, Volume 26, Issue 17, pp 9163–9178 | Cite as

Porous cellulose beads reconstituted from ionic liquid for adsorption of heavy metal ions from aqueous solutions

  • Bo Li
  • Yuanfeng PanEmail author
  • Qi Zhang
  • Zhihong Huang
  • Jie Liu
  • Huining XiaoEmail author
Original Research


Modified porous cellulose beads (MCBs) with typical sizes ranging from 2 to 3 mm were successfully fabricated via acidic precipitation from the cellulose dissolved in ionic liquid, followed by surface-grafting with aminoguanidine hydrochloride using glutaric anhydride as a coupling agent. The nano-sized calcium carbonate (30% wt on dry cellulose) was added to cellulose solution prior to the precipitation in acidic medium in an attempt to promote the formation of the pore structure of cellulose beads. Modified cellulose powders (MCPs) (size 150 μm) were prepared by precipitating the solution of the cellulose which reacted with glutaric anhydride homogeneously in ionic liquid, followed by grafting with aminoguanidine hydrochloride. The pseudo-second-order kinetic model and the Langmuir isotherm model described the adsorption process well. The maximum adsorption capacities of MCBs towards Hg(II) and Cu(II) were 581.4 and 94.88 mg/g; whereas the maximum adsorption capacities of MCPs for Hg(II) and Cu(II) were 625 and 98.52 mg/g, respectively. The results demonstrated that both MCBs and MCPs are highly effective and promising as green-based adsorbents for the removal of heavy metal ions in aqueous systems, Hg2+ in particular.


Adsorption Cellulose Bioadsorbent Ionic liquid Heavy metal ions 



This work was supported by the Fundamental Research Funds for the Central Universities (No. 2018QN090), NSF China (Nos. 21466005 and 51379077) and NSERC Canada.


  1. Abraham E, Deepa B, Pothan LA, Jacob M, Thomas S, Cvelbar U, Anandjiwala R (2011) Extraction of nanocellulose fibrils from lignocellulosic fibres: a novel approach. Carbohydr Polym 86(4):1468–1475. CrossRefGoogle Scholar
  2. Azubuike CP, Rodríguez H, Okhamafe AO, Rogers RD (2012) Physicochemical properties of maize cob cellulose powders reconstituted from ionic liquid solution. Cellulose 19(2):425–433. CrossRefGoogle Scholar
  3. Cao J, Peng LQ, Du LJ, Zhang QD, Xu JJ (2017) Ultrasound-assisted ionic liquid-based micellar extraction combined with microcrystalline cellulose as sorbent in dispersive microextraction for the determination of phenolic compounds in propolis. Anal Chim Acta 963:24–32. CrossRefPubMedGoogle Scholar
  4. Deguchi S, Tsujii K, Horikoshi K (2006) Cooking cellulose in hot and compressed water. Chem Commun 31:3293–3295. CrossRefGoogle Scholar
  5. Eliodorio KP, Andolfatto VS, Martins MRG, de Sa BP, Umeki ER, Morandim-Giannetti AD (2017) Treatment of chromium effluent by adsorption on chitosan activated with ionic liquids. Cellulose 24(6):2559–2570. CrossRefGoogle Scholar
  6. Farrow C, McBean E, Huang G, Yang AL, Wu YC, Liu Z, Dai ZN, Fu HY, Cawte T, Li YP (2018) Ceramic water filters: a point-of-use water treatment technology to remove bacteria from drinking water in Longhai City, Fujian Province China. J Environ Inform 32(2):63–68. CrossRefGoogle Scholar
  7. French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21(2):885–896. CrossRefGoogle Scholar
  8. Gan S, Zakaria S, Chia CH, Kaco H, Padzil FN (2014) Synthesis of kenaf cellulose carbamate using microwave irradiation for preparation of cellulose membrane. Carbohydr Polym 106:160–165. CrossRefPubMedGoogle Scholar
  9. Gao S, Luo TT, Zhou Q, Luo WJ, Li HF, Jing LR (2018) Surface sodium lignosulphonate-immobilized sawdust particle as an efficient adsorbent for capturing Hg2+ from aqueous solution. J Colloid Interface Sci 517:9–17. CrossRefPubMedGoogle Scholar
  10. Hadavifar M, Bahramifar N, Younesi H, Rastakhiz M, Li Q, Yu J, Eftekhari E (2016) Removal of mercury(II) and cadmium(II) ions from synthetic wastewater by a newly synthesized amino and thiolated multi-walled carbon nanotubes. J Taiwan Inst Chem Eng 67:397–405. CrossRefGoogle Scholar
  11. Han JQ, Zhou CJ, French AD, Han GP, Wu QL (2013) Characterization of cellulose II nanoparticles regenerated from 1-butyl-3-methylimidazolium chloride. Carbohydr Polym 94(2):773–781. CrossRefPubMedGoogle Scholar
  12. Hokkanen S, Bhatnagar A, Sillanpaa M (2016) A review on modification methods to cellulose-based adsorbents to improve adsorption capacity. Water Res 91:156–173. CrossRefPubMedPubMedCentralGoogle Scholar
  13. Hu XJ, Wang JS, Liu YG, Li X, Zeng GM, Bao ZL (2011) Adsorption of chromium (VI) by ethylenediamine-modified cross-linked magnetic chitosan resin: isotherms, kinetics and thermodynamics. J Hazard Mater 185(1):306–314. CrossRefPubMedGoogle Scholar
  14. Ikeda K, Umeno D, Saito K, Koide F, Miyata E, Sugo T (2011) Removal of boron using nylon-based chelating fibers. Ind Eng Chem Res 50(9):5727–5732. CrossRefGoogle Scholar
  15. Isa MH, Ezechi EH, Ahmed Z, Magram SF, Kutty SRM (2014) Boron removal by electrocoagulation and recovery. Water Res 51(6):113–123. CrossRefPubMedGoogle Scholar
  16. Janin A, Blais JF, Mercier G, Drogui P (2009) Selective recovery of Cr and Cu in leachate from chromated copper arsenate treated wood using chelating and acidic ion exchange resins. J Hazard Mater 169:1099–1105. CrossRefPubMedGoogle Scholar
  17. Kadokawa JI, Murakami MA, Takegawa A, Kaneko Y (2009) Preparation of cellulose–starch composite gel and fibrous material from a mixture of the polysaccharides in ionic liquid. Carbohydr Polym 75(1):180–183. CrossRefGoogle Scholar
  18. Kim YK, Bae K, Kim Y, Harbottle D, Lee JW (2018) Immobilization of potassium copper hexacyanoferrate in doubly crosslinked magnetic polymer bead for highly effective Cs+ removal and facile recovery. J Ind Eng Chem 68:48–56. CrossRefGoogle Scholar
  19. Li RJ, Liu LF, Yang FL (2014) Removal of aqueous Hg(II) and Cr(VI) using phytic acid doped polyaniline/cellulose acetate composite membrane. J Hazard Mater 280:20–30. CrossRefPubMedGoogle Scholar
  20. Li J, Zheng L, Liu HB (2017) A novel carbon aerogel prepared for adsorption of copper(II) ion in water. J Porous Mater 24(6):1575–1580. CrossRefGoogle Scholar
  21. Li F, Zeng XY, Liang YY, Huang GR, Wen YM (2018a) A field study of factors that affect acid-volatile sulfide concentrations. J Environ Inform 32(2):125–136. CrossRefGoogle Scholar
  22. Li L, Lqbal J, Zhu Y, Zhang P, Chen WC, Bhatnagar A, Du YP (2018b) Chitosan/Ag-hydroxyapatite nanocomposite beads as a potential adsorbent for the efficient removal of toxic aquatic pollutants. Int J Biol Macromol 120:1752–1759. CrossRefPubMedGoogle Scholar
  23. Li Y, Xiao HN, Pan YF, Wang LD (2018c) Novel composite adsorbent consisting of dissolved cellulose fiber/microfibrillated cellulose for dye removal from aqueous solution. ACS Sustain Chem Eng 6(5):6994–7002. CrossRefGoogle Scholar
  24. Li YP, Han M, Wang YL, Liu Q, Zhao WF, Su BH, Zhao CS (2018d) A mussel-inspired approach towards heparin-immobilized cellulose gel beads for selective removal of low density lipoprotein from whole blood. Carbohydr Polym 202:116–124. CrossRefPubMedGoogle Scholar
  25. Li B, Li M, Zhang JY, Pan YF, Huang ZH, Xiao HN (2019) Adsorption of Hg(II) ions from aqueous solution by diethylenetriaminepentaacetic acid-modified cellulose. Int J Biol Macromol 122:149–156. CrossRefPubMedGoogle Scholar
  26. Liu XY, Chang PR, Zheng PW, Anderson DP, Ma XF (2015) Porous cellulose facilitated by ionic liquid [BMIM]Cl: fabrication, characterization, and modification. Cellulose 22(1):709–715. CrossRefGoogle Scholar
  27. Lu J, Yan F, Texter J (2009) Advanced applications of ionic liquids in polymer science. Prog Polym Sci 34(5):431–448. CrossRefGoogle Scholar
  28. Luo XG, Zeng J, Liu SL, Zhang LN (2015) An effective and recyclable adsorbent for the removal of heavy metal ions from aqueous system: magnetic chitosan/cellulose microspheres. Bioresour Technol 194:403–406. CrossRefPubMedGoogle Scholar
  29. Pan YF, Cai PX, Farmahini-Farahani M, Li YD, Hou XB, Xiao HN (2016a) Amino-functionalized alkaline clay with cationic star-shaped polymer as adsorbents for removal of Cr(VI) in aqueous solution. Appl Surf Sci 385:333–340. CrossRefGoogle Scholar
  30. Pan YF, Wang FT, Wei TY, Zhang CL, Xiao HN (2016b) Hydrophobic modification of bagasse cellulose fibers with cationic latex: adsorption kinetics and mechanism. Chem Eng J 302:33–43. CrossRefGoogle Scholar
  31. Pan YF, Shi X, Cai PX, Guo TX, Tong ZF, Xiao HN (2018) Dye removal from single and binary systems using gel-like bioadsorbent based on functional-modified cellulose. Cellulose 25(4):2559–2575. CrossRefGoogle Scholar
  32. Quan SL, Kang SG, Chin IJ (2010) Characterization of cellulose fibers electrospun using ionic liquid. Cellulose 17(2):223–230. CrossRefGoogle Scholar
  33. Remesan R, Bray M, Mathew J (2018) Application of PCA and clustering methods in input selection of hybrid runoff models. J Environ Inform 31(2):137–152. CrossRefGoogle Scholar
  34. Salem A, Sene RA (2011) Removal of lead from solution by combination of natural zeolite–kaolin–bentonite as a new low-cost adsorbent. Chem Eng J 174(2–3):619–628. CrossRefGoogle Scholar
  35. Singha AS, Guleria A (2014) Chemical modification of cellulosic biopolymer and its use in removal of heavy metal ions from wastewater. Int J Biol Macromol 67:409–417. CrossRefPubMedGoogle Scholar
  36. Sun C, Ni JD, Zhao CY, Du JM, Zhou CG, Wang SG, Xu CH (2017) Preparation of a cellulosic adsorbent by functionalization with pyridone diacid for removal of Pb(II) and Co(II) from aqueous solutions. Cellulose 24(12):5615–5624. CrossRefGoogle Scholar
  37. Swatloski RP, Spear SK, Holbrey JD, Rogers RD (2002) Dissolution of cellulose with ionic liquids. J Am Chem Soc 124:4974–4975. CrossRefGoogle Scholar
  38. Vitz J, Erdmenger T, Haensch C, Schubert US (2009) Extended dissolution studies of cellulose in imidazolium based ionic liquids. Green Chem 11(3):417–424. CrossRefGoogle Scholar
  39. Wang XJ, Xu XM, Liang X, Wang Y, Liu M, Wang X, Xia SQ, Zhao JF, Yin DQ, Zhang YL (2011) Adsorption of copper(II) onto sewage sludge-derived materials via microwave irradiation. J Hazard Mater 192(3):1226–1233. CrossRefPubMedGoogle Scholar
  40. Wang H, Ma LJ, Cao KC, Geng JX, Liu J, Song Q (2012) Selective solid-phase extraction of uranium by salicylideneimine-functionalized hydrothermal carbon. J Hazard Mater 229:321–330. CrossRefPubMedGoogle Scholar
  41. Wang JL, Wei LG, Ma YC, Li KL, Li MH, Yu YC, Wang L, Qiu HH (2013a) Collagen/cellulose hydrogel beads reconstituted from ionic liquid solution for Cu(II) adsorption. Carbohydr Polym 98(1):736–743. CrossRefPubMedGoogle Scholar
  42. Wang ZD, Yin P, Qu RJ, Chen H, Wang CH, Ren SH (2013b) Adsorption kinetics, thermodynamics and isotherm of Hg(II) from aqueous solutions using buckwheat hulls from Jiaodong of China. Food Chem 136(3–4):1508–1514. CrossRefPubMedGoogle Scholar
  43. Wang WX, Mozuch MD, Sabo RC, Kersten P, Zhu JY, Jin YC (2016) Endoglucanase post-milling treatment for producing cellulose nanofibers from bleached eucalyptus fibers by a supermasscolloider. Cellulose 23(3):1859–1870. CrossRefGoogle Scholar
  44. Wang FT, Pan YF, Cai PX, Guo TX, Xiao HN (2017) Single and binary adsorption of heavy metal ions from aqueous solutions using sugarcane cellulose-based adsorbent. Bioresour Technol 241:482–490. CrossRefPubMedGoogle Scholar
  45. Wang X, Jiang SJ, Cui S, Tang YH, Pei ZF, Duan HR (2019) Magnetic-controlled aerogels from carboxylated cellulose and MnFe2O4 as a novel adsorbent for removal of Cu(II). Cellulose 26(8):5051–5063. CrossRefGoogle Scholar
  46. Xin XY, Huang G, An CJ, Raina-Fulton R, Weger H (2019) Insights into long-term toxicity of triclosan to freshwater green algae in lake erie. Environ Sci Technol 53(4):2189–2198. CrossRefPubMedGoogle Scholar
  47. Xu H, Pan W, Wang R, Zhang D, Liu C (2012) Understanding the mechanism of cellulose dissolution in 1-butyl-3-methylimidazolium chloride ionic liquid via quantum chemistry calculations and molecular dynamics simulations. J Comput Aided Mol Des 26(3):329–337. CrossRefPubMedGoogle Scholar
  48. Yu JG, Yang JW, Liu BX, Ma XF (2009) Preparation and characterization of glycerol plasticized-pea starch/ZnO-carboxymethylcellulose sodium nanocomposites. Bioresour Technol 100(11):2832–2841. CrossRefPubMedGoogle Scholar
  49. Zhang S, Dokko K, Watanabe M (2015) Porous ionic liquids: synthesis and application. Chem Sci 6(7):3684–3691. CrossRefPubMedPubMedCentralGoogle Scholar
  50. Zhang H, Wu XQ, Yuan YN, Han DD, Qiao FX, Yan HY (2018) An ionic liquid functionalized graphene adsorbent with multiple adsorption mechanisms for pipette-tip solid-phase extraction of auxins in soybean sprouts. Food Chem 265:290–297. CrossRefPubMedGoogle Scholar
  51. Zirak M, Abdollahiyan A, Eftekhari-Sis B, Saraei M (2018) Carboxymethyl cellulose coated Fe3O4@SiO2 core-shell magnetic nanoparticles for methylene blue removal: equilibrium, kinetic, and thermodynamic studies. Cellulose 25(1):503–515. CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.Department of Environment Science and EngineeringNorth China Electric Power UniversityBaodingChina
  2. 2.Guangxi Key Lab of Petrochemical Resource Processing and Process Intensification Technology, School of Chemistry and Chemical EngineeringGuangxi UniversityNanningChina
  3. 3.Sheng Qing Environmental Protection Technology Co., LtdKunmingChina
  4. 4.Department of Chemical EngineeringUniversity of New BrunswickFrederictonCanada

Personalised recommendations