Environmental Science and Pollution Research

, Volume 25, Issue 21, pp 21058–21069 | Cite as

The removal of silver nanoparticle by titanium tetrachloride and modified sodium alginate composite coagulants: floc properties, membrane fouling, and floc recycle

  • Ziyang Wang
  • Yan Wang
  • Cong Yu
  • Yanxia Zhao
  • Meixia Fan
  • Baoyu Gao
Research Article


In this study, a modified sodium alginate (MSA) composited with TiCl4 was used to treat the synthetic Ag nanoparticles (AgNPs) water in coagulation-ultrafiltration process. The floc properties and membrane fouling of TiCl4 and MSA composite coagulants (TiCl4 + MSA) were investigated by a laser diffraction instrument and ultrafiltration fouling model. The recycle of the AgNP-containing flocs was evaluated by XRD and photocatalytic experiments. The results showed that TiCl4 + MSA could achieve better coagulation performance than TiCl4 alone with AgNP and DOC removal up to 97 and 59% at the optimum condition (pH = 5 and dosage = 12 mg TiCl4/L). TiCl4 + MSA produced larger and looser flocs than TiCl4 and TiCl4 + SA composite coagulant (TiCl4 + SA), which was benefit for the inhibition of subsequence membrane fouling. The strongly attached external fouling resistance (Ref-s) and the reversible internal fouling resistance (Rif-r) of TiCl4 + MSA were only 43 and 39.2% of those achieved by TiCl4 at the optimal coagulation condition. Besides, the adopted AgCl-TiO2 could be recycled from AgNP-containing flocs. And MSA could promote the form of TiO2 anatase. It gives us a possible way for silver nanoparticle recycle.


Nanoparticles Coagulation Ultrafiltration Flocs Recycle 


Funding information

This study was supported by the Chinese National Science and Technology (No. 21377072, No. 51508308, No.51478250) and the Outstanding Young and Middle-Aged Scientists Research Fund of Shandong Province (BS2012HZ004).

Supplementary material

11356_2018_2240_MOESM1_ESM.docx (1.7 mb)
ESM 1 (DOCX 1744 kb)


  1. Aboul-Gheit AK, El-Desouki DS, El-Salamony RA (2014) Different outlet for preparing nano-TiO2 catalysts for the photodegradation of Black B dye in water. Egypt J Pet 23:339–348CrossRefGoogle Scholar
  2. Addamo M, Augugliaro V, Di Paola A, García-López E, Loddo V, Marcì G, Palmisano L (2005) Preparation and photoactivity of nanostructured TiO2 particles obtained by hydrolysis of TiCl4. Colloids Surf A Physicochem Eng Asp 265:23–31CrossRefGoogle Scholar
  3. Brar SK, Verma M, Tyagi RD, Surampalli RY (2010) Engineered nanoparticles in wastewater and wastewater sludge—evidence and impacts. Waste Manag 30:504–520CrossRefGoogle Scholar
  4. Cao J, Xu B, Luo B, Lin H, Chen S (2011) Preparation, characterization and visible-light photocatalytic activity of AgI/AgCl/TiO2. Appl Surf Sci 257:7083–7089CrossRefGoogle Scholar
  5. Chen KL, Mylon SE, Elimelech M (2007) Enhanced aggregation of alginate-coated iron oxide (hematite) nanoparticles in the presence of calcium, strontium, and barium cations. Langmuir 23:5920–5928CrossRefGoogle Scholar
  6. Chen Y, Lin A, Gan F (2006) Preparation of nano-TiO2 from TiCl4 by dialysis hydrolysis. Powder Technol 167:109–116CrossRefGoogle Scholar
  7. Choo KH, Choi SJ, Hwang ED (2007) Effect of coagulant types on textile wastewater reclamation in a combined coagulation/ultrafiltration system. Desalination 202:262–270CrossRefGoogle Scholar
  8. Choo KH, Lee CH (1996) Membrane fouling mechanisms in the membrane-coupled anaerobic bioreactor. Water Res 30:1771–1780CrossRefGoogle Scholar
  9. Dong B-z, Chen N-y, Jin-chu (2007) Effect of coagulation pretreatment on the fouling of ultrafiltration membrane. J Environ Sci 19:278–283CrossRefGoogle Scholar
  10. Farkas J, Peter H, Christian P, Gallego Urrea JA, Hassellov M, Tuoriniemi J, Gustafsson S, Olsson E, Hylland K, Thomas KV (2011) Characterization of the effluent from a nanosilver producing washing machine. Environ Int 37:1057–1062CrossRefGoogle Scholar
  11. Ghernaout D (2014) The hydrophilic/hydrophobic ratio vs. dissolved organics removal by coagulation—a review. J King Saud Univ - Sci 26:169–180CrossRefGoogle Scholar
  12. Hay MB, Myneni SCB (2007) Structural environments of carboxyl groups in natural organic molecules from terrestrial systems. Part 1: infrared spectroscopy. Geochim Cosmochim Acta 71:3518–3532CrossRefGoogle Scholar
  13. Ivan Donati KID, Borgogna M, Paoletti S, Skjåk-Bræk G (2005) Tailor-made alginate bearing galactose moieties on mannuronic residues: selective modification achieved by a chemoenzymatic strategy. Biomacromolecules 6:88–98CrossRefGoogle Scholar
  14. Jo HJ, Choi JW, Lee SH, Hong SW (2012) Acute toxicity of ag and CuO nanoparticle suspensions against Daphnia magna: the importance of their dissolved fraction varying with preparation methods. J Hazard Mater 227-228:301–308CrossRefGoogle Scholar
  15. Kim B, Park CS, Murayama M, Jr MFH (2010) Discovery and characterization of silver sulfide nanoparticles in final sewage sludge products. Environ Sci Technol 44:7509–7514CrossRefGoogle Scholar
  16. Lee JH, Yang YS (2005) Effect of hydrolysis conditions on morphology and phase content in the crystalline TiO2 nanoparticles synthesized from aqueous TiCl4 solution by precipitation. Mater Chem Phys 93:237–242CrossRefGoogle Scholar
  17. Levard C, Mitra S, Yang T, Jew AD, Badireddy AR, Lowry GV, Brown GE Jr (2013) Effect of chloride on the dissolution rate of silver nanoparticles and toxicity to E. coli. Environ Sci Technol 47:5738–5745CrossRefGoogle Scholar
  18. Li T, Zhu Z, Wang D, Yao C, Tang H (2006) Characterization of floc size, strength and structure under various coagulation mechanisms. Powder Technol 168:104–110CrossRefGoogle Scholar
  19. Liu G, Zhang M, Jin Y, Fan X, Xu J, Zhu Y, Fu Z, Pan X, Qian H (2017) The effects of low concentrations of silver nanoparticles on wheat growth, seed quality, and soil microbial communities. Water Air Soil Pollut 228:348CrossRefGoogle Scholar
  20. Lohwacharin J, Takizawa S (2009) Effects of nanoparticles on the ultrafiltration of surface water. J Membr Sci 326:354–362CrossRefGoogle Scholar
  21. Mao R, Wang Y, Zhang B, Xu W, Dong M, Gao B (2013) Impact of enhanced coagulation ways on flocs properties and membrane fouling: increasing dosage and applying new composite coagulant. Desalination 314:161–168CrossRefGoogle Scholar
  22. Meier C, Voegelin A, APd R, Sarret G, Mueller CR, Kaegi R (2016) Supporting information for: Transformation of silver nanoparticles in sewage sludge during incineration. Environ Sci Technol 50:3505CrossRefGoogle Scholar
  23. Miao AJ, Luo Z, Chen CS, Chin WC, Santschi PH, Quigg A (2010) Intracellular uptake: a possible mechanism for silver engineered nanoparticle toxicity to a freshwater alga Ochromonas danica. PLoS One 5:e15196CrossRefGoogle Scholar
  24. Na SH, Shon HK, Kim JB, Park HJ, Kim JH (2011) Preparation and characterization of titania nanoparticle produced from Ti-flocculated sludge with paper mill wastewater. J Ind Eng Chem 17:277–281CrossRefGoogle Scholar
  25. Sadanandam G, Valluri DK, Scurrell MS (2017) Highly stabilized Ag2O-loaded nano TiO2 for hydrogen production from glycerol: water mixtures under solar light irradiation. Int J Hydrog Energy 42:807–820CrossRefGoogle Scholar
  26. Sand A, Vyas A, Gupta AK (2016) Graft copolymer based on (sodium alginate-g-acrylamide): characterization and study of water swelling capacity, metal ion sorption, flocculation and resistance to biodegradability. Int J Biol Macromol 90:37–43CrossRefGoogle Scholar
  27. Shon HK, Vigneswaran S, Kandasamy J, Zareie MH, Kim JB, Cho DL, Kim J-H (2009) Preparation and characterization of titanium dioxide (TiO2) from sludge produced by TiCl4 flocculation with FeCl3, Al2(SO4)3 and Ca(OH)2 coagulant aids in wastewater. Sep Sci Technol. 44:1525–1543CrossRefGoogle Scholar
  28. Snodgrass WJ, Clark MM, O'Melia CR (1984) Particle formation and growth in dilute aluminum(III) solutions: characterization of particle size distributions at pH 5.5. Water Res 18:479–488CrossRefGoogle Scholar
  29. Sun Q, Li Y, Tang T, Yuan Z, Yu CP (2013) Removal of silver nanoparticles by coagulation processes. J Hazard Mater 261:414–420CrossRefGoogle Scholar
  30. Sun Y, Wang Y, Xue N, Yu C, Meng Y, Gao B, Li Q (2017) The effect of DOM on floc formation and membrane fouling in coagulation/ultrafiltration process for treating TiO2 nanoparticles in various aquatic media. Chem Eng J 316:429–437CrossRefGoogle Scholar
  31. Tang T (2012) Release and removal mechanism of nanosilver particles by coagulantion process. Dissertation, Anhui University of Science and TechnologyGoogle Scholar
  32. Tkaczyk M, Krzak-Ros J, Kaleta J (2012) Evaluation of mechanical and physicochemical properties of protection coatings obtained by the sol-gel method. Mater Sci 48:323–331CrossRefGoogle Scholar
  33. Wang B, Shui Y, He M, Liu P (2017) Comparison of flocs characteristics using before and after composite coagulants under different coagulation mechanisms. Biochem Eng J 121:107–117CrossRefGoogle Scholar
  34. Wang D, Wu R, Jiang Y, Chow CWK (2011) Characterization of floc structure and strength: role of changing shear rates under various coagulation mechanisms. Colloids Surf A Physicochem Eng Asp 379:36–42CrossRefGoogle Scholar
  35. Wang D, Zhao T, Yan L, Mi Z, Gu Q, Zhang Y (2016a) Synthesis, characterization and evaluation of dewatering properties of chitosan-grafting DMDAAC flocculants. Int J Biol Macromol 92:761–768CrossRefGoogle Scholar
  36. Wang J, Guan J, Santiwong SR, Waite TD (2008) Characterization of floc size and structure under different monomer and polymer coagulants on microfiltration membrane fouling. J Membr Sci 321:132–138CrossRefGoogle Scholar
  37. Wang JP, Chen YZ, Yuan SJ, Sheng GP, Yu HQ (2009a) 18 Synthesis and characterization of a novel cationic chitosan-based flocculant with a high water-solubility for pulp mill wastewater treatment. Water Res 43:5267–5275CrossRefGoogle Scholar
  38. Wang L, Niu C-G, Wang Y, Wang Y, Zeng G-M (2016b) The synthesis of Ag/AgCl/BiFeO3 photocatalyst with enhanced visible photocatalytic activity. Ceram Int 42:18605–18611CrossRefGoogle Scholar
  39. Wang Y, Gao BY, Xu XM, Xu WY, Xu GY (2009b) Characterization of floc size, strength and structure in various aluminum coagulants treatment. J Colloid Interface Sci 332:354–359CrossRefGoogle Scholar
  40. Wang Y, Li X, Wu C, Zhao Y, Gao BY, Yue Q (2014) The role of sodium alginate in improving floc size and strength and the subsequent effects on ultrafiltration membrane fouling. Environ Technol 35:10–17CrossRefGoogle Scholar
  41. Wang Y, Xue N, Chu Y, Sun Y, Yan H, Han Q (2015) CuO nanoparticle–humic acid (CuONP–HA) composite contaminant removal by coagulation/ultrafiltration process: the application of sodium alginate as coagulant aid. Desalination 367:265–271CrossRefGoogle Scholar
  42. Wu C, Wang Y, Gao B, Zhao Y, Yue Q (2012) Coagulation performance and floc characteristics of aluminum sulfate using sodium alginate as coagulant aid for synthetic dying wastewater treatment. Sep Purif Technol 95:180–187CrossRefGoogle Scholar
  43. Yukselen MA, Gregory J (2004) The reversibility of floc breakage. Int J Miner Process 73:251–259CrossRefGoogle Scholar
  44. Zhao Y, Sun Y, Tian C, Gao B, Wang Y, Shon H, Yang Y (2017) Titanium tetrachloride for silver nanoparticle-humic acid composite contaminant removal in coagulation-ultrafiltration hybrid process: floc property and membrane fouling. Environ Sci Pollut Res Int 24:1757–1768CrossRefGoogle Scholar
  45. Zhao YX, Gao BY, Wang Y, Shon HK, Bo XW, Yue QY (2012) Coagulation performance and floc characteristics with polyaluminum chloride using sodium alginate as coagulant aid: a preliminary assessment. Chem Eng J 183:387–394CrossRefGoogle Scholar
  46. Zhao YX, Gao BY, Zhang GZ, Qi QB, Wang Y, Phuntsho S, Kim JH, Shon HK, Yue QY, Li Q (2014) Coagulation and sludge recovery using titanium tetrachloride as coagulant for real water treatment: a comparison against traditional aluminum and iron salts. Sep Purif Technol 130:19–27CrossRefGoogle Scholar
  47. Zhao YX, Phuntsho S, Gao BY, Huang X, Qi QB, Yue QY, Wang Y, Kim JH, Shon HK (2013) Preparation and characterization of novel polytitanium tetrachloride coagulant for water purification. Environ Sci Technol 47:12966–12975CrossRefGoogle Scholar
  48. Zhou XH, Huang BC, Zhou T, Liu YC, Shi HC (2015) Aggregation behavior of engineered nanoparticles and their impact on activated sludge in wastewater treatment. Chemosphere 119:568–576CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  1. 1.Shandong Key Laboratory of Water Pollution Control and Resource Reuse, School of Environmental Science and EngineeringShandong UniversityJinanChina
  2. 2.Key Laboratory for Special Functional Aggregated Materials of Education Ministry, School of Chemistry and Chemical EngineeringShandong UniversityJinanChina
  3. 3.Department of Laboratory MedicineUniversity of WashingtonSeattleUSA

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