Abstract
To remove NO and SO2 from flue gas simultaneously, a heterogeneous catalytic oxidation system was developed with the nanoscale zero-valent iron (nZVI), vaporized H2O2, and sodium humate (HA-Na) acting as the catalyst, oxidant, and absorbent, respectively. The experimental results indicated that the desulfurization was mainly influenced by the absorption, and the denitrification was significantly affected by the catalytic oxidation parameters. Under the optimal conditions, the simultaneous removal efficiencies of SO2 and NO were 100 and 88.4%, respectively. The presence of ·OH during the removal process was proved by the scavenger tests, and the production of ·OH with and without nZVI was indirectly evaluated by the electron paramagnetic resonance (EPR) and methylene blue experiments. Moreover, the fresh and aged nZVI were characterized by a series of techniques and the results suggested that the redox pair Fe2+/Fe3+ released by nZVI could react with H2O2 to provide the sustainable ·OH, which was important for the oxidation from NO and SO2 to NO3− and SO42−. The removal mechanism was proposed preliminarily based on the correlative experiments, characterizations, and references.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Bai M, Zhang Z, Bai M (2012) Simultaneous desulfurization and denitrification of flue gas by •OH radicals produced from O2 + and water vapor in a duct. Environ Sci Technol 46(18):10161–10168. https://doi.org/10.1021/es3013886
Chekli L, Bayatsarmadi B, Sekine R, Sarkar B, Shen AM, Scheckel KG, Donner E (2016) Analytical characterisation of nanoscale zero-valent iron: a methodological review. Anal Chim Acta 903:13–35. https://doi.org/10.1016/j.aca.2015.10.040
Cheng R, Cheng C, Liu GH, Zheng X, Li GQ, Li J (2015) Removing pentachlorophenol from water using a nanoscale zero-valent iron/H2O2 system. Chemosphere 141:138–143. https://doi.org/10.1016/j.chemosphere.2015.06.087
Costa RCC, Moura FCC, Ardisson JD, Fabris JD, Lago RM (2008) Highly active heterogeneous Fenton-like systems based on Fe0/Fe3O4 composites prepared by controlled reduction of iron oxides. Appl Catal B 83(1–2):131–139. https://doi.org/10.1016/j.apcatb.2008.01.039
Dinesh GK, Anandan S, Sivasankar T (2016) Synthesis of Fe/ZnO composite nanocatalyst and its sonophotocatalytic activity on acid yellow 23 dye and real textile effluent. Clean Technol Environ 18(6):1889–1903. https://doi.org/10.1007/s10098-016-1117-z
Ding J, Zhong Q, Zhang SL (2014a) Simultaneous removal of NOX and SO2 with H2O2 over Fe based catalysts at low temperature. RSC Adv 4(11):5394–5398. https://doi.org/10.1039/c3ra46418k
Ding J, Zhong Q, Zhang SL, Song F, Bu Y (2014b) Simultaneous removal of NOX and SO2 from coal-fired flue gas by catalytic oxidation-removal process with H2O2. Chem Eng J 243:176–182. https://doi.org/10.1016/j.cej.2013.12.101
Ding J, Zhong Q, Zhang SL, Cai W (2015) Size- and shape-controlled synthesis and catalytic performance of iron–aluminum mixed oxide nanoparticles for NOX and SO2 removal with hydrogen peroxide. J Hazard Mater 283:633–642. https://doi.org/10.1016/j.jhazmat.2014.10.010
Fang P, Cen C, Wang X, Tang Z, Tang Z, Chen D (2013) Simultaneous removal of SO2, NO and Hg0 by wet scrubbing using urea + KMnO4 solution. Fuel Process Technol 106:645–653. https://doi.org/10.1016/j.fuproc.2012.09.060
Guo R, Pan W, Zhang X, Ren J, Jin Q, Xu H, Wu J (2011) Removal of NO by using Fenton reagent solution in a lab-scale bubbling reactor. Fuel 90(11):3295–3298. https://doi.org/10.1016/j.fuel.2011.06.030
Guo L, Shu Y, Gao J (2012) Present and future development of flue gas control technology of DeNOX in the world. Energy Procedia 17:397–403. https://doi.org/10.1016/j.egypro.2012.02.112
Hu G, Sun Z, Gao H (2010) Novel process of simultaneous removal of SO2 and NO2 by sodium humate solution. Environ Sci Technol 44(17):6712–6717. https://doi.org/10.1021/es101892r
Huang X, Ding J, Zhong Q (2015) Catalytic decomposition of H2O2 over Fe-based catalysts for simultaneous removal of NOX and SO2. Appl Sur Sci 326:66–72. https://doi.org/10.1016/j.apsusc.2014.11.088
Iwamori S, Nishiyama N, Oya K (2016) A colorimetric indicator for detection of hydroxyl radicals in atmosphere using a methylene blue dye based on nafion film. Polym Degrad Stab 123:131–136. https://doi.org/10.1016/j.polymdegradstab.2015.11.020
Jin D, Deshwal B, Park Y, Lee H (2006) Simultaneous removal of SO2 and NO by wet scrubbing using aqueous chlorine dioxide solution. J Hazard Mater 135(1–3):412–417. https://doi.org/10.1016/j.jhazmat.2005.12.001
Lee SY, Kim D, Choi S, Lee D, Choi JY, Kim H (2014) Porous multi-walled carbon nanotubes by using catalytic oxidation via transition metal oxide. Microporous Mesoporous Mater 194:46–51. https://doi.org/10.1016/j.micromeso.2014.03.040
Liao Q, Sun J, Gao L (2009) Degradation of phenol by heterogeneous Fenton reaction using multi-walled carbon nanotube supported Fe2O3 catalysts. Colloid Surf A 345(1–3):95–100. https://doi.org/10.1016/j.colsurfa.2009.04.037
Liu YX, Zhang J, Sheng CD, Zhang YC, Zhao L (2010) Simultaneous removal of NO and SO2 from coal-fired flue gas by UV/H2O2 advanced oxidation process. Chem Eng J 162(3):1006–1011. https://doi.org/10.1016/j.cej.2010.07.009
Liu YX, Zhou JF, Zhang YC, Pan JF, Wang Q, Zhang J (2015) Removal of Hg0 and simultaneous removal of Hg0/SO2/NO in flue gas using two Fenton-like reagents in a spray reactor. Fuel 145:180–188. https://doi.org/10.1016/j.fuel.2014.12.084
Liu YX, Wang Q, Pan JF (2016) Novel process on simultaneous removal of nitric oxide and sulfur dioxide using vacuum ultraviolet (VUV)-activated O2/H2O/H2O2 system in a wet VUV-spraying reactor. Environ Sci Technol 50(23):12966–12975. https://doi.org/10.1021/acs.est.6b02753
Mills A, Hazafy D (2009) Nanocrystalline SnO2-based UVB-activated, colourimetric oxygen indicator. Sensors Actuators B Chem 136(2):344–349. https://doi.org/10.1016/j.snb.2008.12.048
Nurmi JT, Tratnyek PG, Sarathy V, Baer DR, Amonette JE, Pecher K, Driessen MD (2005) Characterization and properties of metallic iron nanoparticles: spectroscopy, electrochemistry and kinetics. Environ Sci Technol 39(5):1221–1230. https://doi.org/10.1021/es049190u
Pham AL, Lee C, Doyle FM, Sedlak DL (2009) A silica-supported iron oxide catalyst capable of activating hydrogen peroxide at neutral pH values. Environ Sci Technol 43(23):8930–8935. https://doi.org/10.1021/es902296k
Ponder SM, Darab JG, Mallouk TE (2000) Remediation of Cr(VI) and Pb(II) aqueous solutions using supported nanoscale zero-valent iron. Environ Sci Technol 34(12):2564–2569. https://doi.org/10.1021/es9911420
Ramirez JH, Maldonado-Hódar FJ, Pérez-Cadenas AF, Moreno-Castilla C, Costa CA, Madeira LM (2007) Azo-dye Orange II degradation by heterogeneous Fenton-like reaction using carbon-Fe catalysts. Appl Catal B 75(3–4):312–323. https://doi.org/10.1016/j.apcatb.2007.05.003
Segura Y, Martínez F, Melero JA, Fierro JLG (2015) Zero valent iron (ZVI) mediated Fenton degradation of industrial wastewater: treatment performance and characterization of final composites. Chem Eng J 269:298–305. https://doi.org/10.1016/j.cej.2015.01.102
National Institute of Standards and Technology U.S. (2012) X-ray photoelectron spectroscopy database. https://srdata.nist.gov/xps/selEnergyType.aspx (accessed 12. Sep.2015)
Wang W, Jin Z, Li T, Zhang H, Gao S (2006) Preparation of spherical iron nanoclusters in ethanol–water solution for nitrate removal. Chemosphere 65(8):1396–1404. https://doi.org/10.1016/j.chemosphere.2006.03.075
Wang Z, Zhou J, Zhu Y, Wen Z, Liu J, Cen K (2007) Simultaneous removal of NOx, SO2 and Hg in nitrogen flow in a narrow reactor by ozone injection: experimental results. Fuel Process Technol 88(8):817–823. https://doi.org/10.1016/j.fuproc.2007.04.001
Wang JL, Xu LJ (2012) Advanced oxidation processes for wastewater treatment: formation of hydroxyl radical and application. Environ Sci Technol 42:251–325. https://doi.org/10.1080/10643389.2010.507698
Wang X, Du Y, Ma J (2016) Novel synthesis of carbon spheres supported nanoscale zero-valent iron for removal of metronidazole. Appl Sur Sci 390:50–59. https://doi.org/10.1016/j.apsusc.2016.08.027
Wu B, Xiong YQ, Ru JB (2016) Removal of NO from flue gas using heat- activated ammonium persulfate aqueous solution in a bubbling reactor. RSC Adv 6:33919–33930. https://doi.org/10.1039/c6ra01524g
Wu B, Xiong YQ, Ge Y (2018) Simultaneous removal of SO2 and NO from flue gas with ·OH from the catalytic decomposition of gas-phase H2O2 over solid-phase Fe2(SO4)3. Chem Eng J 331:343–354. https://doi.org/10.1016/j.cej.2017.08.097
Xing Y, Li L, Lu P, Cui J, Li Q, Yan B, Wang M (2017) Simultaneous purifying of Hg0, SO2 and NOx from flue gas by Fe3+/H2O2: the performance and purifying mechanism. Environ Sci Pollut Res 25(7):6456–6465. https://doi.org/10.1007/s11356-017-0948-4
Xu L, Wang J (2011) A heterogeneous Fenton-like system with nanoparticulate zero-valent iron for removal of 4-chloro-3-methyl phenol. J Hazard Mater 186(1):256–264. https://doi.org/10.1016/j.jhazmat.2010.10.116
Yamashita T, Hayes P (2008) Analysis of XPS spectra of Fe2+ and Fe3+ ions in oxide materials. Appl Surf Sci 254(8):2441–2449. https://doi.org/10.1016/j.apsusc.2007.09.063
Zha S, Cheng Y, Gao Y, Chen Z, Megharaj M, Naidu R (2014) Nanoscale zero-valent iron as a catalyst for heterogeneous Fenton oxidation of amoxicillin. Chem Eng J 255:141–148. https://doi.org/10.1016/j.cej.2014.06.057
Zhang Z, Chen X, Heck P, Xue B, Liu Y (2015) Empirical study on the env-ironmental pressure versus economic growth in China during 1991–2012. Resour Conserv Recycl 101:182–193. https://doi.org/10.1016/j.resconrec.2015.05.018
Zhao Y, Guo TY, Chen Z, Du Y (2010) Simultaneous removal of SO2 and NO using M/NaClO2 complex absorbent. Chem Eng J 160(1):42–47. https://doi.org/10.1016/j.cej.2010.02.060
Zhao Y, Han YH, Ma TZ, Guo TX (2011) Simultaneous desulfurization and denitrification from flue gas by ferrate (VI). Environ Sci Technol 45(9):4060–4065. https://doi.org/10.1021/es103857g
Zhao Y, Hao RL, Wang T, Yang C (2015) Follow-up research for integrative process of pre-oxidation and post-absorption cleaning flue gas: absorption of NO2, NO and SO2. Chem Eng J 273:55–65. https://doi.org/10.1016/j.cej.2015.03.053
Zhao Y, Hao RL, Yuan B, Jiang JJ (2016a) Simultaneous removal of SO2, NO and Hg0 through an integrative process utilizing a cost-effective complex oxidant. J Hazard Mater 301:74–83. https://doi.org/10.1016/j.jhazmat.2015.08.049
Zhao WK, Zhang SL, Ding J, Deng ZY, Guo L, Zhong Q (2016b) Enhanced catalytic ozonation for NOx removal with CuFe2O4 nanoparticles and mechanism analysis. J Mol Catal A 424:153–161. https://doi.org/10.1016/j.molcata.2016.08.007
Zhao Y, Hao RL, Xue FM, Feng YN (2017a) Simultaneous removal of multi-pollutants from flue gas by a vaporized composite absorbent. J Hazard Mater 321:500–508. https://doi.org/10.1016/j.jhazmat.2016.09.044
Zhao Y, Yuan B, Hao RL, Tao ZC (2017b) Low-temperature conversion of NO in flue gas by vaporized H2O2 and nanoscale zerovalent iron. Energy Fuel 31(7):7282–7289. https://doi.org/10.1021/acs.energyfuels.7b00588
Zhou T, Li Y, Ji J, Wong F, Lu X (2008) Oxidation of 4-chlorophenol in a heterogeneous zero valent iron/H2O2 Fenton-like system: kinetic, pathway and effect factors. Sep Purif Technol 62(3):551–558. https://doi.org/10.1016/j.seppur.2008.03.008
Acknowledgements
The authors appreciate the financial support by a grant from the National key R&D Program of China (No. 2017YFC0210603) and (No. 2016YFC0203701, No. 2016YFC0203705), National Science Technology Support Plan of China (No. 2014BAC23B04-06), Beijing Major Scientific and Technological Achievement Transformation Project of China (No.Z151100002815012), and the Fundamental Research Funds for the Central Universities (NO.2015ZZD07 and 2016XS109).
Author information
Authors and Affiliations
Corresponding author
Additional information
Responsible editor: Vítor Pais Vilar
Electronic supplementary material
ESM 1
(DOCX 1697 kb)
Rights and permissions
About this article
Cite this article
Zhao, Y., Yuan, B., Shen, Y. et al. Simultaneous removal of NO and SO2 from flue gas using vaporized H2O2 catalyzed by nanoscale zero-valent iron. Environ Sci Pollut Res 25, 25526–25537 (2018). https://doi.org/10.1007/s11356-018-2628-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11356-018-2628-4