Table 8-3 Commonly Used Coagulants and Limes in Water-Treatment Practice Chemis! , Stamloel— oloar uk Soubity Chemical Water Tame” Srenvme Forma “wane” APPAR — any, $ERIC Srwanay‘Gorment|comtnt Da kg/m kgim? 56 wh % wiw aan Uniiaten— AYSO BHO 12871 Wier 15018 Weysole ABAOAS 727K tare one vu eso 230 —Yelows 962 Appon FINS. 210 own ump Foie on (lst Fe{SO,9H,0. 56202 Ret ron FF reinsu7 - - -_ -— Tigi ene Fe{S0,)691%0 106464 Rell 0-157 Veysohble Fe:101-120 568-640 01-13 ‘ea = =—=—S Mg* + CO;” 2001075 Flue gas desulfurization CaSO, 9 Ca?* + S0,2- 4010-5 Hardness removal, scaling Mg(OH)) Mg ?*+20H™ 900 107! Hardness removal, scaling AIH); @ AI*+ 30H” 1 = 10-8 Coagulation Fe(OH); Fe*+30H” 6 00 10-8 Coagulation, iron removal, corrosion Fe(OH); «> Fe*+ 20H” Se 10715 Coagulation, iron removal, corrosion Mn(OH); <> Mn?*+30H™ — 1 00 10736 ‘Manganese removal Mn(OH), ¢ Mn?*+20H™ 8 10-4 Manganese removal Cu(OH); > Cu*+20H” 210719 Heavy metal removal ‘Zn(OH)3 > Zn?* + 20H™ 3010-17 Heavy metal removal Ni(OH); <= Ni?* + 20H 2 107!® Heavy metal removal Cr(OH); © Cr* + 30H” 60107! Heavy metal removal “Source: Adapted in part fom References | and 25, Ferric Chloride: 2FeCl; +3Ca(HCO5), > 2Fe(OH);(s) + 3CaCl; + 6CO, ( 2% 1625 3x 100 2x107 3x11 6x44 (as CaCO) Alum 12((SO,)3*14H,0) + 3Ca(HCOs ), ¢ (2Al(OH);)(s) + 3CaSO, + 6CO, + 14H,0 | 594 3x 100 2x78 3x136 6x44 14x18 The following observations can be made on these reactions (Eqs. (8.3), (8.4), and (8.5 +1 mg of ferric sulfate will produce approximately 0.54 mg of insoluble Fe(OH) pres tates and will consume approximately 0.75 mg of alkalinity (expressed as CaCO3). +1 mg of ferric chloride will produce approximately 0.66 mg of Fe(OH)s precipitates will consume approximately 0.92 mg of alkalinity (expressed as CaCO),+1 mg alum [Alp(SO4)3*14H,0] will produce approximately 0.26 mg of insoluble Al(OH), precipitates and will consume approximately 0.51 mg of alkalinity (expressed as CaCO) Because of the consumption of alkalinity, CO) is produced during coagulation. The pH value may also be lowered after the coagulation process, depending on the amount of coagulant applied and the initial alkalinity in the raw water. The stoichiometric equations can be used to estimate the coagulant quantity requirement; however, the actual amounts of coagulant required for destabilization of colloids may depend, not only on the reaction stoichiometry, but also on ciher operational conditions such as ionic species, pH value, temperature, type and properties of particles, mixing-energy input, and the effective content of metal ions in the coagulant. The retal-ion content ina liquid commercial coagulant is typically in the range of 10-15% by liquid weight. The physical and chemical properties of commonly used coagulants are summarized in Table 8-3 Water Softening Hardiness in water is caused mainly by calcium and magnesium ions. ‘These cations typically cause carbonate hardness if associated with alkalnity-causing anions in water (hydroxide (OH™), carbonate (CO;?-), and bicarbonate (HCO3"). Calcium and magne- sium may also be combined with other anions, such as sulfate (SO,?-), chloride (CI), and nitrate (NO;"). Hardness in this form is known as non-carbonate hardness. As indicated in Table 8-2, calcium carbonate and magnesium hydroxide are relatively insoluble (Ky = 5 so 10°? and 9 ce 10!2), while other products of hardness are quite soluble. Inthe softening process, the chemical reactions increase the concentrations of calcium carbonate and magnesium hydroxide, thys removing calcium and magnesium as precipitates. Figure 8-6 illustrates the relationship between carbon dioxide (CO) and various forms of alkalinity. Eqs. (8.6) and (8.7) represent the chemical reactions between carbon dioxide and alkalinity ions. CO, +H,0 © H,CO, © H’ + HCO; (86) CO, + OH” & HCO, © H” + CO" (87) At lower pH values (below 4.5), carbon dioxide isin equilibrium and no alkalinity exists. ‘At moderate pH values (between 4.5 and 8.3), the reaction represented by Eqs. (8.3), (8.4), and (85) shifts tothe right. Carbon dioxide concentrations begin to reduce and bicarbonate (HCO; ) ions are formed. At high pH values (above 8.3), bicarbonates are converted into carbonate (CO,?*) ions, with the maximum concentration occurring at a pH value of 10,5.'° ‘These relationships between carbon dioxide and alkalinity are utilized in water softening {to remove hardness and alkalinity. The pH of the solution is raised to increase the concentrations of carbonate and hydroxide ions. These ions combine with calcium and magnesium to form cal- cium carbonate and magnesium hydroxide precipitates, ‘The pH can be raised by adding any ionic compound containing hydroxide ions. The chemical most commonly used is either lime (CaO) or hydrated lime (Ca(OH). The physicalHc Alkalinity 08 CoC0s, mg/t oF eH Figure 8-6 Equilibrium concentrations of CO, and alkalinity with respect to pH. (Note: The tem- perature is 25°C, and the total alkalinity is 100 mg/L as CaCO) ‘and chemical properties of commercial lime products are included in Table 8-3. The chemical reactions of lime softening with hydrated lime are illustrated in Eqs. (8.8) through (8.10). CO, + Ca(OH), € CaCO4(s) + HO (88) Ca(HCO,), + Ca(OH), € 2CaCO,(s) +240 69) Mg(HCO,), + 2Ca(OH), € 2CaCO,(s) + Mg(OH),(s) + 2H,0 (6.10) | noncarbonate hardness is to be removed, the lime softening process alone will be unsuc- ccessfu! in the removal of calcium and magnesium. In this case, soda ash (NaCOs) is used. The ch reactions involved in lime-soda processes are represented by Eqs. (8.11)-(8.13).* CaSO, + NayCO, © CaCO4(s) + NaySO, 1) MgSO, + Na;CO, + MgCO, +Na,SO, 8.12) MgCO, + Ca(OH), ¢ Mg(OH)(s) + CaCOs(9) 813) ‘To calculate the chemical dosage requirements forthe softening reactions, the concentra- tions of calcium, magnesium, total alkalinity, and carbon dioxide are required. The amount of lime required is expressed by Eq. (8.14).! [Ca(OH),] = [CO;] + [HCO}] + [Mg"*) + [excess lime] (14)where [Ca(OH] = amount of Cx(OH), required for softening in me/L (C0) = concentration of CO in me/L. {HCO™ = concentration of HCO™ in me/L [Mg] = concentration of Mg?* in me/L. [excess lime] = addtional amount of lime needed to maintain an elevated pH value, usually 1 imelL. ‘The dosage of soda ash required is expressed by Eq, (8.15).!27 [Na,CO5] = [Ca”*] + [Mg”*] - [Alkalinity] (B13) where {NeC03} = amount of NsgCO, quired for nonearbonate softening in me [Ca?*] = concentration of Ca* in me/L. [Alkalsity}=concentatin of alkalinity in mefl ‘The concentrations in Eqs. (8.14) and (8.15) are in me/L. To calculate the amount of lime or soda ash required in mg/L, multiply by their respective equivalent weights as shown by Eqs. (8.16) and (8.17).!27 Lime required in mg/L = [Ca(OH),] x 37.0 816) Soda ash required in mg/L. = [NagCO,] x 53 (en) ‘The use of Eqs. (8.14)-(8.17) is illustrated in the following example, Example: Calculate the amount of lime and soda ash required for water-softening, rhe com centration of hardness and alkalinity-causing components are given below. The exces. ime is 1.0 mefL., Worecular —— Equivatent ——Equivatant — Components Concentration _ Weight Weight Cone, mel mgt rs cat 70 mt 40 20 390 Mee 40mg. 2% 2 333 HCO 250 mg 6 6 410 coe 2mgiL 60 30 0.07 on 0.02 mg/L 7 7 0.0012Solution: Calculate the amount of lime required. [Ca(OH),] = [CO] + [HCO5] + [Mg?*) + [excess lime] 0.45 + 4.10 + 3.33 + 1.00 8.88 me/L Lime required = 8.88 me/L 37 = 328 mg/L as Ca(OH)) Calculate the amount of soda ash required. [Na,CO3] = Ca’* + Mg”* - [Al] = [Ca"*] + [Mg”*] - (LHCO3] + [(CO}"] + [OH] = 3.50 + 3.33 — 4.10 + 0.07 + 0.0012 2.66 me/L Soda ash required = 2,66 me/L. ce 53 = 141 mg/L. as Na;CO3 ‘The chemical dosages calculated from Eqs. (8-12) and (8-14) will result in softening of the water to approximately 35 mg/L of CaCO3 and 25 mg/L of Mg(OH) (expressed as CaCO,).27 These concentrations are more than the theoretical concentrations calculated by the solubility ‘products but represent the lowest concentrations achievable by chemical precipitation. Removal of hardness to this level is, however, adequate for most domestic water uses. The lime-soda softening process leaves the water saturated with Mg(OH)2 and CaCOs, and with an elevated pH. A process known as tecarbonation is used to lower the pH into the 9.2 927 range, thus restabilizing CaCOs,'2” In this process, carbon dioxide is added to the water. This lowers the pH and converts CO3?- to more stable HCO ions. Iron and Manganese Removal Iron and manganese are often present in groundwater supplies or in water drawn from the hypolimnion of a reservoir. Under anaerobic conditions, bacteria reduce iron and manganese to the Fe? and Min?* valence state, a more soluble state, Likewise, when waters containing Fe and Ma ions are exposed to air, these ions are oxidized to a less soluble Fe™* and Mn°* valence state that causes red or brown stains on plumbing fixtures and laundry. Therefore, removal of iron and manganese is desirable. Eqs. (8.18) and (8.19) represent the chemical reac~ tions of iron and manganese oxidation. 4Fe?* +0, + 10H,0 — 4Fe(OH)s + 8H (8.18) 2Mn?* +0, +2H,0 > 2Mn0, + 4H" 6.19) Removal is accomplished by oxidizing the Fe™* and Mn ions and removing the prec tates by sedimentation and filtration. One method of accomplishing oxidation is by aeration. The aeration process is discussed in Chapter 6. The aeration process is most suecessful in removing iron and manganese when the pH ofthe solution is above 8.5 and stacked-tray aerators with coke beds are employed.” The aeration process is usually unsuccessful at removal of iron in the che-lated form. In this form, the iron ion is bound to a larger molecule that is also dissolved in the water. Iron in the chelated form must be removed by chemical oxidation, as described next. In the chemical oxidation process, a strong oxidant such as ozone, permanganate, hydro- gen peroxide, chlorine, or chlorine dioxide is used.78 Iron is effectively removed at a neutral pH by any of these oxidants. Manganese can also be removed by permanganate oxidation at neu- tral pH levels. The remaining chemicals require a pH in excess of 8.3 for effective removal of manganese.?”8 Iron and manganese precipitates are also removed by coagulation and filtration. These pre- cipitates coat the filter and enhance the removal of colloids, but, if a chlorine residual is not maintained across the filters, bacterial growth in the precipitate coating will reduce the iron and manganese back to soluble Fe** and Mn?* state and causes resolubilization.>