纳米片层铁锰双金属催化剂活化过

doi:10.16085/j.issn.1000-6613.2022-0001

化工进展 ›› 2022, Vol. 41 ›› Issue (10): 5661-5668.DOI: 10.16085/j.issn.1000-6613.2022-0001

纳米片层铁锰双金属催化剂活化过

薛雨微¹^,²(), 叶校圳³, 曾静³, 王永全³(), 洪俊明¹^,²()

^1.华侨大学化工学院，福建厦门 361021
^2.福建省工业废水生化处理工程技术研究中心，福建厦门 361021
^3.厦门烟草工业有限责任公司，福建厦门 361021

收稿日期:2022-01-01 修回日期:2022-03-16 出版日期:2022-10-20 发布日期:2022-10-21
通讯作者: 王永全,洪俊明
作者简介:薛雨微（1998—），女，硕士研究生，主要研究方向为水处理高级氧化。E-mail：yuwei_xue2021@126.com。
基金资助:
国家自然科学基金(51978291);福建省科技项目(2021I0030);厦门市科技计划(3502Z20226012)

Pretreatment of tobacco sugar flavoring wastewater by nano layered iron-manganese bimetallic catalysts activating peroxymonosulfate

XUE Yuwei¹^,²(), YE Xiaozhen³, ZENG Jing³, WANG Yongquan³(), HONG Junming¹^,²()

^1.College of Chemical Engineering, Huaqiao University, Xiamen 361021, Fujian, China
^2.Fujian Province Engineering Research Center of Industrial Wastewater Biochemical Treatment, Xiamen 361021, Fujian, China
^3.Xiamen Tobacco Industrial Company Limited, Xiamen 361021, Fujian, China

Received:2022-01-01 Revised:2022-03-16 Online:2022-10-20 Published:2022-10-21
Contact: WANG Yongquan, HONG Junming

摘要/Abstract

摘要：

以烟草行业糖香料废水为研究对象，首先调查了某糖香料调配中心废水的水质情况。采用共沉淀法制备纳米片层铁锰双金属催化剂激活过一硫酸盐（PMS）产生自由基对烟草糖香料废水开展预处理研究。采用透射电子显微镜（TEM）、X射线粉末衍射仪（XRD）、X射线能谱分析（EDS）和比表面积测试（BET）对催化剂进行表征。通过因素实验分析降解过程中废水的化学需氧量和氨氮降解情况，在反应时间6h、PMS浓度为4mmol/L、催化剂投加量为0.6g/L的最佳条件下，COD去除率76.5%、氨氮去除率96.3%，降解过程符合一级动力学（R²＞0.9）。降解前后水样的三维荧光和气相色谱显示，难降解物质被转化为可生物利用的有机碳源，表明这一体系作为预处理有助于提高生化段的处理效率，对高级氧化法在污水预处理中的实际应用具有良好的应用前景。

关键词: 过一硫酸盐, 催化剂活化, 糖香料废水, 化学需氧量, 纳米片层, 自由基

Abstract:

Water quality investigation were carried out on the waste water from a sugar and spice kitchen. The nano iron manganese catalyst was synthesized by co-precipitation method and utilized to activate peroxymonosulfate to produce active radicals for the degradation of sugar flavoring wastewater. The catalyst was characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), X-ray energy spectrometry (EDS) and Brunauer Emmett Teller (BET). Effects of different condition factors on the degradation efficiencies of COD and ammonia nitrogen were investigated. Under the optimum conditions of 6h reaction time, PMS concentration 4mmol/L and catalyst dosage 0.6g/L, the removal rates of COD and ammonia nitrogen were 76.5% and 96.3% respectively, and the degradation process followed first-order kinetics (R²>0.9). Three-dimensional fluorescence and gas chromatography analysis of the water samples before and after degradation showed that the nonbiodegradable substances were converted into bioavailable organic carbon sources, which indicated that this system as a pretreatment could help to improve the biochemical treatment efficiency and thus has a good application prospect in advanced oxidation of wastewater treatment.

Key words: peroxymonosulfate, catalyst activation, sugar flavoring wastewater, chemical oxygen demand, nano layered iron, radical

中图分类号:

薛雨微, 叶校圳, 曾静, 王永全, 洪俊明. 纳米片层铁锰双金属催化剂活化过[J]. 化工进展, 2022, 41(10): 5661-5668.

XUE Yuwei, YE Xiaozhen, ZENG Jing, WANG Yongquan, HONG Junming. Pretreatment of tobacco sugar flavoring wastewater by nano layered iron-manganese bimetallic catalysts activating peroxymonosulfate[J]. Chemical Industry and Engineering Progress, 2022, 41(10): 5661-5668.

图/表 16

表1 烟草糖香料生产线产污情况

生产线名称	名称	每月产生量/t	COD/mg·L^-1
201料液调配线	过期废料液	0.8~1	52000
	换牌清洗液	94.5	50000
	除异味换水	10	4800
	换牌清洗液	48.6	16000
303香料基调配线	换牌清洗水	32.4	19000
	除异味换水	4.5	3200
303提取线	除异味换水	2.5	1920

表2 混合水样水质情况

混合废水指标	值
COD/mg·L^-1	12240
氨氮/mg·L^-1	2246.39
pH	5.46
浊度/NTU	5.03

图1 纳米片层铁锰催化剂的XRD图

图2 纳米片层铁锰催化剂的TEM图

图3 纳米片层铁锰催化剂的EDS分析

图4 纳米片层铁锰催化剂的BET分析

图5 不同PMS浓度对COD降解效率和降解动力学的影响

表3 不同PMS初始浓度对COD降解的动力学速率常数

PMS浓度/mmol·L^-1	K/h^-1	R²
2	0.128	0.988
4	0.156	0.989
6	0.173	0.986

图6 不同PMS浓度对氨氮降解效率的影响

图7 降解过程水样的pH变化曲线

图8 不同催化剂浓度对COD降解效率和降解动力学的影响

表4 不同催化剂浓度对COD降解的动力学速率常数

催化剂浓度/g·L^-1	K/h^-1	R²
0.2	0.156	0.989
0.4	0.183	0.969
0.6	0.232	0.956

图9 不同催化剂浓度对氨氮降解效率的影响

图10 降解前后水样的气相色谱图

图11 降解前后水样的有机质三维荧光分析

图12 纳米片层铁锰催化剂可重用性实验

参考文献 29

1	李泠槿. 烟草香料厨房管理控制系统的设计与实现[D]. 绵阳: 西南科技大学, 2021.
	LI Lingjin. Design and realization of tobacco spice kitchen management control system[D]. Mianyang: Southwest University of Science and Technology, 2021.
2	郭俊成, 程晓蕾. 烟用香精香料浅述[J]. 烟草科技, 1996, 29(2): 14-15.
	GUO Juncheng, CHENG Xiaolei. The brief description of flavors and fragrances for tobacco[J]. Tobacco Science & Technology, 1996, 29(2): 14-15.
3	李东峰. 卷烟香料厨房清洗装置的改进[J]. 科技风, 2008(7): 26.
	LI Dongfeng. Improvement of cigarette spice kitchen cleaning device[J]. Technology Wind, 2008(7): 26.
4	张洋, 赵静. 烟草废水处理工艺的研究进展[J]. 资源节约与环保, 2020(1): 75-76.
	ZHANG Yang, ZHAO Jing. Research progress of tobacco wastewater treatment process[J]. Resource Economization & Environmental Protection, 2020, (1): 75-76.
5	赵军胜, 潘昊, 潘俊鸥, 等. 基于·OH的高级氧化技术及其组合技术的研究进展[J]. 石油和化工设备, 2021, 24(8): 12-14.
	ZHAO Junsheng, PAN Hao, PAN Junou, et al. Research progress of advanced oxidation technology and combination technology based on ·OH[J]. Petro & Chemical Equipment, 2021, 24(8): 12-14.
6	何玉洁, 陈卫, 郑晓英, 等. 芬顿氧化PAM助凝法预处理高浓度烟草香料废水试验[J]. 河海大学学报(自然科学版), 2012, 40(5): 525-529.
	HE Yujie, CHEN Wei, ZHENG Xiaoying, et al. Pretreatment experiment of high-concentration aromatic tobacco flavor wastewater with Fenton reagent and PAM coagulation [J]. Journal of Hohai University (Natural Science Edition), 2012, 40(5): 525-529.
7	孙宇, 陈顺辉, 徐桂军, 等. ZVI/Fe²⁺/H₂O₂类Fenton法深度处理烟草薄片废水[J]. 工业水处理, 2020, 40(1): 78-82.
	SUN Yu, CHEN Shunhui, XU Guijun, et al. Advanced treatment of papermaking-reconstituted tobacco slice wastewater by ZVI/Fe²⁺/H₂O₂ Fenton-like process[J]. Industrial Water Treatment, 2020, 40(1): 78-82.
8	陈赛艳, 李友明, 雷利荣. 造纸法再造烟叶废水的臭氧氧化法预处理[J]. 烟草科技, 2014, 47(12): 27-31.
	CHEN Saiyan, LI Youming, LEI Lirong. Ozone oxidation pretreatment of wastewater from paper-making process reconstituted tobacco production[J]. Tobacco Science & Technology, 2014, 47(12): 27-31.
9	武梦雨. 紫外光类芬顿高级氧化技术深度处理市政污水的研究[D]. 北京: 北京化工大学, 2020.
	WU Mengyu. Study on advanced treatment of municipal wastewater by ultraviolet-Fenton like advanced oxidation technology[D]. Beijing: Beijing University of Chemical Technology, 2020.
10	翟俊, 柳沛松, 赵聚姣. 过一硫酸盐碱催化处理染料废水[J]. 中国环境科学, 2020, 40(2): 647-652.
	ZHAI Jun, LIU Peisong, ZHAO Jujiao. Treatment of dye wastewater by base catalysis of peroxymonosulfate (PMS)[J]. China Environmental Science, 2020, 40(2): 647-652.
11	佘月城, 董正玉, 吴丽颖, 等. MnFe₂O₄活化过一硫酸盐降解废水中LAS[J]. 中国环境科学, 2019, 39(8): 3323-3331.
	SHE Yuecheng, DONG Zhengyu, WU Liying, et al. Degradation of LAS in wastewater by peroxymonosulfate activated by MnFe₂O₄ [J]. China Environmental Science, 2019, 39(8): 3323-3331.
12	邵强, 郭轶琼. 铁锰催化剂活化过硫酸盐去除水中苯酚的研究[J]. 工业水处理, 2020, 40(7): 94-97.
	SHAO Qiang, GUO Yiqiong. Removal of phenol from water by activation of persulfate with Fe-Mn catalyst[J]. Industrial Water Treatment, 2020, 40(7): 94-97.
13	刘术辉, 刘斌, 徐大伟, 等. 层状双金属氢氧化物防腐蚀涂层材料的研究进展[J]. 中国腐蚀与防护学报, 2022, 42(1): 16-24.
	LIU Shuhui, LIU Bin, XU Dawei, et al. Research progress on anti-corrosion coatings of layered double hydroxides[J]. Journal of Chinese Society for Corrosion and Protection, 2022, 42(1): 16-24.
14	李立, 吴丽颖, 董正玉, 等. 高晶度Mn-Fe LDH催化剂活化过一硫酸盐降解偶氮染料RBK₅ [J]. 环境科学, 2020, 41(6): 2736-2745.
	LI Li, WU Liying, DONG Zhengyu, et al. Degradation of RBK₅ by high crystallinity Mn-Fe LDH catalyst activating peroxymonosulfate[J]. Environmental Science, 2020, 41(6): 2736-2745.
15	WANG X Q, XIE Y, CHEN K, et al. Bioleaching assisted conversion of refractory low-grade ferruginous rhodochrosite to Mn-Fe based catalysts for sulfathiazole degradation[J]. Chemical Engineering Journal, 2022, 427: 130804.
16	郑怀礼, 蒋君怡, 万鑫源, 等. 磁性纳米材料吸附处理工业废水的研究进展[J]. 中国环境科学, 2021, 41(8): 3555-3566.
	ZHENG Huaili, JIANG Junyi, WAN Xinyuan, et al. Adsorption treatment of industrial wastewater by magnetic nanoparticles: a review[J]. China Environmental Science, 2021, 41(8): 3555-3566.
17	DONG Z Y, ZHANG Q, CHEN B Y, et al. Oxidation of bisphenol A by persulfate via Fe₃O₄-α-MnO₂ nanoflower-like catalyst: mechanism and efficiency[J]. Chemical Engineering Journal, 2019, 357: 337-347.
18	LI L, ZHANG Q, SHE Y C, et al. High-efficiency degradation of bisphenol A by heterogeneous Mn-Fe layered double oxides through peroxymonosulfate activation: performance and synergetic mechanism[J]. Separation and Purification Technology, 2021, 270: 118770.
19	VERNEKAR D, SAKATE S S, RODE C V, et al. Water-promoted surface basicity in FeO(OH) for the synthesis of pseudoionones (PS) and their analogues[J]. Journal of Catalysis, 2019, 378: 80-89.
20	OTGONJARGAL E, KIM Y S, PARK S M, et al. Mn-Fe layered double hydroxides for adsorption of As(Ⅲ) and As(Ⅴ)[J]. Separation Science and Technology, 2012, 47(14/15): 2192-2198.
21	何余生, 李忠, 奚红霞, 等. 气固吸附等温线的研究进展[J]. 离子交换与吸附, 2004, 20(4): 376-384.
	HE Yusheng, LI Zhong, XI Hongxia, et al. Research progress of gas-solid adsorption isotherms[J]. Ion Exchange and Adsorption 2004, 20(4): 376-384.
22	杜娜娜, 杜仙格, 曹昉, 等. Co_1.5Fe_1.5O₄@MWCNTs非均相催化PMS降解水中苯酚[J]. 工业水处理, 2020, 40(7): 65-69.
	DU Nana, DU Xiange, CAO Fang, et al. Degradation of phenol in water by Co_1.5Fe_1.5O₄@MWCNTs heterogeneously catalyzed PMS[J]. Industrial Water Treatment, 2020, 40(7): 65-69.
23	SHE Y C, HONG J M, ZHANG Q, et al. Revealing microbial mechanism associated with volatile fatty acids production in anaerobic acidogenesis of waste activated sludge enhanced by freezing/thawing pretreatment[J]. Bioresource Technology, 2020, 302: 122869.
24	黄焕娣. 水解酸化-微生物电辅助系统处理抗生素废水的效能研究[D]. 哈尔滨: 哈尔滨工业大学, 2015.
	HUANG Huandi. Antibiotic wastewater treatment in coupled hydrolysis acidification and microbial electro-assisted system[D]. Harbin: Harbin Institute of Technology, 2015.
25	CHEN W, WESTERHOFF P, LEENHEER J A, et al. Fluorescence excitation-emission matrix regional integration to quantify spectra for dissolved organic matter[J]. Environmental Science & Technology, 2003, 37(24): 5701-5710.
26	邓禺南, 陈炜鸣, 罗梓尹, 等. MnO₂催化O₃处理准好氧矿化垃圾床渗滤液尾水中难降解有机物[J]. 中国环境科学, 2018, 38(11): 4130-4140.
	DENG Yunnan, CHEN Weiming, LUO Ziyi, et al. Removal of refractory organics from SAARB treated landfill leachate by O₃/MnO₂ process[J]. China Environmental Science, 2018, 38(11): 4130-4140.
27	张雪宁. 可溶性微生物产物作为电子供体强化SBR脱氮的效能与机制[D]. 哈尔滨: 哈尔滨工业大学, 2020.
	ZHANG Xuening. Performance and mechanism of utilizing soluble microbial products as electron donors for denitrification in sequencing batch reactor[D]. Harbin: Harbin Institute of Technology, 2020.
28	CARBONERAS M B, VILLASENOR J, FENANDEZ-MORALES F J, et al. Biological treatment of wastewater polluted with an oxyfluorfen-based commercial herbicide[J]. Chemosphere, 2018, 213: 244-251.
29	黄丽坤, 李哲, 王广智, 等. 紫外催化过硫酸盐深度处理垃圾焚烧厂渗滤液[J]. 中国环境科学, 2021, 41(1): 161-168.
	HUANG Likun, LI Zhe, WANG Guangzhi, et al. Advanced treatment of landfill leachate by ultraviolet catalytic persulfate[J]. China Environmental Science, 2021, 41(1): 161-168.

[1]	白志华, 张军. 二乙烯三胺五亚甲基膦酸/Fenton体系氧化脱除NO[J]. 化工进展, 2023, 42(9): 4967-4973.
[2]	徐沛瑶, 陈标奇, KANKALA Ranjith Kumar, 王士斌, 陈爱政. 纳米材料用于铁死亡联合治疗的研究进展[J]. 化工进展, 2023, 42(7): 3684-3694.
[3]	吴锋振, 刘志炜, 谢文杰, 游雅婷, 赖柔琼, 陈燕丹, 林冠烽, 卢贝丽. 生物质基铁/氮共掺杂多孔炭的制备及其活化过一硫酸盐催化降解罗丹明B[J]. 化工进展, 2023, 42(6): 3292-3301.
[4]	詹咏, 王慧, 韦婷婷, 朱星宇, 王先恺, 陈思思, 董滨. Mn²⁺强化臭氧调理对生物处理工艺的污泥原位减量效果[J]. 化工进展, 2023, 42(6): 3253-3260.
[5]	王庆宏, 姜晨旭, 王鑫, 余美琪, 朱帅, 李一鸣, 陈春茂. 天然矿物催化氧化水中难降解有机污染物研究进展[J]. 化工进展, 2023, 42(1): 417-434.
[6]	张华, 刘光全, 张晓飞, 罗臻. 电脱盐废水稳定性分析及破乳技术[J]. 化工进展, 2022, 41(9): 5047-5054.
[7]	伊学农, 李京梅, 高玉琼. 紫外-高铁酸盐体系氧化降解水中的萘普生[J]. 化工进展, 2022, 41(8): 4562-4570.
[8]	潘杰, 王明新, 高生旺, 夏训峰, 韩雪. 氮硫掺杂生物炭/过一硫酸盐体系降解水中磺胺异唑[J]. 化工进展, 2022, 41(8): 4204-4212.
[9]	何畅帆, 赵小航, 章雪莹, 何林, 隋红, 李鑫钢. 过一硫酸盐-高铁酸盐-FeS体系土柱淋洗修复邻二氯苯污染土壤[J]. 化工进展, 2022, 41(5): 2743-2752.
[10]	甄建政, 聂士松, 潘世元, 吕维扬, 姚玉元. 多维度碳基负载金属催化剂活化PMS降解水中污染物的研究进展[J]. 化工进展, 2022, 41(4): 1858-1872.
[11]	熊哲, 邓伟, 刘佳, 汪雪棚, 徐俊, 江龙, 苏胜, 汪一, 胡松, 向军. 生物油非催化热转化过程中受热结焦特性研究进展[J]. 化工进展, 2022, 41(4): 1802-1813.
[12]	许泽涛, 曹怡婷, 王俏, 王志红. 固相钴基催化剂活化过一硫酸盐在水处理中的研究进展[J]. 化工进展, 2022, 41(2): 730-739.
[13]	马颢菲, 苑鹏, 沈伯雄. 钙钛矿型光催化剂的制备及脱除典型气态污染物的研究进展[J]. 化工进展, 2022, 41(2): 721-729.
[14]	徐铭骏, 郭兆春, 李立, 朱紫琦, 张倩, 洪俊明. 纳米片状Mn₂O₃@α-Fe₃O₄活化过碳酸盐降解偶氮染料[J]. 化工进展, 2022, 41(2): 1043-1053.
[15]	吕朋, 何畅帆, 何林, 李鑫钢, 隋红. 含重质油污泥非均相氧化降解特性及其强化机制[J]. 化工进展, 2022, 41(11): 6149-6157.

纳米片层铁锰双金属催化剂活化过

Pretreatment of tobacco sugar flavoring wastewater by nano layered iron-manganese bimetallic catalysts activating peroxymonosulfate

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 16

参考文献 29

相关文章 15

编辑推荐

Metrics

本文评价