Transactions of Tianjin University

, Volume 25, Issue 5, pp 527–539 | Cite as

Performance Evaluation of Modified Black Clay as a Heterogeneous Fenton Catalyst on Decolorization of Azure B Dye: Kinetic Study and Cost Evaluation

  • Vijyendra Kumar
  • Prabir GhoshEmail author
Research Article


Black clay (BC) was used as a catalyst for the decolorization of Azure B dye by Fenton process. BC was modified by acid, alkali, distilled water, and calcination to check their changes in characterization and efficiency on decolorization of Azure B. Among three modified catalysts, maximum decolorization was obtained by acid-modified BC (AMBC) catalyst due to the highest removal of impurities, comparatively. The characterization of AMBC was done by Fourier-transform infrared spectroscopy and X-ray diffraction spectroscopy which show the presence of metal ion. The BET surface area, pore volume, pore size, and density of AMBC were calculated to be 79.402 m2/g, 0.0608 m3/g, 0.00306 nm, and 16 g/cm3, respectively. The highest decolorization of 97.59% was achieved only in 10 min using AMBC at optimized calcination of 100 °C and 3 h of aging. AMBC was considered as the main catalyst for optimizing the different process parameters. Optimized conditions were obtained: pH 2, 0.2 mL of H2O2, catalyst dose 0.3 g, room temperature (30 °C), and stirring speed 400 r/min. The catalyst has showed excellent stability and reusability. It could remove more than 85% of color even after four cycles of run and less than negligible leaching of iron. AMBC has good recycling ability among other modified catalysts. To check the selectivity of catalyst, different dyes such as Congo red and mixed dye (mixture of Azure B and Congo red) decolorization were studied. In the present work, kinetic study was also carried out and a three-stage decolorization process was found.


Black clay Azure B Heterogeneous Fenton process Wastewater treatment 



This work is supported by Department of Science & Technology—Science & Engineering Research Board (No. YSS/2014/000996, India).


  1. 1.
    Azbar N, Yonar T, Kestioglu K (2004) Comparison of various advanced oxidation processes and chemical treatment methods for COD and color removal from a polyester and acetate fiber dyeing effluent. Chemosphere 55(1):35–43Google Scholar
  2. 2.
    Barros WRP, Steter JR, Lanza MRV et al (2016) Catalytic activity of Fe3−xCuxO4 (0 ≤ x ≤ 0.25) nanoparticles for the degradation of Amaranth food dye by heterogeneous electro-Fenton process. Appl Catal B Environ 180:434–441Google Scholar
  3. 3.
    Salazar R, Ureta-Zañartu MS, González-Vargas C et al (2018) Electrochemical degradation of industrial textile dye disperse yellow 3: role of electrocatalytic material and experimental conditions on the catalytic production of oxidants and oxidation pathway. Chemosphere 198:21–29Google Scholar
  4. 4.
    Wang J, Zhang T, Mei Y et al (2018) Treatment of reverse-osmosis concentrate of printing and dyeing wastewater by electro-oxidation process with controlled oxidation–reduction potential (ORP). Chemosphere 201:621–626Google Scholar
  5. 5.
    Sadek AM, Hazzaa RA, Abd-El-Magied MH (2016) Study on the treatment of effluents from paint industry by modified electro-Fenton process. Am J Chem Eng 4(1):1–8Google Scholar
  6. 6.
    Vinosha PA, Das SJ (2018) Investigation on the role of pH for the structural, optical and magnetic properties of cobalt ferrite nanoparticles and its effect on the photo-Fenton activity. Mater Today Proc 5(2):8662–8671Google Scholar
  7. 7.
    Xu HY, Wang Y, Shi TN et al (2018) Heterogeneous Fenton-like discoloration of methyl orange using Fe3O4/MWCNTs as catalyst: Kinetics and Fenton-like mechanism. Front Mater Sci 12(1):34–44Google Scholar
  8. 8.
    Phan TTN, Nikoloski AN, Bahri PA et al (2018) Optimizing photocatalytic performance of hydrothermally synthesized LaFeO3 by tuning material properties and operating conditions. J Environ Chem Eng 6(1):1209–1218Google Scholar
  9. 9.
    Subramanian G, Madras G (2018) Potentiation of hydrogen peroxide mediated water decontamination using thioglycolic acid. J Environ Chem Eng 6(2):2200–2205Google Scholar
  10. 10.
    Ayodhya D, Veerabhadram G (2018) A review on recent advances in photodegradation of dyes using doped and heterojunction based semiconductor metal sulfide nanostructures for environmental protection. Mater Today Energy 9:83–113Google Scholar
  11. 11.
    Ioannidi A, Frontistis Z, Mantzavinos D (2018) Destruction of propyl paraben by persulfate activated with UV-A light emitting diodes. J Environ Chem Eng 6(2):2992–2997Google Scholar
  12. 12.
    Pothanamkandathil V, Singh RK, Philip L et al (2018) Effect of recycling overhead gases on pollutants degradation efficiency in gas-phase pulsed corona discharge treatment. J Environ Chem Eng 6(1):923–929Google Scholar
  13. 13.
    Katheresan V, Kansedo J, Lau SY (2018) Efficiency of various recent wastewater dye removal methods: a review. J Environ Chem Eng 6(4):4676–4697Google Scholar
  14. 14.
    Zamora-Garcia IR, Alatorre-Ordaz A, Ibanez JG et al (2018) Efficient degradation of selected polluting dyes using the tetrahydroxoargentate ion, Ag(OH)4, in alkaline media. Chemosphere 191:400–407Google Scholar
  15. 15.
    Shakoor S, Nasar A (2018) Adsorptive decontamination of synthetic wastewater containing crystal violet dye by employing Terminalia arjuna sawdust waste. Groundw Sustain Dev 7:30–38Google Scholar
  16. 16.
    Zhang H, Xue G, Chen H (2017) Magnetic biochar catalyst derived from biological sludge and ferric sludge using hydrothermal carbonization: Preparation, characterization and its circulation in Fenton process for dyeing wastewater treatment. Chemosphere 191:64–71Google Scholar
  17. 17.
    Aveiro LR, Da Silva AGM, Candido EG (2018) Application and stability of cathodes with manganese dioxide nanoflowers supported on Vulcan by Fenton systems for the degradation of RB5 azo dye. Chemosphere 208:131–138Google Scholar
  18. 18.
    Chen Y, Feng L, Li H (2018) Biodegradation and detoxification of Direct Black G textile dye by a newly isolated thermophilic microflora. Bioresour Technol 250:650–657Google Scholar
  19. 19.
    Palas B, Ersöz G, Atalay S (2018) Catalytic wet air oxidation of Reactive Black 5 in the presence of LaNiO3 perovskite catalyst as a green process for azo dye removal. Chemosphere 209:823–830Google Scholar
  20. 20.
    Jinisha R, Gandhimathi R, Ramesh ST et al (2018) Removal of rhodamine B dye from aqueous solution by electro-Fenton process using iron-doped mesoporous silica as a heterogeneous catalyst. Chemosphere 200:446–454Google Scholar
  21. 21.
    Fan J, Zhao Z, Ding Z et al (2018) Synthesis of different crystallographic FeOOH catalysts for peroxymonosulfate activation towards organic matter degradation. RSC Adv 8(13):7269–7279Google Scholar
  22. 22.
    Nidheesh PV, Zhou M, Oturan MA (2018) An overview on the removal of synthetic dyes from water by electrochemical advanced oxidation processes. Chemosphere 197:210–227Google Scholar
  23. 23.
    Darabdhara G, Das MR (2018) Bimetallic Au–Pd nanoparticles on 2D supported graphitic carbon nitride and reduced graphene oxide sheets: a comparative photocatalytic degradation study of organic pollutants in water. Chemosphere 197:817–829Google Scholar
  24. 24.
    Yang M, Wu B, Li Q et al (2018) Feasibility of the UV/AA process as a pretreatment approach for bioremediation of dye-laden wastewater. Chemosphere 194:488–494Google Scholar
  25. 25.
    Phan TTN, Nikoloski AN, Bahri PA (2018) Heterogeneous photo-Fenton degradation of organics using highly efficient Cu-doped LaFeO3 under visible light. J Ind Eng Chem 61:53–64Google Scholar
  26. 26.
    Hamaloğlu KÖ, Sağ E, Bilir A (2018) Monodisperse-porous titania microspheres and their gold decorated forms as new photocatalysts for dye degradation in batch fashion. Mater Chem Phys 207:359–366Google Scholar
  27. 27.
    Sudha M, Bakiyaraj G, Saranya A et al (2018) Prospective assessment of the Enterobacter aerogenes PP002 in decolorization and degradation of azo dyes DB 71 and DG 28. J Environ Chem Eng 6:95–109Google Scholar
  28. 28.
    Sheng Y, Sun Y, Xu J et al (2018) Fenton-like degradation of rhodamine B over highly durable Cu-embedded alumina: kinetics and mechanism. AIChE J 64:538–549Google Scholar
  29. 29.
    Qin Q, Liu Y, Li X (2018) Enhanced heterogeneous Fenton-like degradation of methylene blue by reduced CuFe2O4. RSC Adv 8:1071–1077Google Scholar
  30. 30.
    Xiao C, Li J, Zhang G (2018) Synthesis of stable burger-like α-Fe2O3 catalysts: formation mechanism and excellent photo-Fenton catalytic performance. J Clean Prod 180:550–559Google Scholar
  31. 31.
    Tantak NP, Chaudhari S (2006) Degradation of azo dyes by sequential Fenton’s oxidation and aerobic biological treatment. J Hazard Mater 136(3):698–705Google Scholar
  32. 32.
    Vasilyeva MS, Rudnev VS, Zvereva AA et al (2018) FeOx, SiO2, TiO2/Ti composites prepared using plasma electrolytic oxidation as photo-Fenton-like catalysts for phenol degradation. J Photochem Photobiol A Chem 356:38–45Google Scholar
  33. 33.
    Ertugay N, Acar FN (2017) Removal of COD and color from Direct Blue 71 azo dye wastewater by Fenton’ s oxidation: kinetic study. Arab J Chem 10(S1):S1158–S1163Google Scholar
  34. 34.
    Yuan F, Liu B, Zhang Y (2016) Segregation and migration of the oxygen vacancies in the Σ3 (111) tilt grain boundaries of ceria. J Phys Chem C 120(12):6625–6632Google Scholar
  35. 35.
    Tang J, Wang J (2017) Fe-based metal organic framework/graphene oxide composite as an efficient catalyst for Fenton-like degradation of methyl orange. RSC Adv 7:50829–50837Google Scholar
  36. 36.
    Shi X, Tian A, You J (2018) Degradation of organic dyes by a new heterogeneous Fenton reagent—Fe2GeS4 nanoparticle. J Hazard Mater 353:182–189Google Scholar
  37. 37.
    Su C, Li W, Liu X et al (2016) Fe-Mn-sepiolite as an effective heterogeneous Fenton-like catalyst for the decolorization of reactive brilliant blue. Front Environ Sci Eng 10(1):37–45MathSciNetGoogle Scholar
  38. 38.
    Farshchi ME, Aghdasinia H, Khataee A (2018) Modeling of heterogeneous Fenton process for dye degradation in a fluidized-bed reactor: kinetics and mass transfer. J Clean Prod 182:644–653Google Scholar
  39. 39.
    Nezamzadeh-Ejhieh A, Hushmandrad S (2010) Solar photodecolorization of methylene blue by CuO/X zeolite as a heterogeneous catalyst. Appl Catal A Gen 388(1–2):149–159Google Scholar
  40. 40.
    Wang S, Peng Y (2010) Natural zeolites as effective adsorbents in water and wastewater treatment. Chem Eng J 156(1):11–24Google Scholar
  41. 41.
    Tan C, Gao N, Fu D et al (2017) Efficient degradation of paracetamol with nanoscaled magnetic CoFe2O4 and MnFe2O4 as a heterogeneous catalyst of peroxymonosulfate. Sep Purif Technol 175:47–57Google Scholar
  42. 42.
    Xia M, Long M, Yang Y et al (2011) A highly active bimetallic oxides catalyst supported on Al-containing MCM-41 for Fenton oxidation of phenol solution. Appl Catal B Environ 110:118–125Google Scholar
  43. 43.
    Hassan H, Hameed BH (2011) Fe-clay as effective heterogeneous Fenton catalyst for the decolorization of reactive blue 4. Chem Eng J 171(3):912–918Google Scholar
  44. 44.
    Wang S, Lu GQ (1998) Effects of acidic treatments on the pore and surface properties of Ni catalyst supported on activated carbon. Carbon 36(3):283–292Google Scholar
  45. 45.
    Azmi NHM, Vadivelu VM, Hameed BH (2014) Iron-clay as a reusable heterogeneous Fenton-like catalyst for decolorization of acid Green 25. Desalin Water Treat 52(28–30):5583–5593Google Scholar
  46. 46.
    Sandhwar VK, Prasad B (2017) Comparative study of electrocoagulation and electrochemical Fenton treatment of aqueous solution of benzoic acid (BA): optimization of process and sludge analysis. Korean J Chem Eng 34(4):1062–1072Google Scholar
  47. 47.
    Xavier S, Gandhimathi R, Nidheesh PV et al (2015) Comparison of homogeneous and heterogeneous Fenton processes for the removal of reactive dye magenta MB from aqueous solution. Desalin Water Treat 53(1):109–118Google Scholar
  48. 48.
    Singh L, Rekha P, Chand S (2016) Cu-impregnated zeolite Y as highly active and stable heterogeneous Fenton-like catalyst for degradation of Congo red dye. Sep Purif Technol 170:321–336Google Scholar
  49. 49.
    Yu L, Chen J, Liang Z et al (2016) Degradation of phenol using Fe3O4–GO nanocomposite as a heterogeneous photo-Fenton catalyst. Sep Purif Technol 171:80–87Google Scholar
  50. 50.
    Zhang J, Zhang X, Wang Y (2016) Degradation of phenol by a heterogeneous photo-Fenton process using Fe/Cu/Al catalysts. RSC Adv 6(16):13168–13176Google Scholar
  51. 51.
    Zhang G, Qin L, Wu Y et al (2015) Iron oxide nanoparticles immobilized to mesoporous NH2–SiO2 spheres by sulfonic acid functionalization as highly efficient catalysts. Nanoscale 7(3):1102–1109Google Scholar
  52. 52.
    Wang Y, Yu Y, Deng C et al (2015) Synthesis of mesoporous MCM-41 supported reduced graphene oxide–Fe catalyst for heterogeneous Fenton degradation of phenol. RSC Adv 5(5):103989–103998Google Scholar
  53. 53.
    Riaz N, Ela N, Khan MS (2011) Effect of photocatalysts preparation methods and light source on Orange II photocatalytic degradation. Sci Technol 6:112–117Google Scholar
  54. 54.
    Peng K, Fu L, Yang H et al (2016) Perovskite LaFeO3/montmorillonite nanocomposites: synthesis, interface characteristics and enhanced photocatalytic activity. Sci Rep 6:19723Google Scholar
  55. 55.
    Olvera-Vargas H, Oturan N, Aravindakumar CT et al (2014) Electro-oxidation of the dye azure B: kinetics, mechanism, and by-products. Environ Sci Pollut Res 21(14):8379–8386Google Scholar
  56. 56.
    Lyu L, Zhang L, Hu C (2015) Enhanced Fenton-like degradation of pharmaceuticals over framework copper species in copper-doped mesoporous silica microspheres. Chem Eng J 274:298–306Google Scholar
  57. 57.
    Rajoriya S, Bargole S, George S (2019) Synthesis and characterization of samarium and nitrogen doped TiO2 photocatalysts for photo-degradation of 4-acetamidophenol in combination with hydrodynamic and acoustic cavitation. Sep Purif Technol 209:254–269Google Scholar
  58. 58.
    Bieseki L, Bertella F, Treichel H et al (2013) Acid treatments of montmorillonite-rich clay for Fe removal using a factorial design method. Mater Res 16(5):1122–1127Google Scholar
  59. 59.
    Wang N, Chen J, Zhao Q et al (2017) Study on preparation conditions of coal fly ash catalyst and catalytic mechanism in a heterogeneous Fenton-like process. RSC Adv 7:52524–52532Google Scholar
  60. 60.
    Xue F, Yang ST, Jin X et al (2016) One-pot modification of Fe3O4 to prepare Fe3O4/SiO2/C nanoparticles and their catalytic activity in Fenton-like process for dye decolouration. Micro Nano Lett 11(11):675–679Google Scholar
  61. 61.
    Ren X, Guo H, Feng J et al (2018) Synergic mechanism of adsorption and metal-free catalysis for phenol degradation by N-doped graphene aerogel. Chemosphere 191:389–399Google Scholar
  62. 62.
    Logita HH, Tadesse A, Kebede T (2015) Synthesis, characterization and photocatalytic activity of MnO2/Al2O3/Fe2O3 nanocomposite for degradation of malachite green. Afr J Pure Appl Chem 9(11):211–222Google Scholar
  63. 63.
    Gogoi A, Navgire M, Sarma KC (2017) Fe3O4–CeO2 metal oxide nanocomposite as a Fenton-like heterogeneous catalyst for degradation of catechol. Chem Eng J 311:153–162Google Scholar
  64. 64.
    Huang Z, Wu P, Li H (2014) Synthesis and catalytic properties of La or Ce doped hydroxy-FeAl intercalated montmorillonite used as heterogeneous photo Fenton catalysts under sunlight irradiation. RSC Adv 4:6500–6507Google Scholar
  65. 65.
    Daud NK, Ahmad MA, Hameed BH (2010) Decolorization of Acid Red 1 dye solution by Fenton-like process using Fe–Montmorillonite K10 catalyst. Chem Eng J 165:111–116Google Scholar
  66. 66.
    Gao Y, Gan H, Zhang G (2013) Visible light assisted Fenton-like degradation of rhodamine B and 4-nitrophenol solutions with a stable poly-hydroxyl-iron/sepiolite catalyst. Chem Eng J 217:221–230Google Scholar
  67. 67.
    Dogra B, Amna S, Park YI (2017) Biochemical properties of water soluble polysaccharides from photosynthetic marine microalgae Tetraselmis species. Macromol Res 25(2):172–179Google Scholar
  68. 68.
    Fida H, Zhang G, Guo S (2017) Heterogeneous Fenton degradation of organic dyes in batch and fixed bed using La–Fe montmorillonite as catalyst. J Colloid Interface Sci 490:859–868Google Scholar
  69. 69.
    Wang Q, Liang S, Zhang G (2019) Facile and rapid microwave-assisted preparation of Cu/Fe–AO–PAN fiber for PNP degradation in a photo-Fenton system under visible light irradiation. Sep Purif Technol 209:270–278Google Scholar
  70. 70.
    Guo Y, Mi X, Li G (2017) Sonocatalytic degradation of antibiotics tetracycline by Mn-modified diatomite. J Chem 2017:1–8Google Scholar
  71. 71.
    Oh SW, Bang HJ, Bae YC (2007) Effect of calcination temperature on morphology, crystallinity and electrochemical properties of nano-crystalline metal oxides (Co3O4, CuO, and NiO) prepared via ultrasonic spray pyrolysis. J Power Sources 173(1):502–509Google Scholar
  72. 72.
    Chen YF, Lee CY, Yeng MY (2003) The effect of calcination temperature on the crystallinity of TiO2 nanopowders. J Cryst Growth 247(3–4):363–370Google Scholar
  73. 73.
    Rokhina EV (2009) Heterogeneous ruthenium-based catalytic systems in wet peroxide oxidation of organic compounds. Dissertation, University of KuopioGoogle Scholar
  74. 74.
    Sun Z, Xiao C, Hussain F (2018) Synthesis of stable and easily recycled ferric oxides assisted by Rhodamine B for efficient degradation of organic pollutants in heterogeneous photo-Fenton system. J Clean Prod 196:1501–1507Google Scholar
  75. 75.
    Ersöz G (2014) Fenton-like oxidation of Reactive Black 5 using rice husk ash based catalyst. Appl Catal B Environ 147:353–358Google Scholar
  76. 76.
    Ma C, He Z, Jia S (2018) Treatment of stabilized land fill leachate by Fenton-like process using Fe3O4 particles decorated Zr-pillared bentonite. Ecotoxicol Environ Saf 161:489–496Google Scholar
  77. 77.
    Saber A, Mortazavian S, James DE (2017) Optimization of collaborative photo-Fenton oxidation and coagulation for the treatment of petroleum refinery wastewater with scrap iron. Water Air Soil Pollut 228:312Google Scholar
  78. 78.
    Szpyrkowicz L, Juzzolino C, Kaul SN (2001) A comparative study on oxidation of disperse dyes by electrochemical process, ozone, hypochlorite and Fenton reagent. Water Res 35(9):2129–2136Google Scholar

Copyright information

© Tianjin University and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of Chemical EngineeringNational Institute of TechnologyRaipurIndia

Personalised recommendations