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ChE 507E

Industrial Waste
Management & Control
Quiz #1, Equalization – Tuesday, Nov. 28, 2017
ChE 507E
Industrial Waste
Management & Control
Wastewater Pre-Treatment Processes

Nov. 23, 2017

Wastewater pH is one of the most common processes
in an industrial pre-treatment system.

Because of the various acids and bases used in

industrial manufacturing, processing, and cleaning
operation, most facilities need to adjust their
wastewater before disposing it to the surface water
or to the treatment plant.

Typical effluent pH:

direct discharge – 6.0 to 9.0 to protect receiving
municipal collection system – 5.5 to 10.0 to protect
the collection system from corrosion from corrosion
and the treatment plant processes for upset or
for biological treatment – 6.5 to 8.5 prior to reactor
pH and pOH
Describes the solution acidic or alkaline condition
The negative logarithm of the active hydrogen ion
concentration [H+] in moles per liter:
pH = - log[H+] = log 1/[H+]

The pH scale runs from 1 to 14

The neutral point (pH = 7.0) is the pH of pure water
at 25oC.
Acidic solution have pH below 7.0, Alkaline solution
have pH above 7.0.
A solution of pH 1 has 1 x 10-1 mole/li of [H+], and a
solution of pH 13 has 1 x 10-13 mole/li of[H+]

At 25oC, in a liter of pure water dissociate producing
identical concentration of free hydrogen and hydroxyl

[H+][OH-] = 10-14

The negative logarithm of hydroxyl ion [OH-]

concentration is called pOH.

pH + pOH = 14

Acid and bases dissociate in water producing [H+]

and [OH-]
Strong acids (like H2SO4) dissociate almost
completely. If 1 x 10-3 mole of strong acid is added
to liter pure water at pH 7, nearly all the acid will
dissociate producing 1 x 10 -3 mole [H+] and the
resulting solution pH would be about 3 5
Acid and bases dissociate in water producing [H+]
and [OH-]
Weak acids (like CH3COOH) dissociate very little
producing less [H+]

Acidity and Alkalinity
Useful concepts in determining neutralization
requirements, because more than just pH
measurement is required to adequately determine how
much acid or base is needed.
In neutralization of solution of strong acid, almost
all of the [H+] are quantified by pH measurement
because of complete dissociation.
In weak acid (like acetic acid), acid ions are are
available in both hydrogen and acetate ions. As the
free hydrogen ion added with the added base hydroxyl
ion to form undissociated wqter, more acetic acid will
disssociate to maintain the [H+] that existed when
the solution was at equilibrium.

Measure of the solution capacity to neutralize a
strong base to a designated pH, expressed as
equivalent amount of CaCO3 (mg/li)
The selected end point measurement had been
standardized at either as
a)“methyl orange end-point” approximately at
4.3 – 4.5
b)“phenolphalein end-point” 8.2-8.4
c)these end-point points corresponds to to the
carbonic acid system (H2CO3, /HCO31- /CO33-)
which is often the dominant buffering system in
wastewater treatment.

Acidity = (50000)(VB)(NB)/VS
VB = Vol. of base used to endpoint
NB = Normality of base used
VS = Vol. of sample

A measure of the solution capacity to neutralize
strong acids, and is expressed as equivalent amount
of (in mg/li ) of CaCO3.
Measure by titration with solution of dilute
sulfuric acid:
a)The 1’st step is phenolpthalein alkalinity (pH
8.3 – 8.5)
b)2’nd step is the methyl orange alkalinity (pH
c)The total alkalinity is the sum of both.

Alkalinity = (50000)(VB)(NB)/VS
50000 = equi. Wt of CaCO3, (mg/li)
VB = Vol. of acid used to endpoint
NB = Normality of acid used
VS = Vol. of sample, li

Example of a Typical Titration Data


Types of processes:
Mixing acidic & alkaline wastewater – this would
require sufficient equalization capacity to effect the
desired neutralization.
Acid waste neutralization thru limestone beds – this
maybe downflow or upflow system.

Acid waste neutralization thru limestone beds –
this maybe downflow or upflow system.

Mixing acid wastes with lime slurry – this
neutralization depend on type of lime used.
Neutralization can also be accomplished by using NaOH,
Na2CO3, NH4OH, or Mg(OH)2.
Basic (alkaline) wastes – any strong acid can be used to
neutralize alkaline waste, but cost consideration limit
the choice to sulfuric or possibly hydrochloric acid. Flue
gases with contain 14% CO2 maybe used by bubbling
thru the wastewater. CO2 in water form carbonic acid
with react with the base

Criteria in selection of neutralizing agents:
The following maybe used to help select
neutralization chemicals:
Type of neutralizing agent – whether base or acid
(or both) will be needed to control the pH. Both are
often needed especially if the wastewater
characteristic is highly variable & the target pH
range is narrow.
Capital cost – installation cost which includesthe
chemical storage tanks & building, pumping &
metering equipments, construction materials, safety
consideration, and the required instrumentation for
process control.

Operating cost – economic evaluation of netralizing
agents. The following equation maybe used:
Calk/acid = (Cbulk)(EW)/(Pbulk)(EWCaCO3)
Calk/acid = cost per unit wt. of alkalinity or
acidity as CaCO3
Cbulk = cost per unit wt. of bulk chemical
EW = equi. Wt. of chemical
Pbulk = fractional purity of bulk chemical
EWCaCO3 = equi. wt of CaCO3 = 50

Reaction time – this will affect the number, size , &
mixing requirements of the pH control vessels.
Solids (sludge) production & disposal – the amount
of solids generated is typically a function of the
wastewater’s composition, the reagents used, & the
final pH. The precipitated solids must be discharged
downstream treatment processes or removed,
processed, and disposed of.
Effects of overdosage – the maximum & minimum,
pH especially if the neutralization preceeds a
biological treatment process. Overdosing a highly
acidic water with caustic soda for example will
produce a very highly pH that may not meet the
succeeding treatment process or discharge

If this is a problem, another base will be considered
– like Mg(OH)2 which which will not raise pH
significantly because it becomes insoluble at pH 9.
Safety and ease of chemical handling – the types
and quantity of chemicals selected determines the
facilities required to receive, unload, store, & deliver
to the pH control system.
Side reactions – these could include soluble salts
produced which maybe objectionable in the effluent,
scale formation, and heat produced.

Common base and acid reagents used:

pH Control System:
A pH control system should consistently adjust the
wastewater pH within process control limit or
acceptable permit.
Batch pH control – typically used in plants with
intermittent or low volume wastewater. A maximum
flow up to 380 m3/day (100,000 gals/ day) is often
cited as applicable for batch control system. It has
the advantage of simplicity in equipments & control
system. The neutralizing agent maybe added during
filling or when the tank is full until the target pH is
reached, maintained for some time, then discharged.

Example of Batch pH Control System

Continous flow pH control – typically used when the
flow rate to be neutralized is > 380 m3/day ( >
100,000 gal/day), although much smaller system had
been implemented. This may have only one pH control
tank or may have multi-stage tanks. For with average
buffering capacity & minimal pH adjustment, one
tank maybe enough; but for widely variable
wastewater requiring large pH change (example 2 to
7), multistage maybe required. In this case pH is
“grossly” adjusted in the 1’st tank, and “fine-tuning”
are done with smaller amounts of agents in
subsequent tanks until the target pH is achieved in
the last tank, The target pH in each tank is
approximated by the titration curve.
Lecture ended here-Nov. 23

Example of 2-tank continous–flow pH Control System

Example of 3-tank continous–flow pH Control System

Mixing Requirement
oReaction tank geometry - for optimum mixing
efficiency, the cylindrical vessel depth should be
about equal its diameter. A square tank should be
approximately cubic. In a continuous –system, the
inlet and the outlet should be at the opposite side of
the reaction vessel to reduce short circuiting. To
avoid whirlpool effect due to the mixer, two or more
baffles should be provided. (baffle width typically
between 1/12 to 1/20 of the tank diameter. Square
tank mixing maybe sufficient without baffles.
oMixing must be provided in reaction vessel to
reduce the neutralization reaction time.

Mechanical mixing is typical. Hydraulic mixing using
circulation pumps or air injection maybe more desirable
The require mixing energy depends on the reaction
time, hydraulic retention time, and type of mixing
provided. The typical power requirement is about 0.04-
0.08 kW/m3 (0.2-0.4 hp/1000 gals.). Refer to Fig. 3.16.
Mixing should provide enough energy so the system’s
“dead time” is no more than 5% of the system’s
retention time. Dead time is the period between the
reagent’s addition and the 1’st detectable change in the
wastewater pH. A short dead time is required so the
control system can adjust the chemical feed rate based
on current information.

Neutralization example problem #1:
A highly acidic wastewater at flow rate of 0.38 m3/min
to be neutralize to pH 7.0 using a 2-stage continous
liming . Detention time for each tank = 5 min. 1’st stage
at pH=3.5, & 2’nd stage at pH =7.0 Based on this
wastewater titration curve (Fig. 3.14), estimate the:
a.) lime required, b.) tanks volume, c.) the power
requirement for each tank (use Fig. 3.16).

From the titration curve, at pH 3.5 & at pH 7.0, lime usage =
2025 & 2250 mg lime/li wastewater, respectively.
1’st stage lime dosage = 0.38 m3/min x 2025 mg lime/li x
1000 li/m3 x 1 kg/1000000 mg = 0.7695 kg lime/min
2’nd stage lime dosage = 0.38 m3/min x (2250-2025) mg lime/li x
1000 li/m3 x 1 kg/1000000 mg = 0.0855 kg lime/min
a.) total lime required = 0.7695 + 0.855 = 0.855 kg/min =
= 1231 kg/day
With 5 min detention time:
b.) Vol. = (0.38 m3/min)x 5 min = 1.9 m3 for each tank.
It was decided to have tanks of diameter = 1.4 m, and
height = 1.25 m (check on vol. = 1.92 m3) so that the
diameter & the depth are approximately equal.

To maintain proper mixing in each tank, the power level required
for each tank is calculated using Fig. 3.16:
ofor detention = 5 min, and
oD/T (turbine dia/tank dia) chosen = 0.33,
othe power level is 0.20 hp/thousand gals
oConverts this to hp or kw of the motor to be provided for
each tank.