E: jobs vu_2004 journal physica

Journal of Physical Sciences, Vol. 10, 2006, 93 – 127 Flocculation : A New Way to Treat the Waste Water
Tridib Tripathy1 and Bhudeb Ranjan De2
1 Narajole Raj College, Narajole, Paschim Medinipur 2 Department of Chemistry, Vidyasagar University, Paschim Medinipur Received 7 November, 2006 ; accepted 8 December, 2006 Pure water is an essential requirement for the survival of human beings. Tomeet the requirements of potable, industrial and agricultural water, the immediateneed is to treat waste water, particularly the sewage sludges and slimes fromthe municipal and industrial effluents respectively. These effluents are highlyundesirable and unsafe. The removal of contaminants from waste water is amust before they can be reused. The removal of contaminants from theseeffluents involves the process of flocculation and coagulation. The purpose ofthe present article is to clarify and explain the processes in details along withthe materials involved in the processes. This will be essential for the presentday life.
Coagulation and Flocculation
Colloidal particles in nature normally carry charges on their surface, which lead to the
stabilisation of the suspension. By addition of some chemicals, the surface property of suchcolloidal particles can be changed or dissolved material can be precipitated so as to facilitatethe separation of solids by gravity or filtration. Conversion of stable state dispersion to theunstable state is termed destabilisation and the processes of destabilisation are coagulationand flocculation1,2. Often the terms coagulation and flocculation are used synonymouslyinspite of existing a subtle difference between the two1,3. If destabilisation is induced throughcharge neutralisation by addition of inorganic chemicals, the process is called coagulation.
On the other hand, the process of forming larger agglomerates of particles in suspension orof small agglomerates already formed as a result of coagulation through high molecularweight polymeric materials is called flocculation. No substantial change of surface charge isaccomplished in flocculation. The agglomerates formed by coagulation are compact andloosely bound, whereas the flocs are of larger size, strongly bound and porous in case offlocculation. In mineral processing industries, the scope of application of flocculants is muchgreater than the coagulants. Coagulants find use in the processing of coal, taconite, soda ash, Tridib Tripathy et al. sand and gravel and to some extent in the uranium industry. Flocculants are widely used inthe processing of coal, bauxite, phosphate, potash sand, gravel, cement, soda ash, copper,silver, gold, beryllium, lead and zinc.
1.1. Stability of colloidal suspension
The attractive force between particles, known as Van der Waal force exit in case of colloidal
particles in suspension. But the electrostatic repulsion of surface charges opposes the particles
to come closer and form agglomerates. The principal mechanism controlling the stability of
both hydrophobic and hydrophilic particles is the electrostatic repulsion4. Hydrophobic surfaces
may acquire an excess of anions or cations at the interface producing an electrical barrier
that can repulse particulates of similar surface potential. Hydrophillic particles acquire surface
charge from dissociation of inorganic groups (carboxylic or other organic acid groups) located
on the particle surface or interface. Besides electrical repulsion, a suspension may be stable
due to the presence of adsorbed water molecules that provide a physical liquid barrier
preventing particulates from making collisions and destabilisation. Particles may acquire
surface charges due to unequal distribution of constituent ions on the particle surface,
preferential adsorption of specific ions, ionisation of surface groups, crystal imperfection, or
any combination of these.
1.2. Electrical double layer
Oppositely charged ions in an electrolytic solution are attracted to the surface of a charged particle and can either be closely associated with the surface or distributed someway into the solution5. Thus the two opposite forces, electrostatic attraction and ionic diffusion,produce a diffuse cloud of ions surrounding the particulate, which can extend up to 300 nm.
This co-existence of original charged surface and the neutralizing excess of counter-ionsover co-ions distributed in a diffused manner are known as the electrical double layer6. Fig.1gives a schematic diagram114 showing the nature of electrical forces around a colloidal particlein bulk solution and the various electrical potentials thus developed in the double layer. Thedouble layer consists of two major regions, an inner layer (called Stern layer) where theinitial layer of adsorbed ions and molecules are located at the particle surface; and the outerlayer (called Gouy-Chapman layer) of oppositely charged counter-ions. The stability of colloidalsuspension is greatly influenced by the potential of the Stern layer. Though this potentialcannot be measured directly, it is approximated to the zeta potential representing the electricalpotential between the shear plane and the bulk solution7. According to Deryagin and Landau8,Verwey and Overbeek9, if the kinetic energy of the particle is larger enough to surmount thepotential hump created between them by way of double layer formation, the particles wouldcoalesce otherwise they would remain as a stable suspension. This theory is popularly knownas DLVO theory.
Flocculation : A new way to treat the waste water 1.3. Zeta potential
A charged particle dispersed in an ionic medium tends to have a concentration of opposite
ions attracted towards it. For example, a negatively charged particle collects a number of
positive counter-ions. As one move further away from the particle, concentration of counter-
ions decreases due to diffusion until ionic equilibrium is reached. A plot of the charge contributed
by these ions versus distance from the particle surface (Fig.1) reveals the familiar exponential
decay. Now, if the particles were imagined to be moving, it would tend to drag its counter-
ions along with it while leaving behind the ions that are further away from its surface. This
would set up a plane of shear – the potential difference at which is called the zeta potential
(ζ).
1.3.1.Principle of measuring zeta potential
Zeta potential is measured10 using the technique of micro-electrophoresis, which was invented by Ware and Flygare and independently by Uzgiris in the early 1970s. However, asper Friend and Kitchener11, zeta potential was calculated using Smouluchowski equation asearly as 1903. The sample to be measured is dispersed in suitable liquid phase and placed inthe path of a beam of laser light. A pair of electrodes is introduced into the sample. Chargedparticles in the sample will move under the influence of an electric field applied across theelectrodes. The direction of the motion indicates the sign of the charge on the particles:negatively charged particles will gravitate towards the positive electrode and vice versa. Thevelocity of particles, per unit electric field, can be measured and is called the electrophoreticmobility (u). Thus, Where v is the particle velocity and E is applied field strength. The equation used for convertingthe observed mobilities into effective electrokinetic potential depends upon the value ofdimensionless quantity ‘ka' in which ‘a' is the radius of the particle (assumed spherical) and‘k' is the quantity given by12.
where, e = Electronic charge,ε = Electrical permittivity of the solventK = Boltzman constantT = Absolute temperature.
From the expression given, k = 1 × 106 cm at 25oC in water (ε/ε = 78) containing 1 mM of 1:1 electrolyte. Values of ‘k' at other concentration follow by simple proportion. If ‘ka' > 200it will be usually sufficiently accurate to use the Smoluchowski formula which in the originalunrationalised form is u = εζ/4πη, where ε is the permittivity of the suspending medium and η is the viscosity.
Tridib Tripathy et al. Typical units would be to have u in micron per second under one volt per cm, in which case for water at 25oC, zeta potential in mV would be given by Significance of the measured zeta potential
The zeta potential is best seen as the potential at the surface of the ‘electrokinetic
unit' moving through the solution. This will not be the mean ‘wall potential', often called W , but can be taken as the mean potential at the ‘outer Stern plate' (OSP). The OSP is seen as
removed from the surface by one hydrated radius of the principal counter-ions (0.2 to 0.5
nm). The electrokinetic entity may well include ions specifically adsorbed from the solutions
and this will be reflected in the value of zeta potential. Certainly the double layer on the
solution side of zeta potential will be purely diffused so that zeta potential is the relevant
potential for all the effects that depend on diffuse layer effects (e.g., inter plate repulsion).
Calculation of particle charge from zeta potential is also possible12.
1.3.3.
Zeta potential and suspension stability
Knowledge of zeta potential can be used to predict and control the stability of
colloidal suspensions or emulsions. Greater the zeta potential, more likely the suspension is toremain in stable form.
Zeta potential is very much dependent on the pH of the suspension. A plot of zeta potential vs pH is called an iso-electric curve. The pH for which zeta potential is zero, iscalled the ‘iso-electric point' or ‘point of zero charge' (PZC).
It has been already pointed out that if the particle surface charge is strong, it results in significant mutual repulsion prohibiting the particles to come closer. If the chargeon these particles is reduced to zero, these repulsion forces are eliminated. Gentle mechanicalagitation will then create numerous particle collisions instead of ‘near misses'. The forces ofadhesion, cohesion, and mechanical interlocking by ‘polymer bridging' will result inagglomeration13.
Turbidity (representing suspended particulate matters) consists of two distinct fractions: a coarse fraction (1 mm to 1 µm) and a colloid fraction (1 µm to 10oA). The coarsefraction may be successfully removed by conventional coagulation/flocculation treatment,but the colloid fraction cannot. As the floc forms during coagulation/flocculation is also of thesame charge as that of the particles before treatment, a mutual repulsion exists between thefloc particles and the colloids, and these repelling forces prevent the colloid from makingpermanent contact with the floc, regardless of agitation. Such colloids can effectively beremoved by lowering the zeta potential of both the floc and colloid to a value of approximatelyzero plus or minus 5 mV12. This can be done by simultaneously employing the proper dosageof an inorganic coagulant coupled with an appropriate organic polyelectrolyte. The watertreatment plant at Waterford, New York, is believed to be the first to demonstrate purificationof water based on the principle of continuously controlled zeta potential.
Flocculation : A new way to treat the waste water Flocculation mchanism
As discussed earlier, the charge structure surrounding the particles is called the
electrical double layer, which, for convenience is divided into Stern, and Gouy-Chapmanlayers. The former is the initial layer of adsorbed ions and molecules located at the particlesurface. The charge presented to the solution at the Stern layer naturally attracts a diffuselayer of free ions with a net different opposite charge, i.e., the Gouy-Chapman layer. Forparticles to make contact and aggregate, the potential at the stern layer must be overcome.
Unfortunately, this potential, which is of interest in determining particle stability, cannot bemeasured experimentally. In order to cause the particles of a stable dispersion to flocculate,it is necessary to provide enough kinetic energy to particles to overcome the potential energybarrier. Alternatively, the barrier can be eliminated by surface-charge neutralization. Thismay be accomplished either by double layer compression (charge neutralization mechanism)or adsorption of flocculant onto the particle surface (bridging mechanism).
Charge neutralization mechanism
Charge neutralization14,15 by double layer compression is accomplished when
flocculation is effective through an increase in solution ionic strength. The expression for theDebye-Huckel length, as derived from the Gouy-Chapman model of the electric doublelayer, is given as K = (4 × 10-3e2NI/εkT)1/2 where, e = electronic charge N = Avogadro's numberI = Ionic strengthε = Electrical permittivity of the solventk = Boltzman constant, andT = Absolute temperature.
Since the double layer thickness is approximated by 1/K, increase in ionic strength (I) decreasesthe thickness of the double layer. This compression allows the approach of the colloidalparticles to where short-range attractive forces predominate over electrostatic repulsiveforces. In the presence of hydrolyzable metal ions such as Al3+ and Fe3+ or polyelectrolytesof opposite charge to colloid surface (see electrostatic patch mechanism), the charge isneutralised by adsorption of these species onto the particle surface. An important case ofthis is the flocculation of negative colloidal particles with cationic polymers. In fact, in manycases, the action of cationic polymers can be explained in terms of their strong adsorption onnegatively charged particles and consequent reduction of double layer repulsion, allowingaggregation to occur. It may be noted that the most effective cationic flocculants are often Tridib Tripathy et al. those of high charge density, with molecular weight playing only a minor role. That chargeneutralization in fact occurs is reported by comparison of zeta-potential measurements withflocculation results, when it is found that optimum flocculation occurs at the point of totalcharge neutralization. For flocculation to proceed with pure charge-neutralization mechanism,it is neutral to expect that zeta-potential will be zero at the point of optimum flocculation. Butin practice, the zeta potential tends to become negative at optimum flocculation with anincrease in molcular weight of the polyelectrolyte. This is because increasing molecularweight of flocculant favours bridging relative to charge neutralization mechanism. Thus inany system where flocculation is affected by the addition of electrolyte or oppositely chargedpolyelectrolyte, it is likely that some degree of charge neutralisation occurs, the extentdepending upon the system characteristics.
Bridging mechanism
Long chain polymers14,15 when added in small dosage to a suspension of colloidal
particles, adsorb onto them in such a manner that an individual chain can become attached totwo or more particles thus "bridging"14 them together (Fig.2.a). But interestingly thisphenomenon is observed up to a particular optimum polymer dosage beyond which flocculationdiminishes, a process being known as steric stabilization (2b). The essential requirements forpolymer bridging are that there should be sufficient unoccupied particle surface for attachmentof polymer segments from chains attached to other particles and that the polymer bridgesshould be of such an extent that they span the distance over which interparticle repulsionprevails. Thus, at lower dosages, there is insufficient polymer to form adequate bridging linksbetween particles. With excess polymer, there is no longer enough bare particle surfaceavailable for attachment of segments and the particles become destabilized, which mayinvolve some steric repulsion. On average, bridging flocculation gives aggregates (flocs)which are much stronger than those produced by addition of salts (i.e., by reduction in electricalrepulsion). However, such stronger flocs produced by the bridging mechanism may not reformonce broken at high shear rates.
Electrostatic patch mechanism
Although the bridging mechanism serves well to interpret the effects of nonionic
and anionic polymers on the flocculation of colloidal particles, agreement with experiment ispoor with respect to action of high-charge cationics on negatively charged colloidal particlesparticularly for molecules of low molecular weight in dilute suspensions. Of particularimportance in determining the flocculation mechanism, is the equilibrium configuration15 ofthe adsorbed polymer. It has been observed that for systems with a flocculant of high cationic16charge in anionic colloidal suspensions, the high interaction energy favours a flattened adsorbedconfiguration (Fig.3) that significantly reduces the formation of loops and trains, which canbridge the suspended particles. In such cases, each charged site on the particle surfacecannot be neutralized individually by an oppositely charged polymer segment simply for Flocculation : A new way to treat the waste water geometric reasons. Polymer chains then adsorb to give "islands" or "patches" of charge,surrounded by areas of opposite charge. Particles with polyelectrolytes adsorbed in this"patchwise" manner can interact in such a way that oppositely-charged areas of differentparticles come in contact giving rise to strong attraction17,18. Mabire19 et al. give asemiquantitative interpretation of the role of molecular weight and cationicity through apatchwork model while studying the flocculation properties of some water soluble cationiccopolymers toward silica suspension. However, Wang and Audebert20 showed that theflocculation of a particle with strongly negative zeta potential such as silica, by cationicpolyelectrolytes obeys mainly electrostatic mechanism for a cationicity > 0.15. On the contraryfor low cationicity (< 0.15) the major effect is the interparticle bridging.
It may be noted that, the electrostatic patch mechanism should predominate in systems characterized by high cationic charge on the flocculant and anionic colloidal solids,especially at low particle concentration. However, bridging may occur in such systems if theparticle concentration is high enough for collisions to take place on a time scale similar to thatrequired for the polymer to attain a flattened configuration. The controlling mechanism offlocculation is then governed by the system and the flocculant.
Flocculating materials
The vast categories of materials used as flocculating agents can be classified broadly
into two categories inorganic and polymeric. (some of the inorganic materials exist in thepolymeric form, e.g., poly (aluminium chloride), are not included in this classification). Thepolymeric materials are further classified into natural and synthetic. The synthetic materialsmay be cationic, anionic or nonionic. A new class of polymeric flocculants i.e., the graftcopolymers have been developed which are synthesized from natural and synthetic polymers.
Inorganic flocculants
Various chemicals21,22 are used in coagulation depending on the characteristics of
the water being used. In some waters, a combination of two or more chemicals producesbetter results than a single chemical. It is usually necessary to perform coagulation tests inthe laboratory to decide which chemical or combination should be used. The inorganicflocculants are mostly based upon the hydrolyzable salts of iron and aluminium.
1.5.1.1. Aluminium compounds
Principal aluminium compounds that are commercially available for suspended solids removal are dry and liquid alum. Commercial dry alum most often used in wastewatertreatment is known as filler alum and has the approximate formula Al (SO ) , 14H O and a molecular weight of about 600. Activated alum contains about 9% sodium silicate, whichimproves the coagulation in some waters. Black alum is the alum containing activated carbon.
Another aluminium compound in use is sodium aluminate. It is much more alkaline compoundthan alum. When added alkalinity is found to be necessary for the efficient coagulation,sodium aluminate may be substituted for all or part of the needed alum dose.
Tridib Tripathy et al. 1.5.1.2. Iron compounds
Iron compounds possess pH coagulation ranges and floc characteristics similar to aluminium sulfate. The cost of iron compounds may often be less than that of alum. However,the iron compounds are generally corrosive and often present difficulties in dissolving, andtheir use may result in high soluble iron concentration in process effluents. The iron saltsmost commonly used as coagulants include ferric sulfate, ferric chloride and ferrous sulfate.
These compounds often produce good coagulation when conditions are too acidic for bestresults with alum. Sometimes the particles are best removed under acidic conditions and ironcompounds give better results.
Polymeric flocculants
Polymeric materials used as flocculants/retention aids are mostly water-soluble
linear polymers23-27 of very high molecular weight. The cationic and anionic counterparts ofthese polymers are known as polyelectrolytes with many characteristic features of theirown. Some of the nonionic water-soluble polymers at times bear some ionic groups as aresult of inadvertent hydrolysis.
1.5.2.1. Cationic polymers
Water-soluble cationic polymers are a class of polyelectrolytes that derive their unique properties from the density and distribution of positive charges along themacromolecular backbone. Chain conformation and solubility of such flocculants depend onthe extent of ionization and interaction with water. Cationic functional groups can stronglyinteract with suspended, negatively charged particles or oil droplets and hence are useful inmany applications, including waste treatment and paper making process. Water-solublepolymers containing cationic charge can be divided into three categories: ammonium (includingamines), sulfonium and phosphonium quaternaries.
Many types of cationic monomers can be home- or copolymerized with acrylamide to yield water soluble polymers with varying positive charge (1-100%). Some of the morewidely used cationic monomers and their structure have been summarized in Fig.4 Cationicmonomers are, in general, more expensive than acrylamide or anionic acrylic monomers.
Random copolymers of acrylamide and acryloyloxyethyltrimethyl ammonium chloride, formed by quaternization of dimethylaminoethyl acrylate with methyl chloride areexclusively used in water industry. The methacrylate analogue with variation of cationiccontent is also commercially available. The quaternized aminoacrylate copolymer havingcharge density (CD) of 30 mol% has been used for clay flocculation studies. In copolymerswith acrylamide, hydrolysis of the ester groups has been investigated and found to be CDand pH dependent with hydrolysis increasing under more alkaline conditions.
Flocculation : A new way to treat the waste water Pol-COOCH CH N+Me → Pol-COO– + HO CH CH N+Me
Cationic polyacrylamides can be prepared by post polymerization functionalization of polyacrylamide. In a Mannich-type reaction, polyacrylamide reacts with formaldehyde toform N-methylol groups, which can be treated with a dialkyl amine such as dimethyl amineto yield pendent amine groups28. The synthesis of a model cationic polymer based on theMannich reaction of polyacrylamine29 has been described. The amine groups can bequaternized subsequently. Another approach to introduce amino groups into polyacrylamideis by reaction with polyamines or by sodium hypochlorite degradation (Hoffmann reaction)30.
Research continues on the synthesis and characterization of homo- and copolymers of quaternary ammonium monomers with acrylamide. Synthesis and characterization of homo-and copolymers of 2-acrylamido-2-methylpropanedimethyl ammonium chloride (AMPDAC)with acrylamide have been reported 31. This monomer is the cationic analogue of the anionicmonomer sodium 2-acrylamide-2-methylpropanesulfonate (NAMPS). Redox polymerizationof a quaternary ammonium acrylic comonomer with acrylamide has also been reported32 One of the cationic systems that has been the subject of some basic research33,34 is the poly (diallyldimethylammonium chloride) and its copolymer with acrylamide. The monomerhas been referred to as DADMAC or DADAAC in the literature. Polymerization of a 50-70% aq. Solution of DADMAC, initiated with peroxide catalyst produces a linear water-soluble polymer known as poly (DADMAC). This first cyclopolymer is of low to mediummolecular weight and in its chloride form has been used in many applications such as papermaking process, water treatment etc. Butler and Angelo33 have established that the freeradical polymerization of DADMAC is intra-molecular and involves a cyclization mechanismto produce a five membered ring. The advantages of this polymer are that it is highly cationic,pH-insensitive, chlorine resistant and as such it is a major representative of cationic flocculants.
The solution properties of poly (DADMAC) in water and salt and interaction with solids,such as silica, suggest the potentially of these polymers as coagulants and flocculants. High-molecular weight copolymers of poly (DADMAC) with acrylamide35,36 have been synthesisedwhich have found applications in sludge conditioning. Butler and Lin37 have synthesised graftcopolymers of acrylamide onto poly (DADMAC) by first making a copolymer of DADMACwith 1-10% of acrylic acid and esterfying it with 3-chloro-1, 2-propane diol to introduce thecis-diol groups. These cis-diol groups serve as grafting sites in presence of ceric ions. A laterapproach38 via a copolymer with 3,4-dihydroxy cyclohexylmethyl acrylate acrylate giveshigher molecular weight material and less homopolymer. Alternating copolymers of low tomedium molecular weight have been prepared from DADMAC and sulfur dioxide and havebeen tested for clay flocculation39. Yulin et al40 have studied the temperature-sensitiveflocculation characteristics of a copolymer of poly (N-isopropyl acrylamide) and poly(DADMAC) with colloidal TiO .
Tridib Tripathy et al. Polyamines, Polyimines and Polyvinylpyridines
Four types of cationic monomers are involved in this class: • Polyamines that are condensation products of amines and halogenated compounds.
• Polyamidoamines that result from the formation of a polyamide followed by reaction with a halogenated compound (e.g. epichlorohydrin).
• Polyethylene imines made by ring-opening polymerization of aziridine and• Polyvinylpyridinium systems.
Polyamines are the step-growth polymerization products of polyfunctional amines and alkyl halides or bifunctional alkyl epoxides and alkyl epoxide derivatives. They are relativelyof low molecular weight (< 105) but have high level of cationicity. Typically in the first case,a poly (ethyl amine) is produced by the reaction of ammonia or low molecular weight alkylpolyamine with ethylene chloride in the presence of aqueous base. This is sometimes followedby reaction with epichlorohydrin. Reaction variables need to be controlled carefully to meetthe molecular weight requirements.
A second family of polyamines is usually prepared from epichlorohydrin and ammonia or monomethylamine or both under basic conditions. The reaction involves a seriesof nucleophilic ring-opening additions and condensations. Depending on reaction conditions,these polyamines tend to be branched, particularly the high molecular weight products.
These are produced by reaction of adipic acid with diethylene triamine, yielding a polyamide with secondary amine groups that react further with epichlorohydrin. The pendentepoxide group may react with the secondary amine group of another polymer chain resultingin cross linking. This must be controlled to render the polymer water-soluble.
Poly (Ethylene Imine) (PEI)
This is a special poly (ethyl amine) produced commercially from ethylene amine (azidine) in an aqueous medium by ring-opening polymerization using CO , a mineral acid or ethylene dichloride as initiator. This product (PEI or polyaziridine) is highly branched, withprimary, secondary and tertiary amine groups. PEI has been used in a number of modelinvestigations of flocculation41.
Poly (2-Vinyl Pyridine) and Poly (4-Vinyl Pyridine)
These can be prepared by conventional free radical techniques. The polymers are quaternized with alkyl derivatives to form strong polyelectrolytes in solution. Cardoso et al42have studied the flocculation characteristics with bentonite clay suspension of a N-oxidetype zwitterionic polymeric flocculant derived from isomers of poly (vinyl pyridine) and poly Flocculation : A new way to treat the waste water (N, N-dimethylaminoethylmethacrylate) by oxidation. The resulting polymers have high watersolubility, chemical stability and ability of chain expansion with increased ionic strength, aproperty highly desirable in the process of flocculation by polymers. In a related communication,Asanov et al.43 have studied the flocculation characteristics of an aqueous suspension ofbentonite with a water-soluble polyelectrolyte based on 2-methyl-5-vinyl pyridine, methacrylicacid and its amides to show that the presence of functional groups like amines and amidesstrengthen the flocculation attributes.
1.5.2.2. Anionic polymers
In anionic flocculants, 1-100% of the monomer units contribute to the charge.
Molecular weights tend to be in the high or very high range. Although several types ofanionic sites in a polymer are possible, the major type in commercial flocculants is the polymershaving carboxylate ions.
Polymers Containing Carboxyl Groups
High molecular weight carboxylic acid polymers based on polyacrylamide are extensively employed as flocculating agents in the water and various process industries,where a low charge density is the general rule. One exception is the separation of red mudfrom alumina where a high charge density polymer performs better. Homopoly (acrylic acid),poly (acrylic acid-co-acrylamide) and hydrolyzed polyacrylamide dominate the anionicflocculant market. Hydrolyzed polyacrylonitrile has been found to be playing a lesser role.
Poly (Acrylic Acid) and Its Salts
Anionic poly (acrylic acid) (PAA) can be synthesized in two ways direct polymerization or hydrolysis. In the direct method, salts of acrylic acid are homopolymerizedor copolymerized by free-radical initiation in aqueous media. Usually the rate of polymerizationof the ionic monomer is slower than the corresponding nonionic monomer, presumably owingto charge repulsion between the growing chain and the incoming ionic monomer. Directpolymerization of acrylic acid salt solutions has some advantages because the non-volatilityof acrylic acid salts allows simultaneous polymerization and spray drying to produce highmolecular weight polymers directly.
Hydrolysis (saponification) is the alternative method for producing anionic poly (acrylic acid). Copolymers with variation in the percent of amide and carboxylic acid groupscan be prepared either by copolymerisation of acrylamide and acrylic acid or its salts, or bypolymerization of acrylamide followed by partial hydrolysis. The former route gives randomcopolymer, whereas some clustering can occur in the alkaline hydrolysis approach.
Polyacrylamide is hydrolyzed readily with alkali (usually sodium hydroxide or sodiumcarbonate) in an aqueous medium. The hydrolysis is relatively rapid upto about 50% conversionof amide groups and then shows down considerably, probably due to neighbouring groupeffects. High molecular weight anionic flocculants with 2-50% of the amide groups hydrolyzed Tridib Tripathy et al. by stoichiometric amounts of alkali are prepared conveniently in this way. Additioncopolymerisation of acrylic acid with acrylamide covers the entire range of anionicity. Therate of copolymerisation is pH dependent and the reactivity ratio for acrylic acidcopolymerisation with acrylamide decreases with increasing pH. Use of anionicpolyacrylamide in flocculation has also been reported44.
Although the carboxyl grouping is a relatively strong acid, the extent of ionization is a function of pH in acidic substrates. Both the inherent acidity of the carboxyl group and the
effect of neighbouring carboxyl groups in the same molecule (electrostatic and statistical)
influence ionization. Electrostatic effects are moderated by ionic strength of the medium and
all these factors influence the conformation of the molecules in solution, which in turn affects
the polymer properties.
Polymers Containing Sulfonic Acid Groups
The sulfonic group is an inherently stronger acid than the carboxyl. Polymers with sulfonic acid moieties, therefore, retain their anionic charge in media with low pH. The major
representatives of polymers containing sulfonic acid are poly (vinyl sulfonic acid) (PVSA)
and poly (styrene sulfonic acid) (PSSA).
Poly (Vinyl Sulfonic Acid) (PVSA)
It is the simplest example of this family of fully ionized strong electrolyte polymers.
It is prepared by polymerization of ethylene sulfonic acid or its sodium salts under free
radical conditions and purified by precipitating aqueous solutions of the sodium salt form with
methanol or dioxane. The ion binding selectivity of the polymer with alkali metals has been
observed in viscosity and phase separation studies. The homopolymers and its copolymers
with methacrylic acid are reported to be useful in deposit control as are the copolymers of
allylsulfonic acid and fumaric acid.
Poly (Styrenic Sulfonic Acid) (PSSA)
Poly (styrenic sulfonic acid) may be prepared by free-radical polymerization of the monomer in solution using the acid, sodium salt or potassium salt form. PSSA may also beprepared by sulfonation of polystyrene or by hydrolysis of poly (n-propyl p-vinylbenzenesulfonate). The sulfonation route requires a careful choice of the sulfonating conditionsnecessary to minimize crosslinking and the formation of insoluble gels. The best reagentappears to be a sulfur trioxide-trialkyl phosphate complex, with the para-isomer as the majorproduct. Very high products of PSSA have been investigated as flocculants for the so-calledred muds in the Bayer process for bauxite to demonstrate the effect of molecular weight onthat substrate45.
Several acrylate or acrylamide polymers containing sulfonate groups are commercially relevant as high molecular weight flocculants or low molecular deposit controlagents46. These include homopolymers of sodium 2-methacryloyloxyethyl sulfonate (SEM)47and sodium 2-acrylamido 2-methyl propyl sulfonate (AMPS)46 (Fig.5). Of these monomers, Flocculation : A new way to treat the waste water 2-sulfoethyl methacrylate is of limited commercial value owing to the hydrolytic instability ofthe ester linkage. The same factor has been a major drawback with 3-sulfo-2-hydroxylpropylmethacrylate (SHPM).
However, 2-Acrylamide-2-methyl propyl sulfonic acid (AMPS) prepared by the reaction of SO with isobutylene followed by Ritter reaction with acrylonitrile48,49 is hydrolytically quite stable. AMPS is highly reactive in both homo- and copolymerisation andcan be incorporated by homogeneous, solution or emulsion polymerization technique. Itsapplications include improving emulsion stability, flocculation, improving dry strength of paper,sludge disposal in boil-water treatment etc. Qin et al.50 have copolymerized sodium allylsulfonate onto acrylamide in an aqueous solution using ammonium persulfate as initiator andstudied their flocculation behaviour in kaolin suspension in presence of calcium ion.
1.5.2.3. Nonionic polymers
For the purpose of classifying as flocculants, a polymer is considered nonionic if less than 1% of the monomer units are charged. In aqueous systems such polymers function
as flocculants primarily by the bridging mechanism. Hence, they must be of high or very high
molecular weight for practical applications. Polyacrylamide is the most prominent member
of this class followed by poly (ethylene oxide).
Polyacrylamide
Acrylamide monomer is polymerized by free radical initiators, e.g. azo compounds, redox catalysts, light and radiation. This monomer is unique among vinyl and acrylic monomersbecause it can be polymerized to ultra-high molecular weight (106-107). This extraordinaryfeature of acrylamide polymerization is attributed, in part, to the ease of purification ofacrylamide monomer and to the unusually high ratio of its propagation to termination rateconstants (K /K ). In fact acrylamide has the highest K /K of any free radically polymerizable monomer. Polyacrylamide can be prepared via solution inverse emulsion, inverse microemulsion
or precipitation techniques. Low temperature initiation, high monomer concentration and a
small amount of added 2-mercapdtobenzimidazole, radical scavenger, are reported to be the
optimal reaction conditions for preparing high molecular weight, soluble polymers. In case of
polymers and copolymers made from acrylamide, some 1-3% of anionic groups are introduced
due to the inadvertent hydrolysis of the amide groups.
However, polyacrylamide with less than 1% hydrolysis can be prepared by careful attention,
the monomer concentration, pH, temperature and initiator, preferably a redox type. The
chemical and physical properties of the polymers often are dependent on synthesis variables.
One feature that has been the subject of many basic investigations is the stability of dilute
aqueous solutions on ageing.
Poly (Ethylene Oxide) (PEO)
PEO resins are commercially made by the catalytic polymerization of ethylene oxide in the presence of one of the several existing catalyst systems. They are available withaverage molecular weight from as low as 200 up to 5×106. The products with a molecular Tridib Tripathy et al. weight below about 25,000 are viscous liquids or waxy solids, commonly referred to as poly(ethylene glycols). Those with a molecular weight range from about 1×105 to 5×106 arecalled poly (ethylene oxide) resins. They are dry, free flowing, white powders completelysoluble in water at temperatures upto 98oC and completely soluble in certain organic solvents.
Aqueous solutions of PEO display increasing pseudoplasticity with increasing molecularweight. High molecular weight polymers of ethylene oxide are susceptible to severe auto-oxidative degradation and loss of viscosity in aqueous solution. The mechanism involves theformation of hydroperoxides that decompose and cause cleavage of the polymer chain. Therate of degradation is increased by heat, UV light, strong acids, and certain transition metals,particularly Fe3+, Cr3+ and Ni2+. Ethyl, isopropyl or allyl alcohols, ethylene glycol or Mn2+ ionsare known to be effective stabilizers of aqueous PEO solutions. The major commercial usesof poly (ethylene oxide) include adhesives, water soluble films, textile sizes, rheology controlagents and thickners, water-retention aids, lubricants, hydrodynamic drag reducing agents,flocculants51, dispersants and additives in medical and pharmaceutical products. The uniquecombination of properties of these polymers had led to developing applications in detergents,solids transport, control of sewer surcharges, dredging and metal-forming lubricants.
1.5.3. Natural polymers
Several naturally derived substances are used as flocculants, most of them being based on a polysaccharide skeleton. Some of them contain anionic groups like carboxyl.
Starch
Among natural flocculants the most widely used are starch and its derivatives.
Starches isolated from different sources are all used to some degree as flocculants, but some
work better with certain substrates than others. It has been reported that the amylose fraction
of starch is superior to amylopectin or native starch in red mud flocculation. Dosage efficiency
and dispersibility of starch flocculants are improved by introduction of cationic and anionic
substituents. Jaernstroem et al;52 have studied the effect of temperature and ionic strength
on the flocculation of a kaolin suspension with cationically modified and converted starch
and compared53 its efficiency with that of poly (vinyl alcohol) and carboxymethyl cellulose.
Weissenborn et al.54,55 have investigated the mechanism of adsorption of wheat starch and
its components (amylopectin and amylose) onto hematite ore. It was observed that wheat
starch and amylopectin adsorbed onto hematite strongly which was proposed to be due to
the formation of a surface complex between the carbonyl groups attached to C-2 and C-3'
atoms of AGUs and surface iron atom hematite. A comparison of the selective flocculation
performance with adsorption results established that flocculation occurs by the classical
bridging mechanism. Application of starch as a selective flocculant has been reported56.
Guar Gum
Guar gum, which structurally comprises of a straight chain of D-mannose with a D-galactose
side chain on approximately every alternate mannose unit, has a molecular weight of the
order of 220,000. As a result of its wide range properties, guar gum is the most extensively
Flocculation : A new way to treat the waste water used gum, both in food and industrial applications. It is nonionic and hence an effective
flocculant over a wide range of pH and ionic strengths. Flocculation57,58 studies of allophanic
clay system with xanthan gum and several of its hydrolytic intermediates have been reported.
In the mining industry guar gum is used as a flocculant or flotation agent, foam stabilizer,
filtration and water treating agent. In the textile industry, it is used as a sizing agent and as a
thickener for dyestuffs. The biggest consumer of guar gum is the paper industry where it
facilitates wet-end processing and improves the properties of the product. However, one
disadvantage of guar gum is its relatively rapid biological decomposition in aqueous solutions,
which, of course, can be controlled by addition of chelating agents and grafting with
polyacrylamide chains59.
Chitin Derivatives and Chitosan
Chitin is water-insoluble high molecular weight polymer of 2-acetamido-2-deoxy-D-
glucopyranosyl units linked through β(1→ 4) D-bonds. This may be converted to chitosan by
partial or complete deacetylation. In the protonated form, this cationic polyelectrolyte is
water soluble60 with a number of potential commercial uses including flocculation,
viscosification, drug delivery etc. Graft copolymers of chitosan61 with acrylethyl
triethylammonium bromide have been tested for flocculation studies in kaolin suspension
with respect to sedimentation rate, residual turbidity etc. Hydroxyethyl chitin and other water-
soluble derivatives are useful wet-end additives in paper-making and flocculants for anionic
waste streams. Use of carboxymethyl chitin62 in the treatment of printing and dyeing waste
water has been reported. Salts of chitosan63 based on maleic acid, acetic acid and HCl have
been shown to be good flocculating agents.
Sodium Carboxymethyl Cellulose
This water soluble gum is produced from alkali cellulose (alkali salt of poly β-D-glucose) and
monochloroacetic acid with degree of substitution in the range of 0.4-1.5. Unlike many
flocculants derived from natural products, it is relatively resistant both to biological and
hydrolytic degradation.
1.5.4. Graft copolymers
Graft copolymerization has been successfully used to alter significantly the soloution properties
of many polymers like starch, cellulose, synthetic polysaccharides etc. by grafting suitable
acrylic polymers onto them. The viscosity, gelling characteristics, solution rheology e.g. degree
of pseudoplasticity, ion compatibility etc. can be drastically altered through graft
copolymerization reaction. Enhanced functionality can also be imparted to substrates which
will allow them to be more effective in flocculation, dispersion and other applications such as
retention aids in paper, dry strength additives etc. Polyelectrolyte side chains can be introduced
onto suitable substrates by either grafting an ion-containing monomer or a suitable monomer
which can then be transformed to an electrolyte by a simple chemical reaction. An example
of the latter is where methylmethacrylate or acrylonitrile can be grafted onto starch and then
Tridib Tripathy et al. transformed by alkaline hydrolysis to acrylic acid or methacrylic acid grafts. Vinyl pyridineor dimethyl aminoethyl methacrylate can be grafted and then subsequently quaternized.
Anionic/Nonionic Graft Copolymers
Most of the prior work on graft copolymerization has been with starch and cellulosics using
either styrene, acrylonitrile-acrylamide or acrylic acid as the grafting monomer employing
the ceric ion or radiation method. The alkaline hydrolysis of starch-g-polyacrylamide produces
a mixture of carboxylic acid and carboxamide groups, but these are little effective in
flocculation. Acrylic acid/methyl cellulose graft copolymers have been used as clay binders
in foundry sands. Water soluble graft copolymers with exceptionally high molecular weight
grafted side chains using acrylamide and acrylic acid have been prepared using ionizing
radiation as the grafting mechanism. These materials are excellent flocculating agents.
Singh et al64-68. have reported the synthesis and applications of graft copolymers of
polyacrylamide onto natural polymer like CMC64, guar gum67, xanthan gum65, starch64 and
amylose66. The drag reducing properties as well as the shear stability of the graft copolymers
were studied. It was found that grafting of polyacrylamide, which is highly prone to shear
degradation onto polysaccharide backbones not only results in efficient drag reducing agents,
but also makes the graft copolymers reasonably shear resistant67. Further, variation in the
number and length of polyacrylamide chains were affected by varying the synthetic
parameters. It was observed that in a series of graft copolymers with a particular
polysaccharide, the one with fewer but longer67 polyacrylamide chains performed the best.The
study of the flocculation behaviour of the graft copolymers showed the same trend. Among
the graft copolymers with various polysaccharides, starch-g-polyacrylamide was the best in
performance68. In another study, Karmakar68 studied the flocculation and rheological studies
of starch-g-polyacrylamide and amylose-g-polyacrylamide. Starch-g-polyacrylamide was
found to be the better in performance.When the performance of amylopectin-g-polyacrylamide
was investigated by Rath and Singh it was found to performs better than any other graft
copolymers and various commercial flocculants. This behaviour was explained by Singh
model which is based on easy approachability of dangling polyacrylamide branches on rigid
amylopectin to contaminants in the industrial effluents. Since in amylopectin-g-polyacrylamide
the polyacrylamide branches are grafted on backbone as well as on amylopectin branches,
this provides better approachability of grafted polyacrylamide branches to contaminants.
Cationic graft copolymers
Various quaternary ammonium monomers have been graft copolymerized onto starch in attempts to prepare improved flocculants and pigment retention aids useful in papermaking. Of particular interest is the work of Fanta et al.69 on the graft copolymerization of 2-hydroxy-3-methyacryloyloxypropyl trimethylammonium chloride onto starch and its evaluationas flocculating agents. Fanta et al70. also investigated the graft copolymers of starch withmixtures of acrylamide and the nitric acid salt of dimethylaminoethyl mehacrylate and Flocculation : A new way to treat the waste water evaluated their flocculation performance. Jones and Jordan71 investigated the graft andterpolymers of starch with 2-hydroxy-3-methacryloyloxypropyl trimethyl ammonium chlorideand acrylamide for use as silica depressants in the flotation-beneficiation of silaceous ores.
Hoover and Sinkovitz72 developed some new cationic graft copolymers made by the graftcopolymerization of diallyldimethylammonium chloride or 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride and acrylamide onto dextran substrate and their use as additivesfor improving the dry strength of paper. Larsson and Wall73 have synthesised cationicamylopectin using 3-chloro-2-hydroxypropyl trimethyl ammonium chloride (QUAB) as themonomer and studied its flocculation performance in colloidal silica suspension.
Because of the unlimited opportunity for structure variation and opportunities for providing multiple functionality, the technology of graft copolymerization is receiving significantattention by current researchers. Out of these efforts mny valuable commercial products areexpected to materialize in the near future.
1.6 Polymers vs Inorganic Flocculants
Polymeric flocculants offer some distinct advantages over inorganic flocculants.
The flocs are larger and stronger and are more rapidly formed. The salt concentration is notincreased and much less sludge is generated. The dosage requirement is quite low (typically1% on a dry weight basis) whereas that of inorganic flocculants may be as high as 20%. Theinorganic flocculants frequently require pH adjustment, which is not necessary with polymericflocculants. Futher, the polymeric flocculants are more convenient and easier to use. However,inorganic flocculants are inexpensive and often used for economic reasons.
1.7 Natural vs Synthetic Flocculants
A comparison of the natural and synthetic polymers may be as follows. Principal advantages of natural polymers are that they are non-toxic and readily available from renewablenatural resources. Unfortunately, their efficiency is low, thus requiring a high dosage thatvaries with origin of natural polymers. The biggest advantage of natural polymers is theirbiodegradability. But this very advantage becomes a drawback in reducing its storage lifeand tells upon their efficiency as a result of molecular breakdown. The synthetic polymerson the other hand are highly efficient with product consistency and uniformity, and biologicalas well as chemical stability. These can be tailored in terms of functional groups, structureand molecular weight to suit to a particular application. However their disadvantages arethat they are mostly non-biodegradable, highly expensive and may be toxic74,75 (it may benoted that the synthetic polymers are not toxic but the associated monomers may be toxic).
1.8 Flocculation : The Test Methods
The principal purpose of a flocculation test76 procedure is to establish the optimal Tridib Tripathy et al. conditions for floc formation, but the nature of test may be greatly influenced by the processconsiderations. If the aim of flocculation process is to clarify turbid water, then the optimumconditions might be judged in terms of minimum supernatant turbidity after sedimentation offlocs. On the other hand, if solids recovery is the main purpose, settling rate could be thechosen parameter. In case of sludge dewatering, flocculants are used to increase filterability,so that filter cake permeability or specific resistance to filtration is considered as the desiredparameter.
It seems reasonable to assume that optimum flocculation condition determined on the basisof different tests should coincide, especially if thorough mixing of additives could be achievedrapidly. However, there is very little evidence on this point in practical systems. In factwhere flocculation is carried out for some specific purpose such as colour or phosphateremoval, then it is the best to monitor the removal directly. Ideally, a flocculation test procedureshould simulate the operation of a full-scale unit and be capable of predicting plant performanceon the basis of laboratory trials. But due to various reasons, such prediction is difficult toachieve and a more realistic aim is to establish optimal chemical conditions in laboratorytrials, which correspond closely to those giving optimum plant performance. The actualperformance of the plant, in terms of clarification, settling rate or other parameters, may notbe the same as that found in the laboratory test under the same chemical conditions, but it ispossible to establish an empirical relationship, which can be used for predictive purposes.
Usually, measurement of three parameters, namely sedimentation rate, settled volume andsupernatant turbidity give information on the state of aggregation of a suspension.
Sedimentation (at fairly high solids concentration) can most conveniently be measured in thezone settling region, where the movement of the boundary layer can be followed with time.
Settled volume of flocs is sometimes used in laboratory evaluation of polymeric flocculants,but is not usually employed in routine tests.
Measurement of supernatant turbidity is frequently employed as an indicator of flocculationperformance. Ideally, a well-flocculated suspension should settle leaving no suspended solidsin the supernatant liquid and hence a very low turbidity. Turbidity measurements are basedon transmitted light or light scattering, the latter being more effective. For very low turbidities,some other measures of solids content like Silting Density Index (SDI) may be moreappropriate. The supernatant turbidity, although a directly relevant parameter in applicationslike water clarification, some difficulties may arise in interpreting the results. For instance,the result may be greatly influenced by a residual haze, which may represent an extremelysmall proportion of the original solids. Incomplete mixing of the flocculant may result in localoverdosing and restabilization of a small number of particles, giving rise to a persistent hazein the supernatant liquid. This effect is likely to occur with polymeric flocculants.
The Jar Test
One of the most common pieces of bench test apparatus found in water treatment laboratories to identify potential coagulation-flocculation conditions in liquid suspensions is Flocculation : A new way to treat the waste water the jar test76,77 apparatus. The test is used to confirm the preferred chemicals and also toidentify the best concentrations. The batch-test consists of using six identical jars containingthe same volume and concentration of feed, which are charged simultaneously with sixdifferent doses of a potentially effective flocculant. The six jars can be stirred simultaneouslyat known speeds. The treated feed samples are mixed rapidly and then slowly and thenallowed to settle. These three stages correspond respectively to the fundamental processesof dispersing the flocculant onto the particle surface, gently sweeping the colloidal particlestogether to form large flocs, and allowing the flocks to settle. These three stages are also anapproximation of the sequences based on the large-scale plants of rapid mix, coagulation-flocculation and settling basins. At the end of the settling period, test samples are drawnfrom the jars and turbidity of supernatant liquid is measured. A plot of turbidity againstflocculant dose gives an indication of the optimum dosage (i.e. the minimum amount requiredto give acceptable clarification). The criteria thus obtained from a bench jar test are thequality of resultant floc and the clarity of the supernatant liquid after settling. The design ofthe full-scale plant process is then done based on the bench-scale selection of chemicals andtheir concentrations.
Unfortunately, the jar test suffers from a number of disadvantages, despite its widespreadapplication. It is a batch test, which can be very time-consuming. A thorough exploration ofoptimum flocculation conditions for raw water can easily take a few days. Such an extensiveseries of trials would require very large volume of sample which may be inconvenient iftesting is to be carried out remote from the raw water source. Finally, the results obtainedfrom a series of jar tests might not correspond to the results obtained on a full-scale plant.
Many new methods78 have been developed to substitute the conventional jar test includingtechniques79,80 for characterization of floc structure.
1.9. Factors Affecting the Flocculation
1.9.1. Effects of polymer molecular weight and charge density
The effects of polymer molecular weight on flocculation81-83 is best described in terms of bridging and electrostatic patch mechanisms. For systems in which bridgingpredominates irrespective of charge, an increase in molecular weight improves flocculation.
At higher molecular weight, as the polymer gets adsorbed, it can extend further away fromthe particle surface and is slower to reach equilibrium. This, in turn, increases particle radiusand collision number and hence flocculation rate. Although anionic charge on polymer canimpede adsorption onto a negative surface, it serves to promote extension of polymer chainthrough mutual charge repulsion, enhancing its approachability. It has been observed thatbeyond an optimum molecular weight, flocculation efficiency decreases which is attributedto steric repulsion between polymer molecules. On the other hand, molecular weight effectsare less well defined in systems where the electrostatic patch mechanism is rate controlling.
Optimum flocculant concentration has been found to be independent of molecular weight but Tridib Tripathy et al. dependent on ionic strength. Adachi et al.84 observed the rate of initial flocculation of apolystyrene latex to be remarkably enhanced by the addition of polyelectrolytes, but theextent of this enhancement decreased with an increase in ionic strength. Equally important isthe configuration of the solvated polymer, particularly in bridging flocculation. Moleculareffects are more apparent when the polymer has a rod-like character.
1.9.2. Conformation of polyelectrolyte in solution
It was observed85 that, in the flocculation of clays by two high molecular weight
polyacrylamides of different degrees of hydrolysis, the high molecular weight, 30% hydrolyzed
polymer performed best. The flocculation diminished beyond an optimum concentration, which
can be explained by bridging mechanism. The higher molecular weight polymers can adsorb
in configurations with loops of greater length extending from particle surface, increasing
collision probability. Particles bridged by 30% hydrolyzed polymer perform best because the
charge not only affects the particle-polymer interaction but also causes an extension of the
solvated polymer chain. At 30% hydrolysis, a balance is reached between the effects of like
charge repulsive forces of the polymer and the particle surface and polymer surface
configuration as it is influenced by the presence of the charged acrylate groups. The
concentration effects are due to the need for vacant surface sites on which a bridging polymer
can adsorb. In a similar study Yu et al.86 have established that polymer conformational87
changes have a beneficial effect on the flocculation of alumina.
1.9.3. Effects of dosing and mixing conditions
The degree of flocculation achieved can be markedly affected by dosing and mixing88-90
conditions. It has been found91 that for high solids concentrations and relatively low polymer
doses, flocculation occurs rapidly, but the flocs are not stable and can be broken at moderate
stirring rates. By reducing the rate of stirring shortly after polymer dosing, floc size (and
settling rate) can be held at plateau levels, without subsequent decline, which, however, is
difficult to achieve in practice because of the precise control required. It has been suggested
that92-93 optimum flocculation occurs when half the area of solid is covered with
polyelectrolytes. At higher concentration the degree of flocculation decreases, and the particles
may be completely covered by the absorbed polymer layer. Thus overdosing can be a serious
mistake in that it may create a well established suspension that is extremely difficult to
separate. But, in principle, a substantial degree of flocculation can be obtained with much
lower polymer dosage than is usually required. Hydrodynamic factors94,95 arising from
mechanical agitation play a significant role in flocculant adsorption. Vigorous agitation of
flocculating suspension causes floc breakage and the exposure of fresh surfaces to polymer
adsorption thereby increasing adsorption capacity. At the same time, however, increased
agitation leads to the production of smaller flocs, indicating that enhanced adsorption does
not compensate for increased floc breakage. In fact the general rule seems that, provided
adsorption does occur, the actual amount adsorbed varies inversely with the extent of
flocculation.
Flocculation : A new way to treat the waste water 1.9.4. Solution properties
Ionic Strength
The configuration of polyelectrolytes in solution is significantly affected by ionic strength and
this effects flocculation. This is indicated by the increased viscosity of a polyelectrolyte
solution as ionic strength decreases. Similar charges on the polymer chain tend to expand the
chain as a result of mutual charge repulsion. As ionic strength increases, these charged sites
are shielded and allow the polymer to fold and assume a smaller hydrodynamic volume, as
indicated by a decrease in solution viscosity. These effects manifest themselves in the
flocculation mechanism. In a high solids system to be flocculated by a high molecular weight
charged polymer, decreasing ionic strength expands the polymer in solution and enhances
bridging by increasing the effective particle radius. In systems where the electrostatic patch
mechanism predominates, the effect of ionic strength is less well understood. On the other
hand, when charge-neutralization mechanism is operative, ionic strength effects will be realized
through double layer compression in systems where flocculant and surface are oppositely
charged.
pH Effects
With inorganic flocculants, the effective species can be a solvated metal ion, which affect flocculation through double-layer compression and Schulze-Hardy effects. With
increase in pH, these species become charged and the mechanism of action changes. When
the colloids are hydrophilic, e.g. humic acids, pH affects protonation. In presence of ionizable
acidic or basic groups, colloid surface charge is affected by pH changes. In organic polymer
flocculation as well, pH can affect polymer activity and the mechanism.
Effect of Particle Size
The importance of particle size variation with regard to flocculation has been investigated by
many researchers96. Moudgil et al.97 have reported that there exists a strong correlation
between aggregation of a given size and the molecular weight of the flocculant. They have
explained the correlation between particle size and flocculant molecular weight in terms of
floc formation forces provided by polymer bridging and floc breaking forces (e.g. turbulence)
encountered in an agitated system. In similar report Mishra et al98 have reported the decreasing
settling rate of coal suspensions with decreased particle size. This has been attributed to an
increase in surface area that increased the charge neutralization capacity of the coal surface
by the flocculant.
1.10 Flocculation : The Applications
1.10.1. Water clarification
Flocculants are used for clarification of potable and industrial process water. Their principal function is the removal of suspended solids, which cause turbidity. Flocculants arealso used in gravity separation and flotation processes for industrial and municipal waterclarification. For wastewater, containing mainly inorganic compounds, anionic flocculants Tridib Tripathy et al. are preferred whereas for organic compounds, cationic flocculants are most often applied.
Polymeric flocculants are employed for wastewater treatment in the metals, chemicals, pulpand paper, food processing, petroleum refining and textile industries.
1.10.2. Paper making
In the process of production of paper from wood and pulp, filler such as clays, titanium dioxide, calcium carbonate etc. are used to provide opacity and whiteness to paper.
However, a significant percentage of the fillers added as well as fiber fines may be lostduring drainage of the wet paper web. The loss of valuable fillers and fines during drainageis significantly reduced by addition of flocculants, the type of which is dependent on thehistory of the pulp. Both alum and cationic polymers are used to neutralize the negativepaper fibers. Because the alum forms small, easily sheared flocs, it may be used in conjunctionwith a high or ultrahigh molecular weight cationic or anionic polymer. Starch and cationicstarch also function as flocculants when added to fiber slurry to increase the wet strength.
An additional benefit of using the flocculants as retention aids in paper industry is that, theresidual polymer left in the stream is very effective in clarifying the "white effluent" formedin the process.
1.10.3. Mineral processing
In all mining operations, solids and liquids must be separated which can be facilitated by flocculants in the thickening of froth flotation concentration and clarification steps. Inmost mineral processing, the suspended fines are impurities arising from crushing and grinding.
They are separated as the solid phase rather than the mineral of interest, which remains insolution, coal being an exception. The mining industries requiring flocculants include coal,iron ore, bauxite and uranium etc. The coal industry is the largest user. Both cationic andanionic flocculants99 are used including some natural polymers. Cationic polymers are ofquaternary ammonium type, e.g. poly (DADMAC) or polyamine especially in the recoveryof coal. The principal anionic synthetic flocculants are poly (acrylamide-acrylate) copolymersalthough nonionic polyacrylamide is also utilized. Among natural polymers used are starch,guar gum, animal glue, lignin (sulfonate) etc.
1.10.4. Selective flocculation
One of the applications that have shown considerable promise in the beneficiation of mineral fines is selective flocculation100-103. This process involves flocculating particles ofone type from a well dispersed suspension of the ore or mixture, followed by separating theflocs by either froth flotation or sedimentation. Selective flocculation, like flotation, takesadvantages of the differences in the physico-chemical properties, but unlike flotation, doesnot depend entirely on the wettability characteristics of the particle surfaces. The selectiveflocculation involves three steps: dispersing the fine particles, selectively adsorbing the polymer Flocculation : A new way to treat the waste water on the active component (flocculating particles of interest) and forming flocs, and separatingthe flocs. The major applications of selective flocculation have been in mineral processing,but many potential uses exist in biological and other colloidal systems102. These includepurification of ceramic powders, separating hazardous solids from chemical wastes andremoval of deleterious components from paper pulp104. Industrial applicability of this processhas so far been limited, e.g. processing of taconite and potash ores, because results obtainedby selectively flocculating natural ores or complex synthetic mixtures often do not correlatewith the selectivity observed in single component systems. Selective flocculation of desiredfraction has become an active area of research in the field of flocculation 105-108 A criticalreview on iron oxide/quartz separation using starch and polyacrylic acid (PAA) indicatesstarch to be a more selective reagent109.The presence of clays, particularly Montmorillonite,is known to have a detrimental effect on the selectivity of separation. To achive the desiredselectivity ( <10% flocculation of clay ), Sodium silicate is to be added. The primary objectiveof adding sodium silicate is to prevent hetero coagulation. Ravisankar et.al110 attemptedselective flocculation of iron oxide-kaolin mixtures using a modified polyacrylamide flocculantcontaining hydroxamate functional groups. Flour apatite, the phosphate fertilizer mineral,occurs in nature. In association with silicate and carbonate minerals. During flotationseparation of apetite a significant proportion of P O values is lost in the form of slimes.
Selective flocculation appears to be promising for recovering the fine phosphate values.
Pradip et,al.111,112 have successfully examined the feasibility of selective flocculation of tribasiccalcium phosphate using hydrolysed polyacrylamide and polyacrylic acid flocculants.
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Flocculation : A new way to treat the waste water Fig. 1 : Electrical double layer
Tridib Tripathy et al. Flocculation : A new way to treat the waste water Fig. 3 : Schematic illustration of electrostatic patch mechanism
Tridib Tripathy et al. Fig. 4 : Cationic monomers (Quaternary ammonium salts)
Flocculation : A new way to treat the waste water Fig. 5 : Anionic monomers of sulphonic acid salts

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