© vom Wet Res. Vo. 28, No. pp. 59-868, 1994 ‘Copyright © 1954 Beer Scene Lid Printed in Great Britain, All sgt eaerved 135984 56.00 +00 DYNAMICS OF COAGULATION OF KAOLIN PARTICLES WITH FERRIC CHLORIDE Hsiao-Wet Cumno!, THEopoRE S. TANAKA? and MENACHEM ELiMeLscu*® ‘Department of Civil and Environmental Enginering, University of California, Los Angeles, (A 90024-1393 and *Metropotitan Water District of Southern California, 700 Moreno Avenue, 1a Verne, CA 91750, USA, (First received October 1982; accepted in revised form June 1983) ‘Abstract—An optical monitoring technique is used to investigate the dynamics of coagulation of kaolin. suspensions with ferric chloride. Particular attention is given to the eflets of coagulant dose, solution pH tnd mixing intensity on coagulation dynamics. Results show that this monitoring method provides ‘valuable information on the dynamics of aggregates in coagulation with Fe(ID salts, ‘Key words—coagulation, ferric chloride, metal salt coagulant, cay particles, monitoring, cougulation 4yeamics, Fe(II) solution chemistry meTRODUCTION Coagulation is an essential process in the overall solid-iquid separation scheme in water and ad- ‘vanced wastewater treatment. Hydrolyzing metal salts, such a5 aluminum end ferric coagulant, are widely used as primary coagulants to promote the formation of aggregates. For optimal performance of subsequent solid-liquid separation processes, itis imperative that aggregates of a certain size, strength and density be formed in the coagulation process (€.8. Ramaley etal, 1981; O’Melia, 1985). In coagulation with hydrolyzing metal salts, these properties are largely determined by coagulant dose, solution pH and mixing intensity (Amirtharajah and O'Mela, 1990: Dentel, 1991). The state of aggregation and dynamics of-aggre- satcsin coagulating suspension can be measured by particle counters (e.g. Lawler ef al, 1983; Frangois, 1988; Amirtharajah and O’Melia, 1990). However, because of breakage of aggregates and formation of gelatinous hydroxide precipitates (Treweck and Morgan, 1977; Lawler ef a, 1983), serious difficulties rise when particle counters are used to measure the size of aggregates formed in coagulation with by- drolyzing metal salts. In addition, particle counters are expensive and are not suitable for obtaining ‘immediate and continuous information about the state of aggregation and dynamics of aggregates in a coagulating suspension, ‘A simple but sensitive optical technique has re- cently been developed to monitor the state of agare- {ation of colloidal suspensions (Gregory, 1985). The technique is based on measurement of turbidity fuc- tuations in flowing suspensions. When a flowing suspension is illuminated by a narrow light beam, the ‘Author to whom all correspondence should be addressed. transmitted light measured by a detector fuctuates about a mean level It ean be shown (Gregory, 1985) that the ratio of the root mean square of the fluctu- ating signal to the mean level is roughly proportional to the size of the aggregates flowing through the detector and to the square root of their concen- tration. This ratio, referred to as flocewlation or coagulation index, can give immediate information on the state of aggregation of particle suspension over the entire period of coagulation. ‘The technique described above has been suocess- fully applied to study the dynamics and mechanisms ‘of coagulation of dilute and concentrated suspensions with polymeric coagulants (e.g. Gregory, 1988; Gregory and Lee, 1990; Li and Gregory, 1991; Gregory and Li, 1991. In this paper, itis shown that this technique can be applied to study the dynamics ‘of coagulation with metal, salt coagulants (ferric chloride). Iti further demonstrated that this method can give valuable insights into the mechanisms of particle ageregation with ferric chloride. BACKGROUND Chemistry of Fe(Il) salts When Fe(III) sats are dissolved in water, the metal jon hydrates, coordinating six water molecules and forming an aquometal ion, Fe(H,0)3*. The aquometal ion can then hydrolyze and form ‘monomeric and polymeric ferric species, the for- ‘mation of which is highly pH dependent (Stumm and Morgan, 1981; O'Melia er al, 1989; Morel and Hering, 1993). It is possible to describe the formation ‘of several hydrolysis species that are positively charged: FeOH?*, Fe(OH);, Fe,(OH){* and Fe(OH)i*; neutral: Fe(OH)§; and negatively charged: Fe(OH); . 559$0 In general, the hydrolysis reactions of Fe(III) in aqueous solution can be writen as XFo" + yH,O= Fe(OH)" +yH* (1) At any pH, the maximum dissolved concentration of Fe(II1 in equilibrium with the hydroxide solid is determined by the solubility ofthe solid phase, inthis ease amorphous ferric hydroxide, am-Fe(OH),(s), and by the extent of formation of monomeric and polymeric hydrolysis species in solution. The solubil- ity diagram of Fe(II), such as that shown in Morel ‘and Hering (1993) or Johnson and Amirtharajah (1983) is very useful to describe the concentrations of the dissolved ferric species as a function of pH, at ‘equilibrium with am-Fe(OH),(s). It can be seen from the solubility diagram that amorphous ferric bydrox- ide is least soluble at a pH close to 8. Ferric adsorption onto particle surfaces can affect both the speciation of ferric in solution and the surface properties of the particles. Adsorption of ferric onto clay particles can occur by formation of surface complexes between ferric and surface hy- droxyl groups of the mineral. For kaolinite, cation adsorption can involve both ion-exchange (particu- larly at low pH) and surface complex formation. This latter reaction is thought to occur predominantly at the basal gibbsite and edge surfaces of the clay mineral (Stumm, 1992). Reaction with monomeric ferric hydrolysis species may be writen in @ general form as = SOH + Fe(OH)?-"* = =SOFe(OH)?="* +H,0 @) Where 1 indicates a surface species. Note thatthe surface-ound ferric can also undergo acid-base reac- tions. In the surface complexation mode, the surface ‘charge ofthe mineral is atibuted to the presence of ‘charged surface species (=SOH! and =SO™, in the absence of any adsorbing species other than protons). ‘Thus, formation of ferrie surface complexes can alter surface charge (Stumm and Morgan, 1981; Stumm, 1992). Adsorption of polymeric ferric species, pecially highly charged species, can dramatically atfect surface charge (Tang and Stumm, 19872, b; O'Melia et al, 1989). In practice, however, the ad- sorption of polymeric species may be indstingush- able from precipitation of am-Fe(OH)s() at the mineral surface. With increasing feric adsorption and surface coverage, the acid-base properties of the surface will be increasingly characteristic of am- FeOH),(). ‘A continuum between surface adsorption (com- plexation) and precipitation is described by the sur- face precipitation model. This model allows for the formation ofa surface phase with a composition that varies continuously between that ofthe criginal solid and that ofa pure precipitate of the adsorbing cation (arly eta, 1985). Formation of the precipitate st ‘the mineral surface, evidenced by a gradual increase Hisxo Wei Crna et al in sorption density of the precipitating cation, occurs below saturation in the bulk solution. Thus, am- Fe(OH),(s) may be formed at the surface of mineral patticles and affect their surface properties, even When the solubility product for am-Fe(OH),(s) is not exceeded in the bulk solution. It should be emphasized thatthe chemistry of ferric adsorption and precipitation in natural waters is ‘much more complicated because of the presence of fhumic substances. Interaction of humic substances with surfaces and dissolved ferric species can ‘markedly influence coagulation processes. It is well known that actual ferric dosages in water treatment are controlled by the concentration of dissolved natural organic matter (Amirtharajah and O’Melia, 1990). These aspects, though beyond the scope of this paper, should be considered in actual treatment practices. Principles of turbidity fluctuations The principles ofthe optical technique used in this study and its application to coagulation processes have been described previously (eg. Gregory, 1985; Gregory and Nelson, 1986). A short description of this technique is given below. ‘When 2 flowing suspension is illuminated by a narrow light beam, the transmitted light intensity, monitored by a photo detector, fluctuates randomly about some mean value. The output from the photo detector consists of a steady (D.C.) signal and a Auetuating (A.C) component. The D.C. value is a measure ofthe average transmitted light intensity and depends on the turbidity of the suspension. The fluctuating (A.C.) component isa result of random variation in the number of particles in the illuminated volume, Tt can be shown (Gregory, 1985) that the root mean square (RMS) value of the fuctuating (A.C) signal is related tothe average number concen- tration and the size of the suspended particles. In practice, itis convenient to divide the RMS value by the steady D.C. value to give a dimensionless term R=RMS(D.C. With the use of this ratio, one can avoid the effects of optical surface fouling and electronic drift Itcan be shown (Gregory and Nelson, 1986) that, for hetorodisperse suspension, the ratio R can be expressed as LY" enon a-(4) @ncp" eo where L is the optical path length, 4 is the effective cross-sectional area of the light beam and Nand C, are the number concentration and scattering cross- section of particles of size i, respectively. This equation demonstrates that the fluctuating signal depends on the square root of particle concentration and on the first power of the scattering eross section. The latter is highly dependent on the size of the suspended particles.Dynamics of coagulation of kaolin sot ‘An analysis of the term (ENC?) in equation (3) reveals that smaller particles have a negligible effect on R, and that, ina coagulating suspension, the larger aggregates have a dramatic influence on R (Gregory and Nelson, 1986). This means that as coagulation progresses, the value of R increases. Although the ratio R does not provide quantitative information on aggregate size, the relative increase in the R value is 2 useful indicator of the degree of coagulation. For «given suspension, it ean be assumed that larger R values imply larger aggregate size. This ratio will be referred to as the “coagulation index” in this study. [MATERIALS AND METHODS. ‘Synthetic kaolin suspension A stock suspension of clay particles was prepared by lispersing purified kaolin in powder form (Fisher Scientific, Pitsburgh, Pa, U.S.A.) in deionized water t0 a concen tration of 10. The test suspensions were prepared by diluting the stock suspension to a desired concentration. All test suspensions contained | mM of sodium bicarbonate to provide alkalinity. The sie distribution ofthe kaolin sus- ‘pension was measured by a particle counter (Multisier TI, Coulter Electronics, Hialeah, Fla, U.S.A) with « 30-um aperture tube (effective range 0.6-18 ump). The partcis in te suspension had a mean volume diameter of 2.1m with a relatively narrow size distribution. The umber and ‘Volume distributions of the clay partcies, presented in the form discussed by Amirharajah and O"Melia (1990), are shown ia Fig. 1, Electrophoretic mobiles of the particles were measured by a Lazer Zee Model SOI apparatus (Pen Kem Inc, Bedford Hill, N-Y., USA), The clay suspen- sions used in the electrophoretic mobility measurements ‘were treated similarly to those used in the coagulation experiments and the results were easly reproduced. It as found that the particles are negatively charged at ‘all pH values examined (From 3.4 0 10.0), Preparation of ferric coagulant solution ‘A concentrated stock solution of fertc chloride was prepared by dissolving analytical reagent-grade FeCi,-6H,O (Fisher Scieniic, Pitsburgh, Pa, USA.) in Asionized water to concentration of 225M, A fresh “ s ANFa(togd,) Gx10%) 10 av/a(iogd,) 640) Fig, 1. Number and volume distributions, 4N/d(log d,) (Gol fine) and 4¥ alg dy) (broken ine) asa function of Jog dof the kaolin suspension used in this work (Nis the number of particles per unit volume of suspension, the volume of particles per unit volume of suspension and 4, is ‘the particle diameter) ‘Congulant ‘Motor Perse amp Fig. 2. Schematic description of the experimental stup for monitoring the dynamics of coagulation by the PDA 2000. coagulant solution of 0.3 M was prepared from the concen ated stock solution before every set of experiments. In all coagulation experiments, erie chloride wat added directly from the 03M coagulant solution. Preliminary experiments, showed that the dosage of coagulant needed to neutralize ‘he negative charge of the particles is larger when more dilute ferric chloride stock solutions are used. The 03M ‘coagulant solution can be classified as type A based on the analysis of Tang and Stumm (1987a, b). They also reported that feric coagulant solutions with concentrations higher than 0.11M are more effective than those of lower concea- tration Experimental setup for monitoring coagulation dynamics Aight scattering instrument with a flow-through detector (PDA 2000, Rank Brothers Lid, Cambridge, UK) was used to monitor the dynamics of coagulation, A schematic siagram of the experimental setup is thown in Fig. 2. The coagulation vessel vas a Liter beaker, mixed by a 162 2S4-mm rectangular fat blade located 45mm above the base of the beaker. The blade was driven by an adjustable speed motor via 2 thin spindle, centrally located in the beaker. A 3mm (.d.) Tygon tube, located 30mm. below the liquid evel, conveyed the suspension to the flow-through detector of the PDA 2000. monitor. The suspension was driven by a peristaltic pump (Mastrtex, Cole Paimer Instrument Comp., Chicago, Ml, USA.) lo: cated downstream of the monitor. The fow rate in the conveying tube was 22cm/min, and the time forthe sample {pass from the coagulation beaker to the flow-through etector was approx. 105. The above conditions (ie. the ‘ow through the sampling tube and the location of the throughout sl the be compared to each other Coagulation experiments A Lelter kaolin suspension, with 10-°M NaHCO, and a solid concentration of 50 mg/l, was used in the coagulation ‘experiments. The experiments were conducted at room temperature (average of 20°C). In these experiments, the target pH was adjusted by adding predetermined amounts of KOH or HCI to the suspension, followed by the addition of ferric chloride with a micropipette directly from the 10.3 M ferc coagulant solution, Rapid mixing for 2min) by ‘magnetic stirring at high speed was initated afer the ‘addition of ferric chloride. At the end of the rapid mixing, small sample was taken by a 25-mi pipette for eectrophor- tic mobility measurements. Following rapid mixing, the