Environmental Science and Pollution Research

, Volume 25, Issue 11, pp 10911–10925 | Cite as

Sorption and recovery of platinum from simulated spent catalyst solution and refinery wastewater using chemically modified biomass as a novel sorbent

  • Dipak J. Garole
  • Bharat C. Choudhary
  • Debajyoti Paul
  • Amulrao U. Borse
Research Article


In this study, Lagerstroemia speciosa biomass modified by polyethylenimine (PEI-LS) was developed as a potential biosorbent for sorption and recovery of platinum(II) from platinum bearing waste solutions. Batch experiments were conducted to study the effect of various parameters on the sorption and recovery of platinum(II) using PEI-LS. The equilibrium time for platinum(II) sorption process was found to be 6 h. Both the sorption kinetics and sorption isotherm data fits pseudo second-order kinetic model and Langmuir isotherm, respectively. The maximum sorption capacity of platinum(II) onto PEI-LS at pH 2 for the studied temperature range (25–45 °C) is in the range of 122–154 mg/g. Evaluation of thermodynamic parameters suggests that the platinum(II) sorption is spontaneous and endothermic in nature. The regeneration of PEI-LS can be achieved using acidic thiourea as an eluent for recovery of platinum from the biosorbent. Fourier transform infrared (FT-IR) analysis suggests many functional groups were involved in platinum(II) sorption onto PEI-LS. Both the scanning electron microscope/energy dispersive spectroscopy (SEM/EDS) and X-ray photoelectron spectroscopy (XPS) analysis suggest a successful modification of raw biomass with PEI. The XPS analysis further concludes that platinum(II) sorption is governed by ion-exchange and co-ordination reaction. Finally, the PEI-LS was shown to recover ≥ 90% of platinum from two simulated solutions: the acid-leached spent catalyst solution and refinery wastewater. The biosorbent developed in this study is a low-cost and eco-friendly media that can be effectively used for platinum recovery from industrial wastewater.


Platinum Biosorption Polyethylenimine Spent catalyst Wastewater 



Thanks are due to the Center for Environmental Science and Engineering, Indian Institute of Technology Kanpur, India for allowing to carry out all experimental work. We sincerely thank anonymous reviewer and Guilherme L. Dotto (Editor) for thoughtful and thorough reviews, which have significantly improved the clarity of the manuscript. This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors.


  1. Akcil A, Vegliò F, Ferella F et al (2015) A review of metal recovery from spent petroleum catalysts and ash. Waste Manag 45:420–433. CrossRefGoogle Scholar
  2. Aksu Z (2002) Determination of the equilibrium, kinetic and thermodynamic parameters of the batch biosorption of nickel(II) ions onto Chlorella vulgaris. Process Biochem 38(1):89–99.
  3. Aw BH, Looh KK, Chan HSO, Tan KL, Hor TSA (1994) X-Ray photoelectron spectroscopic characterization of [{Pt(PPh 3 ) 2 (μ 3 -S)} 2 PtCl 2 ], [{Pt 2 (PPh 3 ) 4 (μ 3 -S) 2 Cu} 2 (μ-dppf)][PF 6 ] 2 [dppf = Fe (C 5 H 4 PPh 2 ) 2 ] and other heterometallic aggregates derived from [{Pt(PPh 3 ) 2 (μ-S)} 2 ]. J Chem Soc, Dalt Trans:3177–3182. doi:, 21
  4. Bayramoglu G, Akbulut A, Arica MY (2015) Study of polyethyleneimine- and amidoxime-functionalized hybrid biomass of Spirulina (Arthrospira) platensis for adsorption of uranium (VI) ion. Environ Sci Pollut Res 22(22):17998–18010.
  5. Biesinger MC, Payne BP, Grosvenor AP, Lau LWM, Gerson AR, Smart RSC (2011) Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni. Appl Surf Sci 257(7):2717–2730. CrossRefGoogle Scholar
  6. Chen JP, Yang L (2005) Chemical modification of Sargassum sp. for prevention of organic leaching and enhancement of uptake during metal biosorption. Ind Eng Chem Res 44(26):9931–9942.
  7. Chen X, Lam KF, Mak SF, Yeung KL (2011) Precious metal recovery by selective adsorption using biosorbents. J Hazard Mater 186(1):902–910. CrossRefGoogle Scholar
  8. Cho CW, Bin KS, Kim S et al (2016) Reusable polyethylenimine-coated polysulfone/bacterial biomass composite fiber biosorbent for recovery of Pd(II) from acidic solutions. Chem Eng J 302:545–551. CrossRefGoogle Scholar
  9. Choudhary BC, Paul D, Borse AU, Garole DJ (2017a) Recovery of palladium from secondary waste using soluble tannins cross-linked Lagerstroemia speciosa leaves powder. J Chem Technol Biotechnol 92(7):1667–1677.
  10. Choudhary BC, Paul D, Borse AU, Garole DJ (2018) Surface functionalized biomass for adsorption and recovery of gold from electronic scrap and refinery wastewater. Sep Purif Technol 195:260–270. CrossRefGoogle Scholar
  11. Choudhary BC, Paul D, Gupta T et al (2017b) Photocatalytic reduction of organic pollutant under visible light by green route synthesized gold nanoparticles. J Environ Sci (China) 55:236–246. CrossRefGoogle Scholar
  12. Deng S, Ma R, Yu Q, Huang J, Yu G (2009) Enhanced removal of pentachlorophenol and 2,4-D from aqueous solution by an aminated biosorbent. J Hazard Mater 165(1-3):408–414. CrossRefGoogle Scholar
  13. Deng S, Ting YP (2005) Polyethylenimine-modified fungal biomass as a high-capacity biosorbent for Cr(VI) anions: sorption capacity and uptake mechanisms. Environ Sci Technol 39(21):8490–8496. CrossRefGoogle Scholar
  14. Dick CR, Ham GE (1970) Characterization of polyethylenimine. J Macromol Sci Part A - Chem 4(6):1301–1314. CrossRefGoogle Scholar
  15. Dong H, Zhao J, Chen J et al (2015) Recovery of platinum group metals from spent catalysts: a review. Int J Miner Process 145:108–113. CrossRefGoogle Scholar
  16. Dwivedi AD, Dubey SP, Hokkanen S, Fallah RN, Sillanpää M (2014) Recovery of gold from aqueous solutions by taurine modified cellulose: an adsorptive-reduction pathway. Chem Eng J 255:97–106. CrossRefGoogle Scholar
  17. Freundlich H (1906) Uber die adsorption in lunsungen. J Phys Chem 57:387–470Google Scholar
  18. Gong QQ, Guo XY, Liang S, Wang C, Tian QH (2016) Study on the adsorption behavior of modified persimmon powder biosorbent on Pt(IV). Int J Environ Sci Technol 13(1):47–54. CrossRefGoogle Scholar
  19. Gurung M, Adhikari BB, Kawakita H, Ohto K, Inoue K, Alam S (2012) Selective recovery of precious metals from acidic leach liquor of circuit boards of spent mobile phones using chemically modified persimmon tannin gel. Ind Eng Chem Res 51(37):11901–11913. CrossRefGoogle Scholar
  20. Hidalgo JM, Zbuzek M, Černý R, Jíša P (2013) Current uses and trends in catalytic isomerization, alkylation and etherification processes to improve gasoline quality. Cent Eur J Chem 12(1):1–13. Google Scholar
  21. Ho YS, McKay G (1999) Pseudo-second order model for sorption processes. Process Biochem 34(5):451–465. CrossRefGoogle Scholar
  22. Hu XJ, song WJ, guo LY et al (2011) Adsorption of chromium(VI) by ethylenediamine-modified cross-linked magnetic chitosan resin: isotherms, kinetics and thermodynamics. J Hazard Mater 185(1):306–314.
  23. Jarvis KE, Parry SJ, Piper JM (2001) Temporal and spatial studies of autocatalyst-derived platinum, rhodium, and palladium and selected vehicle-derived trace elements in the environment. Environ Sci Technol 35(6):1031–1036. CrossRefGoogle Scholar
  24. Jha MK, Lee JC, Kim MS et al (2013) Hydrometallurgical recovery/recycling of platinum by the leaching of spent catalysts: a review. Hydrometallurgy 133:22–32. CrossRefGoogle Scholar
  25. Karhu H, Kalantar A, Väyrynen IJ et al (2003) XPS analysis of chlorine residues in supported Pt and Pd catalysts with low metal loading. Appl Catal A Gen 247(2):283–294. CrossRefGoogle Scholar
  26. Khambhaty Y, Mody K, Basha S, Jha B (2009) Kinetics, equilibrium and thermodynamic studies on biosorption of hexavalent chromium by dead fungal biomass of marine Aspergillus niger. Chem Eng J 145(3):489–495.
  27. Khunathai K, Inoue K, Ohto K et al (2013) Adsorptive recovery of palladium(II) and platinum(IV) on the chemically modified-microalgal residue. Solvent Extr Ion Exch 31(3):320–334. CrossRefGoogle Scholar
  28. Kim S, Choi YE, Yun YS (2016) Ruthenium recovery from acetic acid industrial effluent using chemically stable and high-performance polyethylenimine-coated polysulfone-Escherichia coli biomass composite fibers. J Hazard Mater 313:29–36.
  29. Kim S, Song MH, Wei W, Yun YS (2015) Selective biosorption behavior of Escherichia coli biomass toward Pd(II) in Pt(IV)-Pd(II) binary solution. J Hazard Mater 283:657–662.
  30. Klein G, Kim J, Himmeldirk K, Cao Y, Chen X (2007) Antidiabetes and anti-obesity activity of Lagerstroemia speciosa. Evid Based Complement Altern Med 4(4):401–407.
  31. Lagergren S (1898) Zur theorie der sogenannten adsorption gelöster stoffle. K Sevenska Vetenskapasakademiens, Handilingar 24:1–39Google Scholar
  32. Lam KF, Yeung KL, McKay G (2006) A rational approach in the design of selective mesoporous adsorbents. Langmuir 22(23):9632–9641. CrossRefGoogle Scholar
  33. Langmuir I (1916) The constitution and fundamental properties of solids and liquids. Part I. Solids. J Am Chem Soc 38(11):2221–2295. CrossRefGoogle Scholar
  34. Lee S-M, Tsai D-H, Hackley VA, Brechbiel MW, Cook RF (2013) Surface-engineered nanomaterials as X-ray absorbing adjuvant agents for Auger-mediated chemo-radiation. Nano 5(12):5252–5256. Google Scholar
  35. Lo YC, Cheng CL, Han YL, Chen BY, Chang JS (2014) Recovery of high-value metals from geothermal sites by biosorption and bioaccumulation. Bioresour Technol 160:182–190. CrossRefGoogle Scholar
  36. Lodeiro P, Sillanpää M (2013) Gold recovery from artificial seawater using synthetic materials and seaweed biomass to induce gold nanoparticles formation in batch and column experiments. Mar Chem 152:11–19. CrossRefGoogle Scholar
  37. Mack CL, Wilhelmi B, Duncan JR, Burgess JE (2011) Biosorptive recovery of platinum from platinum group metal refining wastewaters by immobilised Saccharomyces cerevisiae. Water Sci Technol 63(1):149–155.
  38. Maiyalagan T, Karthikeyan S (2013) Film-pore diffusion modeling for sorption of azo dye on to exfoliated graphitic nanoplatelets. Indian J Chem Technol 20:7–14Google Scholar
  39. Mao J, Lee SY, Won SW, Yun YS (2010) Surface modified bacterial biosorbent with poly(allylamine hydrochloride): development using response surface methodology and use for recovery of hexachloroplatinate(IV) from aqueous solution. Water Res 44(20):5919–5928. CrossRefGoogle Scholar
  40. Marinho RS, da SCN, Afonso JC, da CJWSD (2011) Recovery of platinum, tin and indium from spent catalysts in chloride medium using strong basic anion exchange resins. J Hazard Mater 192(3):1155–1160. CrossRefGoogle Scholar
  41. Mohamed RR, Elella MHA, Sabaa MW (2015) Synthesis, characterization and applications of N-quaternized chitosan/poly(vinyl alcohol) hydrogels. Int J Biol Macromol 80:149–161.
  42. Morcali MH, Zeytuncu B, Yucel O (2013) Platinum uptake from chloride solutions using biosorbents. Mater Res 16(2):528–538. CrossRefGoogle Scholar
  43. Parajuli D, Khunathai K, Adhikari CR et al (2009) Total recovery of gold, palladium, and platinum using lignophenol derivative. Miner Eng 22(13):1173–1178. CrossRefGoogle Scholar
  44. Park J, Won SW, Mao J, Kwak IS, Yun YS (2010) Recovery of Pd(II) from hydrochloric solution using polyallylamine hydrochloride-modified Escherichia coli biomass. J Hazard Mater 181(1-3):794–800.
  45. Ramakul P, Yanachawakul Y, Leepipatpiboon N, Sunsandee N (2012) Biosorption of palladium(II) and platinum(IV) from aqueous solution using tannin from Indian almond (Terminalia catappa L.) leaf biomass: kinetic and equilibrium studies. Chem Eng J 193–194:102–111.
  46. Reddad Z, Gerente C, Andres Y, Le Cloirec P (2002) Adsorption of several metal ions onto a low-cost biosorbent: kinetic and equilibrium studies. Environ Sci Technol 36:2067–2073. CrossRefGoogle Scholar
  47. Shang M, Liu Y, Liu S et al (2016) A novel graphene oxide coated biochar composite: synthesis, characterization and application for Cr(VI) removal. RSC Adv 6(88):85202–85212.
  48. Song W, Zhang M, Liang J, Han G (2015) Removal of As(V) from wastewater by chemically modified biomass. J Mol Liq 206:262–267. CrossRefGoogle Scholar
  49. Sun X, Yang L, Li Q et al (2015) Polyethylenimine-functionalized poly(vinyl alcohol) magnetic microspheres as a novel adsorbent for rapid removal of Cr(VI) from aqueous solution. Chem Eng J 262:101–108. CrossRefGoogle Scholar
  50. Tavassolirizi Z, Shams K, Omidkhah MR (2015) Platinum recovery from model media and a Pt–Sn/alumina spent catalyst extract using corn husk-based adsorbent. J Ind Eng Chem 23:119–127. CrossRefGoogle Scholar
  51. Wang S, Vincent T, Roux JC et al (2017a) Pd(II) and Pt(IV) sorption using alginate and algal-based beads. Chem Eng J 313:567–579.
  52. Wang S, Vincent T, Roux JC et al (2017b) Innovative conditioning of algal-based sorbents: macro-porous discs for palladium sorption. Chem Eng J 325:521–532. CrossRefGoogle Scholar
  53. Weber WJ, Morris JC (1963) Kinetics of adsorption on carbon from solution. J Sanit Eng Div 89:31–60Google Scholar
  54. Wojnicki M, Socha RP, Luty-Błocho M, Fitzner K (2017) Kinetic studies of the removal of Pt(IV) chloride complex ions from acidic aqueous solutions using activated carbon. React Kinet Mech Catal 120(2):715–734. CrossRefGoogle Scholar
  55. Won SW, Kotte P, Wei W et al (2014) Biosorbents for recovery of precious metals. Bioresour Technol 160:203–212. CrossRefGoogle Scholar
  56. Won SW, Mao J, Kwak IS et al (2010) Platinum recovery from ICP wastewater by a combined method of biosorption and incineration. Bioresour Technol 101(4):1135–1140. CrossRefGoogle Scholar
  57. Won SW, Park J, Mao J, Yun YS (2011) Utilization of PEI-modified Corynebacterium glutamicum biomass for the recovery of Pd(II) in hydrochloric solution. Bioresour Technol 102(4):3888–3893.
  58. Xia T, Guan Y, Yang M et al (2014) Synthesis of polyethylenimine modified Fe3O4 nanoparticles with immobilized Cu2+ for highly efficient proteins adsorption. Colloids Surf Physicochem Eng Asp 443:552–559.
  59. Xu H, Tan L, Dong H, He J, Liu X, Qiu G, He Q, Xie J (2017) Competitive biosorption behavior of Pt(IV) and Pd(II) by Providencia vermicola. RSC Adv 7(51):32229–32235.
  60. Yan Y, An Q, Xiao Z et al (2017) Flexible core-shell/bead-like alginate@PEI with exceptional adsorption capacity, recycling performance toward batch and column sorption of Cr(VI). Chem Eng J 313:475–486. CrossRefGoogle Scholar
  61. Zalupski PR, McDowell R, Dutech G (2014) The adsorption of gold, palladium, and platinum from acidic chloride solutions on mesoporous carbons. Solvent Extr Ion Exch 32(7):737–748. CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  • Dipak J. Garole
    • 1
    • 4
  • Bharat C. Choudhary
    • 1
    • 2
  • Debajyoti Paul
    • 2
    • 3
  • Amulrao U. Borse
    • 1
  1. 1.School of Chemical SciencesNorth Maharashtra UniversityJalgaonIndia
  2. 2.Centre for Environmental Science & EngineeringIndian Institute of Technology KanpurKanpurIndia
  3. 3.Department of Earth Sciences, Indian Institute of Technology KanpurKanpurIndia
  4. 4.Directorate of Geology and Mining, Government of MaharashtraNagpurIndia

Personalised recommendations