Industrial Waste Treatment

Basics
By Definition pH is the measure of
free hydrogen activity in water and
can be expressed as :
pH= -log[H+] and pOH= -log[OH-]
Measured on a scale of 0-14,
solutions with a pH of less than 7.0
are acids while solutions with a pH of
greater than 7.0 are bases.
In very simple terms bases are used to
neutralize acids, while acids are used to
neutralize bases.
The byproducts are normally salts (which
may or may not be soluble) and water.
Definition
“Neutralization” can be defined as the
treatment of industrial waste so that it
is neither too acidic nor too alkaline
for safe discharge.
There are several possible reasons
that an industry neutralized its
wastewater during the twentieth
century and will continue to do so:
Reasons……..
1. To make industrial waste compatible (in
terms of pH) with municipal sewage
when joint treatment is practiced
2. To continue reason no. 1; more
specifically, to make certain that its pH
does not kill or otherwise inactivate the
microorganisms that are being used to
biologically oxidize the organic matter
content
3. To prevent corrosion of pipelines and
equipment leading from the industry to its
ultimate destination
4. To comply with effluent standards for
excessive acid or alkaline conditions in
sewers or receiving waters.
5. To continue reason no. 4; more
specifically, to make certain that the waste
discharge pH does not kill fish or
otherwise affect other organisms in
receiving waters
Excessively acid or alkaline wastes
should not be discharged into a receiving
stream without treatment.
A stream even in the lowest
classification—that is, one classified for
waste disposal and/or navigation—is
adversely affected by low or very high pH
values.
This adverse condition is even more
critical when sudden slugs of acids or
alkalis are imposed upon the stream.
 Methods – outline
There are many acceptable methods
for neutralizing over acidity or over
alkalinity of wastewater, such as:
(1) mixing wastes so that the net effect
is a near-neutral pH;
(2) passing acid wastes through beds
of limestone;
(3) mixing acid wastes with lime slurries
(4) adding the proper proportions of
concentrated solutions of caustic soda
(NaOH) or soda ash (NA2CO3) to acid
wastes;
(5) blowing waste boiler-flue to alkaline
wastes;
(6) producing CO2 in alkaline wastes; and
(7) adding sulfuric acid to alkaline wastes.
Neutralization Tank Sizing
Engineers size treatment tanks to allow
adequate retention of the influent for pH
measurement and subsequent reagent
addition.
Good engineering practice for pH control
requires 15 to 30 minutes retention time.
Retention time is calculated by dividing
the tank volume by the average influent
flow rate.
Typical pH Neutralization Tank
Piping
pH Neutralization Tank Inlet & Outlet
Location
Part-I
1. Mixing Wastes
Mixing of wastes can be accomplished
within a single plant operation or between
neighboring industrial plants.
Acid and alkaline wastes may be
produced individually within one plant and
proper mixing of these wastes at
appropriate times can accomplish
neutralization, although this usually
requires some storage of each waste to
avoid slugs of either acid or alkali
If one plant produces an alkaline
waste that can be pumped
conveniently to an area adjacent to a
plant discharging an acid waste, an
economical and feasible system of
neutralization results for each plant.
2. Limestone Treatment for Acid Wastes
Passing acid wastes through beds of
limestone was one of the original methods
of neutralizing them.
The wastes can be pumped up or down
through the bed, depending on the head
available and the cost involved, at a rate of
about 1 gallon/min (gpm) per square foot
(ft2) or less. Neutralization proceeds
chemically according to the following typical
reaction:
CaCO3 + H2SO4 → CaSO4 + H2CO3
Disposing of the used limestone beds can
be a serious drawback to this method of
neutralization, because the used
limestone must be replaced by fresh
limestone at periodic intervals, with the
frequency of replacement depending on
the quantity and quality of acid wastes
being passed through a bed.
When there are extremely high acid
loads, foaming may occur, especially
when organic matter is also present in the
waste.
3. Lime-
Lime-Slurry Treatment for Acid Wastes
Mixing acid wastes with lime slurries
is an effective procedure for
neutralization.
The reaction is similar to that
obtained with limestone beds.
In this case, however, lime is used up
continuously because it is converted
to calcium sulfate and carried out in
the waste.
Though slow acting, lime
possesses a high neutralizing
power and its action can be made
effective by heating or
oxygenating the mixture.
It is relatively inexpensive, but in
large quantities, cost can be an
important factor.
Hydrated lime is sometimes difficult to
handle, because it tends to arch, or
bridge, over the outlet in storage bins
and possesses poor flow properties,
but it is particularly adaptable to
neutralization problems involving
small quantities of acid waste, as it
can be stored in bags without special
storage facilities.
4. Caustic-
Caustic-Soda Treatment for Acid
Wastes
Adding concentrated solutions of caustic
soda or sodium carbonate to acid wastes
in the proper proportions results in faster,
but more costly, neutralization.
Smaller volumes of the agent are required,
because these neutralizers are more
powerful than lime or limestone.
Another advantage is that the reaction
products are soluble and do not increase
the hardness of receiving waters.
Caustic soda is normally bled into the
suction side of a pump discharging acid
wastes.
This method is suitable for small volumes,
but for neutralizing large volumes of
acid wastewater, special proportioning
equipment should be provided, as well
as a suitably sized storage tank for the
caustic soda with a multiple speed
pump for direct addition of the alkali to
the flow of acid wastes.
When sodium hydroxide is used as a
neutralizing agent for carbonic and
sulfuric acid wastes, the following
reactions take place:
Na2CO3 + CO2 + H2O → 2NaHCO3,
carbonic acid waste
2NaOH + CO2 → Na2CO3 + H2O;
NaOH + H2SO4 → NaHSO4 + HOH,
sulfuric acid waste
NaHSO4 + NaOH → Na2SO4 + HOH.
Both these neutralizations take place
in two steps and the end-products
depend on the final pH desired.
For example, one treatment may
require a final pH of only 6, and thus,
NaHSO4 would make up the greater
part of the products; another
treatment may require a pH of 8, with
most of the product being Na2SO4.
Part-II
1. Using Waste Boiler-
Boiler-Flue Gas
Blowing waste boiler-flue gas through alkaline
wastes is a relatively new and economical
method for neutralizing them. Most of the
experimental work has been carried out on
textile.
Well-burned stack gases contain approximately
14% carbon dioxide.
CO2 dissolved in wastewater will form carbonic
acid (a weak acid), which in turn reacts with
caustic wastes to neutralize the excess
alkalinity as follows:
 CO2 + H2O → H2CO3,
flue gas wastewater carbonic acid
H2CO3 + 2NaOH → Na2CO3 + 2H2O,
carbonic acid caustic soda in wastewater soda
ash
H2CO3 + Na2CO3 → 2NaHCO3 + H2O.
Excess carbonic acid soda ash in waste
sodium bicarbonate in waste
The equipment required usually consists of
a blower placed in the stack, a gas pipeline
to carry the gases to the waste-treatment
site, a filter to remove sulfur and unburned
carbon particles from gases, and a gas
diffuser to disperse the stack gases in the
wastewater.
Stack gases evolve hydrogen sulfide from
wastewater that contains any appreciable
quantity of sulfur, and this H2S must be
burned, absorbed, or vented positively to the
upper atmosphere to prevent nuisance
conditions.
2. Carbon Dioxide Treatment for
Alkaline Wastes
Bottled CO2 is applied to wastewater in
much the same way as compressed air is
applied to activated-sludge basins.
It neutralizes alkaline wastes on the
same principle as boiler-feed gases (i.e.,
it forms a weak acid [carbonic acid] when
dissolved in water) but with much less
operating difficulty.
The cost may be prohibitive (the
financial burden of it is significantly
greater than the benefit ) however,
when the quantity of alkaline wastes
is large.
A textile mill producing about 6 million
gallons/day of alkaline waste studied the
practical aspects of this method and
found that installation of the equipment
necessary to provide bottled CO2 would
cost about $150,000 and the power and
fuel to generate it about $275/day—a
considerable expense, even for so large a
plant.
3. Sulfuric Acid Treatment for Alkaline
Wastes
The addition of sulfuric acid to alkaline
wastes is a fairly common, but expensive,
means of neutralization.
Storage and feeding equipment
requirements are low as result of its great
acidity, but it is difficult to handle because
of its corrosiveness.
The neutralization reaction that
occurs when it is added to
wastewater is as follows:
2NaOH + H2SO4→ Na2SO4 +
2H2O
wastewater sulfuric acid as
neutralizer resulting neutral salt
 Objective Questions
1. Using boiler flue gas is method of
neutralizing ________ wastes.
2. Well-burned stack gases contain
approximately _____% carbon dioxide.
 Theory Questions
Q1. Discuss necessity of Neutralization.
Q2. Enlist and discuss methods of
neutralization of acidic wastes.
Q3. Enlist and discuss methods of
neutralization of alkaline wastes.