In situ kinetics and flocs conformation studies of kaolinite flocculated by Chi-g-CPAM

Abstract

This study presents a comparative study of the flocculation behavior of kaolinite induced by chitosan-graft-poly(acrylamide-dimethyl diallyl ammonium chloride) (Chi-g-CPAM) and a commercial cationic polyacrylamide (CPAM). The flocculation behaviour was characterised in terms of both flocculation kinetics and the corresponding morphology changes during flocculation. Both Chi-g-CPAM and CPAM were grafted from silica wafers by means of atom transfer radical polymerization (ATRP). The quartz crystal microbalance with dissipation (QCM-D) tests were conducted. The equilibrium time flocculated by Chi-g-CPAM was found to be 0.46 times as that of CPAM, together with a larger total mass of kaolinite layer. The flocculation behaviour by Chi-g-CPAM can be well captured by a pseudo-first-order model. In contrast, the presence of CPAM leads to a more complex kinetics. A relatively larger fitting slope (0.4663) was obtained at the initial stage but the fitting slope droped to 0.2026 after 800 min, indicating a densification process caused by CPAM. The flocculation kinetics of CPAM can be captured by the Elovich model for the inital stage but the combination of pseudo-first-order and pseudo-second-order models for the latter stages, which can be attributed to the long chain of CPAM. With a dosage of 75 g/t, the settling test with Chi-g-CPAM exhibits the same turbidity in the supernatant but a smaller layer thickness of the settlement compared to CPAM. The study enables a better understanding of the flocculation behavior and contributes to the development of efficient flocculants in mineral processing and tailings treatment.

Keywords

Chi-g-CPAM / flocculation / QCM-D / kinetics / conformation

References

[1] T.G. Ambaye, M. Vaccari, S. Prasad, E.D. van Hullebusch, and S. Rtimi, Preparation and applications of chitosan and cellulose composite materials, J. Environ. Manage., 301(2022), art. No. 113850.

[2] Bertoni FA, González JC, García SI, Sala LF, Bellú SE. Application of chitosan in removal of molybdate ions from contaminated water and groundwater. Carbohydr. Polym., 2018, 180, 55.

[3] Salehizadeh H, Yan N, Farnood R. Recent advances in polysaccharide bio-based flocculants. Biotechnol. Adv., 2018, 36(1): 92.

[4] C.L. Vieira, F.O.S. Neto, V.H. Carvalho-Silva, and R. Signini, Design of apolar chitosan-type adsorbent for removal of Cu(II) and Pb(II): An experimental and DFT viewpoint of the complexation process, J. Environ. Chem. Eng., 7(2019), No. 3, art. No. 103070.

[5] Y.J. Sun, S.B. Zhou, S.Y. Pan, S.C. Zhu, Y. Yu, and H.L. Zheng, Performance evaluation and optimization of flocculation process for removing heavy metal, Chem. Eng. J., 385(2020), art. No. 123911.

[6] X.M. Tang, T. Huang, S.X. Zhang, W. Wang, and H.L. Zheng, The role of sulfonated chitosan-based flocculant in the treatment of hematite wastewater containing heavy metals, Colloids Surf. A, 585(2020), art. No. 124070.

[7] Subramaniam S, Foo KY, Yusof ENM, Jawad AH, Wilson LD, Sabar S. Hydrothermal synthesis of phosphorylated chitosan and its adsorption performance towards Acid Red 88 dye. Int. J. Biol. Macromol., 2021, 193, 1716.

[8] Wang JP, Chen YZ, Zhang SJ, Yu HQ. A chitosan-based flocculant prepared with gamma-irradiation-induced grafting. Bioresour. Technol., 2008, 99(9): 3397.

[9] Lu X, Xu YH, Sun WQ, Sun YJ, Zheng HL. UV-initiated synthesis of a novel chitosan-based flocculant with high flocculation efficiency for algal removal. Sci. Total Environ., 2017, 609, 410.

[10] Zeng T, Hu XQ, Wu H, Yang JW, Zhang HB. Microwave assisted synthesis and characterization of a novel bio-based flocculant from dextran and chitosan. Int. J. Biol. Macromol., 2019, 131, 760.

[11] Wang DF, Zhao TQ, Yan LQ, Mi ZM, Gu Q, Zhang YM. Synthesis, characterization and evaluation of dewatering properties of chitosan-grafting DMDAAC flocculants. Int. J. Biol. Macromol., 2016, 92, 761.

[12] Yang K, Wang G, Chen XM, Wang X, Liu FL. Treatment of wastewater containing Cu²⁺ using a novel macromolecular heavy metal chelating flocculant xanthated chitosan. Colloids Surf. A, 2018, 558, 384.

[13] N.S.M. Hatta, S.W. Lau, M. Takeo, et al., Novel cationic chitosan-like bioflocculant from Citrobacter youngae GTC 01314 for the treatment of kaolin suspension and activated sludge, J. Environ. Chem. Eng., 9(2021), No. 4, art. No. 105297.

[14] N. Molaei, S.C. Chelgani, and E.R. Bobicki, A comparison study between bioflocculants and PAM for dewatering of ultrafine phyllosilicate clay minerals, Appl. Clay Sci., 218(2022), art. No. 106409.

[15] Y.J. Sun, D. Li, X. Lu, J.W. Sheng, X. Zheng, and X.F. Xiao, Flocculation of combined contaminants of dye and heavy metal by nano-chitosan flocculants, J. Environ. Manage., 299(2021), art. No. 113589.

[16] Zhu HC, Zhang Y, Yang XG, et al. One-step green synthesis of non-hazardous dicarboxyl cellulose flocculant and its flocculation activity evaluation. J. Hazard. Mater., 2015, 296, 1.

[17] Zheng D, Song WD, Tan YY, Cao S, Yang ZL, Sun LJ. Fractal and microscopic quantitative characterization of unclassified tailings flocs. Int. J. Miner. Metall. Mater., 2021, 28(9): 1429.

[18] S. Lv, W.J. Peng, Y.J. Cao, et al., Synthesis and characterisation of a novel pH-sensitive flocculant and its flocculation performance, J. Mol. Liq., 348(2022), art. No. 118480.

[19] Y. Xu, K.M. Gan, S.Y. Liang, H.T. Liu, and Q.H. Wang, Investigation and optimization of chitosan performance in flocculating Kaolin suspensions using a real-time suspending solid concentration measuring method, Water, 13(2021), No. 4, art. No. 513.

[20] J. Zeng, D.Q. Zhang, W.F. Liu, et al., Preparation of carboxymethylated lignin-based multifunctional flocculant and its application for copper-containing wastewater, Eur. Polym. J., 164(2022), art. No. 110967.

[21] Wang DL, Zhang QL, Chen QS, Qi CC, Feng Y, Xiao CC. Temperature variation characteristics in flocculation settlement of tailings and its mechanism. Int. J. Miner. Metall. Mater., 2020, 27(11): 1438.

[22] M.X. Wang, L. Feng, X.Y. You, and H.L. Zheng, Effect of fine structure of chitosan-based flocculants on the flocculation of bentonite and humic acid: Evaluation and modeling, Chemosphere, 264(2021), art. No. 128525.

[23] Wang SS, Zhang L, Yan B, Xu HL, Liu QX, Zeng HB. Molecular and surface interactions between polymer flocculant chitosan-g-polyacrylamide and kaolinite particles: Impact of salinity. J. Phys. Chem. C, 2015, 119(13): 7327.

[24] R.J. Xu, W.J. Zou, T. Wang, J. Huang, Z.J. Zhang, and C.Y. Xu, Adsorption and interaction mechanisms of Chi-g-P(AM-DMDAAC) assisted settling of kaolinite in a two-step flocculation process, Sci. Total Environ., 816(2022), art. No. 151576.

[25] S.C. Medina, A.S.F. Farinha, A.H. Emwas, A. Tabatabai, and T. Leiknes, A fundamental study of adsorption kinetics of surfactants onto metal oxides using quartz crystal microbalance with dissipation (QCM-D), Colloids Surf. A, 586(2020), art. No. 124237.

[26] Kou J, Xu SH. In situ kinetics and conformation studies of dodecylamine adsorption onto zinc sulfide using a quartz crystal microbalance with dissipation (QCM-D). Colloids Surf. A, 2016, 490, 110.

[27] Teng FC, Liu QX, Zeng HB. In situ kinetic study of zinc sulfide activation using a quartz crystal microbalance with dissipation (QCM-D). J. Colloid Interface Sci., 2012, 368(1): 512.

[28] M. Borsari, N. Braidi, M. Buffagni, et al., Copper-catalyzed ARGET ATRP of styrene from ethyl α-haloisobutyrate in EtOAc/EtOH, using ascorbic acid/Na₂CO₃ as reducing system, Eur. Polym. J., 157(2021), art. No. 110675.

[29] A. Taniguchi, S. Tamura, and T. Ikegami, The relationship between polymer structures on silica particles and the separation characteristics of the corresponding columns for hydrophilic interaction chromatography, J. Chromatogr. A, 1618(2020), art. No. 460837.

[30] Nazari Pour S, Ghugare SV, Wiens R, Gough K, Liu S. Controlled in situ formation of polyacrylamide hydrogel on PET surface via SI-ARGET-ATRP for wound dressings. Appl. Surf. Sci., 2015, 349, 695.

[31] Mirzaeinejad M, Mansoori Y, Amiri M. Amino functionalized ATRP-prepared polyacrylamide-g-magnetite nanoparticles for the effective removal of Cu(II) ions: Kinetics investigations. Mater. Chem. Phys., 2018, 205, 195.

[32] C.H. Shi, W.Q. Sun, Y.J. Sun, L. Chen, Y.H. Xu, and M.D. Tang, Synthesis, characterization, and sludge dewaterability evaluation of the chitosan-based flocculant CCPAD, Polymers, 11(2019), No. 1, art. No. 95.

[33] W.J. Zou, L. Gong, J. Huang, et al., Probing the adsorption and interaction mechanisms of hydrophobically modified polyacrylamide P(AM-NaAA-C16DMAAC) on model coal surface: Impact of salinity, Miner. Eng., 141(2019), art. No. 105841.

[34] Paul S, Paul D, Basova T, Ray AK. Studies of adsorption and viscoelastic properties of proteins onto liquid crystal phthalocyanine surface using quartz crystal microbalance with dissipation technique. J. Phys. Chem. C, 2008, 112(31): 11822.

[35] Wang S, Song XP, Wang XJ, Chen QS, Qin JC, Ke YX. Influence of coarse tailings on flocculation settlement. Int. J. Miner. Metall. Mater., 2020, 27(8): 1065.

[36] Özacar M, Şengil A. A kinetic study of metal complex dye sorption onto pine sawdust. Process Biochem., 2005, 40(2): 565.

[37] Cheung CW, Porter JF, McKay G. Elovich equation and modified second-order equation for sorption of cadmium ions onto bone char. J. Chem. Technol. Biotechnol., 2000, 75(11): 963.

[38] Chien SH, Clayton WR. Application of Elovich equation o the kinetics of phosphate release and sorption in soils. Soil Sci. Soc. Am. J., 1980, 44(2): 265.

[39] Sedeva IG, Fornasiero D, Ralston J, Beattie DA. The influence of surface hydrophobicity on polyacrylamide adsorption. Langmuir, 2009, 25(8): 4514.

[40] Teng H, Hsieh CT. Activation energy for oxygen chemisorption on carbon at low temperatures. Ind. Eng. Chem. Res., 1999, 38(1): 292.

[41] Yang Z, Yang H, Jiang ZW, et al. Flocculation of both anionic and cationic dyes in aqueous solutions by the amphoteric grafting flocculant carboxymethyl chitosan-graft-polyacrylamide. J. Hazard. Mater., 2013, 254–255, 36.

[42] Feng L, Li XH, Lu WC, et al. Preparation of a graft modified flocculant based on chitosan by ultrasonic initiation and its synergistic effect with kaolin for the improvement of acid blue 83 (AB 83) removal. Int. J. Biol. Macromol., 2020, 150, 617.

[43] Feng L, Zheng HL, Tang XM, et al. The investigation of the specific behavior of a cationic block structure and its excellent flocculation performance in high-turbidity water treatment. RSC Adv., 2018, 8(27): 15119.

[44] Liu BZ, Zheng HL, Wang YL, et al. A novel carboxyl-rich chitosan-based polymer and its application for clay flocculation and cationic dye removal. Sci. Total Environ., 2018, 640–641, 107.