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NEUTRALIZATION
Acid-base reactions are among the most prevalent of the chemical processes used
in water conditioning. It is fortunate that commercially available acids and bases
are relatively low in cost. Typical costs of acids and bases used in water treatment
are shown in Table 13.1, which also indicates the relative value of these materials
on an equivalent basis.
In addition to these chemicals, there are chemical wastes having residual acid
or base values that can be used for neutralization in waste treatment. For exam-
ple, pickle liquor from the steel industry is useful both for its acid value and for
the iron it contains as a coagulant; sludge from lime-soda water softening is a
good source of alkali for neutralization of acid wastes.
Progress in the neutralization of an acid or base is easily measured by pH.
However, the practicality of using pH to control the neutralization reaction is
greatly influenced by the buffer capacity of the water. For example, it is much
easier to neutralize an acidic waste containing hydrochloric acid to a pH of 7.5
with sodium carbonate than with caustic soda. This is illustrated by Figure 13.1.
Treating an acidic wastewater may be relatively easy because the allowable
effluent pH range is fairly broad, usually 5 to 9. However, adjustment of the sta-
bility index of a water requires controlling pH to a rather narrow range, so the
equipment for feeding acid or alkali to achieve a specified stability index in pro-
cess water is generally more sophisticated than equipment used in a wastewater
treatment plant.
The correction of the stability index with lime is shown in Figure 13.2. This is a
relatively common problem, although lime is not always used because it is more
difficult to handle than liquid caustic or soda ash. When used in large quantities,
it is purchased as CaO (see Table 45.1 for various forms of lime) and slaked to
Ca(OH)2. A typical feeding system is shown in Figure 13.2. Figure 13.3 shows
incremental additions of lime to a water requiring stabilization. The first incre-
ment of 6 mg/L is added for neutralization of all of the CO2; additional lime then
converts HCO3 to CO32" in successive steps. The resulting pH and stability index
at each increment is shown in the same tabulation. These data are plotted in Fig-
ure 13.4. Assuming the goal is a stability index of 7, the graph shows that this can
be accomplished with approximately 13 mg/L lime as CaCO3, resulting in a pH
of approximately 9.1.
TABLE 13.1 Acid and Alkali Costs for Neutralization
Equiv.
cost,6 C/lb
Cost," Ib/lb CaCO3
Chemical Specification e/lb CaCO3 equivalent
Sulfuric acid [H2SO4 (oil of vitriol)] 66 Be 93% 4.5C 1.05 4.7
Hydrochloric acid [HCl (muriatic acid)] 20 Be 32% 3.0C 2.28 6.8
Limestone (CaCO3) 200 mesh, 93% 1.2< 1.08 1.3
Quicklime (CaO) Lump, 90% 2Ad 0.62 1.5
i.iy 0.62 1.1
Hydrated lime [Ca(OH)2]' PuIv, 93% 2Ad 0.80 1.9
Soda ash (Na2CO3) Light, 50% Na2O 8.5* 1.06 9.0
6.8C 1.06 7.2
Caustic soda (NaOH) Dry 28* 0.80 22.4
Dry 24* 0.80 19.2
50% liquid 18 0.80 14.4
Sodium bicarbonate (NaHCO3) Dry, 99% 16.3* 1.68 27.4
Ammonia (NH3) Liquid 12C 0.34 4.1
a
Cost is given in cents per pound of product as shipped, not including freight, except for 50% liquid
caustic, where cost is 0/lb NaOH.
b
Cost per Ib as CaCO3 [($/lb) X (Ib product/lb CaCO3 equivalent)].
c
Bulk cost in tank cars, tank trucks, or hopper cars.
d
Cost in bags.
e
Cost in drums.
^Available as a slurry in some locations.
pH objective
Constituent As A B C D E F
Calcium CaCO3 60 66 70 75 80
Magnesium 20 20 20 20 20
Sodium 10 10 10 10 10
M AIk. CaCO 3 55 61 65 70 75
P AIk. n O 4 9 14
Carbon Dioxide 6 6 O O n
Silica 5 5 5 5 5
Iron Fe n.3 0.1 0.1 n.i 0.1
Turbidity O O O O O
TDS 100 106 110 115 120
Color O
FIG. 13.2 Correction of stability index with lime. Goal: stability index (S.I.) of 7.0.
Dust shield
Slaking water Water spray
Grit discharge
Liquid level
FIG. 13.3 Device for slaking and feeding large quantities of lime in water treatment plants, (a)
Photo of slaker-feeder assembly, (b) Cutaway showing details of operation. (Courtesy of Wallace
& Tiernan Division, Pennwalt Corporation.)
Stability index,O
PH 1 *
Stability index
Recarbonation Iqnitor
chamber
Flow pH cell
meter
dc pH meter and controller
Acid power
tank
C o n t r o l line to a d j u s t
Motor pump s t r o k e
M AIk. CaCO 3 50 50 50 50 50 50
P AIk. 30 25 20 15 10 5
Carbon Dioxide O O O O O O
Silica 10 10 10 10 10 10
Iron Fe O O O O O O
Turbidity O O O O O O
TDS 250 250 250 250 250 250
Color O O O O O O
0
S.I. @ 7O F 5.60 5.95 6.15 6.25 6.35 6.40
FIG. 13.7 (a) Correction of stability index with CO2 (recarbonation of lime-softened
water).
The results of sulfuric acid addition and recarbonation are markedly different,
as shown by Figures 13.7(2 and b. These are compared in Figure 13.8. Here the
safety features and buffer capacity of recarbonation are apparent when the goal is
simply to increase the stability index above 6. As noted in Chapter 10, recarbon-
ation can be troublesome if the water to be treated is in equilibrium with CaCO3
and contains an excess of hydroxyl alkalinity. Before the CO2 can produce bicar-
bonate alkalinity from CO32-, it must first react with the OH', thus
2OH- + CO2 - CO32- + H2O (1)
and the increase in carbonate concentration will precipitate CaCO3often plug-
ging the filter beds downstream. So there are aspects other than safety, expe-
M AIk. CaCO 3 50 45 40 35 30 25
P AIk. 30 25 20 15 10 5
Carbon Dioxide O O O O
Silica 10 10 10 10 10 10
Iron Fe O O O O O O
Turbidity O O O O O O
TDS 250 250 250 250 250 250
Color O O O O O O
Constituent As A B C D E F
Calcium CaCO 3 Nil Nil Nil Nil
Magnesium Nil Nil Nil Nil
Sodium 125 125 125 1250
Silica 3 3 3 30
Iron Fe O O O O
Turbidity O O O O
TDS 150 150 150 1500
Color O O O O
power plant. The risk is minimized by adding the acid ahead of rather than down-
stream of the zeolite softener, since the sodium zeolite could pick up hydrogen
ions in the event of accidental overfeed of acid.
An operation of this kind, and even less sensitive situations, requires the
installation of properly designed feed systems to avoid the consequences of over-
or underfeeding acid. Figure 13.6 illustrates a system that can handle the chemical
injection problem by proportioning the flow of chemical to the flow of water to
be treated and correcting the basic dosage with a pH controller, which in this case
adjusts the stroke of the pump. In this system, there must be adequate lag built
into the mixing chamber in which the pH is measured so that the controller can
FIG. 13.10 Chart of pH recorder monitoring the effluent from an ion-
exchange neutralizer. (Courtesy of Cochrane Division, the Crane
Company.)
ACID WATERS
By definition, in water chemistry, free mineral acidity is present when a water has
a pH value below 4.4 to 4.6, the end point of the methyl orange titration. (See
Table 4.3 and Figure 4.5.) It can be calculated from the definition of pH that a
water with a pH of 4.0 contains about 5 mg/L of hydrogen ion as CaCO3 (Table
4.3). So it may be assumed that this water could be neutralized to the methyl
orange end point simply by the addition of 5 mg/L of lime or other alkali, as
CaCO3. However, this would be a completely erroneous assumption if the water
contains heavy metals in solution, for these metal ions are also acids, just as the
hydrogen ion is. One definition of an acid is a "proton donor," and the heavy
metal ions act in this role in neutralizing alkalies:
Fe2+ + 2 NaOH - Fe(OH)2 + 2 Na+ (2)
2+ +
Zn H- 2 NaOH - Zn(OH)2 + 2 Na (3)
2+ +
Cu H- 2 NaOH Cu(OH)2 H- 2 Na (4)
Many mine waters are acidic and also contain metals in solution, as shown in
Table 13.2. The alkali required to neutralize the hydrogen ion in this example is
Concentration, mg/L
Ions As such As CaCO3
Hydrogen 0.1 5
Aluminum 26.1 145
Manganese 8.8 16
Zinc 2.2 3
Copper 0.3 1
Cobalt 2.0 4
Iron 0.5 1
Total acids 175
only 5 mg/L as CaCO3; but the total alkali demand for both the H + ion and the
metal ion "proton donors" is 175 mg/L as CaCO3. An even larger dosage of alkali
is required, of course, to raise the pH further to an acceptable level for heavy
metals precipitation (usually above 8.5) and final discharge to a receiving stream.