화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Korean Journal of Chemical Engineering, Vol.39, No.2, 377-388, February, 2022
DOI10.1007/s11814-021-0917-y  Export Citation
Synthesis and characterization of cross linked N-methylene phosphonic chitosan resin chelated with Al(III) for use as adsorbent for fluoride removal from aqueous solutions
Junyu Fan, Longhua Yu1, Xin Zhou, and Jie Liu†
  • Department of Military Facilities, Army Logistics Academy, Chongqing, 401311, China
  • 1School of Environmental Science and Engineering, Hunan University, Changsha, 410082, China
E-mail:
Excessive fluoride in groundwater is becoming a worldwide environmental problem increasing the risk of fluorosis. In this study, an eco-friendly new defluorination resin (Al-CPCM) was synthesized by a modified emulsion method. The skeleton of the resin is cross-linked N-methylene phosphonic chitosan and the incorporated Al(III) is the binding site of fluoride. The batch experiments conducted using pure synthetic sodium fluoride solutions showed that Al-CPCM exhibited a fast fluoride removal within 30min, maintained stability from pH 3-10. Effect of presence of other anions was studied by adding one extra anion at a time and it was observed that presence of phosphate and carbonate ions significantly degraded the adsorption capacity of the resin. The maximum adsorption capacity was 15.067mg/g at 30 °C and the adsorption behavior was well-fitted with the pseudo-second-order kinetic model and Hill isotherm model. The results of in-situ flow ATR-FTIR and thermodynamics studies show that the fluoride adsorption dominantly implemented by ion exchange with surface hydroxyl of chelated Al3+ in the resin. In addition, the adsorption capacity only decreased by 5.5% after six successive sorption/desorption cycles, indicating a better regeneration efficiency among other defluorinated resins. Finally, a column experiment was performed using ground water and, in this case, it is observed that the adsorption capacity of the resin was much lower and the decrease in adsorption capacity after elution/regeneration is was larger (both mainly due to the presence of alternate anions/cations in the feed solution). More elaborate column experiments with real-life groundwater samples are required to assess the suitability of the proposed resin for use as a commercial adsorbent.
Keywords:Chitosan;Amino-methyl Phosphonic Resin;Aluminum Complex;Emulsion Polymerization;Defluorination
  1. Srivastava S, Flora S, Curr. Environ. Health Rep., 7, 140 (2020)
  2. Huang D, Yang J, Wei X, Qin J, Ou S, Zhang Z, Zou Y, Environ. Pollut., 222, 118 (2017)
  3. He X, L PI, Ji Y, Wang Y, Su Z, Elumalai V, Expo. Health, 12, 355 (2020)
  4. Sharma P, Baruah J, Deka D, Kaushik P, Harnessing wetlands for sustainable livelihood, Notion Press, Chennai (2019).
  5. Chen J, Wu H, Qian H, Gao Y, Expo. Health, 9, 183 (2017)
  6. Xu C, Wu X, Qian C, Zhu G, Appl. Geochem., 98, 404 (2018)
  7. Meenakshi S, Viswanathan N, J. Colloid Interface Sci., 308(2), 438 (2007)
  8. Phillips DH, Gupta BS, Mukhopadhyay S, Gupta AKS, J. Environ. Manage., 215, 132 (2018)
  9. Millar GJ, Couperthwaite SJ, Wellner DB, Macfarlane DC, Dalzell SA, J. Water. Process Eng., 20, 113 (2017)
  10. Li R, Tian X, Ashraf I, Chen B, J. Chromatogr. A, 1613, 460697 (2020)
  11. Shin E, Dreisinger D, Burns A, Desalination, 505, 114985 (2021)
  12. Ding J, Pu L, Wang Y, Wu B, Yu A, Zhang X, Pan B, Zhang Q, Gao G, Environ. Sci. Technol., 52, 12602 (2018)
  13. Jana S, Ray J, Mondal B, Pradhan S, Tripathy T, Colloids Surf. A: Physicochem. Eng. Asp., 553, 472 (2018)
  14. Zhang M, Yang P, Lan G, Liu Y, Cai Q, Xi J, Environ. Sci. Pollut. Res., 27, 38617 (2020)
  15. Liu R, Du J, Zhang Z, Li H, Lu J, Cheng Y, Lv Y, Wang H, Carbohydr. Polym., 205, 83 (2019)
  16. Kwon BG, Chugn SY, Park SS, Saido K, Environ. Pollut., 234, 167 (2018)
  17. Pincus LN, Petrovic PV, Gonzalez IS, Stavitski E, Fishman ZS, Rudel HE, Anastas PT, Zimmerman JB, Chem. Eng. J., 412, 128582 (2021)
  18. Pincus LN, Melnikov F, Yamani JS, Zimmerman JB, J. Hazard. Mater., 358, 145 (2018)
  19. Liu Q, Zhang L, Yang B, Huang R, Int. J. Biol. Macromol., 77, 15 (2015)
  20. Jinfang L, Qian L, Huang R, Guodong W, J. Rare. Earth., 34, 1053 (2016)
  21. Karthik R, Meenakshi S, Int. J. Biol. Macromol., 67, 210 (2014)
  22. Antony R, Arun T, Manickam STD, Int. J. Biol. Macromol., 129, 615 (2019)
  23. Singh T, Mccarron PA, Woolfson AD, Donnelly RF, Eur. Polym. J., 45, 1239 (2009)
  24. Juang RS, Chen ML, Ind. Eng. Chem. Res., 36(3), 813 (1997)
  25. Hill AV, J. Physiol., 40, 190 (1910)
  26. Palimaka P, Pietrzyk S, Arch. Metall. Mater., 59, 71 (2014)
  27. Guo Z, Xing R, Liu S, Zhong Z, Ji X, Wang L, Li P, Carbohydr. Polym., 342, 1329 (2007)
  28. Ramos V, Rodrıguez N, Dıaz M, Rodrıguez M, Heras A, Agullo E, Carbohydr. Polym., 52, 39 (2003)
  29. Chen CY, YAng CY, Chen AH, J. Environ. Manage., 92, 796 (2011)
  30. Bunton C, Mhala M, Oldham K, Vernon C, J. Chem. Soc. (Resumed), 3293 (1960).
  31. Atangana E, J. Polym. Environ., 27, 2281 (2019)
  32. Udoetok IA, Dimmick RM, Wilson LD, Headley JV, Carbohydr. Polym., 136, 329 (2016)
  33. Ramos V, Rodriguez N, Henning I, et al., Carbohydr. Polym., 64, 328 (2006)
  34. Sing KS, Adv. Colloid Interface Sci., 76, 3 (1998)
  35. Razmi FA, Ngadi N, Wong S, Inuwa IM, Opotu LA, J. Clean Prod., 231, 98 (2019)
  36. Liu BJ, Wang DF, Yu GL, Meng XH, Chem. Eng. J., 228, 224 (2013)
  37. Lee Y, Lee W, J. Hazard. Mater., 178(1-3), 187 (2010)
  38. Mohamed RR, Elella MHA, Sabaa MW, Int. J. Biol. Macromol., 80, 149 (2015)
  39. Dadhich P, Das B, Dhara S, Carbohydr. Polym., 133, 345 (2015)
  40. Zuniga A, Neran RF, Albertengo L, Rodriguez MS, Carbohydr. Polym., 202, 1 (2018)
  41. Khaleel A, Dellinger B, Environ. Sci. Technol., 36, 1620 (2002)
  42. Biber MV. Stumm W, Environ. Sci. Technol., 28, 763 (1994)
  43. Zong Z, Kimura Y, Takahashi M, Yamane H, Polymer, 41(3), 899 (2000)
  44. Zhirong L, Uddin MA, Zhanxue S, Spectroc. Acta Pt. A-Molec. Biomolec. Spectr., 79, 1013 (2011)
  45. Preethi J, Karthikeyan P, Vigneshwaran S, Meenakshi S, Chemosphere, 262, 128317 (2021)
  46. Varrot A, Tarling CA, Macdonald JM, Stick RV, Zechel DL, Withers SG, Davies GJ, J. Am. Chem. Soc., 125(25), 7496 (2003)
  47. Ma P, Ding W, Yuan J, Yi L, Zhang H, Environ. Res., 184, 109309 (2020)
  48. Ho YS, J. Hazard. Mater., 136(3), 681 (2006)
  49. Dragan ES, Humelnicu D, Dinu MV, Olariu RI, Chem. Eng. J., 330, 675 (2017)
  50. Hu XJ, Wang JS, Liu YG, Li X, Zeng GM, Bao ZL, Zeng XX, Chen AW, Lonf F, J. Hazard. Mater., 185, 306 (2011)
  51. Najafpour G, Int. J. Eng., 29, 1319 (2016)
  52. Hena S, J. Hazard. Mater., 181(1-3), 474 (2010)
  53. Zhang ZH, Wang XJ, Wang H, Zhao JF, Chem. Eng. J., 344, 53 (2018)
  54. Lin JY, Chen YL, Hong XY, Huang CP, Huang CP, J. Colloid Interface Sci., 561, 275 (2020)
  55. Ingle NA, Dubey HV, Kaur N, Sharma I, J. Health Res. Rev., 1, 1 (2014)
  56. Wang X, Chen C, Du J, Tan X, Xu D, Yu S, Environ. Sci. Technol., 39, 7084 (2005)
  57. Robshaw TJ, Dawson R, Bonser K, Ogden MD, Chem. Eng. J., 367, 149 (2019)
  58. Nasr AB, Charcosset C, Amar RB, Walha K, Desalination Water Treat., 54, 1604 (2015)
  59. Viswanathan N, Meenakshi S, J. Hazard. Mater., 162(2-3), 920 (2009)
  60. Yu YQ, Zhou Z, Ding ZX, Zuo MM, Cheng JM, Jing CY, J. Hazard. Mater., 377, 267 (2019)
  61. Samatya S, Mizuki H, Ito Y, Kawakita H, Uezu K, React. Funct. Polym., 70(1), 63 (2010)