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Lime Softening is an operation Carbonate—not Alkalinity—is the water) then the cut-off points for
which has been used for the past main player of lime softening hardness and flowrate could be
150 years to remove hardness and chemistry. However alkalinity fails decreased.
soften the water. This article will to represent carbonate species’
Hardness practically, means the
discuss lime softening through a concentration accurately;
summation of calcium and
new perspective, instead of going especially when pH is either very
magnesium ions. The concept of
through the detailed chemical high or very low. There are also
lime softening is to remove
equations; we will focus on interferences like carboxylic acids
“hardness-causing” ions by
“practical conclusion” of the in Alkalinity measurement which
converting them to particles. A
reactions. In addition, the term make it inaccurate.
lime softener is actually a reactor,
“alkalinity” will deliberately not be
An old rule of thumb is that lime a precipitator and a clarifier. All
brought up, even though
softening is the method of choice these units together make the lime
traditionally it is part of the
for hardnesses higher than 100-150 softener a complicated unit
chemistry of lime softening.
mg/L and flowrates larger than 200 operation. The block flow diagram
Alkalinity is a “loose” definition of
m3/h. However, if water is of a typical lime softener is
carbonate species’ concentration.
“problematic” (e.g. a high TDS depicted in Fig – 1.
Fig -1
In the reactor, the hardness ions residence time for sedimentation There are three main types of lime
react with added chemicals which and the generation of clear water. softening systems; Cold Lime
convert them to small suspended Softener (CLS), Warm Lime
Therefore, lime softening consists
solids. In the precipitation section, Softener (WLS), and Hot Lime
of three separate sections: reaction
where precipitation/crystallization Softener (HLS). As you may
(which converts hardness to a low
is the main process, small particles notice, this classification is based
solubility salts), precipitation
are promoted mechanically and on the operating temperature of the
(which happens after
chemically to cause the bigger system, though there is not a clear
oversaturation of water with low
particles (generally bigger than and cut distinction between them.
soluble salts), and the
100micron) to settle quickly. The operating temperature range of
sedimentation of generated
Clarifier is the section that each system is tabulated in Table –
particles.
provides enough area and 1.
CLS 15 °C - 60 °C
WLS 60 °C - 85 °C
HLS 90 °C - 105 °C
The first invented lime softener industrial water treatments. HLS is Through Steam Generators
was the cold one, CLS, and was very popular for treating make up (OTSG’s), and both generate water
used for softening potable water. water for high pressure boilers with almost the same level of
CLS was very popular until which need very low hardness feed hardness practically. Table-3
recently when municipalities waters. HLS and WLS are used in shows a summary of differences
stopped softening the potable oil extraction facilities to soften between WLS and HLS.
water. WLS and HLS are the the produced water to prepare
versions which are popular in boiler feed water for Once
In the following section the tasks process. At first sight, lime right side of formula, OH which
& duties of each segment of a lime softening seems strange: removing represents a “base”.
softener is explained. hardness by adding lime which is a
The system removes hardness
REACTOR type of hardness. Unlikely as it
components by converting it to the
may seem, it works! Lime (CaO)
Reactions and Stoichiometry low soluble salt versions of
or hydrated lime (Ca(OH)2) can be
of lime softening hardness ions: removing calcium
used for this purpose. Technically,
by converting it to calcium
“Lime” in the name of “lime we do not like the Ca portion of
carbonate (CaCO3) and removing
softening” is based on it being the the lime formula; it is that hardness
main added chemical in this we want to remove. We like the
©2013 ENGROWTH TRAINING INC. ENGEDU.CA PAGE 3
magnesium by converting it to As it was mentioned converting add carbonate content of water.
magnesium hydroxide (Mg(OH)2). Mg to Mg(OH)2 can be done by Even though Soda ash is a base by
adding a base to the system. The itself but it cannot be replaced by
CaCO3 can be generated by adding
cheapest base is Lime. But any other base. The reason is here
sufficient CO3=, carbonate, to
hydrated lime, caustic, and even we are looking for a compound
calcium, while Mg(OH)2 can be
soda ash may be used for this which provide carbonate species’
generated using the sufficient
purpose. “Caustic Softening” can in water.
amount of OH. The name of this
be used in smaller capacity
operation is “Excess Lime In applications where Lime and
operations when the high cost of
Softening”. Soda Ash both need to be added, it
Caustic is not important and they
is claimed that instead; Caustic,
Since removing magnesium want to avoid headaches of using
NaOH, can be added. The ground
hardness is more expensive than Lime slurry and involved dirtiness.
for this claim is this reaction
removing calcium hardness, in
Converting Ca to CaCO3 would be equation: Ca(OH)2 + Na2CO3
cases where magnesium
easy if we had enough carbonate CaCO3 + NaOH Hydrated lime
concentration is low (<40 ppm) or
species in water. The good news is and soda ash react and generate
residual tolerable hardness at
that Carbone equilibrium is a big caustic. Although the logic behind
downstream of lime softener in not
part of the equilibriums in natural this theory is correct, but this
small enough, then the lime
waters. Therefore, the only thing application decreases the
softening process can be done by
that should be done is to “push” flexibility of operation because by
removing calcium through
the equilibrium to produce a higher adding Caustic, a fixed ratio of
converting it to calcium carbonate
concentration of CO3=. In the Ca(OH)2 and Na2CO3 is always
(CaCO3) and magnesium to
HCO3- H++ CO3= reaction, by applied.
magnesium carbonate (MgCO3).
consuming more H+, equilibrium
Magnesium carbonate has a higher When lime usage is low, hydrated
“leans” to the right and generates
solubility than Mg(OH)2, thus lime is the first choice but in
more CO3=. And “consuming” H+
producing a water with higher higher usages (more than 100-200
means adding base to the system.
residual hardness. The name of this m3/hr) lime and dolomite will be
operation is “Lime Softening”. The This is an incredibly convenient more competitive choices.
amount of required chemicals and occurrence; By adding a base to
generated sludge is different in the system, we make a good To be able to predict the type and
lime softening operations environment to convert Calcium to amount of required chemicals in a
compared to excess lime softening. Calcium Carbonate and at the lime softener at the beginning,
same time, Magnesium to different types of hardness in water
Usually Excess Lime Softening is should be identified.
Magnesium Hydroxide.
the more attractive choice for
water treaters even though it If there are not enough carbonate Hardness can be categorized as
consumes more lime. Therefore, species in the system, then they “temporary hardness” and
for the rest of this article we will should be added through an “permanent hardness” (Table -4).
be focusing on “excess lime external source. Soda Ash
softening”. (Na2CO3) is a popular chemical to
The type of hardness, if it is calcium type or magnesium type, or temporary or permanent can be determined from water
analysis and using Table – 5 in mg/L as CaCO3. In the table, whenever you are faced with a negative number, use zero
instead.
Table - 5
Table - 6 summarizes the main duty of each chemical in a hardness removal task. This table can be used instead of a
traditional ladder diagram which was more tedious. For example the table shows that for removing temporary calcium
hardness, lime is the only required chemical.
Table - 6
From the Table – 6 or 7 it is Magnesium hardness is the only The Table – 8 shows the chemical
noticed Lime is required for all hardness which needs addition of consumption per mass (weight) of
temporary harnesses. For two chemical for removal. different types of hardnesses in
permanent Calcium hardness only water as CaCO3.
Soda ash is needed. Permanent
Temporary Hydrated Lime: 0.74 time mass Hydrated Lime: 1.48 time
of Temporary Ca Hardness in mg mass of Temporary Mg
of CaCO3 Hardness in mg of CaCO3
Thermodynamics of lime surface of water in the reactor, the Those equilibriums basically
softening second one is the equilibrium of compete with each other to define
ions with precipitated calcium outlet hardness content. In the
For hardness, there could be three carbonate and magnesium same conditions, the minimum
groups of reactions that dominate hydroxide, and the last one is hardness attained in the dominant
the outlet concentration of carbonate system equilibrium in condition of system is the second
hardness ions. The first one is the closed systems. The action area of equilibrium or precipitation
equilibrium of carbonate system in each equilibrium are depicted in reactions.
open systems with air at the Fig-2.
Fig- 2
In equilibrium with
CO2 in Atmosphere
In equilibrium with
Carbonate &
Bicarbonate in
Water
In equilibrium with
Sludge
In the first mechanism, hardness which is controlled by In the second mechanism, Ksp or
concentration is determined by concentration of carbon dioxide solubility product of precipitants
carbonate concentration in water (CO2) in the air. determine the hardness in outlet.
Fig-3
°c
°c
°c
Fig-3 is developed by solving the Kinetics of Lime Softening crystallization rate of Mg(OH)2
multiple equilibriums occur in a and CaCO3 respectively.
The speed of a reaction depends
lime softener. One limitation that
mainly on temperature, the PRECIPITATOR
Fig-3 has is that Solubility
presence of excess reactants,
Product(Ksp) of Magnesium The main duty of the precipitator is
keeping precipitates in contact
Hudroxide considered constant and to provide a good environment to
with reactants, and eliminating or
independent of the temperature. promote precipitation and
decreasing interfering ions.
This limitation is because crystallization. However,
temperature dependency of Ksp of Having excess OH- in water (high crystallization is not the main
Mg(OH)2 is not available. PH) and keeping low free purpose. In crystallization the goal
carbonate (CO3=) will increase is generating crystals with a size
Table - 8
Type Description
These two theoretical types of designs are closer to mixed sludge sludge blanket mode (Table 9).
recycled sludge lime softeners type and others are closer to sludge However operation of a sludge
(solid contact or sludge blanket) blanket type. Generally speaking, blanket lime softener in solid
are at two ends of the spectrum, it WLS’s work mainly based on solid contact mode is doable.
could be assumed that some contact type and HLS’s work in
WLS HLS
Solid Contact
Sludge blanket
Table- 10
The consistency of sludge is composition of solids. High solid—makes the sludge lighter
determined not only by its water percentage of magnesium and hard to dewater but less
content, but also by its hydroxide—which is a gelatinous abrasive. Water with a high
©2013 ENGROWTH TRAINING INC. ENGEDU.CA PAGE 9
calcium content leads to a sludge
which is easy to dewater but more Related courses by Mohammad Toghraei
abrasive. Course Duration
Desludging from the bottom of the Water Treatment in the Oil Industry 2 days
lime softening basin is usually
De-oiling: Removing Oil from Water 1 day
intermittent. This intermittent
operation is not due to designer or Unified Approach to Water and Wastewater Treatment 2 days
operator preference but rather a
result of the low flowrate of sludge For more information please visit: engedu.ca
in most lime softening operations.
and even work as a partial
This flowrate causes the sludge to
disinfection basin.
settle as it passes through small
bore pipes (2” if it supposed to go
Magnesium oxide (Magox) is used
over the pipe rack). The other
for silica removal, the mechanism
reason for intermittent desludging
of which utilizes adsorption and
is the prevention of wasting water
possibly partial reaction. Silica
along with a too-dilute sludge.
will co-precipitate with
Generally the de-sludging duration
magnesium oxide/hydroxide in
is the time it takes to empty the
high pH environment, and may be
sludge pit which happens after
observed as magnesium silicate in
each lap of the rake(if sludge
co-precipitated sludge.
collection is by rake rotation)or
time for sludge to “slide” the
bottom cone(if sludge collection is
by the high slope of bottom of the Mohammad Toghraei, P.Eng. is currently
lime softener). The sludge can be an independent Consultant and is the
just landfilled or sent to further instructor of several Process engineering
units for dewatering. courses with “Progress Seminars Inc.”. He
can be reached through his website
www.engedu.ca .
Other Tasks for Lime Toghraei has over 20 years’ experience in
Softener the field of industrial water treatment. His
main expertise is in the treatment of
wastewater from oil and petrochemical
The precipitation that results in complexes. For the past nine years he has
lime softeners can be taken taken on different technical and leadership
advantage of. All other types of roles in water treatment areas of SAGD
projects. Toghraei has received a B.Sc. in
precipitation removal methods,
chemical engineering from Isfahan
which are a group of removal University of Technology and an M.Sc. in
methods for dissolved water environmental engineering from the
contaminants, can be done in lime University of Tehran, and is a member of
softeners too. In this respect, the APEGA.