Evaluation of polymeric flocculants for oily water systems using a photometric dispersion analyzer

During oil production and treatment, oil-in-water (O/W) emulsions are formed. These dispersions require treatment prior to disposal. In order to improve oil/water separation processes through any physical process (decanting, flotation, centrifuging etc), the particle size of the dispersed phase should be increased. This may be obtained by a flocculation process, which consists in the agglomeration of several particles or drops using as flocculating agent hydrophilic high molecular weight macromolecules. Poly (ethylene-b-propylene oxide) and poly (vinyl alcohol) polymers have been evaluated as flocculating agents for oily water systems. Their performance is related to the particle size increase of the dispersed phase. In this work, a photometric dispersion analyzer (PDA) has been used to accomplish the oil drop agglomeration. Synthetic as well as produced water was used. Data are in good agreement with previous tests. Qualitative information related to aggregates or particle size distribution of the oily water systems can be obtained using PDA.     

Polyvinyl pyridines as flocculating agents

Summary High molecular weight poly 2- and 4-vinyl pyridines were synthesized by ionic polymerisation and their flocculation efficiency tested against kaolin and silica dispersions at pH 3. Low additions of the polymers, around 3 parts per 10₃ parts solid, destabilize the dispersions and clarify silica dispersions to a remarkable extent; however, over-addition of polymer leads to partial restabilization. The flocculation efficiency improves with increase of solids content, especially with clay dispersions. Flocculation efficiency increases with polymer molecular weight, especially over the lower part of the range covered, but is relatively independent of pH in the range 2–4. Quaternization of poly(4-vinyl pyridine) with bromobutane produces a good flocculant for aqueous silica dispersions in which the degree of restabilization on over-dosing depends on the KCI content. TheN-oxide derivatives of the vinyl pyridine polymers do not affect the colloidal stability of silica dispersions. The observations are interpreted in terms of bridging flocculation by the cationic polymer molecules between anionic surface sites on the solid particles.     

Colloidal stability and drug incorporation aspects of micellar-like PLA–PEG nanoparticles

The drug delivery properties of a series of poly(lactic acid)–poly(ethylene glycol) (PLA–PEG) micellar-like nanoparticles have been assessed in terms of their colloidal stability and their ability to incorporate a water soluble drug. These studies have focused on a range of PLA–PEG copolymers with a fixed PEG block (5 kDa) and a varying PLA segment (3–110 kDa). In aqueous media, these copolymers formed micellar-like assemblies following precipitation from water miscible solvents. There was a controlled increase in the particle size as the molecular weight of the PLA block was increased. The characteristics of the PEG corona were also highly dependent on the PLA moiety. Copolymers with a low molecular weight PLA block (3–15 kDa) formed highly colloidally stable dispersions, with a complete PEG surface coverage. However, increasing the molecular weight of the PLA block resulted in significantly less colloidally stable nanoparticle dispersions, which flocculated in solvents that were significantly better than θ-solvents for the stabilising PEG chains. This can be attributed to a reduced PEG surface coverage and the probable presence of naked PLA ‘patches’ on the particle surface. These larger PLA–PEG nanoparticles (30:5–110:5) were found to be stabilised in the presence of serum components, which are thought to adsorb into the gaps on the particle surface and prevent flocculation. All of the dispersions were found to be stable under physiological conditions and therefore suitable for in vivo administration. A reasonable loading (3.1% w/w) of the micellar-like PLA–PEG 30:5 nanoparticles with the water soluble drug procaine hydrochloride was achieved. The incorporated drug was found to have no effect on the nanoparticle structure or recovery, which can be attributed to the micellar character of these assemblies and the presence of the stabilising PEG chains.     

Freeze–thaw stability of water-in-oil emulsions

Factors influencing water-in-oil emulsion stability during freeze/thaw-cycling, namely interfacial crystallization vs. network crystallization and the sequence of crystallization events (i.e., dispersed vs. continuous phase or vice versa), are assessed. We show that destabilization is most apparent with a liquid-state emulsifier and a continuous oil phase that solidifies prior to the dispersed phase. Emulsions stable to F/T-cycling are obtained when the emulsifier crystallizes at the oil–water interface or in emulsions where the continuous phase crystallizes after the dispersed aqueous phase. The materials used are two food-grade oil-soluble emulsifiers – polyglycerol polyricinoleate (PGPR) and glycerol monostearin (GMS) and two continuous oil phases with differing crystallization temperatures – canola oil and coconut oil. Emulsion stability is assessed with pulsed field gradient NMR droplet size analysis, sedimentation, microscopy and differential scanning calorimetry. This study demonstrates the sequence of crystallization events and the physical state of the surfactant at the oil–water interface strongly impact the freeze–thaw stability of water-in-oil emulsions.     

Flocculation studies of non-aqueous poly(methyl methacrylate) dispersions stabilized by AB block copolymers of polystyrene and poly(dimethyl siloxane)

Summary Well defined non-aqueous dispersions of poly(methyl methacrylate) stabilized by AB block copolymers of polystyrene and poly(dimethyl siloxane) were prepared with a dispersion medium consisting of a binary mixture of n-heptane and ethanol. Flocculation was induced by cooling, and the lower critical flocculation temperature was studied as a function of the molecular weight and composition of the stabilizing copolymer, the particle size of the dispersion, and the surface coverage of the particles. The theta temperature for poly(dimethyl siloxane) homopolymer in the same binary liquid mixture was determined by two procedures. The lower critical flocculation temperature was found to be close to the theta temperature and was independent of the length of the stabilizing poly(dimethyl siloxane) chains for the molecular weight range 3200-48000.

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Zusammenfassung Gut definierte, durch AB-Block-Copolymere von Polystyrol und Polydimethylsiloxan stabilisierte nichtwässerige Dispersionen von Polymethylmethacrylat wurden mit binären Mischungen von Heptan und Äthylalkohol als Dispersionsmittel hergestellt. Die Flockung wurde durch Abkühlung herbeigeführt und die untere kritische Flockungstemperatur wurde als Funktion des Molekulargewichts und der Zusammensetzung des stabilisierenden Copolymeren, der Größe der dispergierten Teilchen und dem Bedeckungsgrad der Teilchenoberfläche studiert. Die Theta-Temperatur des Polydimethylsiloxan-Homopolymers in derselben binären flüssigen Mischung wurde durch zwei Verfahren bestimmt. Es wurde gefunden, daß die untere kritische Flockungstemperatur nahe an der ThetaTemperatur liegt und im Molekulargewichtsbereich 3200–48000 von der Länge der stabilisierenden Polydimethylsiloxan-Ketten unabhängig ist.

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With 2 figures and 2 tables     

Cationic flocculants carrying hydrophobic functionalities: applications for solid/liquid separation

The flocculation behaviors of three series of polycations with narrow molecular weight distributions carrying hydrophobic substituents on their backbones [poly(N-vinylbenzyl-N,N,N-trimethylammonium chloride), poly(N-vinylbenzyl-N,N-dimethyl-N-butylammonium chloride), and poly(N-vinylbenzylpyridinium chloride)] were investigated in dispersions of monodisperse polystyrene latexes and kaolin. Apparently, the charge density of the polycations decreases with increasing substituent hydrophobicity and increasing molecular weight of the polyelectrolytes. The necessary amount of flocculant for phase separation in dispersions with high substrate surface charge densities increases with increasing hydrophobicity of the polyelectrolyte. Nevertheless, the introduction of hydrophobic functionalities is beneficial, resulting in a substantial broadening of the range between the minimum and maximum amounts of flocculant necessary for efficient flocculation (flocculation window). An increase in ionic strength supports this effect. When the substrate has a low charge density, the hydrophobic interactions play a much more significant role in the flocculation process. Here, the minimum efficient doses remained the same for all three polyelectrolytes investigated, but the width of the flocculation window increased as the polycation hydrophobicity and the molecular weight increased. The necessary amount of flocculant increased with an increase in particle size at constant solid content of the dispersion, as well as with a decreasing number of particles at a constant particle size.     

Colloidal dispersions of polyindole

Polyindole dispersions consisting of 20–30-nm-sized nanoparticles are prepared by chemical oxidation with ferric chloride using sodium dodecyl sulphate, poly(vinyl alcohol) and poly(vinyl acetate) as steric stabilizers. Pure acetonitrile and acetonitrile–water mixtures are used as solvents. The particle size depended on the concentrations of monomer and the steric stabilizer. The dispersions are characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform IR spectroscopy, thermal analysis and cyclic voltammetry techniques.     

Ultrafiltration of triglyceride from biodiesel using the phase diagram of oil–FAME–MeOH

To continuously obtain biodiesel of high purity, a membrane separator integrated with liquid–liquid extraction for the oil–FAME–MeOH system is studied. The liquid–liquid phase equilibrium data for the oil–FAME–MeOH are determined experimentally and compared with the general prediction of the modified UNIFAC. The tie line test demonstrates that composition of the methanol-rich phase is free of TG at 20 °C. Using the continuous cross-flow ultrafiltration, the oil-rich phase can be rejected by the ceramic membranes while the methanol-rich phase permeates through the membranes. When the feed bulk composition is controlled within the two-phase zone, such as the oil:FAME:MeOH of 20:30:50 wt.%, the permeate is found to be free of oil while the obtained permeate flux is higher than 300 kg/m² h under the transmembrane pressure of 600 mmHg and the inlet flow rate of 300 ml/min at 20 °C. By contrast, it shows almost no separation when the inlet concentration of oil–FAME–MeOH locates on its boundary line or within the single-phase zone. The quantitative filtration tests show that the compositions in the two liquid phases and the operating parameters are also considered simultaneously to screen the origin oil and get the FAME product of high purity.     

The partition of ethoxylated non-ionic surfactants between two non-miscible phases

The partition of a polydispersed ethoxylated non-ionic surfactant in equilibrated oil–water systems has been studied at 25 °C. The model surfactant used was a commercial sample of nonylphenol ethoxylated with 10 moles of ethylene oxide (NPEO₁₀). The partition isotherms over the range of surfactant concentration including the critical micelle concentration (CMC) were made with n-hexane, i-octane and n-decane as oil phases. Each partition isotherm exhibits a change of slope that matched the CMC value of surfactant determined by surface tension measurements on aqueous solutions. During the partition of NPEO₁₀ in the oil–water systems, the oligomer distribution in the oil and water phases changed because of fractionation. Below CMC, the mean ethoxylation degree in the oil phase was smaller, whereas in water it was higher than the mean initial value of the surfactant. Moreover, the mean ethoxylation degree in both oil and water phase was practically independent of surfactant concentration. Above CMC, the mean distribution of ethoxymers decreased in both phases. This was ascribed to the competition between micelles from water and the oil phase for the more hydrophobic species of the surfactant. The mean distribution of ethoxymers in the aqueous phase asymptoted to a value that was the mean of the surfactant itself, whereas it steeply decreased in the organic phase.     

Grafting polyelectrolytes onto polyacrylamide for flocculation 2. Model suspension flocculation and sludge dewatering

Low-molecular-weight high-charge-density cationic poly(diallyldimethylammonium chloride) (polyDADMAC) was grafted onto high-molecular-weight nonionic polyacrylamide (PAM) via a free radical mechanism using a gamma radiation technique. The graft copolymers having various charge densities were evaluated as flocculants for titanium dioxide (TiO₂) model suspensions, and as conditioners for a pulp and paper mill sludge. Their flocculation performance was optimized with respect to polymer composition, gamma irradiation time and polymer dosage. Measurements included turbidity, particle size distribution and drainage rates. The graft copolymers showed a significant improvement over the homopolymers and dual polymer systems in their flocculation and sludge dewatering performance. Received: 6 April 1998 Accepted in revised form: 28 August 1998     

Electrophoretic mobility of poly(acrylic acid)-coated alumina particles

The effect of poly (acrylic acid) (PAA) adsorption on the electrokinetic behavior of alumina dispersions under high pH conditions was investigated as a function of polymer concentration and molecular weight as well as the presence, concentration and ion type of background electrolyte. Systems of this type are relevant to nuclear waste treatment, in which PAA is known to be an effective rheology modifier. The presence of all but the lowest molecular weight PAA studied (1800) led to decreases in dynamic electrophoretic mobility at low polymer concentrations, attributable to bridging flocculation, as verified by measurements of particle size distribution. Bridging effects increased with polymer molecular weight, and decreased with polymer concentration. Increases in background electrolyte concentration enhanced dynamic electrophoretic mobility as the polymer layers were compressed and bridging was reduced. Such enhancements were reduced as the cation was changed from K(+) to Na(+) to Cs(+).     

Synthesis and micellar behavior of poly(vinyl alcohol-<Emphasis Type="Italic">b</Emphasis>-styrene) copolymers containing PVA blocks with different syndiotacticity

Poly(vinyl alcohol-b-styrene) (poly(VA-b-St)) diblock copolymers with different syndiotacticity of poly(vinyl alcohol) (PVA) block were synthesized via consecutive telomerization, atom transfer radical polymerization, and saponification. These amphiphilic block copolymeric micelles were prepared by dialysis against water. Dynamic light scattering and transmission electron micrograph measurements confirmed the formation of a micelles, and the size of a micelle was less than 100 nm and increased with the molecular weight of polystyrene (PS) block. From the fluorescence emission spectrum measurements using pyrene as a fluorescence probe, the copolymers formed micelles with critical micelle concentration (CMC) in the range of 0.125–4.47 mg/l. The CMC values increase with decrease of the molecular weight of the PS block and increase of the syndiotacticity of PVA block. Kinetic stability study of micelles showed increased stability for block copolymers containing PVA block with higher syndiotacticity.     

In situ polymerization and morphology of polypyrrole obtained in water‐soluble polymer templates

Several water‐soluble polymers were used as templates for the in situ polymerization of pyrrole to determine their effect on the generation of nanosized polypyrrole (PPy) particles. The polymers used include: polyvinyl alcohol (PVA), polyethylene oxide (PEO), poly(vinyl butyral), polystyrene sulfonic acid, poly(ethylene‐alt‐maleic anhydride) (PEMA), poly(octadecene‐alt‐maleic anhydride), poly(N‐vinyl pyrrolidone), poly(vinyl butyral‐co‐vinyl alcohol‐co‐vinyl acetate), poly(N‐isopropyl acrylamide), poly(ethylene oxide‐block‐propylene oxide), hydroxypropyl methyl cellulose, and guar gum. The oxidative polymerization of pyrrole was carried out with FeCl₃ as an oxidant. The morphology of PPy particles obtained after drying the resulting aqueous dispersions was examined by optical microscopy, and selected samples were further analyzed via atomic force microscopy. Among the template polymers, PVA was the most efficient in generating stable dispersions of PPy nanospheres in water, followed by PEO and PEMA. The average size of PPy nanospheres was in the range of 160 nm and found to depend on the molecular weight and concentration of PVA. Model reactions and kinetics of the polymerization reaction of pyrrole in PVA were carried out by hydrogen ¹H NMR spectroscopy using ammonium persulfate as an oxidant. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

The Properties of Polymer-Containing BeO Dispersions in an Acetone–Chloroform Binary Medium

The properties of Newtonian and concentrated (non-Newtonian) BeO dispersions in solutions of acidic poly(vinyl acetate-co-vinyl chloride) in binary mixtures of chloroform (a Lewis acid) and acetone (a Lewis base) of different compositions were studied. In contrast to systems characterized by strong acid–base interactions at the particle–medium interface, the role of the steric stabilization factor was found to be extremely low in the studied dispersions. Polymer-containing BeO dispersions in acetone had the highest kinetic stability due to the specific interactions of this solvent with BeO particles and polymer macromolecules contributing to the redispersion of particles and the formation of protective solvation shells. The obtained data on the effect of the dispersion medium composition on the rheological properties of concentrated BeO dispersions can be used for the selection of optimal regimes for preparation of pastes for high-temperature ceramics.     

Transport of Water and Ions Through a Clay Membrane

Colloidal platinum nanoparticles were prepared by ethanol reduction of PtCl(6)(2-) in the presence of poly(N-vinylformamide) (PNVF), poly(N-vinylacetamide) (PNVA), or poly(N-vinylisobuty-ramide) (PNVIBA). The effects of molecular weight and molar ratio of monomeric unit/Pt on the particle sizes and size distributions were characterized by transmission electron microscopy and UV-visible spectroscopy. The flocculation behavior of the polymer-stabilized colloidal Pt nanoparticles was studied with respect to the effects of temperature, addition of inorganic salts, and composition of the mixed solvents. The dispersion stability of the platinum colloids stabilized by poly(N-isopropylacrylamide) (PNIPAAm) and poly(vinylpyrrolidone) (PVP) was also examined. The sequence of polymer-stabilized platinum colloids in increasing order of dispersion stability was found to be PNIPAAm-Pt相似文献   

Synthesis and application of ammonium-based poly(ionic liquids) as novel cationic flocculants

The efficient and environmentally friendly method for preparation of novel flocculants using ILs with non-toxic anions are presented. Poly(ionic liquids) (PILs) were prepared by the photopolymerization of polymerizable ILs. All monomers were obtained via anion exchange reaction. Additionally, the polymers were fully characterized by ¹H NMR and FTIR spectroscopy, thermal analysis and gel permeation chromatography. Furthermore, these cationic polymers containing harmless anions were used as flocculants. The efficiency was tested using the yeast suspension as a model system of negatively charged particles. The synthesized water-soluble PILs exhibited high molecular weight and significant flocculation efficiency in the wide range of concentrations. Furthermore, the results of experiments show that flocculation of yeast occurs by charge neutralization and bridging mechanism.     

Brush macro‐RAFT agent mediated dispersion polymerization of styrene in the alcohol/water mixture

Dispersion RAFT polymerization of styrene in the alcohol/water mixture mediated with the brush macro‐RAFT agent of poly[poly(ethylene oxide) methyl ether vinylphenyl‐co‐styrene] trithiocarbonate [P(mPEGV‐co‐St)‐TTC] with similar molecular weight but different chemical composition is investigated. Well‐controlled RAFT polymerization including an initial slow homogeneous polymerization and a subsequent fast heterogeneous polymerization at almost complete monomer conversion is achieved. The molecular weight of the synthesized block copolymer increases linearly with the monomer conversion, and the polydispersity is relatively narrow (PDI < 1.3). The RAFT polymerization kinetics is dependent on the chemical composition in the brush macro‐RAFT agents, and those with high content of hydrophobic segment lead to fast RAFT polymerization. The growth of the block copolymer nano‐objects during the RAFT polymerization is explored, and various block copolymer nano‐objects such as nanospheres, worms, vesicles and large‐compound‐micelle‐like particles are prepared. The parameters such as the chemical composition in the brush macro‐RAFT agent, the chain length of the solvatophobic block, the concentration of the feeding monomer and the solvent character affecting the size and morphology of the block copolymer nano‐objects are investigated. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3177–3190     

The Effect of Fatty Alcohols and Valeric Acid on the Regions of Existence of a Three-Phase System Containing Water, Oil, and Surfactant

For different water–oil–surfactant systems with added aliphatic alcohols and valeric acid, conditions for the formation of the microemulsion (third) phase containing approximately equal amounts of oil and water were determined. It was established that the microemulsion phases are formed in the initial two-phase system (oil-in-water microemulsion–oil) on adding alcohols or the acid, which can be more hydrophilic or more hydrophobic than micelle-forming surfactants. Concentrations of alcohols necessary for the transformation of the three-phase system into the two-phase one were determined. The influence of energy parameters of surfactants and structural characteristics of the alcohol and basic micelle-forming surfactant on the stability of the three-phase system is discussed.     

Effect of Neck Formation on the Measurement of Dynamic Interfacial Tension in a Drop Volume Tensiometer

Dynamic interfacial tension values obtained by drop volume tensiometry will be affected under certain experimental conditions by the formation of a neck between the drop and the capillary tip. This phenomenon must be accounted for to obtain accurate values of interfacial tension. In this work, neck formation for a water–mineral oil system is studied under conditions where hydrodynamic effects can be neglected. A model originally developed for the determination of the surface tension of a suspended drop is modified for application to dynamic interfacial tensions of surfactant-containing liquids. The model relates apparent values of interfacial tension calculated from drops possessing necks to actual values. Experiments with Span 80 (sorbitan monooleate) and sodium dodecyl sulfate (SDS) surfactants in a mineral oil–water system are used to test the validity of the developed model. For the small tip diameter used, good agreement is obtained for Span 80 up to the critical micelle concentration, and for low concentrations of SDS, when the surfactant adsorption is diffusion-limited. In both cases, the neck diameter of the growing drop can be considered constant over the range of dynamic interfacial tensions tested.     

Agglomération contrôlée de latex par formation de complexes tensioactifs anioniques : copolymères à blocs à base de poly(oxyde d’éthylène)

For polystyrene–poly(ethylene oxide) (PS–PEO) diblock copolymers, as micellar dispersions in aqueous medium, the formation of complexes with anionic surfactants, such as sodium dodecylsulfate (SDS) could be confirmed. The number of SDS molecules fixed per EO unit is close to the values reported for the SDS–PEO homopolymer interaction. Advantage of this type of complexation was taken to develop a controlled agglomeration process for SDS stabilized PS and PVC latexes by using as agglomerants ‘hairy’ latexes of PS and PVC that have been synthesized in the presence of PS–PEO block copolymers and that carry therefore a fringe of PEO sequences on their surface. The complexation of SDS by these surface-anchored PEO chains leads to the destabilization of the anionic latex, which has a tendency to precipitate onto the surface of the agglomerant latex. The average particle size and the size distribution of the agglomerated particles were studied as a function of the weight and number ratio of the two types of latexes involved in the agglomeration process, as well as in function of the surface coverage by SDS and PEO respectively. By adjusting these parameters, it was possible to obtain, with an efficiency of almost 100%, latex agglomerates with a monomodal distribution in the size range of 1 to 40 μm. An agglomeration mechanism could be outlined taking into account the complexation capacity and the specific surface of the agglomerating ‘hairy’ latex. To cite this article: P. Peter et al., C. R. Chimie 6 (2003).