The effect of polyacrylic acid on the surface properties of calcite and fluorite aiming at their selective flotation
Chenhu Zhang 1  
,   Zhiyong Gao 1,   Yuehua Hu 1,   Wei Sun 1,   Honghu Tang 1,   Zhigang Yin,   Jianyong He 1,   Qingjun Guan 1,   Yangge Zhu 2
More details
Hide details
School of Mineral Processing and Bioengineering, Central South University, Changsha 410083, China
State Key Laboratory of Mineral Processing, Beijing General Research Institute of Mining and Metallurgy, Beijing 102600, China
Chenhu Zhang   

Central South University, 932 southlushan road, 410083 changsha, China
Physicochem. Probl. Miner. Process. 2018;54(3):868–877
In this study, the polyacrylic acid (PAA) was studied as a selective depressant for calcite in the selective flotation of fluorite and calcite, and the implications of this process for the separation of fluorite ore were studied using micro-flotation tests, and the results were analyzed with Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) analyses. The flotation tests indicated that the preferential adsorption of PAA onto calcite rather than sodium oleate (NaOl) could selectively depress the flotation of calcite, allowing its separation from fluorite at pH 7. The zeta potential of calcite became more negative with the addition of PAA rather than with NaOl. However, the characteristic features of PAA adsorption were not observed for fluorite, suggesting that NaOl preferentially adsorbed on the surface of fluorite, or that PAA could be replaced by NaOl on the fluorite surface. FT-IR and XPS analysis were utilized to obtain a better understanding of the mechanism by which PAA was more strongly adsorbed on the calcite surface than NaOl. This was revealed to occur through chemical bonding between the carboxyl group of PAA and the hydroxyl groups of the Ca species on the calcite surface, modifying the structure of the adsorbed layer. A possible adsorption mechanism, along with a postulated adsorption mode for the surface interaction between PAA and calcite, is proposed.
LOPEZ-VALDIVIESO A., ROBLEDO-CABRERAA A. and BA U-S., 2000. Flotation of celestite with the anionic collector sodium dodecyl sulfate. Effect of carbonate ions, International Journal of Mineral Processing, 60(2), 79-90.
AL MAHROUQI D., VINOGRADOV J. and JACKSON M.D., 2017. Zeta potential of artificial and natural calcite in aqueous solution, Advances in Colloid and Interface Science, 240, 60-76.
ALIAGA W., SAMPAIO C.H., BRUM I.A.S., FERREIRA K.R.S. and BATISTELLA M.A., 2006. Flotation of high-grade fluorite in a short column under negative bias regime, Minerals Engineering, 19(13),1393-1396.
ALEXANDER M.R., PAYAN S. and DUC T.M., 2015. Interfacial interactions of plasma‐polymerized acrylic acid and an oxidized aluminium surface investigated using XPS, FTIR and poly(acrylic acid) as a model compound, Surface and Interface Analysis, 26(13), 961-973.
ANIRUDHAN T.S., SHAINY F. and CHRISTA J., 2016. Synthesis and characterization of polyacrylic acid- grafted-carboxylic graphene/titanium nanotube composite for the effective removal of enrofloxacin from aqueous solutions: Adsorption and photocatalytic degradation studies, Journal of Hazardous Materials, 324(B), 117-130.
BAHADUR S., GONG D. and ANDEREGG J., 1996. Investigation of the influence of CaS, CaO and CaF2 fillers on the transfer and wear of nylon by microscopy and XPS analysis, Wear., 197(1-2), 271-279.
BO F., XIANPING L., JINQING W. and PENGCHENG W., 2015. The flotation separation of scheelite from calcite using acidified sodium silicate as depressant, Minerals Engineering, 80, 45-49.
BILLINGHAM J., BREEN C. and YARWOOD J., 1997. Adsorption of polyamine, polyacrylic acid and polyethylene glycol on montmorillonite: An in situ study using ATR-FTIR, Vib. Spectrosc., 14(1), 19-34.
CASTRO F.H.B.D. and HOCES M.C.D., 1993. Influence of quebracho and sodium silicate on flotation of celestite and calcite with sodium oleate, International Journal of Mineral Processing, 37(3-4), 283-298.
CASTRO F.H.B.D., HOCES M.C.D. and BORREGO A.G., 1998. The effect of pH modifier on the flotation of celestite with sodium oleate and sodium metasilicate, Minerals Engineering, 11(10), 989-992.
CHADA V.G.R., HAUSNER D.B., STRONGIN D.R., ROUFF A.A. and REEDER R.J., 2005. Divalent Cd and Pb uptake on calcite {101-4} mathContainer Loading Mathjax cleavage faces: An XPS and AFM study, Journal of Colloid and Interface Science, 288(2), 350-360.
CIZAIRE L., MARTIN J.M., MOGNE T.L. and GRESSER E., 2004. Chemical analysis of overbased calcium sulfonate detergents by coupling XPS, ToF-SIMS, XANES, and EFTEM, Colloids and Surfaces A: Physicochemical and Engineering Aspects, 238(1-3), 151–158.
DALBY K.N., NESBITT H.W., ZAKAZNOVA-HERZOG V.P. and KING P.L., 2007. Resolution of bridging oxygen signals from O 1s spectra of silicate glasses using XPS: Implications for O and Si speciation, Geochimica et Cosmochimica Acta, 71(17), 4297-4313.
DAS K.K. and SOMASUNDARAN P., 2004. A kinetic investigation of the flocculation of alumina with polyacrylic acid, Journal of Colloid and Interface Science, 271(1), 102-109.
DRZYMALA J. and FUERSTENAU D.W., 2014. Selective flocculation of hematite in quartz–hematite–ferric ion–polyacrylic acid system. Part 2. Effect of grinding and a hydrofluoric treatment on selectivity of flocculation, International Journal of Mineral Processing, 129, 1-5.
GAO Z., BAI D., SUN W., CAO X. and HU Y., 2015. Selective flotation of scheelite from calcite and fluorite using a collector mixture, Minerals Engineering, 72, 23-26.
HU Y. and XU Z., 2003. Interactions of amphoteric amino phosphoric acids with calcium-containing minerals and selective flotation, International Journal of Mineral Processing, 72(1-4), 87-94.
HUANG Y.C., FOWKES F.M., LLOYD T.B. and SANDERS N.D., 1991. Adsorption of calcium ions from calcium chloride solutions onto calcium carbonate particles, Langmuir, 7(8), 1742-1748.
KANG J., CHEN C., SUN W., TANG H., YIN Z., LIU R., HU Y. and NGUYEN A.V., 2017. A significant improvement of scheelite recovery using recycled flotation wastewater treated by hydrometallurgical waste acid, Journal of Cleaner Production, 151, 419-426.
LI S, LEROY P, HEBERLING F, DEVAU N, JOUGNOT D and CHIABERGE C., 2016. Influence of surface conductivity on the apparent zeta potential of calcite, Journal of Colloid and Interface Science, 468, 262-275.
LIU C., FENG Q., ZHANG G., CHEN W. and CHEN Y., 2016. Effect of depressants in the selective flotation of scheelite and calcite using oxidized paraffin soap as collector, International Journal of Mineral Processing, 157, 210-215.
FREE M.L., MILLER J.D., 1996. The significance of collector colloid adsorption phenomena in the fluorite/oleate flotation system as revealed by FTIR/IRS and solution chemistry analysis, International Journal of Mineral Processing, 48(3-4), 197-216.
MILLER J.D., FA K., CALARA J.V. and PARUCHURI V.K., 2004. The surface charge of fluorite in the absence of surface carbonation, Colloids and Surfaces A: Physicochemical and Engineering Aspects, 238(1-3) 91-97.
SADOWSKI Z., 1993. The influence of the sodium oleate adsorption on the behavior of calcite suspensions, Chemical Engineering Science, 48(2), 305-312.
SHI Q., FENG Q., ZHANG G. and DENG H., 2014, A novel method to improve depressants actions on calcite flotation, Minerals Engineering, 55, 186-189.
ASSEMI S., NALASKOWSKI J., MILLER J.D., and JOHNSON W. P., 2006. Isoelectric Point of Fluorite by Direct Force Measurements Using Atomic Force Microscopy, Langmuir, 22(4), 1403-1405.
SONG S., LOPEZ-VALDIVIESO A., MARTINEZ-MARTINEZ C. and TORRES-ARMENTA R., 2006. Improving fluorite flotation from ores by dispersion processing, Minerals Engineering, 19(9), 912-917.
TANG Y., YANG W., YIN X., YING L., YIN P. and WANG J., 2008. Investigation of CaCO3 scale inhibition by PAA, ATMP and PAPEMP, Desalination, 228(1-3), 55-60.
YUAN P-Q., CHENG Z-M., ZHOU Z-M., YUAN W-K. and SEMIAT R., 2008. Zeta potential on the anti-scalant modified sub-micro calcite surface, Colloids and Surfaces A: Physicochemical and Engineering Aspects, 328(1-3), 60-66.
ZAWALA J., DRZYMALA J. and MALYSA K., 2008. An investigation into the mechanism of the three-phase contact formation at fluorite surface by colliding bubble, International Journal of Mineral Processing, 88(3-4), 72-79.
ZENG G., LIU Y., LIN T., YANG G., PANG Y., ZHANG Y., ZHOU Y., LI Z., LI M. and LAI M., 2015. Enhancement of Cd(II) adsorption by polyacrylic acid modified magnetic mesoporous carbon, Chemical Engineering Journal, 259, 153-160.
ZHANG Y. and SONG S., 2003. Beneficiation of fluorite by flotation in a new chemical scheme, Minerals Engineering, 16(7), 597-600.
ZHOU W., MORENO J., TORRES R. and SONG H.V.S., 2013. Flotation of fluorite from ores by using acidized water glass as depressant, Minerals Engineering, 45, 142-145.