Simultaneous NO and SO2 removal by aqueous persulfate activated by combined heat and Fe2+: experimental and kinetic mass transfer model studies

  • Yusuf G. Adewuyi
  • Md Arif Khan
Environmental and Sustainable Chemical Engineering


This study evaluates the chemistry, kinetics, and mass transfer aspects of the removal of NO and SO2 simultaneously from flue gas induced by the combined heat and Fe2+ activation of aqueous persulfate. The work involves experimental studies and the development of a mathematical model utilizing a comprehensive reaction scheme for detailed process evaluation, and to validate the results of an experimental study at 30–70 °C, which demonstrated that both SO2 and Fe2+ improved NO removal, while the SO2 is almost completely removed. The model was used to correlate experimental data, predict reaction species and nitrogen-sulfur (N-S) product concentrations, to obtain new kinetic data, and to estimate mass transfer coefficient (KLa) for NO and SO2 at different temperatures. The model percent conversion results appear to fit the data remarkably well for both NO and SO2 in the temperature range of 30–70 °C. The conversions ranged from 43.2 to 76.5% and 98.9 to 98.1% for NO and SO2, respectively, in the 30–70 °C range. The model predictions at the higher temperature of 90 °C were 90.0 and 97.4% for NO and SO2, respectively. The model also predicted decrease in KLa for SO2 of 1.097 × 10−4 to 8.88 × 10−5 s−1 (30–90 °C) and decrease in KLa for NO of 4.79 × 10−2 to 3.67 × 10−2 s−1 (30–50 °C) but increase of 4.36 × 10−2 to 4.90 × 10−2 s−1 at higher temperatures (70–90 °C). This emerging sulfate-radical-based process could be applied to the treatment of flue gases from combustion sources.

Graphical abstract


Nitric oxide Sulfur dioxide Kinetic mass transfer model Oxidation Activated persulfate Temperature 



The authors wish to acknowledge the contribution of the National Science Foundation (NSF) for the funding received via Grant CBET-0651811.

Supplementary material

11356_2018_2453_MOESM1_ESM.docx (31 kb)
ESM 1 (DOCX 31 kb)


  1. Adewuyi YG (2005a) Sonochemistry in environmental remediation. 1. Combinative and hybrid sonophotochemical oxidation processes for the treatment of pollutants in water. Environ Sci Technol 39:3409–3420. CrossRefGoogle Scholar
  2. Adewuyi YG (2005b) Sonochemistry in environmental remediation. 2. Heterogeneous sonophotocatalytic oxidation processes for the treatment of pollutants in water. Environ Sci Technol 39:8557–8570. CrossRefGoogle Scholar
  3. Adewuyi YG, Carmichael GR (1982) A theoretical investigation of gaseous absorption by water droplets from SO2-HNO3-NH3-CO2-HCl mixtures. Atmos Environ 16:719–729. CrossRefGoogle Scholar
  4. Adewuyi YG, Khan NE (2012) Modeling the ultrasonic cavitation-enhanced removal of nitrogen oxide in a bubble column reactor. AIChE J 58:2397–2411. CrossRefGoogle Scholar
  5. Adewuyi YG, Khan MA (2015) Nitric oxide removal by combined persulfate and ferrous–EDTA reaction systems. Chem Eng J 281:575–587. CrossRefGoogle Scholar
  6. Adewuyi YG, Khan MA (2016) Nitric oxide removal from flue gas by combined persulfate and ferrous–EDTA solutions: effects of persulfate and EDTA concentrations, temperature, pH and SO2. Chem Eng J 304:793–807. CrossRefGoogle Scholar
  7. Adewuyi YG, Owusu SO (2003) Aqueous absorption and oxidation of nitric oxide with oxone for the treatment of tail gases: process feasibility, stoichiometry, reaction pathways, and absorption rate. Ind Eng Chem Res 42:4084–4100. CrossRefGoogle Scholar
  8. Adewuyi YG, Owusu SO (2006) Ultrasound-induced aqueous removal of nitric oxide from flue gases: effects of sulfur dioxide, chloride, and chemical oxidant. J Phys Chem A 110:11098–11107. CrossRefGoogle Scholar
  9. Adewuyi YG, Sakyi NY (2013a) Removal of nitric oxide by aqueous sodium persulfate simultaneously activated by temperature and Fe2+ in a lab-scale bubble reactor. Ind Eng Chem Res 52:14687–14697. CrossRefGoogle Scholar
  10. Adewuyi YG, Sakyi NY (2013b) Simultaneous absorption and oxidation of nitric oxide and sulfur dioxide by aqueous solutions of sodium persulfate activated by temperature. Ind Eng Chem Res 52:11702–11711. CrossRefGoogle Scholar
  11. Adewuyi YG, Cho S-Y, Tsay R-P, Carmichael GR (1984) Importance of formaldehyde in cloud chemistry. Atmos Environ 18:2413–2420. CrossRefGoogle Scholar
  12. Adewuyi Y, He X, Shaw H, Lolertpihop W (1999) Simultaneous absorption and oxidation of NO and SO2 by aqueous solutions of sodium chlorite. Chem Eng Commun 174:21–51. CrossRefGoogle Scholar
  13. Adewuyi YG, Khan MA, Sakyi NY (2014) Kinetics and modeling of the removal of nitric oxide by aqueous sodium persulfate simultaneously activated by temperature and Fe2+. Ind Eng Chem Res 53:828–839. CrossRefGoogle Scholar
  14. Adewuyi YG, Sakyi NY, Khan MA (2018) Simultaneous removal of NO and SO2 from flue gas by combined heat and Fe2+ activated aqueous persulfate solutions. Chemosphere 193:1216–1225. CrossRefGoogle Scholar
  15. Aher A, Papp J, Colburn A, Wan H, Hatakeyama E, Prakash P, Weaver B, Bhattacharyya D (2017) Naphthenic acids removal from high TDS produced water by persulfate mediated iron oxide functionalized catalytic membrane, and by nanofiltration. Chem Eng J 327:573–583. CrossRefGoogle Scholar
  16. Ajdari S, Normann F, Andersson K, Johnsson F (2015) Modeling the nitrogen and sulfur chemistry in pressurized flue gas systems. Ind Eng Chem Res 54:1216–1227. CrossRefGoogle Scholar
  17. Ajdari S, Normann F, Andersson K, Johnsson F (2016) Reduced mechanism for nitrogen and sulfur chemistry in pressurized flue gas systems. Ind Eng Chem Res 55:5514–5525. CrossRefGoogle Scholar
  18. Andreoni V, Miola A, Perujo A (2008) Cost effectiveness analysis of the emission abatement in the shipping sector emissions. European Commission Joint Research Centre Institute for Environment and Sustainability, Luxembourg. CrossRefGoogle Scholar
  19. Buxton GV, Greenstock CL, Helman WP, Ross AB (1988) Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (·OH/·O) in aqueous solution. J Phys Chem Ref Data 17:513–886. CrossRefGoogle Scholar
  20. Cai X, Sun W, Xu C, Cao L, Yang J (2016) Highly selective catalytic reduction of NO via SO2/H2O-tolerant spinel catalysts at low temperature. Environ Sci Pollut Res 23:18609–18620. CrossRefGoogle Scholar
  21. Chiu C-H, Hsi H-C, Lin H-P (2015) Multipollutant control of Hg/SO2/NO from coal-combustion flue gases using transition metal oxide-impregnated SCR catalysts. Catal Today 245:2–9. CrossRefGoogle Scholar
  22. Dai Y, Deng T, Wang J, Xu K (2004) Enhancement of oxygen gas–liquid mass transfer with colloidal gas aphron dispersions. Colloids Surf A Physicochem Eng Asp 240:165–171. CrossRefGoogle Scholar
  23. Ding F, Chen H, Zhang S, Zhao T, Liu N (2017) Effect of chelating agents on Reactive Green 19 decolorization through Fe0-activated persulfate oxidation process. J Environ Manag 200:325–334. CrossRefGoogle Scholar
  24. Drzewicz P, Perez-Estrada L, Alpatova A, Martin JW, Gamal El-Din M (2012) Impact of peroxydisulfate in the presence of zero valent iron on the oxidation of cyclohexanoic acid and naphthenic acids from oil sands process-affected water. Environ Sci Technol 46:8984–8991. CrossRefGoogle Scholar
  25. Fang G-D, Dionysiou DD, Wang Y, Al-Abed SR, Zhou D-M (2012) Sulfate radical-based degradation of polychlorinated biphenyls: effects of chloride ion and reaction kinetics. J Hazard Mater 227-228:394–401. CrossRefGoogle Scholar
  26. Fogler HS (2006) Elements of chemical reaction engineering, 4th edn. Prentice Hall, Upper Saddle RiverGoogle Scholar
  27. Geißler M, Van Eldik R (1994) Product identification and kinetic data for the reaction of S(IV) with N(III) oxoacids in aqueous solution in the absence and presence of metal ions. Polyhedron 13:2983–2991. CrossRefGoogle Scholar
  28. Gligorovski S, Strekowski R, Barbati S, Vione D (2015) Environmental implications of hydroxyl radicals (•OH). Chem Rev 115:13051–13092. CrossRefGoogle Scholar
  29. Han D, Wan J, Ma Y, Wang Y, Li Y, Li D, Guan Z (2015) New insights into the role of organic chelating agents in Fe(II) activated persulfate processes. Chem Eng J 269:425–433. CrossRefGoogle Scholar
  30. House DA (1962) Kinetics and mechanism of oxidations by peroxydisulfate. Chem Rev 62:185–203. CrossRefGoogle Scholar
  31. Huang K-C, Zhao Z, Hoag GE, Dahmani A, Block PA (2005) Degradation of volatile organic compounds with thermally activated persulfate oxidation. Chemosphere 61:551–560. CrossRefGoogle Scholar
  32. Hutson ND, Krzyzynska R, Srivastava RK (2008) Simultaneous removal of SO2, NOX, and Hg from coal flue gas using a NaClO2-enhanced wet scrubber. Ind Eng Chem Res 47:5825–5831. CrossRefGoogle Scholar
  33. Ibrahim S (2016) Process evaluation of a SOx and NOx exhaust gas cleaning concept for marine application. Chalmers University of Technology, GothenburgGoogle Scholar
  34. Janik I, Bartels DM, Jonah CD (2007) Hydroxyl radical self-recombination reaction and absorption spectrum in water up to 350 °C. J Phys Chem A 111:1835–1843. CrossRefGoogle Scholar
  35. Jethani KR, Suchak NJ, Joshi JB (1990) Selection of reactive solvent for pollution abatement of NOx. Gas Sep Purif 4:8–28. CrossRefGoogle Scholar
  36. Khan NE, Adewuyi YG (2010) Absorption and oxidation of nitric oxide (NO) by aqueous solutions of sodium persulfate in a bubble column reactor. Ind Eng Chem Res 49:8749–8760. CrossRefGoogle Scholar
  37. Khan NE, Adewuyi YG (2011) A new method of analysis of peroxydisulfate using ion chromatography and its application to the simultaneous determination of peroxydisulfate and other common inorganic ions in a peroxydisulfate matrix. J Chromatogr A 1218:392–397. CrossRefGoogle Scholar
  38. Khan MA, Adewuyi YG (2017) High pressure reactive distillation simulation and optimization for the esterification of pyrolysis bio-oil. Process Eng J 1:73–85Google Scholar
  39. Kolthoff IM, Miller IK (1951) The chemistry of persulfate. I. The kinetics and mechanism of the decomposition of the persulfate ion in aqueous medium. J Am Chem Soc 73:3055–3059. CrossRefGoogle Scholar
  40. Korell J, Paur H-R, Seifert H, Andersson S (2009) Simultaneous removal of mercury, PCDD/F, and fine particles from flue gas. Environ Sci Technol 43:8308–8314. CrossRefGoogle Scholar
  41. Krzyzynska R, Hutson ND (2012) Effect of solution pH on SO2, NOx, and Hg removal from simulated coal combustion flue gas in an oxidant-enhanced wet scrubber. J Air Waste Manage Assoc 62:212–220. CrossRefGoogle Scholar
  42. Liang C, Guo Y-Y (2010) Mass transfer and chemical oxidation of naphthalene particles with zerovalent iron activated persulfate. Environ Sci Technol 44:8203–8208. CrossRefGoogle Scholar
  43. Liang C, Wang Z-S, Mohanty N (2006) Influences of carbonate and chloride ions on persulfate oxidation of trichloroethylene at 20 °C. Sci Total Environ 370:271–277. CrossRefGoogle Scholar
  44. Liang C, Huang C-F, Chen Y-J (2008) Potential for activated persulfate degradation of BTEX contamination. Water Res 42:4091–4100. CrossRefGoogle Scholar
  45. Liang C, Chen Y-J, Chang K-J (2009) Evaluation of persulfate oxidative wet scrubber for removing BTEX gases. J Hazard Mater 164:571–579. CrossRefGoogle Scholar
  46. Littlejohn D, Chang SG (1984) Identification of species in a wet flue gas desulfurization and denitrification system by laser Raman spectroscopy. Environ Sci Technol 18:305–310. CrossRefGoogle Scholar
  47. Littlejohn D, Chang SG (1986) Determination of nitrogen-sulfur compounds by ion chromatography. Anal Chem 58:158–160. CrossRefGoogle Scholar
  48. Littlejohn D, Chang SG (1994) Oxidative decomposition of nitrogen-sulfur oxides. Ind Eng Chem Res 33:515–518. CrossRefGoogle Scholar
  49. Littlejohn D, Hu KY, Chang SG (1986) Kinetics of the reaction of nitric oxide with sulfite and bisulfite ions in aqueous solution. Inorg Chem 25:3131–3135. CrossRefGoogle Scholar
  50. Liu Y, Adewuyi YG (2016) A review on removal of elemental mercury from flue gas using advanced oxidation process: chemistry and process. Chem Eng Res Des 112:199–250. CrossRefGoogle Scholar
  51. Liu Y, Zhang J (2017) Removal of NO from flue gas using UV/S2O8 2− process in a novel photochemical impinging stream reactor. AIChE J 63:2968–2980. CrossRefGoogle Scholar
  52. Matzek LW, Carter KE (2016) Activated persulfate for organic chemical degradation: a review. Chemosphere 151:178–188. CrossRefGoogle Scholar
  53. Neta P, Huie RE (1986) Rate constants for reactions of nitrogen oxide (NO3) radicals in aqueous solutions. J Phys Chem 90:4644–4648. CrossRefGoogle Scholar
  54. Normann F, Jansson E, Petersson T, Andersson K (2013) Nitrogen and sulphur chemistry in pressurised flue gas systems: a comparison of modelling and experiments. Int J Greenhouse Gas Control 12:26–34. CrossRefGoogle Scholar
  55. Oblath SB, Markowitz SS, Novakov T, Chang SG (1981) Kinetics of the formation of hydroxylamine disulfonate by reaction of nitrite with sulfites. J Phys Chem 85:1017–1021. CrossRefGoogle Scholar
  56. Oblath SB, Markowitz SS, Novakov T, Chang SG (1982) Kinetics of the initial reaction of nitrite ion in bisulfite solutions. J Phys Chem 86:4853–4857. CrossRefGoogle Scholar
  57. Owusu SO, Adewuyi YG (2006) Sonochemical removal of nitric oxide from flue gases. Ind Eng Chem Res 45:4475–4485. CrossRefGoogle Scholar
  58. Palash SM, Kalam MA, Masjuki HH, Masum BM, Rizwanul Fattah IM, Mofijur M (2013) Impacts of biodiesel combustion on NOx emissions and their reduction approaches. Renew Sust Energ Rev 23:473–490. CrossRefGoogle Scholar
  59. Qian Y, Guo X, Zhang Y, Peng Y, Sun P, Huang C-H, Niu J, Zhou X, Crittenden JC (2016) Perfluorooctanoic acid degradation using uv–persulfate process: modeling of the degradation and chlorate formation. Environ Sci Technol 50:772–781. CrossRefGoogle Scholar
  60. Rezaei F, Rownaghi AA, Monjezi S, Lively RP, Jones CW (2015) SOx/NOx removal from flue gas streams by solid adsorbents: a review of current challenges and future directions. Energy Fuel 29:5467–5486. CrossRefGoogle Scholar
  61. Seinfeld JH, Pandis SN (2006) Atmospheric chemistry and physics: from air pollution to climate change. Second edn. Wiley, New JerseyGoogle Scholar
  62. Skalska K, Miller JS, Ledakowicz S (2010) Trends in NOx abatement: a review. Sci Total Environ 408:3976–3989. CrossRefGoogle Scholar
  63. Susianto PM, Zoulalian A (2001) Influence of the pH on the interactions between nitrite and sulfite ions. Kinetic of the reaction at pH 4 and 5. Ind Eng Chem Res 40:6068–6072. CrossRefGoogle Scholar
  64. Susianto PM, Pétrissans A, Zoulalian A (2005) Experimental study and modelling of mass transfer during simultaneous absorption of SO2 and NO2 with chemical reaction. Chem Eng Process Process Intensif 44:1075–1081. CrossRefGoogle Scholar
  65. Tsitonaki A, Petri B, Crimi M, Mosbaek H, Siegrist RL, Bjerg PL (2010) In situ chemical oxidation of contaminated soil and groundwater using persulfate: a review. Crit Rev Environ Sci Technol 40:55–91. CrossRefGoogle Scholar
  66. Turšič J, Grgić I, Bizjak M (2001) Influence of NO2 and dissolved iron on the S(IV) oxidation in synthetic aqueous solution. Atmos Environ 35:97–104. CrossRefGoogle Scholar
  67. Wu B, Xiong Y, Ru J, Feng H (2016) Removal of NO from flue gas using heat-activated ammonium persulfate aqueous solution in a bubbling reactor. RSC Adv 6:33919–33930. CrossRefGoogle Scholar
  68. Xiao R, Luo Z, Wei Z, Luo S, Spinney R, Yang W, Dionysiou DD (2018) Activation of peroxymonosulfate/persulfate by nanomaterials for sulfate radical-based advanced oxidation technologies. Curr Opin Chem Eng 19:51–58. CrossRefGoogle Scholar
  69. Xu W, Adewuyi YG, Liu Y, Wang Y (2018) Removal of elemental mercury from flue gas using CuOx and CeO2 modified rice straw chars enhanced by ultrasound. Fuel Process Technol 170:21–31. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Chemical, Biological, and Bioengineering DepartmentNorth Carolina Agricultural and Technical State UniversityGreensboroUSA

Personalised recommendations