基于活性污泥焚灰的类Fenton催化剂的制备及其对亚甲基蓝的降解性能

doi:10.15541/jim20230580

无机材料学报 ›› 2024, Vol. 39 ›› Issue (10): 1135-1142.DOI: 10.15541/jim20230580 CSTR: 32189.14.10.15541/jim20230580

基于活性污泥焚灰的类Fenton催化剂的制备及其对亚甲基蓝的降解性能

蔡梦宇(), 李杨虹淼, 杨彩云, 周雨婷, 吴昊()

燕山大学环境与化学工程学院, 河北省水体重金属深度修复与资源利用重点实验室, 秦皇岛 066004

收稿日期:2023-12-18 修回日期:2024-05-06 出版日期:2024-10-20 网络出版日期:2024-05-16
通讯作者: 吴昊, 讲师. E-mail: hwu@ysu.edu.cn
作者简介:蔡梦宇(1998-), 男, 硕士研究生. E-mail: c18503338109@163.com
基金资助:
河北省自然科学基金(B2024203014);河北省引进留学人员资助项目(C20230326);河北省中央引导地方科技发展资金(236Z3604G);秦皇岛市科学技术研究与发展计划(202101A268);燕山大学基础研究与创新培育项目(2021LGQN018)

Activated Sludge Incineration Ash Derived Fenton-like Catalyst: Preparation and Degradation Performance on Methylene Blue

CAI Mengyu(), LI-YANG Hongmiao, YANG Caiyun, ZHOU Yuting, WU Hao()

Hebei Key Laboratory of Heavy Metal Deep-Remediation in Water and Resource Reuse, School of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004, China

Received:2023-12-18 Revised:2024-05-06 Published:2024-10-20 Online:2024-05-16
Contact: WU Hao, lecturer. E-mail: hwu@ysu.edu.cn
About author:CAI Mengyu (1998-), male, Master candidate. E-mail: c18503338109@163.com
Supported by:
Hebei Natural Science Foundation(B2024203014);Hebei Province Foundation of Returned Talent(C20230326);Central Guidance on Local Science and Technology Development Fund of Hebei Province(236Z3604G);Science and Technology Research and Development Plan of Qinhuangdao(202101A268);Cultivation Project for Basic Research and Innovation of Yanshan University(2021LGQN018)

摘要/Abstract

摘要：

载铁沸石因其来源广泛、制备简便及环境毒性低等特点, 被广泛用于催化类Fenton反应产生·OH, 以高效处理有机污染物。然而, 传统载铁沸石的制备成本高且Fe²⁺再生困难, 限制了其在催化类Fenton反应中的工业化应用。基于此, 本研究以污水处理厂活性污泥焚烧处理后的灰分为原料, 选择性回收其中的硅、铝和铁等元素。制备的Fe²⁺-方钠石(FSD)可用于类Fenton反应活化过氧乙酸(PAA), 以高效降解水溶液中的亚甲基蓝(MB)。结果表明:FSD可在较宽的pH范围内催化PAA生成·OH、¹O₂和R-O·等多种活性氧物种, 进而通过羟基化或亚砜化途径催化降解MB。以0.5 mol/L Fe²⁺制备的FSD用量为0.3 g/L, PAA浓度为0.3 mmol/L时, FSD/PAA体系可在20 min内完全降解40 mg/L MB。此外, FSD中的还原性硫组分可促进Fe²⁺再生, 维持其催化活性。且FSD/PAA体系可在不同水质和生活污水中高效降解多种污染物, 具有性能优良和适用性广的优点。

关键词: 活性污泥, 方钠石, 类Fenton降解, 过氧乙酸, 亚甲基蓝

Abstract:

Fe@zeolite materials are widely applied in the production of ·OH by catalyzing Fenton-like reactions for degradation of recalcitrant organic pollutants due to their comprehensive sources, simple preparation and low environmental impact. However, the high cost of Fe@zeolite synthesis and the lack of Fe²⁺ regeneration strategy are serious issues that limit the application of Fe@zeolite as a Fenton-like catalyst in industrial-scale systems. In this study, the ash generated from activated sludge incineration treatment was utilized as raw material to selective recover Si, Al and Fe, preparing Fe²⁺-sodalite (FSD) material. Consequently, it was used as a Fenton-like catalyst to activate peroxyacetic acid (PAA) for the degradation of methylene blue (MB) in wastewater. Results indicated thatFSD was capable of effectively catalyzing PAA to generate various active oxygen species such as ·OH, ¹O₂ and R-O· in a wide pH range, thereby degrading MB through hydroxylation and sulfonation pathways. MB can be completely removed during 20 min under optimized conditions of 0.3 mmol/L PAA and 0.3 g/L FSD prepared with 0.5 mol/L Fe²⁺. In addition, the reductive S species in FSD can maintain its catalytical activity by enhancing Fe²⁺ regeneration, and the FSD/PAA system has been proven to be effective in the degradation of various organic pollutants under practical and complex environmental conditions.

Key words: activated sludge, sodalite, Fenton-like degradation, peroxyacetic acid, methylene blue

中图分类号:

X705

蔡梦宇, 李杨虹淼, 杨彩云, 周雨婷, 吴昊. 基于活性污泥焚灰的类Fenton催化剂的制备及其对亚甲基蓝的降解性能[J]. 无机材料学报, 2024, 39(10): 1135-1142.

CAI Mengyu, LI-YANG Hongmiao, YANG Caiyun, ZHOU Yuting, WU Hao. Activated Sludge Incineration Ash Derived Fenton-like Catalyst: Preparation and Degradation Performance on Methylene Blue[J]. Journal of Inorganic Materials, 2024, 39(10): 1135-1142.

图/表 12

图1 SD、FSD和RFSD的XRD图谱

Fig. 1 XRD patterns of SD, FSD and RFSD

图2 Fe2+负载前后(a, b) SD与(c, d) FSD的SEM照片

Fig. 2 SEM images of (a, b) SD and (c, d) FSD before and after loading Fe2+

图3 不同体系对MB的降解性能对比

Fig. 3 MB degradation performances in different systems

图4 (a)催化剂负载液Fe2+浓度、(b)氧化剂用量及(c)催化剂用量对FSD/PAA体系降解MB的影响

Fig. 4 Effects of (a) concentration of Fe2+ loading solution, (b) oxidant dosage and (c) catalyst dosage on degradation of MB by FSD/PAA system

图5 不同淬灭剂对优化FSD/PAA体系降解MB的影响

Fig. 5 Effect of different quenchers on degradation of MB by the optimized FSD/PAA system

图6 催化反应前后(a, c)FSD与(b, d)RFSD的(a, b)XPS总谱图和(c, d) Fe2p XPS谱图

Fig. 6 (a, b) Total and (c, d) Fe2p XPS spectra of (a, c) FSD and (b, d) RFSD before and after catalytical reaction

图7 MB在FSD/PAA体系中的降解路径及中间产物

Fig. 7 Degradation pathways and intermediates of MB in the FSD/PAA system

图8 水中共存物种、水质条件对最优FSD/PAA体系降解MB的影响

Fig. 8 Effects of co-existed substrates and water conditions on the degradation of MB by the optimized FSD/PAA system (a-d) Effects of (a) NO3-, (b) SO42-, (c) CO32-, and (d) HA on MB degradation by the optimized FSD/PAA system; (e) Effect of deionic water (DW), tap water (TW) and lake water (LW) on the degradation performance of MB by the optimized FSD/PAA system; (f) Performance of the optimized FSD/PAA system in actual wastewater; Colorful figures are available on website

图9 FSD/PAA体系在20 min内对不同污染物的降解效果

Fig. 9 Degradation performance of different pollutants by FSD/PAA system during 20 min

表S1 不同水样水质条件

Table S1 Characterizations of different water samples

Item	TW	LW	Wastewater
TOC/(mg·L^-1)	16.7	28.8	188.1
F^-/(mg·L^-1)	0.1	0.1	0.2
Cl^-/(mg·L^-1)	23.2	24.3	51.1
K⁺/(mg·L^-1)	30.9	35.6	64.4
Mg²⁺/(mg·L^-1)	16.7	21.4	96.5

表S2 梯度洗脱测量有机污染物的HPLC条件

Table S2 HPLC conditions for phase gradient elution measuring concentrations of organic contaminants

Compound	Column temperature/℃	Flow rate/ (mL·min^-1)	Wavelength/ nm	Phase mobile phase	Phase elution gradient
MB	40	0.2	254	Ammonium acetate (A)+ acetonitrile (B)	0-1-9-14 min, 10%B-10%B-90%B-90%B
SMX	40	0.3	275	0.1% Formic acid solution (A)+ methanol (B)	0-1-1-3.5-5 min, 20%B-20%B-51.25%B-51.25%B
GM	40	0.3	278	0.1% Formic acid solution (A)+ acetonitrile (B)	0-0.5-1-4-6 min, 5%B-5%B-30%B-30%B
MDZ	40	0.8	318	Ultrapure water (A)+ acetonitrile (B)	0-0.5-3-5 min, 6%B-5%B-20%B-90%B
CIP	40	0.3	278	Ultrapure water (A)+ acetonitrile (B)	0-0.5-3-5 min, 6%B-5%B-20%B-90%B
RHB	40	0.2	554	0.1% Formic acid solution (A)+ acetonitrile (B)	0-5-8 min, 5%B-95%B-95%B
TC	40	0.3	360	Ultrapure water (A)+ acetonitrile (B)	0-0.5-3-5 min, 6%B-5%B-20%B-90%B

图S1 pH对FSD/PAA体系降解MB的影响

Fig. S1 Effect of pH on the degradation of MB by the FSD/PAA system

参考文献 26

[1]	XIANG Y, YANG K, ZHAI Z, et al. Molybdenum co-catalytic promotion for Fe³⁺/peroxydisulfate process: performance, mechanism, and immobilization. Chemical Engineering Journal, 2022, 438: 135656.
[2]	LI L, YIN Z, CHENG M, et al. Insights into reactive species generation and organics selective degradation in Fe-based heterogeneous Fenton-like systems: a critical review. Chemical Engineering Journal, 2023, 454: 140126.
[3]	LIU L, YU R H, ZHAO S X, et al. Heterogeneous Fenton system driven by iron-loaded sludge biochar for sulfamethoxazole- containing wastewater treatment. Journal of Environmental Management, 2023, 335: 117576.
[4]	YANG C Y, WU H, CAI M, et al. Valorization of biomass-derived polymers to functional biochar materials for supercapacitor applications via pyrolysis: advances and perspectives. Polymers, 2023, 15: 2741.
[5]	WANG J, TANG J. Fe-based Fenton-like catalysts for water treatment: preparation, characterization and modification. Chemosphere, 2021, 276: 130177.
[6]	AROCKIARAJ M, CLEMENT J, et al. Quantitative structural descriptors of sodalite materials. Journal of Molecular Structure, 2021, 1223: 128766.
[7]	ZHAO D, ARMUTLULU A, CHEN Y, et al. Highly efficient removal of Cu(II) using mesoporous sodalite zeolite produced from industrial waste lithium-silicon-fume via reactive oxidation species route. Journal of Cleaner Production, 2021, 319: 128682.
[8]	SCHNELL M, HORST T, QUICKER P. Thermal treatment of sewage sludge in Germany: a review. Journal of Environmental Management. 2020, 263: 110367.
[9]	ZHAO S, YAN K, WANG Z, et al. Does anaerobic digestion improve environmental and economic benefits of sludge incineration in China? Insight from life-cycle perspective. Resources, Conservation & Recycling, 2023, 188: 106688.
[10]	蔡梦宇, 杨彩云, 吴昊, 等. 厌氧消化沼渣的生物电化学深度稳定化及能源回收. 燕山大学学报, 2023, 47(6): 519.
[11]	GUO X L, YUAN S T, XU Y, et al. Effects of phosphorus and iron on the composition and property of Portland cement clinker utilized incinerated sewage sludge ash. Construction and Building Materials, 2022, 341: 127754.
[12]	BUTA M, HUBENY J, ZIELINSKI W, et al. Sewage sludge in agriculture-the effects of selected chemical pollutants and emerging genetic resistance determinants on the quality of soil and crops--a review. Ecotoxicology and Environmental Safety, 2021, 214: 112070.
[13]	LIU Z Z, MAYER B, VENKITRSHWARAN K, et al. The state of technologies and research for energy recovery from municipal wastewater sludge and biosolids. Current Opinion in Environmental Science & Health, 2020, 14: 31.
[14]	LIU Y, HE X, DUAN X, et al. Photochemical degradation of oxytetracycline: influence of pH and role of carbonate radical. Chemical Engineering Journal, 2015, 276(15): 113.
[15]	KIM J, ZHANG T Q, LIU W, et al. Advanced oxidation process with peracetic acid and Fe(II) for contaminant degradation. Environmental Science and Technology, 2019, 53(22): 13312.
[16]	WANG L, YAN T, TANG R, et al. Motivation of reactive oxidation species in peracetic acid by adding nanoscale zero-valent iron to synergic removal of spiramycin under ultraviolet irradiation: mechanism and N-nitrosodimethylamine formation potential assessment. Water Research, 2021, 205: 117684.
[17]	CHEN S, CAI M, LIU Y, et al. Effects of water matrices on the degradation of naproxen by reactive radicals in the UV/peracetic acid process. Water Research, 2019, 150(1): 153.
[18]	XIANG Y, YUAN D, ZHU E, et al. Efficacious reduction of ferric ions by molybdenum carbide in the peroxydisulfate Fenton-like reaction for dexamethasone degradation. ACS Applied Materials ＆ Interfaces, 2023, 3(3): 857.
[19]	AO X, ELORANTA J, HUANG C, et al. Peracetic acid-based advanced oxidation processes for decontamination and disinfection of water: a review. Water Research, 2021, 188: 116479.
[20]	WOLSKI L, ZIOLEK M. Insight into pathways of methylene blue degradation with H₂O₂ over mono and bimetallic Nb, Zn oxides. Applied Catalysis B: Environmental, 2018, 224: 634.
[21]	MONDAL S, REYES M E D A, PAL U. Plasmon induced enhanced photocatalytic activity of gold loaded hydroxyapatite nanoparticles for methylene blue degradation under visible light. RSC Advances, 2017, 7: 8633.
[22]	XIA S, ZHANG L, PAN G, et al. Photocatalytic degradation of methylene blue with a nanocomposite system: synthesis, photocatalysis and degradation pathways. Physical Chemistry Chemical Physics, 2015, 17: 5345. DOI PMID
[23]	LIU Y, JIN W, ZHAO Y, et al. Enhanced catalytic degradation of methylene blue by α-Fe₂O₃/graphene oxide via heterogeneous photo-Fenton reactions. Applied Catalysis B: Environmental, 2017, 206: 642.
[24]	WANG S, WANG H, LIU Y, et al. Effective degradation of sulfamethoxazole with Fe²⁺-zeolite/peracetic acid. Separation and Purification Technology, 2020, 233: 115973.
[25]	WANG J, WANG Z, CHENG Y, et al. Molybdenum disulfide (MoS₂): a novel activator of peracetic acid for the degradation of sulfonamide antibiotics. Water Research, 2021, 201: 117291.
[26]	WANG J, XIONG B, LEI M, et al. Applying a novel advanced oxidation process of activated peracetic acid by CoFe₂O₄ to efficiently degrade sulfamethoxazole. Applied Catalysis B: Environmental, 2021, 280: 119422.

基于活性污泥焚灰的类Fenton催化剂的制备及其对亚甲基蓝的降解性能

Activated Sludge Incineration Ash Derived Fenton-like Catalyst: Preparation and Degradation Performance on Methylene Blue

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 12

参考文献 26

相关文章 15

编辑推荐

Metrics

本文评价

[1]	王梦桃, 索军, 方东, 易健宏, 刘意春, Olim RUZIMURADOV. ITO/TiO₂纳米管阵列复合材料的可见光催化性能[J]. 无机材料学报, 2023, 38(11): 1292-1300.
[2]	迟聪聪, 屈盼盼, 任超男, 许馨, 白飞飞, 张丹洁. SiO₂@Ag@SiO₂@TiO₂核壳结构的制备及其光催化降解性能[J]. 无机材料学报, 2022, 37(7): 750-756.
[3]	周帆, 毕辉, 黄富强. 用稻壳制备亚甲基蓝高吸附容量的超高比表面积活性炭[J]. 无机材料学报, 2021, 36(8): 893-903.
[4]	张晓锋,张冠华,孟跃,薛继龙,夏盛杰,倪哲明. 席夫碱钴改性CoCr-LDHs材料光催化降解亚甲基蓝研究[J]. 无机材料学报, 2019, 34(9): 974-982.
[5]	隋丽丽,王润,赵丹,申书昌,孙立,徐英明,程晓丽,霍丽华. 多级结构α-MoO₃空心微球的构筑及其对有机染料的吸附性能[J]. 无机材料学报, 2019, 34(2): 193-200.
[6]	赵海兵, 徐海峰, 杨克伟, 林辰学, 冯苗, 于岩. Mg掺杂TiO₂纳米晶光氧化还原染料的可逆颜色转变研究[J]. 无机材料学报, 2018, 33(10): 1124-1130.
[7]	喻洋, 佟明兴, 何玉兰, 陈辉, 高静, 李国华. 介孔TiO₂/WO₃空心球的制备及其可见光光催化性能[J]. 无机材料学报, 2017, 32(4): 365-371.
[8]	徐明丽, 段奔, 张英杰, 杨国涛, 董鹏, 夏书标, 杨显万. 碳纳米管载体改性条件对Pt纳米粒子电催化氧化性能的影响[J]. 无机材料学报, 2015, 30(9): 931-936.
[9]	彭丹, 郑学军, 谢澍梵, 罗晓菊, 王丁. GaN/ZnO复合体的制备及光催化性能[J]. 无机材料学报, 2014, 29(9): 956-960.
[10]	陈渊, 周科朝, 黄苏萍, 李志友, 刘国聪. 水热法制备Cu掺杂可见光催化剂BiVO₄及其光催化性能研究[J]. 无机材料学报, 2012, 27(1): 19-25.
[11]	刘国聪, 李海斌, 董辉. La掺杂TiO₂介孔微球的超声水热合成和光催化性能[J]. 无机材料学报, 2011, 26(7): 739-746.
[12]	舒火明, 谢吉民, 许晖, 李华明, 徐远国, 顾正. ZnO/AgNbO₃光催化剂的表征及活性研究[J]. 无机材料学报, 2010, 25(9): 935-941.
[13]	陈怡,施利毅,袁帅,吴钧,张美红,方建慧. TiO₂纳米管阵列薄膜光电协同降解亚甲基蓝的研究[J]. 无机材料学报, 2009, 24(4): 680-684.
[14]	江芳,邵飞. SiO₂柱层状钛酸的制备及光催化性能[J]. 无机材料学报, 2008, 23(6): 1263-1266.
[15]	传秀云,卢先春,卢先初. 负载TiO₂的硅藻土对亚甲基蓝的光降解性能研究[J]. 无机材料学报, 2008, 23(4): 657-661.