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Manual

Operator Training Manual

Chemistry of Precipitation Softening


The reactions of calcium and magnesium ions with carbonate and hydroxide alkalinities are
basic to lime softening. Control of softening chemistry is dependent on understanding the
influences of the following:

Raw water hardness and alkalinity


Effect of pH on the species of alkalinity present in the water
Expected solubility of calcium carbonate and magnesium hydroxide

Alkalinity
Alkalinity is the acid neutralizing ability of water determined by acid titration analysis. Total
alkalinity is also known as M, or methyl orange alkalinity.
Another important measure of alkalinity is P alkalinity, also called phenolphthalein
alkalinity, that exists above the phenolphthalein endpoint range of pH 8.28.4. P and
M alkalinity are both determined by acid titration.
Alkalinity in raw water is usually in the form of bicarbonate salts. Hardness and alkalinity in
natural waters result from dissolved CO2 dissolving deposits of calcium and magnesium in
the earths strata.
1.

H2O + 2CO2 + MgO Mg(HCO3)2

2.

H2O + CO2 + CaCO3 Ca(HCO3)2

The balance between carbon dioxide and bicarbonate ion shifts as the pH of the water
changes. Figure 1 shows the approximate relationship between pH, CO2 concentration
(as CaCO3), and M alkalinity. If any two of the above are known through analysis, the third
value can be determined. Reduction of carbon dioxide occurs until the pH exceeds 8.2, the
phenolphthalein endpoint. Above this pH, no free CO2 exists, and some of the bicarbonate
ion converts to carbonate. At a pH above 8.2, free hydroxide (OH-) begins to appear.
Significant free hydroxide does not exist until pH exceeds 9.8. Also, above this pH,
HCO3- drops to low levels, with the carbonate (CO3=) concentration predominating.

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Figure 1. Approximate Relationship of Carbon Dioxide, Alkalinity, and pH


Value

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Figure 2 is theoretical and only approximates the real world. Real observation may vary to
some degree from the chart. One can imply that:

If P = M, only hydroxide is present.

In the pH range 8.210.2, bicarbonate is in equilibrium with carbonate. Carbonate is


favored at high pH. P alkalinity appears, and P is less than M.

At pH 10.2, only carbonate exists. Here, 2PM = 0, or 2P = M.

Above pH 10.2, only carbonate and hydroxide are in solution, and P is greater than
1/2 M.

At the phenolphthalein endpoint, only HCO3- exists; no CO3-2 or CO2 is present.

At pH between 4.2 and 8.2 (phenolphthalein endpoint), carbon dioxide, carbonic acid,
and bicarbonate are in equilibrium. Titration will show only M alkalinity, no P.

Below pH 4.2 (the methyl orange endpoint), free acid (H+), carbonic acid (H2CO3), and
CO2 coexist. Only a highly acid-contaminated raw water would have this pH. In this
range, M = 0.

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Figure 2. Alkalinity Species as a Function of pH

H2CO3

HCO3-

CO3=

H2CO3

HCO3-

CO3=

OH-

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According to the above, the following species cannot coexist in water:

Carbon dioxide and carbonate


Carbon dioxide and hydroxide
Bicarbonate and hydroxide

Alkalinity concentrations are calculated from P and M titrations. These are useful
approximations, but may be subject to interferences, such as the presence of ammonia. When
the presence of ammonia is suspected, a direct OH titration should be performed with
BaCl2.

Hardness
Hardness is soluble calcium and magnesium salts in water. Hardness ions are classified as
either temporary or permanent hardness. Temporary hardness is associated as an alkaline salt
that will precipitate upon heating; permanent hardness is associated as an acid salt.
3.

Ca(HCO3) 2 + heat CaCO3 + H2O + CO2

4.

Mg(HCO3) 2 + heat Mg(OH) 2 + 2CO2

When calcium, magnesium, and bicarbonate are expressed as CaCO3, then 1 ppm of hardness
is associated with 1 ppm of alkalinity. If M alkalinity exceeds total hardness, the excess
alkalinity is associated with sodium. The class of hardness and alkalinity present in raw water
can be determined from hardness and alkalinity titrations. It also shows the magnesium and
calcium compounds encountered in lime softening. The solubility of some salts and
insolubility of others shown is the basis for lime softening.

Precipitation Softening Reactions


The prime objective of lime softening is conversion of dissolved calcium and magnesium
salts of insoluble magnesium hydroxide (Mg(OH)2) and calcium carbonate (CaCO3).
5.

Ca+2 + CO3-2 CaCO3

6.

Mg+2 + 2OH- Mg(OH)2

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Alkalinity Reactions
Alkalinity is the largest factor in determining potential softening results. Alkalinity tests
establish chemical dosage control and are used to troubleshoot softener operations.
When softening a typical water, the following chemistry occurs:

Most raw waters fall in the pH range of 6.08.0. To soften the water, hydroxide alkalinity
in the form of lime, Ca(OH)2, or caustic, NaOH, is added to adjust the pH upward. The
OH- reacts to neutralize carbon dioxide:
7.

CO2 + OH- = HCO3-

When the pH reaches 8.2, all carbon dioxide has reacted to form bicarbonate.

Above pH 8.2, additional hydroxide neutralizes bicarbonate:


8.

HCO3- + OH- = HCO3- CO3-2 + H2O

It is this carbonate that reacts with calcium to produce calcium carbonate precipitate.
The neutralization of HCO3- continues until pH 10.2, when all of the HCO3- is
converted. As more carbonate is produced, approaching a pH of 10.2, more calcium can
precipitate.

Above pH 10.2, free hydroxide remains, which then can precipitate with magnesium.

It is significant that precipitation occurs only when the required alkalinity is present. If
calcium does not precipitate below pH 8.2 (CO3= is not present), magnesium is not removed
in appreciable amounts below pH 10.2 (where 2P-M is less than zero, no hydroxide is
present). In practice, however, a small percentage of the magnesium will precipitate during
any lime softening operation because of localized high pH near the lime feed point.

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Reactions with Lime


Lime (Ca(OH)2) is the most commonly used and least expensive source of hydroxide. Lime
is available in two forms, hydrated (Ca(OH)2) and pebble (CaO). Hydrated lime is a powder,
typically 93 percent purity, and comes in bag or bulk. It is fed as a slurry. Pebble lime is
generally in lump form, typically 95 percent purity, and delivered in bulk. Pebble lime,
unlike hydrated, cannot be used as is. It must be hydrated (slaked) before use.
9.

CaO + H2O Ca(OH)2

CaO will not soften water until it is slaked. A slaker is a mechanical feeder that incorporates
a mixing section for preparation of a highly concentrated (approximately 30 percent) slurry
of CaO and water. Under temperatures approaching boiling, the product is quickly hydrated.
Pebble lime is less expensive than hydrated lime and is the form used by most large lime
users.

Carbon Dioxide Removal


When lime is added to a raw water, the lime reacts with CO2:
10.

CO2 + Ca(OH)2 CaCO3 + H2O

Notice that carbon dioxide consumes lime. This equation, as with all equations in softening,
assumes enough lime is added to raise the pH above the minimum value for precipitation. For
example, if only enough lime is added to a pH 6.0 water to raise the pH to 7.0, equation
#10 will not occur. Below pH 8.2, only HCO3- exists (see Figure 2), and Ca(HCO3) 2 is
soluble. The pH must be increased to above 8.2 through additional lime feed to form the
carbonate required for the precipitation observed in the equation above.

Lime Reaction with Temporary Hardness


11.

Ca(HCO3)2 + Ca(OH) 2 2CaCO3 + 2H2O

12.

Mg(HCO3)2 + Ca(OH)2 CaCO3 + MgCO3 + 2H2O

13.

MgCO3 + Ca(OH)2 CaCO3 + Mg(OH)2

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Notice that the calcium added with the lime is also removed from the water. So, for each ppm
of raw water calcium and magnesium hardness removed, 2 ppm of solids precipitate. To
estimate sludge production using lime, multiply the pounds of lime added by 2.7.

Lime Reactions with Noncarbonate Hardness


14.

CaSO4 + Ca(OH)2 No Reaction

15.

MgSO4 + Ca(OH)2 Mg(OH)2 + CaSO4

Lime alone will not remove noncarbonate hardness. Lime will exchange calcium for
magnesium hardness, but net hardness remains the same (equation 15). This means when
using lime alone, the total hardness reduction cannot exceed the raw water M. Additional
alkalinity, added as soda ash, is needed to complete the softening process when noncarbonate
hardness is present.

Reaction with Soda Ash


Soda ash, Na2CO3, is added to supplement natural bicarbonate alkalinity and to remove
noncarbonate hardness. Soda ash is a powder, typically 98 percent purity, available in bags or
bulk. It is easily dissolved in water and added to the system.
16.

CaSO4 + Na2CO3 CaCO3 + Na2SO4

Calcium noncarbonate hardness, CaSO4, may be in the raw water or may be formed by
reaction with magnesium noncarbonate hardness.

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Figure 3. Soda Ash for Complete Softening

Example:

Raw water hardness (HR)


Bicarbonate (M alkalinity)
Noncarbonate hardness
Soda ash dosage

=
=
=
=

300
150
150
1.65 pounds/1,000 gallons

Soda ash = 0.0088 (HR - M) + 0.4

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Reactions with Sodium Hydroxide


Caustic, NaOH, is more expensive than lime, but will have advantages in raw waters with
high noncarbonate hardness. Caustic is rarely fed alone, because of economics. Lime and
caustic are usually fed together. Caustic is generally used as a 50 percent solution. Flake
caustic is available but is not used by large water producers because of handling problems.

Reaction with Carbon Dioxide


17.

CO2 + 2NaOH Na2CO3 + H2O

Caustic forms soda ash when reacted with carbon dioxide.

Reaction with Carbonate Hardness


18.

2NaOH + Ca(HCO3)2 CaCO3 + Na2CO3 + 2H2O

19.

4NaOH + Mg(HCO3) 2 Mg(OH)2 + 2Na2CO3 + 2H2O

Not only is hardness removed, but soda ash is formed.

Reactions with Noncarbonate Hardness


20.

MgSO4 + 2NaOH Mg(OH)2 + Na2SO4

21.

CaSO4 + 2NaOH No Reaction

Although caustic does not directly react with calcium noncarbonate hardness (equation 21),
Na2CO3 from reactions 17, 18, and 19 will react with the CaSO4. This means that permanent
hardness can be removed with caustic. Caustic will be used only on waters with
noncarbonate hardness, generally as a soda ash replacement. Twice the hardness can be
removed with caustic as with lime, and this is its chief advantage. Caustic adds soluble
sodium, and fewer solids are precipitated when using caustic instead of lime. The use of
caustic is more expensive than using lime and soda ash.

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Estimating Results and Dosages


Looking at the previous reactions, it might be concluded that all hardness can be removed by
lime softening, but it cannot. Calcium carbonate and magnesium hydroxide are slightly
soluble; some calcium and magnesium will always remain in solution. Reviewing some
examples of softening will help demonstrate what happens as water is softened.

Lime-Soda Softening
Raw waters with Ca hardness exceeding M alkalinity are most commonly lime-soda
softened. Complete lime softening is the addition of excess amounts of lime and soda ash to
drive the hardness down to the lowest practical limits.
Additions of lime and then soda ash allow for maximum cold lime softening results.

Lime-Caustic Softening
The finished water results that can be achieved by lime-soda softening can also be obtained
with lime-caustic. The ratio of lime and caustic must be balanced to achieve the same result.

Factors Influencing Softening Results


When estimating softening results, assumptions are made about the solubility of calcium
carbonate and magnesium hydroxide. These assumptions allow us to estimate the
composition of a finished water; however, there are a number of practical factors that affect
solubility and rates of precipitation and, therefore, actual plant results.
A solubility curve for calcium carbonate is attached. The curve is based on typical softening
results for 6070F water. This curve illustrates the type of finished water results found in
actual cold lime softening operations. Settled water calcium and carbonate analyses were
observed in cold lime softening plants and the results plotted to form the curve. Because
these are typical results obtained at a number of plants during spring/summer conditions, this
is an expected solubility curve.

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Figure 4. Using the Calcium Carbonate Expected Solubility Curve

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Factors Affecting Solubility


Water Temperature
Higher temperature water encourages more complete, more rapid reactions. The solubility of
calcium carbonate is inversely proportional to temperature. Hot process softening is
employed to take advantage of this phenomenon. Colder water during the winter will affect
the results of a cold process plant softening surface water.
Reaction Time
An important mechanism in precipitation softening is crystal growth. Since growth of the
precipitated particles occurs over time, residence time for the reaction is critically important.
This is particularly important to remember in jar testing, where a short, five-minute slow mix
will not be sufficient. Short circuiting in a clarifier will reduce reaction time and hence affect
completeness of reaction.
Sludge Contact
Sludge contact is the intimate mixing of previously formed particles with chemically treated
influent water. The rate of hardness removal is directly related to the surface area of growing
crystals. Generally, the more particles, the faster, more complete the hardness reduction.
Upflow, solids contact clarifiers with sludge beds are more efficient than horizontal clarifiers
with no sludge bed; however, within any type of clarifier, there is never enough solids
contact or long enough residence time to reach the theoretical result.
Mixing Energy
The more mixing in the flocculation zones, the better the solids contact and more complete
the softening.
Contaminants
Orthophosphates, polyphosphates, and some organics can interfere with the crystal growth
process of calcium carbonate. These materials can occur in water contaminated with
industrial and municipal waste and in water recycled from cooling towers and other process
operations.

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Metallic Salts
The addition of metallic salts such as ferric salts, alum, and sodium aluminate improves
completeness of reaction by reducing the solubility of both calcium carbonate and
magnesium hydroxide.
The mechanism for enhanced precipitation of magnesium hydroxide by inorganic salts is not
fully understood, but is best explained when using sodium aluminate. Magnesium hydroxide
precipitate is a positively charged particle, while the hydrolysis product of sodium aluminate
is negatively charged. The charge difference enhances magnesium hydroxide removal
through a charge neutralization, coagulation process.
The magnesium hydroxide/sodium aluminate floc tends to collect, or adsorb, the fine calcium
carbonate particles and sweep them out of the water.
Polymers
Anionic polyelectrolytes are effective at low dosages in flocculating suspended solids and
improving effluent clarity and sludge bed compaction.

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Figure 5. Magnesium Hydroxide Solubility Curve

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Another way to increase magnesium precipitation is to increase the lime dosage. Magnesium
hydroxide, being positively charged, will itself coagulate negatively charged calcium
carbonate fines, which will improve clarity. At times, through coagulation of colloidal
calcium carbonate, the additional Mg(OH)2 may improve calcium carbonate precipitation
enough that there is a shift in the solubility line toward more complete precipitation. This is
an exception to the rule that a change in lime dosage will not shift the solubility curve;
however, the usual result of adding increased lime above pH 10.2 is a simple exchange of
calcium hardness for magnesium. Therefore, an increase in O reading to get better overall
hardness removal may be effective in some, but not all, waters.
Alum and iron salts generally are not as effective as sodium aluminate for improving
hardness removal. The hydrous floc formed by these products will have a similar sweeping
action, but does not act with the same, effective calcium carbonate absorption. It is
improved calcium carbonate, as well as magnesium hydroxide removal, that makes
sodium aluminate perform economically compared to alum and iron salts.
Besides providing better coagulation, sodium aluminate is alkaline and adds caustic to the
water, reducing noncarbonate hardness.
22.

Na2Al2O4 + 4H2O 2Al(OH)2 + 2NaOH

23.

2NaOH + MgSO4 Mg(OH)2 + Na2SO4

Alum and iron salts are acidic, react with lime, and add noncarbonate hardness.
24.

Al2(SO4)3 + 6H2O 2Al(OH)3 + 3H2SO4

25.

Fe(SO4)3 + 6H2O 2Fe(OH)3 + 3H2SO4

26.

H2SO4 + Ca(OH)2 CaSO4 + H2O

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Use of Solubility Factors


Following are some examples using the concepts of dosage and solubility curve.

Plant results, cold lime softening:


Ca
P
M

=
=
=

55 ppm
17 ppm
30 ppm

The plant feeds lime and soda ash. They usually experience calcium lower than
30 ppm. What is wrong?
The first thing to do when softening results are in question is to determine finished
water concentrations of both hardness and alkalinity.
By calculation from P and M:
P
HCO3
CO3

>
=
=

M
0
2(M-P) = 26 ppm

OH

2P-M = 4 ppm

Since the species of interest is calcium, the concentrations required are:


Ca
CO3

=
=

55 ppm
26 ppm

This is on the expected solubility curve, but the plant usually experiences less than 30
ppm calcium. The only way to get to less than 30 ppm on the expected softening curve
is to increase carbonate concentrations. Since soda ash provides carbonate, it is likely
that the plant is not feeding as much soda ash as needed to push the carbonate up and
drive calcium down. The feeder may be broken, plugged, or out of calibration.

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Plant results, cold lime softening:


Ca
P
M

=
=
=

55 ppm
36 ppm
66 ppm

The plant feeds lime only and feels results are good.
First, determine alkalinities:
P
HCO3

>
=

OHCO3=

=
=

2P-M = 6 ppm
2(M-P) = 60 ppm

Ca = 55 ppm, CO3= = 60 ppm is not an expected result. The plant is not doing as well as
it could. Without more details, one can only suggest that the factors affecting solubility
be checked. Is the water unusually cold for this time of the year? Has the plant
increased flow, reducing residence time? Are there contaminants in the water? Is
coagulant being fed to speed reactions? Could results improve through sludge recycle
or increased mixing? These should all be considered.
Silica Removal
Lime softening is also used for silica removal. Although cold lime softening is only
marginally effective on waters containing less than 10 ppm silica (typically 10 percent
reduction), any reduction may be important for some industrial plants. One effective method
for removing silica is through precipitation of magnesium hydroxide, which absorbs silica.
This means high pH (10.210.5) operation of the softener and use of sodium aluminate to
enhance removal of magnesium. Increasing solids contact with previously formed
magnesium hydroxide will also improve silica removal.

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Another method for increasing silica removal is the addition of supplemental magnesium.
Magnesium oxide, MgO, is the common source. Magnesium oxide is a powder that is
slurried and added to the process. No addition of alkalinity is required for precipitation, just
hydration to form magnesium hydroxide.
27.

MgO + H2O Mg(OH)2

Another source of MgO is the substitution of dolomitic lime for regular lime. Dolomite is
lime that is high in MgO (30 to 35 percent) and that is available as hydrate
(Mg(OH)2 + Ca(OH)2) or pebble form (MgO + CaO), which must be slaked. When feeding
dolomitic lime, enough dolomite is fed to provide the desired Mg addition, and standard lime
feed is reduced equivalent to the lime in the dolomite. The dosage of dolomitic lime required
in cold lime softening is determined by trial and error, but the low efficiency of silica
removal seldom makes the addition economical.

Program Selection
At AEP-Lawrenceburg, the cold lime softening program includes lime, ferric chloride, and a
anionic flocculant, P817E.

Ferric Chloride
This product is available in liquid form. Ferric chloride, FeCl3 acts as a coagulant and
improves the settled water clarity. More importantly, ferric chloride improves hardness
reduction in applications where the softening pH is carried above 10.0 to obtain magnesium
removal. Since it provides improved hardness reduction, ferric chloride cannot, in most
cases, be simply replaced by a polymer coagulant, or flocculant.

Coagulants
Calcium carbonate clarification is enhanced through the use of a coagulant. Calcium
carbonate precipitates are negatively charged, similar to raw water turbidity, and are
coagulated by polymer coagulants. If surface water is being softened, coagulants are added to
help coagulate the turbidity in the water source. Coagulants also have some flocculation
ability and will reduce floc carryover and increase the density of the solids in the sludge bed.
Dosages are 13 ppm.

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Anionic Flocculants
When heavy carryover is a problem, anionic flocculants are effective in improving turbidity
removal. Coagulants will provide some flocculation and are easier to feed than flocculants
and should be evaluated first for carryover control. However, dosages are higher than those
for flocculants, and in cases of severe carryover, coagulants are not active enough. Generally,
an anionic flocculant added to a ferric chloride softening program will produce good water.
ChemTreat P817E is the anionic flocculant used at AEP-Lawrenceburg. Product dosages are
0.11 ppm, depending upon the current conditions.

Jar Testing
As with conventional raw water clarifications, the jar test is the method used to screen
programs. Softening jar tests are more involved than clarification jar tests, and the person
testing must understand the chemistry of softening. There are two purposes for running lime
softening jar tests:

Demonstration of clarification
Demonstration of hardness and alkalinity removal

When the customer is interested in seeing if the program produces clarity in the jar equal to
that in his plant program, a clarification jar test may be all that is needed.
A typical jar test sequence to demonstrate clarification in lime softening is:
Rapid mix:
Slow mix:
Settle:

3 minutes
10 minutes
5 minutes

Lime dosage should be very close to plant dosages when jar tests are run. Check if pH is as
high as in the plant, or that the settled water OH- alkalinity (2P-M) is at least as high as in the
plant. Magnesium precipitation will improve clarity, and if a jar has more magnesium
precipitation because of higher pH, it will look better than a jar with no magnesium
reduction, regardless of which polymers or inorganic salts are added.
Often, the plant supervisor needs to be shown the better chemical analyses (hardness and
alkalinity reduction). In this case, a different jar test is required. Longer mixing is required to
make reactions more complete, and analyses for hardness, calcium, P, and M must be run.
A typical sequence follows:
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Rapid mix:
Slow mix:
Settle:

3 minutes
20 minutes (minimum)
5 minutes

Jar tests indicate trends in water analyses, but because of imprecise lime dosages from jar to
jar and insufficient reaction time, results will not be as complete as results that can be
achieved in the plant. Always run a jar test with plant dosages as a standard to compare with
the treatment program.
When running lime softening jar tests, be particularly careful about lime addition. If the stock
slurry of lime is not well shaken when an aliquot is drawn for addition to the jar, an inexact
amount of lime will be added to that jar. Also, check the strength of the stock lime slurry.
The plant may indicate that they feed 100 ppm of lime, but when 100 ppm of lime is added to
the jar from the stock slurry, the pH is low, as if not enough lime were added. A common
cause is that the plant feeds calcium oxide, and the jar test solution is calcium hydroxide. To
equal 100 ppm of calcium oxide, approximately 130 ppm of calcium hydroxide must be fed.

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Storing, Handling, and Feeding Emulsion Flocculants


Introduction: Emulsion flocculants are suspensions of minute beads of high molecular
weight polymer, with the beads then emulsified into an oil carrier. The minute beads are
approximately 1 micron in diameter and contain concentrated polymer dissolved in water.
These concentrated polymer beads or hydrogels are dispersed in the carrier of high
flashpoint mineral oil by means of a dispersing surfactant which keeps the hydrogels from
coalescing into larger droplets. Because the hydrogels are denser than the oil carrier, they are
prone to settle over time resulting in concentrated polymer solids on the bottom of a
container and oil on the top. This separation will be faster if the droplets are large, so
keeping the droplets small and well dispersed is important for stability of the product.
Because the polymer hydrogels are coated in mineral oil, preparing a solution of the polymer
for use requires diluting the product in water, typically at a concentration of 0.2% to 2.0% as
product. An additional surfactant in the product formulation is known as an inverting
surfactant. Its function is to allow water to cut through the mineral oil and contact the
hydrogels and allow them to solubilize in the water. The level of inverting surfactant in the
product is very important. If there is too little inverting surfactant, the product is difficult to
get fully into solution or activated. If there is too much inverting surfactant, the product is
prone to absorbing moisture from the air and this form gels or skins in the product.
Because the hydrogels are made up of very tightly coiled, concentrated polymer beads,
mixing energy and time are required for full contact of the hydrogels with the water, and to
enable the polymer chains to fully uncoil.
The polymer chains may be cationic, anionic, or nonionic, and the amount of charge on the
polymer chains varies. The charge on the chain helps to uncoil the chain, so a higher charged
polymer will open faster than a low charged or uncharged polymer.
Because the polymer chains are very long the polymer solutions are quite viscous. The
viscosity of the solution is directly related to the molecular length of the polymer chain, the
concentration of the polymer solution, and the amount of charge on the molecule. A 1%
solution of highly charged polymer such as 60% mole charged P-835E will be more viscous
than a 1% solution of 10% mole charged PG-906.
Emulsion flocculants are typically made as co-polymers of acrylamide, a nonionic building
block, along with a charge bearing monomer. In the case of anionic flocculants, the anionic
charge is provided by co-polymerizing acrylic acid along with the acrylamide monomer. The
ratio of acrylic acid to acrylamide determines the degree of charge on the molecule.

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In the case of anionic flocculants, the cationic charge is provided by co-polymerizing


AETAC, a methyl acrylate derived cationic monomer along with the acrylamide monomer.
The ratio of AETAC to acrylamide determines the degree of charge on the molecule.
The ratio of charged monomer to acrylamide is recorded on a molar basis, so we refer to a
product in which 40% of the units that make up the polymer chain are from a charge bearing
monomer as being a 40% mole charged flocculant. P-834E is an example of a 40% mole
charged cationic flocculant; therefore the polymer chain has 40% of the links made of
AETAC and 60% made of acrylamide. P-816E is a 40% mole charged anionic flocculant;
40% of the links are made of acrylic acid and 60% are made of acrylamide.
Storing and Handling:
Temperature: For best results, emulsion flocculants should be stored indoors at a constant
temperature between 40o and 80o F. At cold temperatures the product becomes more
viscous and harder to pump. If the temperature swings broadly during the day, it is very easy
to have condensation form inside the container and droplets of water enter the product and
form lumps or gels, or even a skin across the top of the container.

If this has occurred, the product can be transferred into a clean container, preferably by
gravity through a large are bag filter with a mesh size of 500 to 1,000 microns.

If the product has been exposed to very low temperatures and has frozen, it will likely lead to
destabilizing the product and the formation of lumps and gels. Thaw the product and filter as
above, and the product may still be usable. If the product has seen repeated freeze-thaw
cycles, it can be completely destabilized and may not be usable.
At very high temperatures the product is more prone to separate, and more difficult to re-mix.
At high temperatures > 90o F for an extended time the product can break down completely.
Appearance: Most emulsion flocculants will be a creamy white, nearly opaque liquid.
Some will be more translucent and more of a pale yellow to amber color. Batch to batch
variations in manufacturing means that a product can be very opaque one time and fairly
translucent the next. This has to do with the size of the hydrogels which are formed in the
manufacturing process, but does not indicate a quality problem.
Separation: After sitting for a period of time, an oil layer will form on the top of the
emulsion polymer. Please note that all emulsion polymers will separate in time. We try to
keep the product as stable as possible, but batch to batch variations will occur. This oil layer
indicates that the product is settling in the container, and the product should be mixed and
homogenized before use.
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The best method of mixing the emulsion polymer is mechanical mixing for a short
period of time; 30 to 60 minutes. Several companies such as Neptune and Lightnin
make mixers designed for mixing drums and totes, and these can be operated manually
or on timers to automatically mix the product daily.

Recirculation of the container is also recommended, and it is best to use a diaphragm or


progressive cavity pump to avoid shearing the product. A centrifugal pump is not
recommended due to high shear. It is best to use a timer to provide 30 to 60 minutes of
recirculation once or twice each day.

Sparging with air can also work but is not recommended because air is often not dry
enough and can introduce moisture into the product. If this is to be done, use only a very
dry air source, and dont over mix.

In any case, the mixing should be intermittent rather than continuous, and done under
low shear conditions. If the mixing is constant or high intensity it can whip up the
emulsion to the consistency of cold cream, and this renders it unusable.

Shelf Life: Because all emulsion polymers will separate over time, the products do have
shelf life limits. Although a product can be mixed and recirculated, over time the complex
chemistry of the emulsion and surfactants can break down, and the products are more prone
to lumps and gels. Typical shelf life is 6 months for these products. If stored unopened in
good temperature conditions the products may be usable for a longer period of time;
conversely, if stored in opened containers under poor heat and humidity conditions the
products can degrade faster.
Water Contamination: The product must be kept dry to avoid lumps or gels from forming
in the product. Unfortunately, the product sometimes becomes contaminated with rain water
or water from a process or wash-up water. If the contamination is not extreme, the product
can likely be filtered to remove lumps and gels which have formed.

If contamination has occurred, the product can be transferred into a clean container,
preferably by gravity through a large area bag filter with a mesh size of 500 to 1,000
microns. Pantyhose can even be used as a filter.

Preparing Solutions for Feeding:


When preparing a polymer solution from an emulsion flocculant product, two distinct
processes take place phase inversion and dissolution. When the product comes into contact
with water, the inverting surfactant dissolves and emulsifies the oil into the water; this is
called inversion. Then the beads or hydrogels come into contact with the water and dissolve;
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this is dissolution. The combination of these two processes is called the activation of the
polymer solution.
The time required for activation, the effective inversion and dissolution is dependent on some
conditions:

Where the water and polymer come together there must be a period of high shear to fully
disperse the hydrogels into the water for maximum contact. This is often by mechanical
mixing or hydraulic mixing.

The concentration of emulsion in water should be between 0.5% and 2.0% as product at
this point so that there is a high enough level of inverting surfactant to emulsify the oil
and allow the water and hydrogels to come into full contact. Higher concentrations may
be too viscous to handle, and low concentrations require longer aging; activation may be
incomplete.

Soft water is better than hard water; high levels of hardness (> 300 to 400 mg/L as
CaCO3) increase the time required for dissolution as calcium and magnesium ions
reduce the efficiency of the inverting surfactant. This effect is also seen with high pH or
high conductivity water.

Warm, but not hot water is better than cold water. The water temperature should be
below 85o F. In the winter, as water gets colder, the speed of dissolution drops off and
the time required for effective activation increases.

Under good temperature and water quality conditions, once the emulsion product has
been dispersed into the water with high mixing energy, the polymer requires at least 15
minutes for full activation.

With this in mind, an ideal polymer feed system needs to combine water and polymer
together at a 0.5% to 2% product concentration in a state of high mechanical or hydraulic
shear. The resulting product solution should then be aged for at least 15 minutes to allow the
hydrogels to fully uncoil. The resulting polymer solution is then fed to the feed point, and
may require additional dilution water so that the polymer contacts the system being treated at
an appropriate concentration.
Direct Polymer Feed Systems: A number of manufacturers make feed equipment which is
designed to feed, dilute and activate an emulsion polymer in-line. Some of these feed
systems do a pretty good job and the level of activation can be > 80%. Examples:

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Stranco Polyblend feeders meter the polymer and water into a mechanically mixed
chamber and then the solution is carried hydraulically to the feed point. Some have the
ability to add secondary dilution water after the mixing chamber.

Fluid Dynamics Dynablend feeders meter the water and polymer together into a
hydraulically mixed cylinder, and the solution is then carried hydraulically to the feed
point. Some have the ability to add secondary dilution water after the mixing chamber.

Neptune Polymaster feeders meter the water and polymer into a small mechanically
mixed chamber. Some have the ability to add secondary dilution water after the mixing
chamber.

Atlantis MDS and LPB feeders meter the water and polymer through high shear
eductors and in-line mixers, and then on to the feed point.

All of these feed systems, and several other brands are used because they are small, relatively
inexpensive and simple to operate. Used properly, they can provide good results, if not
perfect results. Some keys to optimizing direct feed systems in practice:

It is best for the polymer feed pump to have a flooded suction. If feeding out of a drum
use a drum cradle so the drum is on its side; if feeding from a tote or bulk tank have the
feed pump low so the polymer flows to the pump. Use a short length of large diameter
hose or pipe to carry the polymer to the pump so there is no chance of starving the pump.
A feed pump is more prone to plugging if the pump is starved and pulling in air with the
polymer.

At the product container, add a calibration draw down cylinder so you can measure how
much polymer is actually being fed. The speed and stroke settings on the pumps are
very approximate, and measuring actual feed rates can help troubleshoot a plugged
pump. If the feed pump is mounted above the drum it is very difficult to actually
measure the polymer feed rate.

Periodically fill the draw down cylinder with mineral oil and pump it through the feed
pump. This helps flush out gels that are accumulating in the pump suction and check
valves.

In line between the container and the pump should be a basket strainer to capture any
lumps or gels which may be formed in the product. The strainer needs to be cleaned out
periodically to make sure the strainer itself does not become a blockage in the line.

Use a positive displacement pump such as a Moyno pump rather than a diaphragm
pump. These are less prone to plugging than diaphragm pumps and put out a continuous
Operator Training Manual

stream of polymer rather than pulsing like a diaphragm pump. It is critical that a
positive displacement pump does not run dry, or it will burn out the stator.

If you do use a diaphragm pump, keep the speed setting high and the strokes low. This
provides a more continuous stream of polymer and avoids the large pulses of polymer
you get when the stroke is high and the speed low.

Water quality and temperature are very important. With limited time for solution
activation, it is important to use warm, good quality water for best results.

Keep the solution strength high ( 0.5% to 2%) at the point of initial mixing. The biggest
mistake made with these feeders is to use too much water so the solution prepared is at a
very low concentration. This drastically reduces the activation efficiency of the feeder,
and reduces the time the water and polymer are under high shear conditions. Cut back
the dilution water flow to keep the activation solution strength high. This is especially
valuable when you have a mixing chamber as low water flow also increases the time that
the solution is under high mixing conditions.

Where additional aging is desired, you can add an aging chamber such as a serpentine of
PVC pipe after the polymer feeder and ahead of any secondary chase water. For
example, 10 feet of 4 ID pipe holds 6.5 gallons of water, so if you have 1 GPM of
polymer solution flowing from your feeder, running through this adds 6.5 minutes of
hydraulic aging time which can be very helpful. You can also add a pressure vessel such
as an empty, clean brominator in line after the feed system to add hydraulic aging time.

Polymer Aging Systems: All of the feed systems listed above can be used to prepare a
solution of polymer into a tank for aging. This can significantly improve the performance of
the product, especially if there are concerns such as cold water or hard water. A good aging
system will use a polymer feed system as described above to prepare the solution into the
tank, and will be controlled by level probes in the tank to prepare the solution as required to
maintain a useable volume of aged, activated emulsion polymer solution. The solution tank
may be large or small, depending on the application. In general, we recommend at least on
hour of hydraulic volume in the tank to allow for aging and activation of polymer at a normal
use rate.
For example, if a polymer product is being fed to a belt filter press at a rate of 1.5 GPH using
a direct feed system this would translate to 150 GPH of 1% solution, or 300 GPH of 0.5%
solution. If we decide that a 0.5% solution is desirable, we would use an aging tank with at
least a 300 gallon working volume. We then need a variable speed solution feed pump which
can supply at least 5.0 GPM of polymer solution to the feed point. To be in the mid range of
the solution feed pump, we would then recommend a 0 to 10 GPM solution feed pump.
Operator Training Manual

In some applications we would also add additional dilution water after the feed pump to
further dilute the polymer for better distribution at the feed point. This dilution water flow
rate is controlled with a rotometer.
Feed systems of this type can be fairly simple, or very complex. Some feed systems measure
water flow and pace polymer feed accordingly to maintain set solution strength; this is
helpful where the water pressure is highly variable. Some measure the flow rate of the
polymer solution to provide very accurate dosing rates.
Obviously, from the size and complexity of the equipment involved, a polymer aging system
is more expensive than a direct feed system, typically 3 times the cost. So, when should you
use an aging system?
1. When the polymer application is critical, but small. For example, trying to feed one
gallon per day of flocculant to a river water clarifier. If we try to use a direct feed
system, we would have to meter 2.6 mls per minute of product continuously. Even if
we can accurately meter this amount of polymer, for effective activation we would
only want 260 mls of dilution water per minute. If instead we prepare this solution
into an aging tank, we can feed 100 gallons daily of a 1.0% solution. This is still
only 0.07 GPM, or 265 mls per minute, but we can meter this much more accurately,
it is much more likely to be effective, and our ability to fine tune dosages is much
greater.
In small applications we can even manually prepare batches of flocculant solution,
and feed it to the feed point with a variable speed pump.
2. When the application is large. If we have a belt filter press that operates 8 hours
daily and uses 25 gallons of polymer each day, this can be done with a 0 to 4 GPH
direct polymer feeder, but we may lose performance if all of the operating conditions
are not perfect. If we operate at 80% activation efficiency, we are using 25 gallons
of product daily to do what 20 gallons of polymer could do under optimal conditions.
Complete activation of the polymer can mean not only less product usage, but also
better performance overall: greater sludge throughput, drier cake, cleaner filtrate,
etc.
At a selling price of $3.00 per lb., it doesnt take very long for a 5 gallon daily
difference in polymer consumption to justify the cost of a feed system.
3. When we have concerns about the operating conditions. Some direct feed systems
work well in the warm months but performance drops off significantly when the

Operator Training Manual

water turns cold. Some are affected by the hardness of the water, and the issue can
be resolved by aging the product.
What can go wrong with the solution? There are two main concerns with the stability of the
emulsion polymer solutions; hydrolysis and chain degradation. Hydrolysis is mostly a
concern for cationic emulsion polymers. Under alkaline water conditions the cationic
monomer charge site will hydrolyze to an anionic acrylate, reducing the cationic charge on
the molecule. This will happen over time in good water but can happen quickly under high
pH and high conductivity water conditions. The viscosity of the solution will degrade and
white precipitates can be seen.
If the water for polymer preparation is alkaline and high in conductivity, the first need is to
increase the solution concentration; a higher concentration is less prone to hydrolysis.
Secondly, reduce the aging time, perhaps by adjusting the level probes in the aging tank so
the polymer is not aged more than 30 minutes. In severe cases, acidifying the polymer
solution to between pH 5.5 and 6.0 can significantly increase the life of the polymer solution.

For example, a 0.5% solution of cationic flocculant that will degrade after 30 minutes
under high pH and conductivity conditions can be made to last 8 hours at a pH of 5.5. A
0.5% solution of cationic polymer which would degrade after 8 hours under moderate
alkalinity conditions can be made to last 48 hours at a pH of 5.5.

Both cationic and anionic flocculants are prone to degradation from free radicals, mostly
formed from ferrous iron and dissolved oxygen. Degradation occurs in about 2 hours at an
iron concentration of 0.5 PPM, faster at higher concentrations. If preparing polymer
solutions in water with a high dissolved iron concentration be careful of the effect that the
iron can have on the product, both for lab testing and for in plant use.
Only ferrous iron Fe++ causes chain degradation, so aerating the water to oxidize the iron to
ferric Fe+++ minimizing the effect. Adding an oxidizer such as perborate will rapidly
oxidize the iron. Increasing the concentration of the emulsion solution also makes the
solution slower to degrade.
This can be a concern when a feed system is shut down over a weekend or for several days.
Polymer solution left in the aging tank can degrade and be worthless when the system is
being restarted. If this is a concern, make sure the feed system is allowed to feed all the
polymer solution out prior to a shutdown, and then make up fresh polymer before restarting.
Spill Containment: If you spill the concentrated emulsion polymer, do not add water! A
small spill can become a very big slippery mess if water is sprayed on the spill.

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The best remedy is to use oil-dry or kitty litter to absorb the spill, and shovel up as much as
possible. Repeat as needed. Once the slippery spill has been absorbed, the residue can be
broken down with rock salt, bleach, or diluted (10%) hydrogen peroxide, then apply more
oil-dry and shovel up this mixture. Do not add water until this step has been taken.
If the prepared emulsion solution spills, it is still very slippery and should be pushed to a
drain with a squeegee if possible. Then, use oil dry to absorb the residue before hosing the
area down.
Product Compatibility: When converting from competitors product to our product, or
even switching from one of our products to another in an account, we need to verify that the
products are physically compatible. Different emulsion manufacturers use their own oil and
surfactant formulations and so they may have interactions. Some guidelines

If your switch just involves changing to a different drum or tote, your primary concern is
the polymer in the hose from the container to the polymer feed pump. If it is not
convenient to replace the line, pump mineral oil through the line and through the pump.
This will flush out the old polymer and allow the new polymer to be introduced.

If you are adding polymer to a storage tank that has a heel of a different product in it,
you need to get a sample of the products and combine them in a jar and see if there is
any lumpimg or gelling over time. If there is any concern, the storage tank should be
cleaned before the new polymer is added.

Operator Training Manual

Controlling Lime Softening Programs


The success of any lime softening program depends on proper control of the settle water
chemical analyses (alkalinity and hardness), as well as clarification results. This is true for
current plant applications and new program evaluations. Good, consistent results depend on
proper control.

Control Tests
Alkalinity titrations are the basis for clarifier chemical dosage control. Results need to be
recorded at proper frequencies to make chemical corrections based on these results.

Specifying Control Ranges


Lime Softening
Hydroxide alkalinity is the control for lime softening. The final hardness result only has
meaning when compared to the finished water alkalinity. Final hardness depends on the
concentration of alkalinity species plus the solubility of calcium carbonate and magnesium
hydroxide. The first requirement in establishing control is determination of OH alkalinity.
Plants operating without free hydroxide levels will have a negative 2(P-M) reading. A
negative reading does not mean negative quantities of hydroxide; it means bicarbonate is still
present. Some plants that desire calcium reduction at the lowest lime dosage, but have no
concern for magnesium reduction, will operate in this range.
When the OH reading drops below the desired range, lime dosage is increased. When the
OH reading goes above the required range, dosage is decreased.
Lime-Soda Softening
Hydroxide and carbonate alkalinity levels are used for controlling lime and soda ash dosages,
respectively. The lime is controlled by maintaining a positive OH reading within specific
control ranges. The soda ash is controlled by the difference between finished water carbonate
and calcium hardness. The difference between carbonate and calcium hardness is excess
carbonate, and the larger the excess, the greater the tendency to drive calcium concentration
down to low levels.

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Excess carbonate is calculated using hardness and alkalinity titrations (the difference
between carbonate and calcium hardness [HCa]), as shown here:
28.

Excess carbonate = CO3-HCa = 2P-HCa

Since hydrate alkalinity is maintained for lime-soda softening, when P is greater than M,
then CO3 = 2P.
Titrations are performed on settled water samples. First, the OH reading is used to control
lime feed. If the lime dosage is in control, the excess carbonate reading (2P-HCa) is
compared to the control range. If the reading is high, soda ash is reduced, or, if low,
increased.
The actual control range depends on how low the finished water calcium must be. Calcium
less than 25 ppm typically requires an excess of 50 ppm carbonate. For higher calcium levels,
a smaller excess is required. The individual plant control ranges for excess carbonate and
hydrate alkalinity (OH reading) are arrived at through trial and error.
In some rare situations, an actual excess carbonate will not exist, and this will calculate as
a negative number. This might occur in a case where high levels of noncarbonate hardness
exist in the raw water and only partial removal of calcium and noncarbonate hardness is
desired by the plant.

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Figure 6. Cold Process Lime Treatment Control Tests

For partial lime softening, keep readings below CO3 line and use lower target area.
For complete lime softening, keep readings above CO3 line and use upper target area.

Operator Training Manual

Troubleshooting
At times, despite proper alkalinity control, hardness concentrations will not go down to
expected levels. Generally, this means one of the softening factors other than concentration is
causing a problem. These factors include time, temperature, mixing, contaminants, and
addition of inorganic salts.
One problem frequently encountered in cold lime softening is post-precipitation. This results
in the deposit of calcium carbonate from the effluent water coating the filter media. It is
evidence of incomplete softening in the clarifier, particularly during the winter. Softening is
incomplete when the expected result is not achieved in the clarifier. In these cases, softening
precipitation usually continues beyond the clarifier in the filters or distribution system.
Recarbonation, the reduction of settled water pH through carbon dioxide or acid addition, can
be used to improve the stability of the water, and minimize post-precipitation.

Controlling Effluent Clarity


As with conventional clarification, control of the clarifier operation and chemical dosage
affect cold lime softening clarity.

Planning an Evaluation
Select Feed Points
Feeding Coagulants (Ferric Chloride)
Feed to the raw water at a location that will assure maximum mixing. In front of the low lift
pump or a control valve are good feed points.

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Established Criteria

Variable
Finished water turbidity
Finished water conductivity

Desired Goal
<10 NTU
<450 mhos

Hardness

<100 ppm

Alkalinity: 2P - M

0 8 ppm

Because of upsets that can occur as you change programs, you may need the flexibility to
produce less than desired results temporarily while you optimize the program and bring it on
line.
Many of the following tests and equipment checks should be run to maintain control, spot
changes in raw water conditions, or identify problems such as feed pump failure:

P, M hardness, raw water, and settled water


Jar tests on raw water
Jar tests on water samples from the center well
Turbidity, raw, settled, and finished
Clarifier operation (for upflow units)
Clarifier flow rate
Filter run length
Chemical feed rates

The plant should be monitoring chemical results on a frequent basis. Other tests should be
run as required.
Evaluating Flocculant
When adding flocculant to any softening program, the important consideration is feed point,
and, for upflow units, bed level control. The raw water line or the clarifier flocculation zone
should be evaluated. When feeding flocculant through the upflow unit, the bed will compact.
Blowdown must be reduced to adjust for this change in density. Also, if too much flocculant
is fed in lime softening, solids may grow too large, actually reducing the surface area

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available for precipitation and contributing to less than expected hardness removal. Begin
feeding flocculant at the full dosage indicated by jars, usually 0.21 ppm.
Evaluating Polymers
If a polymer is fed to completely replace an inorganic coagulant to reduce cost, TDS, or
sludge volume, two things may happen:

The sludge solids will become less fluid, perhaps to the point where they will build
excessive torque on the sludge removal rakes.
Softening efficiency will drop.

The degree of these effects will determine if the program will be a success. Add the polymer
to replace inorganic salt. A polymer can also be fed in conjunction with sodium aluminate.
Dosage for polymers is 13 ppm.
Evaluating Sodium Aluminate
Whenever sodium aluminate is fed, improvements in finished water analyses, hardness, and
alkalinity will occur. Have the objectives of the evaluation in mind. Are you looking for
better water quality or lower total chemical cost? The exact control for the OH reading and,
if feeding soda ash, for the excess carbonate reading, will depend on plant objectives. When
using sodium aluminate, the lowest OH reading control limit is generally 2(P-M) = -5 ppm.
The ultimate control range that best fits plant conditions and goals is determined through trial
and error.
In some waters, when replacing acid salts, clarity using sodium aluminate alone will not meet
water quality goals. A coagulant addition will help bring the program into line. In cases of
heavy carryover, a flocculant may be needed.
In a horizontal clarification unit, begin evaluation by completely replacing any acid salt with
sodium aluminate. A typical dosage is 20 ppm liquid sodium aluminate or 10 ppm dry
sodium aluminate. In an upflow unit, alum or iron salt replacement is also a one-step
changeover. Any coagulant or flocculant being fed as part of the program should be started
along with the sodium aluminate. Watch clarifier mechanical control, since a sludge density
change will occur when switching to the sodium aluminate program. Begin by cutting
blowdown by one-half and make adjustments from there. At times, a sodium
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aluminate/polymer program can reduce sludge bed volume so quickly that, unless blowdown
is reduced, the bed can be blown out of the clarifier in 816 hours.

Common Insoluble Impurities


Soluble Components

Precipitates

Calcium

Calcium carbonate, CaCO3

Magnesium

Magnesium hydroxide, Mg(OH)2

Carbonate alkalinity and


carbon dioxide

Calcium carbonate

Iron

Ferric hydroxide, Fe(OH)3

Manganese

Manganese oxide, MnO2

Phosphate

Various forms of calcium phosphate

Silica

Various indefinite combinations with


Mg, Ca, and added coagulants (iron,
alum, sodium aluminate, polycationics)

Operator Training Manual

Alkalinity Relationships

HCO3-

CO3-2

OH-

P < M

M2P

2P

P = M

2P

P > M

2(MP)

2PM

P = M

When
P = O

This table is based on the following relationships:

P alkalinity = OH- + CO3=

M alkalinity = HCO3- + CO3= + OH-

O Reading = OH-

For example, if titrations show:

P = 40 ppm

M = 90 ppm

Then P < M, and:

HCO3 = M-2P = 10 ppm (as CaCO3)

CO3 = 2P = 80 ppm (as CaCO3)

OH = 0 ppm

Operator Training Manual

Characteristics of Magnesium and Calcium Hardness

Compound

Solubility

Class

Comments

Mg(HCO3)2

Very soluble

Carbonate or temporary
hardness; precipitation upon
heating.

When Mg, Ca, HCO3 are


expressed (as CaCO3),
1 ppm of hardness with
1 ppm alkalinity.

NaHCO3

Very soluble

Sodium alkalinity

Present when alkalinity is


greater than hardness.

MgSO4
CaSO4

Soluble*

Noncarbonate or permanent
hardness; do not precipitate
upon heating.

Most common form of


noncarbonate hardness,
present when hardness is
greater than carbonate
alkalinity.

MgCl2
MgNO3
CaCl2
CaNO3

Very soluble

Noncarbonate hardness

Only present when hardness


is greater than alkalinity and
sulfate.

Mg(OH)2
CaCO3

Insoluble

Softening precipitates

Insolubility is basis for


precipitation softening.

MgCO3

Very soluble

Present during softening but


do not precipitate.

Soluble
Ca(OH)2

*In most lime softening situations, the concentration of sulfate remains low enough that
precipitation of calcium sulfate is not a factor. In other water systems, such as open
recirculating cooling water systems, the sulfate can increase to concentrations where
precipitation occurs.

Operator Training Manual

Estimated Results and Dosages for Partial Lime Softening


Case 1Caraw Exceeds Mraw
Estimated Results
CO3
HCO3

=
=

35 ppm
0

OH
CO2

=
=

0
0

M
P

=
=

35
17.5

Mg reduction = 10 percent of raw Mg


Total hardness reduction = total alkalinity reduction

Dosage (as chemical, not as CaCO3 equivalent):


ppm Ca(OH)2 =

74 (2CO2 + M + 10% Mg)


% lime purity

ppm CaO

56 (2CO2 + M + 10% Mg)


% pebble lime purity

See the following table for CO2 estimation.

Operator Training Manual

Case 2Mraw Exceeds Caraw


Estimated Results
Ca
Mg reduction
Alkalinity reduction
CO3

=
=
=
=

35 ppm
10% of raw Mg
hardness reduction
30 ppm

pH 9
HCO3

=
=

10.0
Mraw - hardness reduction - 30 ppm

Dosage (as chemical)


ppm Ca(OH)2 =

74 (2CO2 + Ca + 10% Mg)


% lime purity

ppm CaO

56 (2CO2 + Ca + 10% Mg)


% pebble lime purity

Operator Training Manual

Factors for Calculating CO2 (as CaCO3) from pH and M Alkalinity

Raw CO2 (as CaCO3)* = R x M Alkalinity


pH

pH

pH

6.0
6.1
6.2
6.3
6.4
6.5
6.6

1.5
1.2
1.0
0.82
0.62
0.51
0.42

6.7
6.8
6.9
7.0
7.1
7.2
7.3

0.33
0.25
0.20
0.15
0.12
0.10
0.082

7.4
7.5
7.6
7.7
7.8
7.9
>8.0

0.062
0.051
0.042
0.033
0.025
0.20
Negligible

*CO2 (as CaCO3) = 1.14 x CO2 (as CO2)

Operator Training Manual

Estimating Results and Dosages for Complete Lime-Soda Softening


Estimated Results
Ca

23

Mg

10

CO

50

OH

30

80

55

pH

10.6

Dosage (as chemicals)


ppm, Ca(OH)2 =

74 (Mg + 2CO2 + M + 30)


% purity

ppm, NaCO3 =

106 (total hardness - M + 50)


% purity

ppm, CaO

56 (Mg + 2CO2 + M + 30)


% purity

Operator Training Manual

Estimated Results and Dosages for Complete Lime-Caustic Softening


Estimated Results
Same as for complete lime-soda softening.

Estimated Dosages (as chemicals, not as CaCO3):


1.

Calculate lime from lime-soda softening.

2.

Calculate soda ash from lime-soda softening.

3.

Do the following calculations, using the calculated lime and ash dosages:
If soda ash = 1.35 x lime:
ppm caustic = 0.75 x (ppm soda ash)
ppm lime = none required
If soda ash is less than 1.35 x lime:
ppm caustic = ppm soda ash x 0.75
ppm lime = ppm calculated lime - (caustic x 0.9)
If soda ash is greater than 1.35 x lime (this is very rare):
ppm caustic = calculated lime x 1.1
ppm ash = calculated ash (caustic x 1.3)

Operator Training Manual

Chemical Control Tests


Test

Frequency

P, M alkalinity titrations

Hourly

OH reading by calculations (2PM)

Hourly

Total and calcium hardness titrations

Every two hours

Magnesium hardness by calculation

Every two hours

Softening Programs
Current Plant Program*
OH reading: none
pH: 9.29.6
Ferric sulfate or alum

Flocculant, starch, or coagulant to


replace as much ferric as possible. pH
probably too low for sodium aluminate.

OH reading: none
pH: 9.29.6
Plant has carryover. Sludge is difficult to
remove from clarifier. No coagulant.

Starch. Feeding sodium aluminate is


possible, but pH may still be too low
for good results. Starch is
recommended because at this pH, little
Mg is removed.

OH reading: 025 ppm


Ferric sulfate or alum, or a polymer
coagulant. Plant may feed soda ash.

Sodium aluminate alone, or sodium


aluminate/coagulant or flocculant.
Hardness removal will improve.

OH reading: 025 ppm


No inorganic used. Competitive flocculant
is being fed. Plant may feed soda ash.

Sodium aluminate and flocculant or


coagulant (if needed). Better quality
water with sodium aluminate.

*OH reading is the amount of OH- alkalinity in the settled water (determined by 2PM).
Lime is added to all programs for pH adjustment.

Operator Training Manual

Control Ranges Using Lime Alone


Control Range

Typical Results

OH reading: -5 to 5 ppm.
This is the most typical range.

Calcium will be near the maximum


practical level.
Carbonate = 35 ppm
Mg removal 1030% of Mg (raw)

OH reading: 515 ppm.


This range (in some cases even higher OH
levels) is used when magnesium reduction
is desired.

Calcium removal usually less than in


above control range, but may improve
in some systems.
Mg removal is greater than for the
above control range, which can lead to
better clarity.
Carbonate less than 35 ppm.

OH reading: zero (less than 5 ppm).


This range is used when good calcium
removal with minimum lime dosage is
required. Industrial plants generally do not
operate in this range.

Calcium removal will be less than


maximum up to maximum practical
level.
Mg = 10% removal or less.

Control Ranges Using Lime-Soda


Control Range

Results

Lime dosage control (2P-M)

Magnesium is always reduced in lime-soda


softening. Higher OH readings remove
additional Mg.

OH reading always positive


Soda-ash control (2P-HCa)

The higher the value of the control limits,


the lower the finished water calcium.

Typical ranges, ppm


-200
020

2040
4060

The range established for the plant depends on its particular goals. The best control range
will result from trial and error experimentation.

Operator Training Manual

TroubleshootingChemical Analyses Problems

Problem

Possible

Action to be C
Taken

a
u
s
e
s
High calcium

Wrong chemical
feed

Check finished water analyses. They should be


in control range. Remember, calcium
precipitates only if sufficient carbonate is
present.
Check to see if feeders are working.

Insufficient mixing

Check to see if mixers are working. Adjust


agitator speed.

Low solids level:


Upflow clarifier

Horizontal
clarifier
Short circuiting
high flow rates

Check five-minute settling test. Check bed


level; reduce blowdown if solids level is too
low.
Evaluate sludge recycle on plant scale.
Check log for flow changes. Check for causes
of short circuiting (broken baffles, dirty
clarifier, broken launderers.)

Contaminants

Low temperature
Need for metal salt
addition

Check for phosphate in water source. Is recycle


water present? Run jars with and without
recycle water present; compare results.
Chlorination can oxidize some problem
contaminants.
Check records for unusually low water
temperatures. Add sodium aluminate.
Add or increase sodium aluminate. Increase
OH reading to precipitate additional
Mg(OH)2.

Operator Training Manual

High magnesium

Wrong chemical
feed

Check finished water analyses. Magnesium


precipitates only in the presence of hydroxide.
Increase OH reading control range.
Same as above.

Any of the causes


listed above for high
calcium

Operator Training Manual

TroubleshootingChemical Analyses Problems (continued)

Problem

Possible

C
a
u
s
e
s

High alkalinity
(High alkalinity is
the other side of high
hardness, since one
is related to the
other.)

Same as above for


calcium

High silica
(In low silica waters
less than 10 ppm,
cold softening is not
very effective for
silica reduction.)

Need for more Mg


precipitation

Filter growth or
post-precipitation

Action to be Taken

Need inorganic salt


Too high an OH
reading (50 ppm or
greater). To reduce
Mg, pH can be
raised enough to
resolubilize silica).
Incomplete reaction

Add sodium aluminate or an acid salt.


Reduce OH reading.

Investigate all the parameters listed above for


high hardness.
Consider recarbonation before the filters.

Operator Training Manual

TroubleshootingClarification Problems

Problem

Possible Causes

Action to be Taken

High carry over


of raw water
turbidity (acidify
waterif
turbidity does not
disappear, it is
clay turbidity)

Uncoagulated
solids

Feed coagulant (polymer or acid salt) or


increase dose.

High carryover
of precipitated
solids

Check feed pumps.


Increased flow
rate

Increase OH reading.

Particles too
small

Increase polymer coagulant, flocculant,


or inorganic salt dosage.

Poor mixing and


bed control and
solids levels
Short filter runs

High carryover

See above.

High filtered
water turbidity

Flow rate

Check flow against design rate.

High carryover
from the clarifier

See above.

Poor filter
efficiency
(% removal)

Feed coagulant filter aid.

Post-precipitation
of solids

Make sure reactions are complete


before filter.

Operator Training Manual

Typical Evaluation Form

Raw Water Analyses

Settled Water

Time

NTU

pH

TH

HCa

NTU

pH

OH

CO3

TH

HCa

9:30

20

7.2

180

240

160

4.0

10.0

30

54

48

112

80

10:30

20

7.2

180

240

160

4.0

10.3

36

60

12

48

104

78

11:30

20

7.1

182

238

162

3.2

10.1

28

52

48

96

74

Finished Water

Upflow Clarifier

Dosage (ppm)

Time

NTU

pH

OH

TH

HCa

WF

BL

ST

Lime

SA

Poly

9:30

1.5

9.8

28

50

110

78

3,000

6'

10

110

15

10:30

1.3

10.0

34

56

12

102

76

3,000

7'

14

104

15

11:30

1.0

9.9

27

48

94

74

3,000

7'

16

104

15

WF

Water flow (gpm)

BL

Bed level

ST

Settling test (%)

SA

Sodium aluminate

9:30:

Ended iron sulfate feed; began polymer, sodium aluminate; reduced blowdown
1 minute to 30 seconds.

10:30:

Turned blowdown off; bed falling; adjusted lime dosage.

11:30:

Reduction in hardness occurring; clarity good.

Operator Training Manual

Step-by-step Lime-Soda Ash Softening, When Raw Water Ca Exceeds M


(all expressed as CaCO3 Equivalents)
Step 1

Step 2

Raw Water

Final result:
add lime
(170 ppm)

Action:
soda ash
(25 ppm)

Final result:
CaCO3
precipitation

TH

200

117

117

92

Ca

150

80

80

55

Mg

50

37

37

37

HCO3

125

CO3

60

60

35

OH

12

12

12

125

72

72

47

CO2

10

Substance

Step 3

Step 4

Raw
Water

Action:
add lime
(55 ppm)

Final result:
Mg(OH)2
precipitation

Action:
soda ash
(100 ppm)

Final result:
CaCO3
precipitation

TH

200

147

120

120

33

Ca

150

110

110

110

23

Mg

50

37

10

10

10

HCO3

125

CO3

35

35

135

48

OH

67

40

40

40

125

102

75

175

88

CO2

10

Substance

Operator Training Manual

Step-by-step Lime Softening, When Raw Water M Exceeds Ca


(all expressed as CaCO3 Equivalents)
Step 1

Step 2

Action:
add lime
(165 ppm)

Initial
result:
Mg(OH)2
precipitation

Intermediate
result:
HCO3
conversion

Final
result:
CaCO3
precipitation

Raw
Water

Action:
add lime
(10 ppm)

Final
result:
CO2 conversion

TH

200

210

210

375

370

370

80

Ca

150

160

160

325

325

325

35

Mg

50

50

50

50

45

45

45

HCO3

300

300

310

310

310

150

150

CO3

320

30

OH

10

165

160

300

310

310

475

470

470

180

CO2

10

10

Substance

Step 3

Raw Water

Action:
add lime
(20 ppm)

Initial result:
HCO3
conversion

Final result:
CaCO3
precipitation

TH

200

100

100

80

Ca

150

55

55

35

Mg

50

45

45

45

HCO3

300

150

130

130

CO3

30

265

50

OH

20

70

300

200

200

180

CO2

10

Substance

Operator Training Manual

Step-by-step Lime Softening, When Raw Water Ca Exceeds M


(all expressed as CaCO3 Equivalents)
Step 1

Step 2

Raw
Water

Action:
add lime
(10 ppm)

Final
result:
CO2 conversion

Action:
add lime
(20 ppm)

Initial
result: HCO3
conversion

Final result:
CaCO3
precipi-tation

TH

200

210

210

230

230

225

Ca

150

160

160

180

180

175

Mg

50

50

50

50

50

50

HCO3

125

125

135

135

115

115

CO3

40

35

OH

10

20

125

135

135

155

155

150

CO2

10

10

Substance

Step 3

Step 4

Raw
Water

Action:
add lime
(120 ppm)

Initial
result:
Mg(OH)2
precipitation

TH

200

345

340

340

105

125

117

Ca

150

295

295

295

60

80

80

Mg

50

50

45

45

45

45

37

HCO3

125

115

115

CO3

35

35

265

35

35

35

OH

120

115

20

20

12

125

270

265

265

55

55

47

CO2

10

Substance

Intermediate
result:
HCO3conversion

Final
result:
CaCO3
precipitation

Action:
add lime
(20 ppm)

Final
result:
Mg(OH)2
precipitation

Operator Training Manual