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CHAPTER 13

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.

EXAMPLES OF ACID-BASE REACTIONS

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.

With caustic soda, NaOH,


or lime, Ca(OH) 2

pH objective

With soda ash, Na 2 CO 3 ,or


powdered limestone, CaCO 3

Initial pH of wastewater to be neutralized

m q / l alkali added as CaCO 3


FIG. 13.1 Neutralization of acidic waste.
Identification of Analyses Tabulated Below:

A. Hypothetical Water p. C + 5 mg/1 Lime (as CaCO3)


B A + 6 mg/1 Lime (as CaCO3) E D + 5 mg/1 Lime (as CaCO3)
c B + 4 mg/1 Lime (as CaCO3) F

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

Total Electrolyte CaCO3 90 96 100 105 110


Bicarbonate CaCO, 5 61 47
Carbonate - S- O -^i-8- 28
Hydroxyl O O O O O
SuI fate 30 30 30 30 30
Chloride 5 5 5 5 5
Nitrate O n O O O

M AIk. CaCO 3 55 61 65 70 75
P AIk. n O 4 9 14
Carbon Dioxide 6 6 O O n

PH 7.3 8.3 8.9 9.3 9.5

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

PH5 & 70 F 8.25 8.2 8.15 8.05 8.0

S. I. @ 70 F 9.2 8.05 7.14 6.8 6.5

FIG. 13.2 Correction of stability index with lime. Goal: stability index (S.I.) of 7.0.

The equivalent weight of commercial lime [93% Ca(OH)2] is approximately 40,


so that lime as calcium carbonate multiplied by 0.8 gives commercial lime
requirements.
Another example of stability index correction is the reduction of the scaling
tendencies of a lime-softened water, which usually remains supersaturated with
calcium carbonate even after filtration. The common practice is to recarbonate
by injection of CO2 gas after the sedimentation basins and ahead of niters (see
Figure 13.5). In some areas liquefied CO2 is readily available and often is a
cheaper reagent than natural gas, burned to produce CO2 as shown in Figure 13.5.
However, the same effect can be achieved by the feeding of sulfuric acid (see Fig-
ure 13.6).
Quicklime Torque controlled water valve

Dust shield
Slaking water Water spray

Grit discharge
Liquid level

Paddles Dilution chamber Weir


Water for grit washing
Slaking Slurry discharge section Discharge port
compartment
Classifier Grit elevator

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

Lime added, mg/l as CaCO 3


(Multiply by 0.8 for commercial
hydrated lime)

FIG. 13.4 Correction of stability index with lime.


Goal: S.I. = 7.0 at 7O0F. Required lime = 13 mg/L as
CaCO3; 10.4 mg/L as 93% CA(OH)2. Control point =
pH9.1

Recarbonation Iqnitor
chamber

FIG. 13.5 Schematic diagram of water flow through recarbonation


basin demonstrating how CO2 bubbles are diffused by the submerged
combustion burner at the bottom of the basin, and then further dis-
persed by the water flow, giving optimum absorption time. (Cour-
tesy of Ozark-Mahoning Company.)
Flow Acid mixing 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

FIG. 13.6 Adjustable stroke pump with variable-speed dc


motor, acid feed proportioned to flow, pH corrected.

Identification of Analyses Tabulated Below:

A. Hypothetical water D. C + 10 mg/1 CO2 as CaCO^


B A + 10 mg/1 CO2 as CaCO 3 E D + 10 mg/1 CO2 as CaCO 3

c B + 10 mg/1 CO2 as CaC03 F E + 10 mg/1 CQ2 as CaCO3


Constituent As A B C D E F
Calcium CaCO 3 140 140 140 140 140 140
Magnesium 60 60 60 60 60 60
Sodium 20 20 20 20 20 20

Total Electrolyte CaCO 3 220 220 220 220 220 220


Bicarbonate CaCO3 O O 10 20 30 40
Carbonate 40 50 40 30 20 10
Hydroxyl 10 O O O O O
Sulfate 70 70 70 70 70 70
Chloride 100 100 100 100 100 100
Nitrate

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

PH 10.3 10.0 9.8 9.7 9.6 9.5

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

pHs @ 7O0F 7.95 7.95 7.95 7.95 7.95 7.95

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-

Identification of Analyses Tabulated Below:

A. Hypothetical Water p. C -H 5 mq/1 H2SO4 as CaCO3


B. + 5 mg/1 H2SO4 as CaCO3 E. D + 5 mg/1 H2SO4 as CaCO3
C. B + 5 mg/1 HoSO4 as CaCO3 F. E + 5 mg/1 H2SO4 as CaCO3
Constituent As A B F
Calcium CaCO3 140 140
Magnesium
140
60 60 -48-48- --48- 60
Sodium 20 20 20 20 20 20

Total Electrolyte CaCO 3 220 220 220 220 220 220


Bicarbonate CaCO, O O O 5 10 15
Carbonate 40 40 30 20 10
Hydroxyl 10 -^- O O O O
Sulfate 70 75 J 80 85 90 95
Chloride 100 100 100 100 100 100
Nitrate O O O O O O

M AIk. CaCO 3 50 45 40 35 30 25
P AIk. 30 25 20 15 10 5
Carbon Dioxide O O O O

PH 10.3 10.0 9.9 9.9 9.8 9.6

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

pHs (70 F 7.95 8.0 8.05 8.1 8.2 8.25

S. I. @ 70 F 5.6 6.0 6.2 6.35 6.6 6.9

FIG. 13.7 (b) Correction of stability index with H2SO4.


diency, and chemical cost involved in choosing between H2SO4 and CO2 for cor-
rection of the stability index.
Simple changes in water alkalinity or acidity without regard to stability index
correction are easily calculated: the reduction of alkalinity, such as application of
acid to a sodium zeolite effluent prior to its use as boiler feedwater, requires the
addition of 1 mg/L commercial 66 Baume sulfuric acid for each milligram per
liter of alkalinity reduction needed. An increase in alkalinity requires the addition
of 0.8 mg/L caustic or lime for each milligram per liter alkalinity increase
required. These changes in alkalinity are calculated on the basis of calcium car-
bonate equivalents and then converted to the equivalent weight of the commer-
cial alkali or acid added to the system.
Of the numerous examples of acid-base neutralization reactions used in waste-
water treatment, one deserving mention is pH control in anaerobic digesters. A
common problem in these digesters is an upset in the biota, causing sudden pro-
duction of acids, with a drop in pH, a loss of control, and a dangerous reduction
in methane production. Sodium bicarbonate is frequently used in this application
because its buffering action prevents the production of an equally damaging high
pH if the reagent is overfed. In this case, the cost per unit of alkali value is of
minor importance compared to the buffering.
An example of the reduction of alkalinity with acid in the treatment of boiler
makeup is shown in Figure 13.9. In this case, the alkalinity is added to the
makeup system ahead of the zeolite. There is some risk in such an operation
because it requires excellent acid feed and control equipment, and protection of
the piping between the injection point and the deaerator, since corrosion could
introduce objectionable iron. However, often the gain in reduced blowdown, with
its attendant heat savings, justifies the installation of sophisticated equipment
that can accomplish these results using a basic system already in operation in the
Stability index (SI) at 7O 0 F

m q / l a c i d i c reagent added as CaCO 3

FIG. 13.8 Comparison of recarbonation to acidification of


lime-softened effluent (data from Figure 13.7).
Identification of Analyses Tabulated Below:

A. Zeolite Softened Makeup (1) p. Concentrated 10 X in Boiler


B After H2SO4 E.

c "B" After Deaerator * (2) F

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

Total Electrolyte CaCO 3 125 125 125 1250


Bicarbonate CaCO, 90 30 30 O
Carbonate O O O 50
Hydroxyl O O O 250
Sulfate 15 75 75 750
Chloride 20 200
20 20
Nitrate O O O O

M AIk. CaCO 3 90 30 30 300


P AIk. O O O 275
Carbon Dioxide 10 70 O O
PH 7.1 5.8 8.3 11.7

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

(1) If max, boilej alkclinity .s 300 mg/1 max. :oncentrition rabio


is 300/90 = 3,3 = 3 0 % blowdown. .
(2) After alkalinity reduction 7 max,, cdnc. is LO (colunn D) .
= 10% blowdowr.. I
* Not including steam gilutionl ~ I I I I
FIG. 13.9 Alkalinity reduction of boiler makeup. Although this example shows the acid applied
to the zeolite effluent, it may be fed to the influent to buffer accidental overfeed. In either case,
the final analyses (columns B, C, and D) are the same.

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.)

function properly without overriding or underriding while hunting for the pH


setpoint.
Ion exchange has been applied to acid-base neutralization problems in a
unique way: Weak base anion exchangers and carboxylic cation exchangers have
the ability to pick up acid and release it as a neutral solution in treating a fluc-
tuating wastewater which is periodically acidic and alkaline. If the excess free acid
is balanced by the alkalinity, regeneration is unnecessary, and only periodic back-
wash is needed to keep the system operating. Although more expensive than a
chemical feed system for the same purpose, it saves space and eliminates the
maintenance costs of equipment and controls inherent in a chemical feeder. This
type of system has been used to neutralize spent demineralizer regenerants. Figure
13.10 shows the pH record of the effluent of an ion exchange neutralizer in this
kind of service. Although the pH fluctuates, it is kept within limits of 6 to 9 usu-
ally specified in municipal sewer codes.

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

TABLE 13.2 Alkali Demand of Mine


Water at pH 4.0

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.

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