Polyacrylamides revisited: flocculation of kaolin suspensions and mature fine tailings

A series of acrylamide‐based water‐soluble (co)polymers was synthesized and they were investigated as flocculants of model kaolin suspensions and mature fine tailings of oil sands. The effects of molar mass, charge density, and polymer concentration on flocculation efficiency were studied by monitoring the initial settling rate during sedimentation. Hydrolyzed polyacrylamide (HPAM) with high molar mass and intermediate acrylic acid contents (0.14–0.41 mol/mol (14–41 mol%)) performed better in flocculation tests on kaolin suspensions requiring lower dose for maximum initial settling rate than native polyacrylamide (PAM). Surface force measurements showed that at low polymer concentrations (1 ppm), the partially‐adsorbed polymer induced a bridging attraction between the mica surfaces. Increasing the polymer concentration to 10 and 50 ppm caused purely repulsive forces. The presence of anionic groups in HPAM led to stronger repulsion, which was also demonstrated by the higher viscosity and larger hydrodynamic radius of the charged polymer. The charge‐induced increase in the viscosity of polymer solutions was suppressed by the screening effect of salts in a buffer solution and reducing the viscosity is desirable in the injection of flocculants in the industrial process.     

Flocculation of kaolin suspension with cationic polymer

Flocculation experiments have been carried out using cationic polymers and kaolin suspensions. The effects of polymer dosage, kaolin concentration, pH, agitation, molecular weight and charge density of polymer, concentration of polymer solution, and addition of inorganic salt were systematically examined. It was found that two optimal points of polymer dosage exist between 0 to 8 × 10^?3 kg/kg-kaolin. The flocs formed at each optimal dosage are different from each other in shape and in size. It is concluded that these two kinds of flocculation are respectively caused by the neutralization of the surface charge of the particles due to the adsorption of free polymer and by the incomplete neutralization owing to the presence of polymer droplets.     

Influence of surfactants on flocculation and dewatering of kaolin suspensions by cationic polyacrylamide (PAM-C) flocculant

This paper reports the result of studies on flocculation and dewatering of kaolin suspensions by cationic polyacrylamide (PAM-C) flocculants in presence of surfactants. The surfactants used were namely anionic sodium dodecyl sulphate (SDS), cationic cetyl trimethyl ammonium bromide (CTAB) and non-ionic TritonX 100, which is a polyoxyethylenic ether compound. The unflocculated kaolin has a very slow settling rate of about 0.03 cm/s and can be improved by more than ten times using PAM-C as a flocculating agent. PAM-C adsorbs on kaolin primarily through electrostatic attraction and the flocculation is governed mainly by charge neutralisation and bridging. Partial pre-coating of kaolin with all three surfactants leads to both physical adsorption as well as chemisorption at PAM-C. Pretreating the kaolin with surfactants can further increase or decrease settling rate depending on the type of surfactant used. However, the flocs thus formed shows better filtration and dewatering behaviour estimated in terms of reduction in specific resistance to filtration (SRF) and cake moisture. The minimum SRF occurs under conditions corresponding to far lower adsorption of PAM-C than that for best flocculation. Simultaneous addition of PAM-C and each of the three surfactants decreases settling rate and sediment volume markedly and does not reduce SRF any further but they all reduce cake moisture substantially. The reduction in cake moisture for different PAM-C: surfactant mixture is in the following order: PAM-C: SDS (1:1)>PAM-C: TX 100(1:1)>PAM-C: CTAB(1:1). Low cake moisture in comparison with PAM-C alone, may be a result of reduction in entrapment of excess water in the smaller flocs formed by simultaneous addition with surfactants and to some extent due to hydrophobicity caused by adsorption of surfactants.     

Synthesis,characterization and application of water‐soluble star polymers based on 2,4,6‐tris‐hydroxymethyl phenol and polyacrylamide

The synthesis of star polymers based on 2,4,6‐tris‐hydroxymethyl phenol (THP) and polyacrylamide (PAM) was carried out by free radical polymerization using potassium persulfate as an initiator. THP was prepared from phenol and formaldehyde by the Lederer?Manasse reaction. Varying the amount of acrylamide monomer, five different grades of star polymer were synthesized (THP‐PAM1 to THP‐PAM5). The star polymers were characterized by infrared spectroscopy, NMR spectroscopy, thermal analysis, viscosity measurements, scanning electron microscopy and X‐ray diffractometry. The flocculation performance of the star polymers was studied in kaolin suspension using the jar test and settling test methods. The flocculation efficiency of the star polymers was compared with commercially available flocculants and linear PAM. Several dye removal tests using methylene blue and various commercial textile acid dyes were performed. UV?visible spectra were employed to determine the reduced presence of dyes in the kaolin suspensions after treatment with star polymers. © 2014 Society of Chemical Industry     

Flocculation behavior of some cationic polyelectrolytes

The settling rates and adsorption isotherms produced by a variety of suites of cationic polyelectrolytes in 3% kaolin suspensions were measured. Settling rates increased with molar mass even for low-mass, high-charge polymers. The very high settling rates produced by cationic copolymers of acrylamide decreased as the charge density of the polymer used increased. Hydrolysis of unbuffered polymers occurred over time and produced large changes in the effectiveness of the polymers. This is attributed to conformational changes. © 1994 John Wiley & Sons, Inc.     

Comparison of two cationic polymeric flocculant architectures on the destabilization of negatively charged latex suspensions

Flocculation studies between cationic polymers and oppositely charged colloidal particles are reported in which both flocculation kinetics and floc structures are systematically investigated. The flocculation rate constant, stability ratio and kinetics laws are experimentally determined using particle counting for two polymer architectures; a cationic linear polymer and a two-branched polymer. Comparisons are also made using NaCl at different ionic concentrations for the destabilization of the colloidal particles. Detailed measurements of electrophoretic mobility and kinetics rate constants on varying the polymer dosage are reported. Results suggest that the polymer architecture plays important roles on the polymer dosage for the rapid destabilization of the colloidal suspension. The branched polymer at optimal dosage exhibits the highest flocculation rate constant, whereas on the other hand, the linear polymer concentration range of flocculation is larger. In both cases, polymer flocculation is more efficient by a factor of 5-6 than charge screening effects due to the presence of salt. Analysis of the stability ratio indicates that tele-bridging flocculation and electrostatic forces dictate the stability of the charged latex particle suspension. It is shown that the fractal concepts which are valid for aggregation processes are also applicable here and branched polymers as well as linear polymers yield to the formation of compact flocs in comparison to those obtained with salt.     

An investigation of the flocculation characteristics of polyacrylamide‐grafted chitosan

To investigate the flocculation characteristics of polyacrylamide (PAM)‐grafted chitosan, a series of PAM‐grafted chitosan copolymer (Chito‐g‐PAM1 to Chito‐g‐PAM4) have been synthesized by ceric ammonium nitrate‐induced solution polymerization technique in nitrogen atmosphere. The flocculation characteristics of the polymer samples (PAM, grafted and ungrafted chitosan) were studied by settling test and jar test methods in the colloidal suspensions of kaolin, iron ore, silica, and bentonite powder. It was found that the settling performance of Chito‐g‐PAM3 is best among the polymer samples. The jar test results indicate that the ungrafted chitosan has better water clarifying performance than both the PAM and grafted chitosan. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The effects of cationic polymers on flocculation of a coal thickener feed in washery water as a function of pH

The flocculation of a thickener feed using three cationic polyacrylamide copolymers of high molar mass and different charge densities was studied at three pHs in washery water. The binding capacities were very dependent on pH but only slightly dependent on the polymeric charge density. The reverse was true for the settling rates. At pH 7, all three polymers were equally effective at clarifying the suspensions, but there were marked differences at pH 4 and 9. For the polymers of highest charge density, reducing the pH increased their effectiveness; for the polymer of lower charge density, changing the pH had little effect on the residual turbidity. © l997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 783–789, 1997     

Flocculation of coal suspension with mono/dual polymer systems and contribution of Ca(II)/Mg(II) ions

In the experimental study carried out on mono-flocculation, anionic and especially non-ionic polymers strongly flocculated the coal suspension than cationic polymer. The dual-flocculation of the coal suspension with cationic and anionic polymer combination was also studied and the high performances of flocculation were also reached with dual-polymer approach. Furthermore, dual-polymer system required lower concentrations for the successful flocculation of coal particles. On the other hand, the pre-destabilization of the coal suspension with calcium and magnesium ions at particular pH and concentrations highly improved the flocculation of fine coal particles with these polymers.     

Kinetic aspects of flocculation by cationic polymers

Flocculation of latex particles by a series of cationic polymers has been investigated, with special attention being paid to the effect of particle concentration. Both initial rate and ultimate extent of flocculation have been examined over a range of polymer concentrations, so that the onset of flocculation and of restabilisation could be established. At low particle concentrations, the effect of the polymers seems to be predominantly charge neutralisation; even high molecular weight polymers do not appear to form ‘bridges’, presumably because of the relatively flat configuration of the adsorbed polymer chains. However, at high particle concentrations, bridging flocculation may occur because adsorbed polymer chains require a finite time to attain their equilibrium configuration. Some practical implications of these findings are briefly discussed.     

Surface modification of sepiolite particles with polyurethane and polyvinyl alcohol

Sepiolite is a clay mineral that has many industrial applications due to its advantageous properties such as white color, low specific gravity, high absorption capacity, chemical composition and low thermal conductivity. In this study, the effect of the addition of polymers, polyvinyl-alcohol and polyurethane, on the rheological properties of the sepiolite dispersions have been investigated. The rheological parameters of clay suspensions can be used to examine particle–particle interactions. The polymers that have been added to the clay suspensions interact with clay particles, depending on their ionic or non-ionic character. Firstly, the sepiolite dispersions were characterized by the rheological properties, mineral structure and content. Then the effect of the polymers on the flow, structural, and surface properties of sepiolite dispersions was investigated by rheological, electrokinetical, and scanning electron microscopy (SEM) measurements. The measurements showed that polymer molecules bind on the surface of sepiolite particles and changed the flow properties of the dispersions as stable dispersions at some certain concentrations. It is also determined that PU polymer covered the surface of the sepiolite faster than PVA, but the coverage of the PVA was much more smoothly. The thermal properties of the sepiolite improved with PVA more than PU, as a result of the homogenous surface coverage.     

Flocculation and sedimentation of cane sugar juice particles with cationic homo‐ and copolymers

Rapid flocculation and sedimentation of suspended particles in primary cane sugar juice is achieved using a high molecular weight anionic polymer flocculant. This work reports on efforts to enhance the performance of an anionic flocculant by the addition of cationic polymers. Homopolymers of poly(trimethylammonium ethyl methacrylate chloride) (TMAEMAC) and cationic copolymers of poly(trimethylammonium ethyl acrylate chloride) (TMAEAC) and acrylamide were synthesized and their performance, to enhance the flocculation and sedimentation of cane sugar juice particles, was evaluated by turbidity and settling rate measurements. The charge–patch mechanism best explains the performance of the homopolymers, whereas the action of the copolymers is attributed to the bridging mechanism. The results of this work indicate that the copolymers are more effective than the homopolymers to aid flocculation and sedimentation of the cane sugar juice particles, and that the best‐performing polymers are those that act by the bridging mechanism. Addition of increased amounts of anionic flocculant did not confer an improvement, suggesting that the cationic bridging flocculant targets a different population of particles that is largely responsible for the residual turbidity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 316–325, 2003     

Solution properties and flocculation of hydrophobically associating cationic fluorinated polyacrylamide

The hydrophobically associating cationic fluorinated polyacrylamide (CFPAM), modified with fluorinated acrylate, 2-(perfluorooctyl)ethyl acrylate (FEA), has been newly synthesized, by free radical micellar copolymerization in aqueous solution. The solution properties of these polymers were investigated in details in this study. In addition, the flocculation of CFPAM was also evaluated. The results showed that there were strong hydrophobic associations in the CFPAM aqueous solution. The addition of NaCl resulted in an increase of solution viscosity, which indicated the good salt-resistant performance of CFPAM. The polymers also exhibited excellent property of temperature and shearing tolerance. Furthermore, the polymer showed high surface activity. At the same time, its flocculation properties were evaluated with kaolin suspensions using a standard jar test. All the results demonstrated the superiority of the cationic fluorinated polyacrylamide as a flocculant.     

Chitosan‐graft‐acrylamide polyelectrolytes: Synthesis,flocculation, and modeling

A series of chitosans have been grafted with quaternary ammonium cationic monomers, as well as acrylamide using Ce(IV) to induce macroradical formation on the polysaccharide backbone. The materials, which have long chain branches per molecule between 0.3 and 5.5, are shown to provide very high specific flocculation efficiency, at the very least equal to the entirely synthetic materials which have been previously documented in the literature. A charge ratio, determined from the polymer concentration at which flocculation takes place, the charge density of the polymer, and the surface charge of the suspended matter are proposed as metrics to evaluate the occurrence of charge neutralization and bridging or charge patch flocculation mechanism. Furthermore, a window of application (WA) for flocculants, which characterizes the region of concentration wherein the polyelectrolyte can remove 99% of the supernatant turbidity, has been defined. It was shown to depend on the square root of the ionic strength and varies inversely with the Debye length, providing a fundamental basis for the concept of the WA. A mathematical expression is presented which links the WA with the salt concentration and the number of branches of the grafted polymer. Grafted chitosans have been shown to be more robust than polyacrylamides in testing against model kaolin suspensions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 885–896, 2006     

Adsorption of Hydroxypropyl Methyl Cellulose in an Aqueous System Containing Multicomponent Oxide Particles

The adsorption behavior of a hydroxypropyl methyl cellulose (HPMC) polymer in aqueous suspensions of alumina, silica, kaolin, and talc powders, two-component combinations, and one three-component combination was determined. Powders were well characterized by chemical analysis, XRD, DRIFT, SEM, particle size, surface area, and density analyses. The zeta-potential of each powder in aqueous suspension was determined over a range of pH to determine particle charging and the isoelectric point for each material. Alumina and silica powders having heavily hydroxylated surfaces were observed not to adsorb the HPMC polymer over a range of pH. The layer-type minerals talc, which was noticeably hydrophobic, and kaolin, which had differently hydrated basal planes, adsorbed the HPMC polymer but in different amounts per unit of surface area. In the two-component systems, HPMC polymer adsorption for systems of dispersed particles of like electrical charge (kaolin + silica, talc + silica or alumina, and kaolin + talc) was proportionate to the sum of the fraction x specific surface area x adsorption capacity for each particle type. In systems where particles had an opposite electrical charge (kaolin + alumina, kaolin + talc + alumina), the HPMC polymer adsorption was significantly lower than that calculated for a dispersed system. SEM analysis showed very fine, nonadsorbing alumina particles predominantly on the faces of the adsorbing kaolin particles that apparently masked polymer adsorption. Results suggested a hydrophobic mechanism for the HPMC polymer adsorption and adsorption on only one face of the kaolin particles.     

Preparation of polyacrylamide grafted collagen extracted from leather wastes and their application in kaolin flocculation

This is probably the first report on the synthesis of a series of novel collagen‐based flocculants (CP11, CP12, and CP13) by grafting polyacrylamide (PAM) chains onto the collagen backbone, which was directly extracted from leather shavings via alkali hydrolysis. The results from FTIR, XRD, ¹H NMR, and TGA well supported that PAM chains had been successfully grafted onto collagen backbone. In addition, the micrographs of SEM revealed that the PAM grafted collagen possessed much more porous and looser surface structures in comparison with virgin collagen. Zeta potential measurement showed that the introduction of branched PAM chains helped to improve the positively charge density. Furthermore, CP12 performed the best in the kaolin flocculation with the highest flocculation rate about 24%·min^?1 and could induce the generation of much larger and denser floccs for the fast settling of kaolin particles. The corresponding flocculation mechanism was also presented by analyzing the collected flocs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41556.     

Effect of molecular weight of poly(N‐isopropyl acrylamide) temperature‐sensitive flocculants on dewatering

The influence of molecular weight (MW) and dose of Poly(N‐isopropyl acrylamide) (PNIPAM) (temperature‐sensitive flocculant) on sedimentation rate, sediment density, and supernatant clarity of silica suspensions was investigated. The addition of PNIPAM resulted in rapid sedimentation (T > critical solution temperature, CST) and low sediment moisture (T < CST). Higher MW polymers resulted in more effective flocculation and sediment consolidation. At 10 ppm, PNIPAM (3.6 million Da) produced 20 m/h settling rate and 48 vol % solids sediment density, whereas 0.23 million Da polymer produced 0.1 m/h settling rate. PNIPAM produces effective flocculation and consolidation by cycling the interparticle interactions between repulsion and attraction as temperature is cycled around the CST. The change in temperature produces a hydrophilic/hydrophobic transition of the polymer, influencing adsorption onto the surface and the inter‐particle forces. Conventional polyacrylamide flocculants (not influenced by temperature), cannot be used to produce both rapid sedimentation and dense sediments. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

The flocculation of kaolin by cationic polyacrylamides and the effect of cationic surfactant on this process

The flocculation of kaolin suspended in a dilute salt solution was studied as a function of the addition of cationic surfactant and cationic polyacrylamide (CPAM) added separately, consecutively, or simultaneously. Cationic polyacrylamide caused flocculation by bridging when added in low concentrations, but at higher concentrations, charge neutralization became the dominant mechanism and the flocculation rate was highly dependent on the charge density of the polymer. Adsorption of sufficient polymer or surfactant (cetyl pyridinium chloride) prevented immediate adsorption of the other, although surfactant could replace polymer after extended agitation. The adsorption of polymer was greatest when small flocs were formed by charge neutralization or by prolonged shaking. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2382–2389, 2002     

Dewatering of Phosphatic Clay Waste by Flocculation

This work focuses on the dewatering of phosphatic clay waste of Egyptian Abu‐Tartur phosphate ore by flocculation using polyacrylamides to enhance the dewatering rate and recycling of the process water. The experimental program includes sieving, hydrocyclone separation and flocculation of the overflow of hydrocyclone. Results revealed that the coarser fraction larger than 32 micron is enriched with P₂O₅ whereas the undersize fraction is only clay. Hydrocyclone successfully separates two cuts; the underflow fraction is enriched with phosphate while the other is just clay. By this technique, the P₂O₅ content is increased from 15.57 % in the feed to 26 % in the underflow cut which constitutes about 39.8 % by weight. Flocculation helps to increase both the settling rate of phosphatic clay waste and recycling the process water. The former criteria increased 37 times by using anionic polyacrylamide (A130) as compared to the natural settling rate of the same waste. Results were explained in the light of a model which suggests that the flocculation mechanism involves two stages: the first stage involves the adsorption of the reagent on the particles whereas the second forms aggregate flocs. Formation of aggregate flocs takes place by tangling the polymer molecules, so that one polymer molecule will be adsorbed at several points on the surface of the particle, leaving loops which may be of varying lengths, projecting out from the surface. Partially covered particles would collide to form bridges.     

Rheological Behavior of Coating Colors: Influence of Thickener

In this work we have investigated the effect of rheology modifiers on the rheological properties of concentrated (65 solids mass%) kaolin suspensions and six different coating colors. Measurements have been performed on kaolin‐based suspensions, without rheology modifier and with either a classic cellulose thickener or associative polymers. It was noticed that suspensions containing a thickener had a much larger viscosity and storage and loss moduli than suspensions containing no rheology modifier. The enhancement of the rheological properties was found to be much more important for the suspensions containing the associative polymer. These observations have been related to steric stabilization of the suspensions, and to the occurrence of entanglements and bridging when the associative polymer was used as the thickener. The influence of the thickener on the rheological properties of the coating colors was found to be similar to that observed for the concentrated kaolin suspensions.