铁基纤维素微球的制备及其活化过硫酸盐降解盐酸四环素

刘瑞龙; 任小花; 国伟林

doi:10.13205/j.hjgc.202307012

铁基纤维素微球的制备及其活化过硫酸盐降解盐酸四环素

doi: 10.13205/j.hjgc.202307012

济南大学水利与环境学院, 济南 250022

基金项目:

国家自然科学基金项目（51908242）；济南大学科技计划项目（XKY1918）

详细信息

作者简介:
刘瑞龙(1997-),男,硕士研究生,主要研究方向为水污染处理工程。947576286@qq.com

通讯作者:
任小花(1986-),女,讲师,主要研究方向为水污染处理工程。stu_renxh@ujn.edu.cn

计量
- 文章访问数: 85
- HTML全文浏览量: 18
- PDF下载量: 3
- 被引次数: 0
出版历程
- 收稿日期: 2022-04-15

PREPARATION OF IRON-BASED CELLULOSE MICROSPHERES AND ITS ACTIVATION ON PERSULFATE TO DEGRADE TETRACYCLINE HYDROCHLORIDE

School of Water Conservancy and Environment, University of Jinan, Jinan 250022, China

摘要

摘要: 铁基催化剂具有优良的活化过硫酸盐的性能，且价廉易得，受到研究者的广泛关注，然而在现阶段研究铁基催化剂多为粉末材料，存在易团聚、回收困难等问题，制约其实际应用。以醋酸纤维素（CA）为载体，采用液滴微流控技术制备了一种具有较高催化活性的微球催化剂（CA-Fe微球）。采用扫描电镜-能谱仪（SEM-EDS）、傅里叶红外变换光谱仪（FTIR）和比表面积分析仪（BET）对催化剂的形貌、结构和组成进行分析。以CA-Fe微球为催化剂活化过二硫酸盐（PS）降解盐酸四环素（TCH）废水，考察初始TCH浓度、CA-Fe微球投加量和PS投加量等操作条件对TCH去除效果的影响。结果表明：CA-Fe微球对PS具有良好的活化性能，CA-Fe/PS体系能够有效去除TCH。在TCH初始浓度为20 mg/L、PS浓度为2 mmol/L、CA-Fe微球投加量为4 g/L条件下，TCH去除率在85%左右。自由基捕获（EPR）和自由基猝灭实验结果揭示，CA-Fe微球/PS体系中存在的活性自由基为·OH和SO₄^-·，且SO₄^-·在TCH降解中起主要作用。循环利用实验表明，CA-Fe微球具有良好的结构稳定性和循环利用性能，3次循环使用后TCH去除率仍保持在80%左右。研究结果可为铁基纤维素微球/PS催化体系在去除抗生素废水领域的应用提供科学依据。
- 铁基纤维素微球 /
- 微流控 /
- 过二硫酸盐 /
- 盐酸四环素 /
- 高级氧化过程
Abstract: Iron-based catalysts have excellent performance in activating persulfate (PS) and are readily available, attracting extensive attention from researchers. However, most of the iron-based catalysts studied at the current stage are powder materials, and there are problems such as easy agglomeration and difficulty in recycling, which restrict their practical application. In this study, a microsphere catalyst (CA-Fe microspheres) with high catalytic activity was prepared using cellulose acetate (CA) as a carrier by droplet microfluidic technology. The morphology, structure and composition of the catalysts were characterized by SEM-EDS, FTIR and BET. The high catalytic degradation of tetracycline hydrochloride (TCH) in aqueous solution was tested by catalytic activation of PS. The effects of initial TCH concentration, the dosage of CA-Fe microspheres and the dosage of PS on TCH degradation were also investigated. The results showed that the CA-Fe microspheres had good activation performance for PS, and TCH could be effectively degraded in the CA-Fe/PS system. In the condition of the initial TCH concentration of 20 mg/L, the PS concentration of 2 mmol/L, and the CA-Fe microspheres dosage of 4 g/L, the degradation rate of TCH was about 85%. The electron paramagnetic resonance (EPR) and free radical quenching studies revealed that both SO₄^-· and·OH radicals were found in the CA-Fe microspheres/PS system, and the SO₄^-· radical played a major role in the degradation of TCH. Furthermore, the CA-Fe microspheres exhibited excellent structural stability and recycling performance, and the TCH degradation rate remained 80% above after three cycles. The results can provide a scientific basis for the application of cellulose-based magnetic microspheres/PS catalytic systems in the field of removing antibiotic wastewater.
- iron-based cellulose microspheres /
- microfluidics /
- persulfate /
- tetracycline hydrochloride /
- advanced oxidation process (AOPs)

HTML全文

参考文献(47)

[1]	ZHANG J J, QIU S, FENG H P, et al.Efficient degradation of tetracycline using core-shell Fe@Fe₂O₃-CeO₂ composite as novel heterogeneous electro-Fenton catalyst[J].Chemical Engineering Journal, 2022, 428:131403.
[2]	WEI Q Q, ZHOU K, CHEN J Y, et al.Insights into the molecular mechanism of tetracycline transport in saturated porous media affected by low-molecular-weight organic acids:role of the functional groups and molecular size[J].Science of the Total Environment, 2021, 799:149361.
[3]	SONG J L, HUANG M H, LIN X H, et al.Novel Fe-based metal-organic framework (MOF) modified carbon nanofiber as a highly selective and sensitive electrochemical sensor for tetracycline detection[J].Chemical Engineering Journal, 2022, 427:130913.
[4]	ALOTHMAN Z A, ALMASOUD N, MBIANDA X Y, et al.Synthesis and characterization of γ-cyclodextrin-graphene oxide nanocomposite:sorption, kinetics, thermodynamics and simulation studies of tetracycline and chlortetracycline antibiotics removal in water[J].Journal of Molecular Liquids, 2022, 345:116993.
[5]	DARVISHI CHESHMEH SOLTANI R, NADERI M, BOCZKAJ G, et al.Hybrid metal and non-metal activation of Oxone by magnetite nanostructures co-immobilized with nano-carbon black to degrade tetracycline:fenton and electrochemical enhancement with bio-assay[J].Separation and Purification Technology, 2021, 274:119055.
[6]	PIMENTEL J A I, DONG C D, GARCIA-SEGURA S, et al.Degradation of tetracycline antibiotics by Fe²⁺-catalyzed percarbonate oxidation[J].Science of The Total Environment, 2021, 781:146411.
[7]	GAO X, CHEN Y Q, KANG Z W, et al.Enhanced degradation of aqueous tetracycline hydrochloride by integrating eggshell-derived CaCO3/CuS nanocomposite with advanced oxidation process[J].Molecular Catalysis, 2021, 501:111380.
[8]	ZHANG J L, JIN X, YANG C H.Efficient removal of organic pollutants in waste sulfuric acid by an advanced oxidation process using coconut shell-derived biochar to produce qualified poly aluminium sulfate[J].Separation and Purification Technology, 2022, 293:121057.
[9]	PARK C M, HEO J, WANG D, et al.Heterogeneous activation of persulfate by reduced graphene oxide-elemental silver/magnetite nanohybrids for the oxidative degradation of pharmaceuticals and endocrine disrupting compounds in water[J].Applied Catalysis B, Environmental, 2018, 225:91-99.
[10]	MASUD M A A, KIM D G, SHIN W S.Highly efficient degradation of phenolic compounds by Fe(Ⅱ)-activated dual oxidant (persulfate/calcium peroxide) system[J].Chemosphere, 2022, 299:134392.
[11]	GAO Y, WANG Q, JI G Z, et al.Degradation of antibiotic pollutants by persulfate activated with various carbon materials[J].Chemical Engineering Journal, 2022, 429:132387.
[12]	ANUSHREE C, NANDA GOPALA KRISHNA D, PHILIP J.Efficient dye degradation via catalytic persulfate activation using iron oxide-manganese oxide core-shell particle doped with transition metal ions[J].Journal of Molecular Liquids, 2021, 337:116429.
[13]	TIAN K, HU L M, LI L T, et al.Recent advances in persulfate-based advanced oxidation processes for organic wastewater treatment[J].Chinese Chemical Letters, 2022, 33(10):4461-4477.
[14]	LIU Q Q, ZHANG L L, CHEN H X, et al.Sulfur and nitrogen co-doped three-dimensional graphene aerogels for high-performance supercapacitors:a head to head vertical bicyclic molecule both as pillaring agent and dopant[J].Applied Surface Science, 2021, 565:150453.
[15]	GE L, SHAO B B, LIANG Q H, et al.Layered double hydroxide based materials applied in persulfate based advanced oxidation processes:property, mechanism, application and perspectives[J].J Hazard Mater, 2022, 424:127612.
[16]	DING X Y, SONG X, CHEN X, et al.Degradation and mechanism of hexafluoropropylene oxide dimer acid by thermally activated persulfate in aqueous solutions[J].Chemosphere, 2021, 286:131720.
[17]	REN T L, MA X W, WU X Q, et al.Degradation of imidazolium ionic liquids in a thermally activated persulfate system[J].Chemical Engineering Journal, 2021, 412:128624.
[18]	ZHANG Y L, CHU W.Bisphenol S degradation via persulfate activation under UV-LED using mixed catalysts:synergistic effect of Cu-TiO₂ and Zn-TiO₂ for catalysis[J].Chemosphere, 2021, 286:131797.
[19]	CHEN T S, MA J S, ZHANG Q X, et al.Degradation of propranolol by UV-activated persulfate oxidation:reaction kinetics, mechanisms, reactive sites, transformation pathways and Gaussian calculation[J].The Science of the Total Environment, 2019, 690:878-890.
[20]	KAN H S, WANG T C, YU J X, et al.Remediation of organophosphorus pesticide polluted soil using persulfate oxidation activated by microwave[J].J Hazard Mater, 2021, 401:123361.
[21]	GARCIA-CERVILLA R, SANTOS A, ROMERO A, et al.Compatibility of nonionic and anionic surfactants with persulfate activated by alkali in the abatement of chlorinated organic compounds in aqueous phase[J].The Science of the Total Environment, 2021, 751:141782.
[22]	SHAN A, IDREES A, ZAMAN W Q, et al.Synthesis of nZVI-Ni@BC composite as a stable catalyst to activate persulfate:trichloroethylene degradation and insight mechanism[J].Journal of Environmental Chemical Engineering, 2021, 9(1):104808.
[23]	MIAO W, LIU Y, WANG D D, et al.The role of Fe-Nx single-atom catalytic sites in peroxymonosulfate activation:formation of surface-activated complex and non-radical pathways[J].Chemical Engineering Journal, 2021, 423:130250.
[24]	DUAN P T, PAN J W, DU W Y, et al.Activation of peroxymonosulfate via mediated electron transfer mechanism on single-atom Fe catalyst for effective organic pollutants removal[J].Applied Catalysis B:Environmental, 2021, 299:120714.
[25]	GAO Y, CONG S B, YU H Y, et al.Investigation on microwave absorbing properties of 3D C@ZnCo₂O₄ as a highly active heterogenous catalyst and the degradation of ciprofloxacin by activated persulfate process[J].Separation and Purification Technology, 2021, 262:118330.
[26]	RAO L J, YANG Y F, LIU X D, et al.Heterogeneous activation of persulfate by supporting ferric oxalate onto activated carbon fibers for organic contaminants removal[J].Materials Research Bulletin, 2020, 130:110919.
[27]	LI T, CHEN C, BROZENA A H, et al.Developing fibrillated cellulose as a sustainable technological material[J].Nature, 2021, 590(7844):47-56.
[28]	FAHIM A M, ABOUZEID R E, KIEY S A A, et al.Development of semiconductive foams based on cellulose- benzenesulfonate/CuFe₂O₄-nanoparticles and theoretical studies with DFT/B3PW91/LANDZ2 basis set[J].Journal of Molecular Structure, 2022, 1247:131390.
[29]	MIAO F, LIU Z H, KANG X C, et al.Electro-enhanced heterogeneous activation of peroxymonosulfate via acceleration of Fe(Ⅲ)/Fe(Ⅱ) redox cycle on Fe-B catalyst[J].Electrochimica Acta, 2021, 377:138073.
[30]	YANG Z, LUO M S, LIU Q L, et al.In situ XRD and raman investigation of the activation process over K-Cu-Fe/SiO₂ catalyst for fischer-tropsch synthesis reaction[J].Catalysis Letters, 2020, 150(8):2437-2445.
[31]	SÁNCHEZ-VELANDIA J E, AGUDELO-CIFUENTES A, VILLA A L.Kinetics of the isomerization of α-pinene epoxide over Fe supported MCM-41 and SBA-15 materials[J].Reaction Kinetics, Mechanisms and Catalysis, 2019, 128(2):1005-1028.
[32]	JI Y F, FERRONATO C, SALVADOR A, et al.Degradation of ciprofloxacin and sulfamethoxazole by ferrous-activated persulfate:implications for remediation of groundwater contaminated by antibiotics[J].The Science of the Total Environment, 2014, 472:800-808.
[33]	WU J X, WANG B, BLANEY L, et al.Degradation of sulfamethazine by persulfate activated with organo-montmorillonite supported nano-zero valent iron[J].Chemical Engineering Journal, 2019, 361:99-108.
[34]	NIU L, ZHANG G M, XIAN G, et al.Tetracycline degradation by persulfate activated with magnetic γ-Fe₂O₃/CeO₂ catalyst:performance, activation mechanism and degradation pathway[J].Separation and Purification Technology, 2021, 259:118156.
[35]	RUAN Y, KONG L J, ZHONG Y W, et al.Review on the synthesis and activity of iron-based catalyst in catalytic oxidation of refractory organic pollutants in wastewater[J].Journal of Cleaner Production, 2021, 321:128924.
[36]	ZHAO G Q, ZOU J C, CHEN X Q, et al.Iron-based catalysts for persulfate-based advanced oxidation process:microstructure, property and tailoring[J].Chemical Engineering Journal, 2021, 421:127845.
[37]	GUO Y X, YAN L G, LI X G, et al.Goethite/biochar-activated peroxymonosulfate enhances tetracycline degradation:inherent roles of radical and non-radical processes[J].Science Total Environment, 2021, 783:147102.
[38]	SU S S, CAO C J, ZHAO Y P, et al.Efficient transformation and elimination of roxarsone and its metabolites by a new α-FeOOH@GCA activating persulfate system under UV irradiation with subsequent As(Ⅴ) recovery[J].Applied Catalysis B:Environmental, 2019, 245:207-219.
[39]	WANG L, MA X L, HUANG G F, et al.Construction of ternary CuO/CuFe₂O₄/g-C₃N₄ composite and its enhanced photocatalytic degradation of tetracycline hydrochloride with persulfate under simulated sunlight[J].J Environ Sci (China), 2022, 112:59-70.
[40]	FENG Q Q, ZHOU J B, LUO W J, et al.Photo-Fenton removal of tetracycline hydrochloride using LaFeO₃ as a persulfate activator under visible light[J].Ecotoxicology and Environmental Safety, 2020, 198:110661.
[41]	ZHANG Y F, WEI J, XING L Y, et al.Superoxide radical mediated persulfate activation by nitrogen doped bimetallic MOF (FeCo/N-MOF) for efficient tetracycline degradation[J].Separation and Purification Technology, 2022, 282:120124.
[42]	ELBENBERGER H, STEENKEN S, O'NEILL P, et al.Pulse radiolysis and electron spin resonance studies concerning the reaction of SO₄.cntdot.- with alcohols and ethers in aqueous solution[J].Journal of Physical Chemistry, 1978, 82:749-750.
[43]	BUXTON G V, GREENSTOCK C L, HELMAN W P, et al.Critical review of rate constants for reactions of hydrated electrons chemical kinetic data base for combustion chemistry[J].Journal of Physical & Chemical Reference Data, 1988, 17:513-886.
[44]	ANIPSITAKIS P G, DIONYSIOU D D.Radical generation by the interaction of transition metals with common oxidants[J].Environmental Science & Technology, 2004, 38:3705-3712.
[45]	WANG R Y, YU Y J, ZHANG R J, et al.Vacancy-rich structure inducing efficient persulfate activation for tetracycline degradation over Ni-Fe layered double hydroxide nanosheets[J].Separation and Purification Technology, 2022, 289:120663.
[46]	DENG J, XIAO L W, YUAN S J, et al.Activation of peroxymonosulfate by CoFeNi layered double hydroxide/graphene oxide (LDH/GO) for the degradation of gatifloxacin[J].Separation and Purification Technology, 2021, 255:117685.
[47]	HOU L H, LI X M, YANG Q, et al.Heterogeneous activation of peroxymonosulfate using Mn-Fe layered double hydroxide:performance and mechanism for organic pollutant degradation[J].Science of the Total Environment, 2019, 663:453-464.