Parameters affecting the performance of polyelectrolytes as aids to water clarification

An investigation of the flocculation of silica and alumina suspensions by a series of synthetic flocculants of a wide range of charge density both anionic and cationic in nature has been carried out. The extent of flocculation was determined by measurements of settling rate, sediment volume and supernatant clarity. The effect of the pH of the suspension on the performance of a number of selected polymers has been investigated. In the systems examined, flocculation was largely controlled by the charge carried by the suspended particles and polymer molecules. The dosage/settling rate characteristics of kaolin suspensions flocculated with non-ionic polymers of varying molecular weight are reported. The dosages of non-ionic polymers required for optimum flocculation of kaolin suspensions of varying solids content have been measured. At low particle concentrations bridging is less effective, and is probably reduced due to the adsorption of polymer molecules on to single particles.     

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     

Synthesis,characterization, flocculation,and rheological characteristics of hydrolyzed and unhydrolyzed polyacrylamide‐grafted poly(vinyl alcohol)

Graft copolymers of poly(vinyl alcohol) and polyacrylamide (PVA‐g‐PAM) were synthesized using a ceric ion–induced solution polymerization technique at 28°C. Three grades of graft copolymers were synthesized with varying acrylamide concentrations. Three grades of hydrolyzed products of PVA‐g‐PAM were synthesized with varying concentrations of sodium hydroxide solution. Hydrolyzed and unhydrolyzed PVA‐g‐PAM were characterized by viscometry, X‐ray diffractometry, infrared spectroscopy, and thermal analysis. Rheological investigation was also carried out on the aqueous solutions of various samples. The flocculation characteristics of various materials were investigated by the use of jar and settling tests in 0.25 and 5 wt %, respectively, using kaolin and iron ore suspensions. Among the series of graft copolymers, the one with fewest but longest PAM chains showed superior performance. The flocculation characteristics of the best‐performing graft copolymer were compared with those of various commercially available flocculants in the two suspensions under investigation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2109–2122, 2006     

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     

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     

Dispersion—flocculation studies on a Goethite-clay system

Dispersion–flocculation studies on a Goethite–clay system using flocculants were carried out as a function of flocculant concentrations, pH of slurry, time of agitation and dispersant dosage. Also, the effects of pH and polymer concentrations on the adsorption behaviour of the system were investigated. Results show that well flocculated goethite was preferentially obtained from 4% goethite/kaolinite clay suspensions, with 50 ppm causticised starch in the slurry at pH values of 3–11·5 and with 50 ppm polyacrylamide at pH values of 3–8. Good flocs were also obtained on flocculation of the goethite suspension with 50 ppm polyacrylamide at pH values of 5–7, while the kaolinite suspension did not respond to the same dosage of causticised starch in the same pH range. Results further reveal that for the goethite/kaolinite suspension, the best results was obtained with 50 ppm polyacrylamide at pH values of 7–10. Based on the data generated in the study, it was concluded that causticised starch is a better flocculant than polyacrylamide for goethite suspensions although polyacrylamide is an excellent flocculant for kaolinite suspensions.     

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     

Highly concentrated cationic flocculants based on 80/20 wt % [2‐(acryloyloxy)ethyl]trimethylammonium chloride/acrylamide in an inverse microemulsion: Influence of the copolymerization variables on the flocculation performance

The influence of the total comonomer concentration (TCC; 30–42 wt %), emulsifier concentration (EC; 7.3–23 wt %), hydrophilic–lipophilic balance (HLB; 9–9.9), crosslinking agent (N,N′‐methylene bisacrylamide) concentration (CAC; 0–122.8 ppm with respect to TCC), and isopropyl alcohol (chain‐transfer agent) concentration (IPC; 0–1.5 wt % with respect to TCC) on the flocculation performance (FP) of 80/20 wt % acrylamide (AM)/[2‐(acryloyloxy)ethyl]trimethylammonium chloride (ADQUAT) copolymers obtained by semicontinuous inverse microemulsion copolymerization was studied with capillary suction time testing for FP assessment on anaerobic digested sludges. FP increased as TCC decreased, was nearly unaffected by EC, was maximum with an HLB of 9.5, decreased strongly with CAC, and showed a peak value with an IPC of 1 wt %. At a very high TCC, copolymer growth in a highly collapsed state resulted in greatly structured, high weight‐average molar mass flocculants with decreased swelling capacities (SCs), which did not favor bridging flocculation, and in increased shielding of their positive charges, which did not favor charge neutralization flocculation. However, industrially needed latices with both high TCC and good FP could be obtained by the addition of isopropyl alcohol, which, below a concentration of 1 wt %, improved FP by decreasing the weight‐average molar mass and thereby enhancing SC while maintaining long enough chains to be effective for bridging flocculation. On the basis of the results, new star‐shaped ADQUAT/AM copolymers are envisioned as flocculants with superior FP. A synthetic route is proposed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Novel,rosin‐based,hydrophobically modified cationic polyacrylamide for kaolin suspension flocculation

A novel, hydrophobically modified cationic polyacrylamide (HMPAM) was synthesized via the copolymerization of acrylamide, diallyl dimethyl ammonium chloride (DMDAAC), and diallylmethyl dehydroabietic acid propyl ester ammonium bromide. Optimum conditions for preparing HMPAM were such that the amount of initiator was 0.075 wt % of the total monomer mass, the monomer concentration was 20 wt %, and the amount of DMDAAC was 18 mol % of the total monomer molar mass. HMPAM was characterized with an UV–visible spectrometer, ¹H‐NMR, Ubbelohde viscometer, rotational viscometer, and rotational rheometer. HMPAM solutions exhibited strong hydrophobic associations, and the critical association concentration of the HMPAM aqueous solution was about 0.7 wt %; the HMPAM solutions also showed salt thickening and shear resistance. The surface morphologies of the freeze‐dried HMPAM samples (1 wt %) were also observed via scanning electron microscopy. Compared with unmodified cationic polyacrylamide, Synthesis of HMPAM‐0.5 exhibited a stronger flocculation capacity, and the optimal transmittance of the supernatants was above 95%. HMPAM‐0.5 showed significant flocculation performances for 3–4 and 3–5 wt % kaolin suspensions at 40 and 50 mg/L, respectively. Moreover, the flocculation performance was enhanced with the addition of NaCl and CaCl₂. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46637.     

Rheology and polymer flooding characteristics of partially hydrolyzed polyacrylamide for enhanced heavy oil recovery

Polymer flooding characteristics of partially hydrolyzed polyacrylamide (HPAM) solution with the addition of NaOH were examined in homogeneous glass‐bead packs. The heavy oil recovery in unconsolidated sandstone formations by applying the alkali‐polymer flooding was observed. Experimental results showed that HPAM solution was sensitive to temperature, salinity, and alkali, finding that alkali‐polymer solutions are more effective in improving viscosity than conventional polymer solutions. The solution of 0.5 wt % NaOH mixed with 1500 ppm HPAM (12 mol % hydrolysis degree) was found to be the optimal choice, which gives rise to the highest viscosity on the rheological characterization. Flood tests using the alkali‐polymer solution showed an increase in oil recovery by 30% over water‐flooding when the water‐cut reached 95%, indicating that alkali‐polymer could be more effective in improving sweep efficiency than polymer flood. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis,characterization, and flocculation characteristics of polyacrylamide‐grafted glycogen

The synthesis of glycogen‐g‐polyacrylamide (Gly‐g‐PAM) was carried out by a ceric ion‐induced solution polymerization technique. Six grades of graft copolymers were synthesized by the variation of catalyst and monomer concentrations. These graft copolymers were characterized by intrinsic viscosity measurements, FTIR spectroscopy, and X‐ray diffraction techniques. Flocculation performance of these graft copolymers were done in kaolin suspension. Of the above grades, the graft copolymer Gly‐g‐PAM 5, which has longer PAM chains, showed best flocculation performance. The flocculation performance of the graft copolymer was compared with commercial flocculants and other PAM‐grafted flocculants developed so far in the authors' laboratory. In all the cases, it was found that the graft copolymer performed the best. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 773–778, 2007     

The flocculation and rheological characteristics of hydrolyzed and unhydrolyzed grafted sodium alginate in aqueous solutions

Sodium alginate is a natural anionic polysaccharide obtained from natural and microbial resources. It is also used as a flocculating agent and thickener. It is grafted with polyacrylamide, in the presence of ceric ammonium nitrate (CAN) as an initiator. The graft copolymer (SAG‐g‐PAM) is again hydrolyzed with some amount of alkali. The flocculation characteristics of hydrolyzed graft copolymer (Hyd SAG‐g‐PAM) are compared with that of the unhydrolyzed ones, in 5 wt % kaolin and 10 wt % iron ore suspensions. The flocculation characteristics of the hydrolyzed graft copolymer are also compared with those of some of the commercial flocculants. The SAG‐g‐PAM and Hyd SAG‐g‐PAM are characterized by IR and intrinsic viscosity measurements. The rheological properties of aqueous solutions of hydrolyzed and unhydrolyzed graft copolymers are measured by Advanced AR‐1000 Rheometer. There is drastic enhancement in flocculation and viscosifying characteristics on hydrolysis of the graft copolymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1480–1488, 2004     

Novel biodegradable flocculating agents prepared by grafting polyacrylamide to Konjac

Grafting copolymers of polyacrylamide (PAM) with Konjac gum (KGM) have been synthesized using ceric‐ion‐induced initiation technique. The copolymers were characterized using several instrumental techniques, including infrared (IR) spectroscopy, elementary analysis, scanning electron microscopy (SEM), size exclusion chromatography (SEC) analysis, and intrinsic viscosity to confirm the success of grafting. The flocculation performance of graft copolymers was characterized by two methods. One was to study the relationship between the flocculants doses in kaolin suspension and the supernatant transmittance, and the other is to examine the time dependence of sediment height of kaolin suspensions. It was found that the graft copolymer is better than KGM and pure PAM. Biodegradation behavior was testified by monitoring the decay of relative viscosities, and approved by KGM ether bonds breaking in IR spectra and the molecule weight reduction in SEC analysis. The results indicate that the grafted KGM copolymers have improved both, flocculation performance and better biodegradable properties than the unmodified parent KGM and pure PAM. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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 and application of salt tolerance amphoteric hydrophobic associative flocculants

A series of amphoteric hydrophobic-associative flocculants with outstanding flocculation efficiency and salt tolerance, poly(acrylamide/acrylic acid/dimethyl benzyl aminoethyl acrylate chloride), are successfully prepared (named AAB series) and used to flocculate the montmorillonite suspensions. The solution properties of AAB copolymer are systematically evaluated by viscometer, rheology and steady-state fluorescence analysis. The results suggest that the space network structure forming via hydrophobic-associating interaction can increase solution viscosity and improve the bridging capacity of copolymers. Meanwhile, the apparent viscosity in salt solution increases with increase in the concentration of salt stemming from the anti-polyelectrolyte effect of polyampholyte. Further, the flocculation performances of flocculants in 1 wt% montmorillonite suspensions are evaluated by turbidity, optimal dosage and settlement rate measurement. The results elaborate that the flocculation performances of amphoteric hydrophobic-associating AAB flocculants are better than that of commercial flocculants (cationic and anionic polyacrylamide) and homemade cationic flocculant (AAB-0-5) independent of the type and concentration of salt. The novel ampholyteric hydrophobic-associative flocculants will exhibit intriguing prospective in industry water treatment, in that the anti-polyelectrolyte effect of polyampholyte and hydrophobic-associating interaction can endow excellent flocculation efficiency and salt tolerance.     

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     

Synthesis of high molecular weight polyacrylamide flocculant by radiation polymerization

The radiation-induced polymerization of acrylamide was studied to prepare a high molecular weight and highly effective polyacrylamide flocculant. Among various solvents, mixtures of water–tert-butyl alcohol and water–acetone were found to be suitable for the synthesis of the high molecular weight polyacrylamide. For polymerization in acetone–water mixtures, the molecular weight of polymer increases with monomer concentration; but at the high concentration, intermolecular imidation of amide groups tends to take place during the polymerization to from crosslinked and water-insoluble polymer. The water-soluble polymer with the largest molecular weight of 6.7 × 10⁶ is produced in the polymerization with monomer concentration of 2.91 moles/1. at 0°C at a dose rate of 6.2 × 10² rad/hr in acetone–water mixture containing 60 vol-% water. The crosslinking of polymer of the formation of water-insoluble polymer could be avoided by the addition of K₂CO₃ or NaOH to raise the pH of the reaction mixture above 6.5. The flocculation effects were evaluated from sedimentation speed of kaolin suspension and transparency of the separated water. The sedimentation speed is proportional to the intrissic viscosity of the polymer in the range of 4 to 23 dl/g. The polymers prepared in this study show much higher sedimentation speed than commercial polyacrylamide flocculants. The transparency of the separated water is higher than 93%, similar to the results with commercial flocculants.     

Flocculation performance of modified chitosan in an aqueous suspension

A cationic moiety, N‐(3‐chloro‐2‐hydroxypropyl)trimethyl ammonium chloride (CHPTAC), was incorporated onto chitosan in an aqueous alkaline solution. Thus, modified chitosan was prepared. A series of modified chitosans with different molecular weights and charge densities were synthesized through the alteration of the molar ratio of CHPTAC to chitosan in the reaction mixture. The synthesized modified chitosans were thereafter characterized by a variety of physicochemical characterization techniques to confirm that modification did take place. Furthermore, the feasibility of applying modified chitosans as flocculants was assessed, and they were compared with the native chitosan in model colloidal suspensions of kaolin and iron‐ore powder. The results indicated that the unmodified chitosan itself was a good flocculating agent. The flocculation performance of the chitosan could be altered by the incorporation of the CHPTAC moiety. Studies showed that not all the modified chitosans had superior flocculation performance versus the native chitosan. Among the different grades, the modified chitosan with a moderate molecular weight and a moderate charge density showed the best flocculation performance in both model suspensions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Comparative studies on the flocculation characteristics of polyacrylamide grafted guar gum and hydroxypropyl guar gum

The synthesis of two polysaccharide‐based graft copolymers with acrylamide, guar gum grafted polyacrylamide (GG‐g‐PAM) and hydroxypropyl guar gum grafted polyacrylamide (HPG‐g‐PAM) is described. The graft copolymers have been characterized by viscometry, infrared spectroscopy and thermal analysis. The flocculation characteristics of the graft copolymers have been studied in kaolin, iron ore, and silica suspensions. For the base polysaccharides guar gum (GG) and hydroxypropyl guar gum (HPG), it is observed that GG exhibits better performance than HPG in all three suspensions. For the graft copolymers, HPG‐g‐PAM shows better performance than GG‐g‐PAM. The flocculation characteristics of the best performing graft copolymer (HPG‐g‐PAM) are compared with various commercially available flocculants in the three suspensions mentioned above. © 2001 Society of Chemical Industry     

Effect of molecular weight and charge density on the performance of polyacrylamide in low‐grade oil sand ore processing

The effect of charge density and molecular weight (MW) of partially hydrolyzed polyacrylamide (HPAM) polymers on their performance in processing low‐grade oil sand ores was investigated. Bitumen extraction and tailings settling tests were carried out and an atomic force microscope (AFM) was used to directly measure the bitumen‐solid and solid‐solid interaction forces. It was found that HPAM polymers with a low MW acted as dispersants in the bitumen extraction process, resulting in low bitumen recovery and slow tailings settling but improved froth quality. In contrast, the use of HPAM polymers with a high MW improved both bitumen recovery and tailings settling but deteriorated froth quality. To achieve high bitumen recovery and fast tailings settling, a HPAM polymer must have a low to medium charge density (～30%) and a high MW (17.5 million Daltons). A stronger clay‐bitumen adhesion force normally resulted in a lower bitumen recovery. Fast tailings settling was achieved in the presence of a strong solid‐solid adhesion force.