去除率/%
1# 500 2 0.2∶5 2 38.69 69.74
2# 600 4 0.4∶5 2 41.97 70.90
3# 700 6 0.6∶5 2 50.38 74.76
4# 600 2 0.6∶5 4 44.20 79.75
5# 700 4 0.2∶5 4 48.07 81.87
6# 500 6 0.4∶5 4 52.30 81.64
7# 700 2 0.4∶5 6 51.61 79.12
8# 600 4 0.6∶5 6 49.20 81.53
9# 500 6 0.2∶5 6 50.39 84.63
COD
去除率		 K1 47.13 44.83 45.72 43.68
K2 45.12 46.41 48.63 48.19
K3 50.02 51.02 47.93 50.40
极差 4.90 6.19 2.91 6.72
对苯二酚
去除率		 K1 78.67 76.20 78.75 71.80
K2 77.39 78.10 77.22 81.09
K3 78.58 80.34 78.68 81.76
极差 1.28 4.14 1.53 9.96

图2

O3质量浓度对对苯二酚去除率和COD去除率的影响"

图3

CoAl2O4/CH投加量对对苯二酚去除率和COD去除率的影响"

图4

pH值对对苯二酚去除率和COD去除率的影响"

图5

1#和9#催化剂的N2吸附/脱附等温线"

图6

1#和9#CoAl2O4/CH催化剂的XRD谱图"

图7

1#催化剂和9#催化剂FESEM照片(×20 000)"

表3

不同催化剂材料的力学性能"

催化剂类型 最大压力/N 抗压强度/MPa
蜂窝陶瓷 4 657 12.50
1#催化剂使用前 6 312 16.49
1#催化剂使用后 6 024 16.17
9#催化剂使用前 5 918 15.89
9#催化剂使用后 5 225 14.11

图8

CoAl2O4/CH催化剂的循环利用次数对对苯二酚去除率的影响"

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