Study on the synergistic heterogeneous Fenton oxidation degradation of benzene containing waste gas using Fe doped UiO-66
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摘要: 采用水热合成法制备了不同掺杂比例Fe负载UiO-66,并借助XRD、SEM、XPS等分析测试手段对催化剂物理化学特性进行分析,通过自制非均相类Fenton体系装置探究不同Fe负载量、H2O2浓度、空塔速率、反应温度等条件下对废气苯的氧化降解效率影响。结果表明,不同Fe负载量的UiO-66均具有较高的结晶度,呈不规则球状;在非均相类Fenton氧化降解苯实验中,30%的Fe负载UiO-66具有最高的苯脱除效率。EPR结果显示,Fe负载量的增大促进·OH的产生,在一定程度上促进苯的氧化降解。过高的反应温度导致H2O2不稳定,非均相类Fenton氧化降解苯的效率随温度的升高先增大后降低。
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关键词:
- 催化剂 /
- 苯 /
- 非均相类Fenton /
- 金属有机骨架 /
- 挥发性有机污染物
Abstract: The UiO-66 catalysts with different doping ratio of Fe were prepared by hydrothermal synthesis method in this study. The physicochemical properties of the catalysts were characterized by means of XRD, SEM and XPS. The benzene removal efficiency of the catalysts was investigated using a bench-scaled heterogeneous Fenton-like system device. The effects of Fe loading amount, H2O2 concentration, superficial velocity and reaction temperature on benzene removal efficiency were studied. The results showed that the Fe doped UiO-66 was irregularly spherical and of high crystallinity. The highest benzene removal efficiency was obtained at 93% over the catalyst with 30% Fe loading. The EPR results proved that increasing Fe loading on UiO-66 evidently promoted the production of ·OH radicals, which promoted the degradation of benzene to a certain extent. The benzene removal efficiency decreased with the rise of temperature at higher range because H2O2 was unstable at high temperature.-
Key words:
- catalyst /
- benzene /
- heterogeneous Fenton /
- metal organic framework /
- volatile organic compounds
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图 9 10% Fe/UiO-66、20% Fe/UiO-66、30% Fe/UiO-66和40% Fe/UiO-66类Fenton反应过程的EPR波谱强度
Figure 9 EPR spectrum intensity of 10% Fe/UiO-66, 20% Fe/UiO-66, 30% Fe/UiO-66 and 40% Fe/Ui O-66 Fenton reaction processes
reaction conditions: H2O2 concentration is 1 mol/L, DMPO concentration is 5 mmol/L and reaction measurement time is 15 min
表 1 催化剂的比表面积及孔容
Table 1 Surface area and pore volume of the catalysts with different Fe loadings
Sample SBET/(m2·g−1) Pore volume/(cm3·g−1) 10% Fe/UiO-66 1007.0 0.346 20% Fe/UiO-66 1021.8 0.333 30% Fe/UiO-66 1210.5 0.428 40% Fe/UiO-66 1169.7 0.440 -
[1] 汤吉昀, 朱超, 张红欣. 分子筛在挥发性有机物处理中的研究[J]. 应用能源技术,2018,,(9):46−49. doi: 10.3969/j.issn.1009-3230.2018.08.011TANG Ji-yun, ZHU Chao, ZHANG Hong-xin. Research on molecular sieve in the treatment of volatile organic compounds[J]. Appl Energy Technol,2018,,(9):46−49. doi: 10.3969/j.issn.1009-3230.2018.08.011 [2] 贾永芹, 张晓晶. 分子筛负载CoOx催化剂用于苯的催化氧化[J]. 环境科学与技术,2018,41(9):28−32.JIA Yong-qin, ZHANG Xiao-jing. Molecular sieve supported CoOx catalyst for catalytic oxidation of Benzene[J]. Environ Sci Technol,2018,41(9):28−32. [3] MARIA L A, VIVIAN S M, VIVIAN S M, BRASILEIRO C, POLLYANA C R. Synthesis of mixed oxide Ti/Fe2O3 as solar light-induced photocatalyst for heterogeneous photo-Fenton like process[J]. J Photochem Photobiol, A, 2021, 404: 112873. [4] KHAN N A, HASAN Z, JHUNG S H. Adsorptive removal of hazardous materials using metal-organic frameworks (MOFs): A review[J]. J Hazard Mater,2013,244-245:444−456. doi: 10.1016/j.jhazmat.2012.11.011 [5] WU J H, XIA Q B, LI Z, PI Y H. Facilitation of the visible light-induced Fenton-like excitation of H2O2 via heterojunction of g-C3N4/NH2-Iron terephthalate metal-organic framework for MB degradation[J]. Appl Catal B: Environ,2017,202:653−663. doi: 10.1016/j.apcatb.2016.09.073 [6] MA X C, LI L Q, CHEN R F, WANG C H, LI H L, WANG S B. Heteroatom-doped nanoporous carbon derived from MOF-5 for CO2 capture[J]. Appl Surf Sci,2018,435:494−502. doi: 10.1016/j.apsusc.2017.11.069 [7] PAN Y, JIANG S S, XIONG W, LIU D R, LUO D. Supported CuO catalysts on metal-organic framework (Cu-UiO-66) for efficient catalytic wet peroxide oxidation of 4-chlorophenol in wastewater[J]. J Hazard Mater,2020,291:109703. [8] GONZALEZ-OLMOS R, MARTIN M J, GEORGI A, KOPINKE F D, OLLER L, MALATO S. Fe-zeolites as heterogeneous catalysts in solar Fenton-like reactions at neutral pH[J]. Appl Catal B: Environ,2012,125:51−58. doi: 10.1016/j.apcatb.2012.05.022 [9] 李银莹. 铁基金属—有机框架非均相类Fenton催化剂降解染料研究[D]. 重庆: 西南大学, 2019.LI Yin-ying Study on Fe-based metal-organic framework heterogeneous Fenton catalyst for degradation of dyes[D]. Chongqing: Southwest University, 2019. [10] SUN Q, LIU M, LI K Y, HAN Y T, ZUO Y, WANG J H, SONG C S, ZHANG G L, GUO X W. Controlled synthesis of mixed-valent Fe-containing metal organic framework for degradation of phenol under mild conditions[J]. Dalton Trans,2016,10:1039. [11] CAVKA J H, JAKOBSEN S, OLSBYE U, GUILLOU N, LAMBERTI C, BORDIGA S, LILLERUD K P. A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability[J]. J Am Chem Soc,2008,130(42):13850−1. doi: 10.1021/ja8057953 [12] WEN C Y, WANG C G, CHEN, L G, ZHANG X H, LIU Q Y, MA L L. Effect of hierarchical ZSM-5 zeolite support on direct transformation from syngas to aromatics over the iron-based catalyst[J]. Fuel,2019,244:492−498. doi: 10.1016/j.fuel.2019.02.041 [13] YU C L, DONG L F, CHEN F, LIU X Q, HUANG B C. Low-temperature SCR of NOx by NH3 over MnOx/SAPO-34 prepared by two different methods: a comparative study[J]. Environ Technol,2017,38:1030−1042. doi: 10.1080/09593330.2016.1216170 [14] SANDRO B, OLIVER K, ARNO T, RODERIK A. The state of the art in selective catalytic reduction of NOx by ammonia using metal-exchanged zeolite catalysts[J]. Catal Rev,2008,50:492−531. doi: 10.1080/01614940802480122 [15] 聂明星. 铁基氧化物非均相类Fenton催化剂的制备及其对四环素的降解研究[D]. 合肥: 中国科学技术大学, 2020.NIE Ming-xing. Study on the Preparation of Iron-based Oxide Heterogenerous Fenton-like catalysts and Degradation of Tetracycline[D]. Hefei: University of Science and Technology of China, 2020. [16] GUO L S, LI J, ZENG Y, KOSOL R, TSUBAKI N. Heteroatom doped iron-based catalysts prepared by urea self-combustion method for efficient CO2 hydrogenation[J]. Fuel,2020,276:118102. [17] SALAZAR-AGUILAR A D, VEGA G, CASAS J A, VEGA-DÍAZ S M, QUINTANILLA A. Direct hydroxylation of phenol to dihydroxybenzenes by H2O2 and Fe-based metal-organic framework catalyst at room temperature[J]. Catalysts,2020,10(2):172. [18] YAMASHITA T, HAYES P. Erratum to "Analysis of XPS spectra of Fe2+ and Fe3+ ions in oxide materials"[J]. Appl Surf Sci,2008,254:2441−2449. doi: 10.1016/j.apsusc.2007.09.063 [19] GONG Z J, WEN F W, ZHAO Z W, LI B W. Combination of catalytic combustion and catalytic denitration on semi-coke with Fe2O3 and CeO2[J]. Catal Today,2018,318:59−65. [20] XU Y, AI X, ZHANG H. The mechanism of degradation of bisphenol A using the magnetically separable CuFe2O4/peroxymonosulfate heterogeneous oxidation process[J]. J Hazard Mater,2016,309:87−96. doi: 10.1016/j.jhazmat.2016.01.023 [21] CHEN H, ZHANG Z L, YANG Z L, YANG Q, LI B, BAI Z Y. Heterogeneous fenton-like catalytic degradation of 2,4-dichlorophenoxyacetic acid in water with FeS[J]. Chem Eng J,2015,273:481−489. doi: 10.1016/j.cej.2015.03.079 [22] WANG Y, LIU Y X, LIU Y. Elimination of nitric oxide using new Fenton process based on synergistic catalysis: Optimization and mechanism[J]. Chem Eng J,2019,372:92−98. doi: 10.1016/j.cej.2019.04.122 [23] XIN S S, LIU G C, MA X H, GONG J X, XIN Y J. High efficiency heterogeneous Fenton-like catalyst biochar modified CuFeO2 for the degradation of tetracycline: Economical synthesis, catalytic performance and mechanism[J]. Appl Catal B: Environ, 2021, 280: 119386. [24] GUO R T, PAN W G, ZHANG X B, REN J X, JIN Q, XU H J, WU J. Removal of NO by using Fenton reagent solution in a lab-scale bubbling reactor[J]. Fuel,2011,90(11):3295−3298. doi: 10.1016/j.fuel.2011.06.030 [25] LIU Y, WANG Y. Removal of gaseous hydrogen sulfide by a Photo-Fenton wet oxidation scrubbing system[J]. Energy Fuels,2019,33(11):10812−10819. [26] 周长松. 铁基非均相类Fenton催化剂脱除烟气中汞的实验与机理研究[D]. 武汉: 华中科技大学, 2016.ZHOU Chang-song. Experimental and mechanism study of elemental mercury removal from flue gas over iron-based Fenton-like catalysts[D]. Wuhan: Huazhong University of Science and Technology, 2016.